TW470783B - Zinciferous plated steel sheet and method for manufacturing same - Google Patents

Abstract

A method for manufacturing a zinciferous plated steel sheet, comprises: forming a zinciferous plating layer on a steel sheet; and forming an Fe-Ni-O film on the zinciferous plating layer. The Fe-Ni-O film is formed by carrying out electrolysis with the steel sheet as a cathode in an aqueous solution, dipping the steel sheet in an aqueous solution, or spraying a mist on a surface of the zinciferous plating layer.

Description

470783

(Please read the precautions on the back before filling this page.) In addition to corrosion resistance and painting adaptablility, it is particularly important that the steel sheet has the excellent press formability, point Weldability and adhesive properties. However, roughly speaking, galvanized steel sheets have a press formability and are relatively cold-rolled steel sheets. The Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs printed the circle. The high-viscosity plated copper has high cracks in the cold space and is used to break the electrical and transverse molds. This copper leads to the formation of near-seed agents. It will create a gap with hair. This is the way to go. Easy to use paint problems. This steel is more a cause of the interface problem. The zinc-rolled sheet is made of high melting gold and cold-plated steel, and it is more and more consistent. The problem is to make the plate strength that is stable and short, and the method can not make the brittle shrinkage difference. It is necessary to have a life-changing change compared to Zizhong.-The formation of the ore-forming ore slip pattern is complete, and the pressure of the good middle school students is not enough to change the board, which is likely to cause the pressure of the melt. The non-greasy steel poles are attributed to the zinc that is removed by the current method, which can be: difficult to formulate the plating in the form of a medium, and even the force of the steel is very slippery. The zinc-resisting agent is over-lubricated, polished, and polished. The moving part is plated with lacquer. The weight of the pressing surface is heavier than that of the slippery. The steel is made of stainless steel, and the melted steel is made of zinc with relatively low viscosity. The paper size is applicable to China National Standard (CNS) A4 (210X 297 mm) 4 470783 A7 B7 Employee Consumer Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs Printing 5. Description of the invention (2— 1 1 | In addition, in the manufacturing process of the car body ηΆ, various adhesives are used to prevent rust and 1 1 1 to suppress vibration. Recently it has been understood that the adhesion of galvanized steel is not as good as cold rolled steel 〆, 1 I For a solution to these problems, Japanese Unexamined Patent Publication No. 〇. Please read 1 I 53 -6 0, 3 32 and N 0, 2- 190, 483--a kind of Table read back 1 1 side I side 1 is intended to be electrolytically treated for impregnation treatment, coating / oxidation treatment or heat treatment 1 I 1 1 > An oxide film mainly containing Z η 0 is formed to improve weldability or processing matter 1 and 1 I method (hereinafter referred to as "prior art 1"). Fill in this book and unexamined patent publication No. 4 ~ 8 8, 196 published a method of immersing a steel sheet containing 1 to 5 60 g / A of sodium phosphate P Η is an aqueous solution of 2 to 6 1 1 I or by electrolysis or spraying the aqueous solution to form an oxide film mainly containing an oxide of phosphorus on a 1 1 surface of a galvanized steel sheet The method of improving the compaction and chemical processability (hereinafter referred to as "prior art 2") is improved. 1 I This is an unexamined patent publication No. 3-191, 0 9 3 Oxide, Μ A method for improving press formability and chemical processability (hereinafter referred to as “K 1 1 1” “Prior Art 3 ") Μ and Japanese Unexamined Patent Publication No. 0.58-1 Μ 67,885 Published __ A method for improving the corrosion resistance of a metal such as Ni and Fe 1 1 1 by electroplating or chemical plating, which is not limited to 1 sheet of galvanized steel sheet. Above (K 下 简 ί Then, the previous technology 4 ”) 0 1 | ο-t. The previous technology described above 1? Steps and problems below. This prior art method is a method of forming an oxide film mainly containing 1 Zr on the surface of the plating layer through I 1 I by any different treatment 9. Its director has a limited reduction of the slip between the stamper and the plated steel 1 1 plate. The effect of resistance 9 is therefore limited to improve the press formability 1 | 〇 and this mainly contains Z η 0. oxygen. Ib film, will cause degradation of adhesion. 1 I previous technology 2 series a a generated mainly on the surface of the ship's steel plate. 1 1 This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 5 470783 Α7 Β7 Employees of the Central Standards Bureau of the Ministry of Economic Affairs Printed by a consumer cooperative V. Description of the invention (3-; 1 1 I Oxide oxide film method 9 Although it has significantly improved the efficiency of press forming 1 1 1 and chemical treatment f, it does cause point fusion and Disadvantage of Adhesion Reduction / -— S 1 I Disadvantages 0 Please read 1 1 | Advanced Technology 3 Series β ί Thin film containing nickel oxide of phase i, although stained on the back surface I can improve the press formability f However, it has the problem of adhesion degradation. 0 1 I means 1 I advanced technology 4-a kind of metal that only produces field technologies such as Ni, Μ improved corrosion resistance 1 I 1 I method 0 However 9 because of the thin film Strong Strong metal properties 9 Μ and metal guide 1 The low wetting ability of this package to the adhesive enables the imc m method to obtain sufficient adhesion. Page 1 I 9 Therefore, its improvement in press formability and spot weldability is less than 0 I 1 1 Summary of the invention 1 1 The invention of the present invention is to provide a galvanized steel sheet with excellent press-forming properties, weldability and adhesion 1 and excellent binding power, and a manufacturing method thereof. Method for steel sheet »1 | It includes the steps of forming a hafnium plating layer on a steel sheet > M and forming a Fe -N 0 film 1 on the galvanizing layer 1 粲 first > the step of forming a Fe -N 0 film It can include a steel sheet with galvanized layer 1 1 formed thereon as a cathode 9 electrolysis in an aqueous solution containing nickel sulfate, ferrous sulfate, and sulfur 1 I ferric acid. The total concentration of some lutetium sulfate, sulfur 1 j ferrous acid, and iron sulfate FE; the ratio of the concentration of 3+ (mo / 1) to the concentration of Fe2 + and 1 1 F €) 3+, and p Η »where: The concentration is in the range of 0 to 12 m 〇 / yi f, and the ratio of the concentration (κι 〇 1 / il) is within the range of (§E > to less than 1 1 1 0), M And ρ Η __ are in the range of 1 to 2 丨 〇1 I Second 9 Steps to form Fe-N ί--0 thin film * — It can be included that a steel plate with a galvanized layer 1 I formed thereon is used as the cathode t For electricity containing nickel sulfate and ferrous sulfate 1 1 This paper size applies Chinese National Standard (CNS) A4 specifications (210X29 < 7 mm)-β-470783 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Inventions Note (4) Electrolysis is performed in the plating solution. The total concentration of sulfuric acid and ferrous sulfate and P 具有 in this electroplating bath, the total concentration of which is in the range of 0.1 to 2 m ο 1 / A, and the pH is in the range of 1 to 3. This electrolytic system is performed under the conditions that the following equations are satisfied: 50 S Ik / (ϋ ^ · Μ) 150 Where M represents the sum of the concentration of nickel ions and ferrous ions (raol / A) in the plating solution; U represents the plating solution The average flow velocity (m / s); and Iκ represents the current density (A / dm2) in electrolysis. Third, the step of forming a Fe-Ni-O thin film may include immersing a steel sheet having a galvanized layer formed thereon, immersed in at least one of ferrous sulfate and ferrous nitrate, and at least one of nickel sulfate and nickel nitrate. One in an aqueous solution. The sum of the iron content Uo 1 / A) and the nickel content Uo 1/1) in the aqueous solution is in the range of 0.1 to 3.0 m ο 1 / A. The iron content (m ο 1 / il) in the aqueous solution ) The ratio of the sum of the iron content (in ο 1 / Jl) and the nickel content (mo 1/1) is in the range of 0.4 to 0.9, and p Η is in the range of 1.0 to 3.5. Within this range, M and temperature are in the range of 20 to 70 ° C. Fourth, the step of forming the Fe-Ni-O thin film may be performed after a steel sheet having a galvanized layer formed thereon is treated in an alkaline solution having a PΗ of at least 10 for a time range of 2 to 30 seconds. The step of forming a Fe-N i -0 thin film may include forming a galvanized layer on the steel sheet containing F e C 1 2 and Ni C 1 2 and p Η between 2.0 and 3.5. Treatment is carried out in an aqueous solution in a temperature range of 20 to 70 ° C. The step of forming the F e-Ni-0 film may include a steel plate having a hafnium plating layer formed thereon, in a temperature range of 20 to 3.5, containing FeCl2 & NiCU, and a pH in the range of 2.0 to 3.5. In the range of ° C, the content of M and Pe (the paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) n I ---------- installation ------ order ------- line (please read the precautions on the back before filling out this page) 470783 A7 B7 V. Description of the invention (5) The solution content is contained in the ratio and the fifth one in the liquid solution. The inner part of the water 1-round T, the range of F, including 9 steps, including a thin film film Θ F, containing 5 3 to 11 spraying liquid-soluble mist as ρ ρ and sub-zero 0 1 Ν and ο 1 × in The total weight of the unit weight of the repetitive package is stopped to form the lower gold shape M and the temperature is sprayed into the shape of V. Above the layer of zinc plating on the above table, the steel plate is left to heat up and the steel plate is heated to M for 2 seconds. 2 The layer of zinc is plated on the sheet steel, which is caused by horses or islands and the inner range is% ο 9 to ο 3

Shaped cloth made of Fe, which can be stepped in six grams. The film is thin and thin-0, which is repeatedly covered by the system. The weight of Fe is equal to the weight of copper. The element of zinc is plated in Jinsheng and the layer of K is zinc. The finely-formed upper layer is plated with zinc and the thin-layered layer is plated with zinc. This is because of the horse race or the island. 内 9 to ο 3 at the rate h -LU * 1 covered with -N i Θ. Encircling the Fank film sheet steel 1-T Fe on the formation of the formation of the first seven layers of zinc plated with pressed IL fire brackets can be stepped on the newly formed upper layer of the film sheet surface (please first (Read the notes on the back before filling out this page).

1T Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs on the basis of the amount of Fe i-coated with 1-pack-N. The total zinc-plated element is a thin layer of gold and M M film-formed on the upper layer. And this is because the Fanke BMW or the island island and the inner range of the range% ο 9 to ο 3 ^ 1M. 0 rate ο h-u- ·-· »li covering the inner surface of the envelope Fe ′ decomposition of the upper soluble surface Μ Table I The liquid zinc of the middle layer is soluble in alkali, or the liquid film dissolves the oxoacid gas in a layer of 1-soaked-N plated Fe steel, which is coated with zinc. The zinc coating on the living layer can cover the film. The paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) 8 470783 A7 B7 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Explanation (6) 1 | Form active and inactive parts * Μ and form active | inactive parts 1 | on the plated layer formed thereon > to form Fe -N-0 film. 1 I nth t The step of forming a Fe 1-0 film may include: making a plated layer first, read the steel plate formed on it, and perform an anode electrical reading in an acidic or alkaline solution. I δ I solution t dissolves the air oxide film 9 existing on the surface of the galvanized layer and forms the active and inactive portions on the surface of the zinc coating Note 1 I | 1 and the active and -fnr matters 1 True I | The active part is formed on the galvanized layer thereon to form Fe -N 1-0¾. The film writing device is tenth to form the Fe -N 1-0 film. This step may include 0.3 to 5. 0¾ Page 1 Tempered rolled copper sheet with galvanized layer formed on it in the range of elongation i 1 1 Alkali treatment of tempered rolled steel sheet in alkaline solution on P Η 1 0 Μ 2 1 1 to 30 seconds Μ and forming an order of Fe-Ni-0 film on the surface of the galvanized layer subjected to alkali treatment < 1 1 tenth > The step of forming the Fe-N • 0 film may include: In the test solution above, the alkali treatment is performed on the steel plate on which the galvanized layer is formed. The time is 1 to 2 to 30 seconds; within the elongation range of (.3 to 5.02), i temper rolling, wire Steel plate subjected to alkali treatment > M and Fe-hi-0 film formed on the surface 1 1 of the tempered rolled steel plate 0 1 I In addition, the present invention provides a galvanized steel plate including: steel plate> 1 1 1 galvanized layer M on the steel sheet and F ((-1 i--0 film formed on the galvanized layer were formed. 1 1 Does this Fe-l · 1 i--〇 film have island shape or mosaic? Shirt-type, with a coating weight of 1 1 Μ F e-bi--0 The total weight of metal elements in the film is in the range of 10 to 1500 i ng / m 2 1 1 »and the surface coverage is in the range of 30 to 9 0% of the encircled 0 1 I This galvanized layer is an alloy zinc immersion ill layer, and the alloy zinc immersion plating layer contains 6 1 I to 1. wt% of 'e, and a sufficient amount of Z 1 η, positive Existing things with 20 1 1 This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) -9-470783 A7 B7 V. Description of invention (7) (Please read the notes on the back before filling This page) to 100s / ni2 coating weight. The Fe-Ni-0 film is formed on the surface of the zinc-plated alloy coating. The Fe-Ni-O film has a total weight of metal elements in the KFe-Ni-0 film, and is a coating weight in the range of 10 to 1500 mg / m2: and an Fe content in the range of 0.004 to 0.9 (wt! The ratio of U to the content of Fe (wt%) and the content of Ni (v / U); M and the oxygen content in the range of 0.5 to 10wt%. The galvanized layer is an alloy zinc impregnated layer; the alloy zinc impregnated layer The plating layer contains 9 to 14 wt.% Fe, a sufficient amount of Zn and inevitable objects, and has a surface alloy phase M of 81 alloy phase and a coating weight of 20 to 100 g / m2. Fe-Ni-0 thin film system Generated on the surface of the alloy zinc-dip coating. The Fe-ίΠ-Ο film has a total weight of metal elements in the MFe-Ni-〇 film based on a coating weight in the range of 10 to 1500 ntg / ra2; and in the range of 0.004 to 0.9 The ratio of Fe content UtiU to Fe content UU) to the sum of Ni content (wU); M and oxygen content in the range of 0.5 to 10 wU. The simple description of the diagram is shown in the figure. The figure is shown in the figure. The figure is a rough outline. It is printed by the Central Standards Bureau of the Ministry of Economic Affairs.略 i 略 Η Slightly 5tr profiler $ Scoop 6 ί β-iB l · — Inch ruler CO Ruler \ — / A type margin circle / | \ margin circle type < f < species 1 Figure of the shape of the \ 1 / B-type margin circle / | \ The type of the marginal circle type II. The diagram of the approximate method of the French method is used to test the combination of the force and stickiness. 4 ο The visual acuity is pulled in and the peel strength is measured in the test. The test force is adhered to the outline. 兑 &; 5 ώ The chart is shown in the paper. The paper dimensions are applicable to the Chinese National Standard (CNS) Λ4 specification (210 X 297 mm) 10 470783 A7 B7 V. Description of the invention (8) The reason for the fact that the steel plate in the middle plate is zinc plated is not as good as the basic case. ; The figure between the rubbing number 34 and the repeated coverage is UL ^ πυ ft 8, the amount of salt in the difference bath, acid renitration, and the salt in the bath, N1 acid, sulfur, and the solution of the salt, the chlorine solution is dissolved in the immersion place. M film Mingcheng said-0 is the lower value of the Ni diagram. Ｐ Tong is not immersed in the case of slicing the steel plate of the phasor repetition in the case of slicing, and the example of the plate is provided with a note of 1 issued. The example given is the figure 9 of the figure ay. The sheet steel. Zinc-plated example has a bright hair certificate of 1. According to the illustration, the outline of the drawing is roughly 10, and the reason is that the details are carefully re-appeared, and then it is shown that it is plated on this roll with hot-rolled steel and zinc back to the steel. In the figure, it is slightly rougher, the whole surface is formed into a thin film, and the whole plate is flat. When the zinc plated surface is used, the example of the body is a plate and steel. The zinc is plated. Gen's Explanatory Diagram is a sketch of the outline of the 11th thin film (please read the precautions on the back before filling out this page). Install. -¾ Printed by the Central Consumer Bureau of the Ministry of Economic Affairs, Consumer Cooperative, and the vertical film Oxygen steel gas-N zinc hollow Fe plating is formed on the surface and the surface surface of the plate is plated with steel and then zinc. The medium pressure is according to its rolling root, and the fire is shown back. Said that the picture line is a brief summary of the 12 outlines. The active part of the electric pole part is insoluble in the living fluid and the acid is active or formed. The upper surface liquid is soluble and the acid is responsible for the precipitation. »Yl dissolution is combined by the force of the dissolving meridian department. The special body of the steel layer zinc zinc plating and the bright film processing are learned from the Department. The evaluation of the plan is based on the clear method of the outline of the 13 method of the fire back plating and the • II principle N place 'The solution under the condition of the alkali condition is under the steel board. The steel description shows the progress in the past and the example is true.' The figure from the bottom of the case is 4 -1. The paper size is applicable to the country of China. Standard (CNS) Λ4 specification (210 X 297 mm) 470783 A7 _B7 _ ^ _ V. Description of the invention (9) The relationship between the coating weight and friction coefficient of the steel plate. Figure 15 shows the difference in coating weight of tH on galvanized steel when K is immersed in chloride bath, sulfate bath, and nitrate bath as the treatment liquid for Fe-Ni-O film. Illustration. Fig. 16 is a graph showing, by way of example, the coating weight of Ni against the galvanized steel sheet with respect to the impregnation time when pΗ is changed. FIG. 17 is a schematic perspective view showing a sample after a forest > cup deep drawing test. FIG. 18 is a schematic cross-sectional view showing a draw bead testing machine for inspecting powdering resistance in an upright manner. FIG. 19 is an enlarged view of a part of FIG. 4. Fig. 2 is a diagram showing the shape and size of the rounded edge tip. Description of specific examples Specific example 1 Printed by the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs The inventors have conducted extensive research to solve the aforementioned problems, and the hairpin is formed by forming appropriate Fe on the surface of the electroplated layer of galvanized steel -N i-〇 film, can greatly improve the press formability, point weldability and adhesion. The findings obtained in this case indicate that appropriate F e-Ni-0 films should meet the following conditions (1) to (3): (1) The coating weight of the film is between 10 and 1,500 mg / m 2 range; (2) the ratio of Fe content in this film U t.%) to the total content of Fe and Ni content (wt.%) (M hereinafter referred to as “Fe ratio in film” "And expressed as" F e / (F e + Ν ί) ") is within the range of 0.05 to 0.9, or more preferably from 0.1 to 0.5; and this paper size applies China National Standard (CNS) A4 (210 X 297 mm) (Please read the notes on the back before filling out this page) -12-470783 A7 B7

Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs I. V. INTRODUCTION (10) 1 1 I (3) ϋ] The gas content of 1 in the film is in the range of 0.5 to 10 W t.%. 〇1 | Galvanized The press formability of the steel sheet is worse than that of the cold-rolled steel sheet, because under the high surface pressure of 1 I, the zinc with a low melting point will stick to the horizontal t and increase the sliding resistance. 0 Please first M 1 1 | To avoid this inconvenience 9 An effective method is to form a thin film on the back I | I surface of the galvanized steel plate with a higher hardness and higher melting point than the zinc or zinc alloy plating layer. Note 1 1 I It will reduce On the surface of the plating layer and the stamper during the press forming process! 1 1 I The sliding resistance r between 1 and I makes the plated steel plate slip into the stamper> Therefore, fill in 1 to improve the press formability. This page, Sw〆1 | The continuous increase point of zinc steel sheet is worse than that of cold rolled steel sheet. Because the molten zinc contacts the copper electrode during welding 1 1 ', a brittle alloy layer is formed. 9 Its 1 1 will cause more serious degradation of the electrode. 0 The method of forming a thin film with a high melting point on the surface of the layer is believed to be effective in improving the weldability of the wall-to-wall spots. 1 1 0 is to improve the spot weldability of the galvanized steel sheet. The results of the study found that the use of Ν metal is particularly effective. Although the original 1 1 is not yet understood, it may be due to the high melting point and high conductivity of the Ni metal. The 0 1 line is known to have colder rolling due to its adhesion. The steel sheet is inferior f, but the reason 1 1 is not clear. 0 Due to the study of the reasons for this inferiority * The inventors have explained 1 I The chemical group of the adhesion is affected by the oxide film on the surface of the galvanized layer Cheng Shou dominates 〇1 1 | More specifically > Although the oxide film on the surface of the cold-rolled steel sheet mainly contains the oxide of 1 1 Fe t, the thin film on the surface of the galvanized layer mainly contains Z η The adhesion of 1 1 oxide varies with the chemical composition of the oxide film. Zr 丨 The oxidation of 1 1 has a lower adhesion than that of oxide. Therefore, it can be used as in the 1 I invention. 9 on the surface of galvanized copper sheet to produce a thin 1 1 I film containing 3 oxides to improve the adhesion. 0 1 1 This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 13-470783 A7 B7 Economy Printed by the Ministry of Standards and Labor, Consumer Cooperatives V. Description of Invention (1) The present invention is based on the discovery 9 described above and developed and provides a 1 I via the surface of the galvanized layer of galvanized steel To form Fe-N i-0 1 I film properly Manufacture of galvanized steel with excellent press formability Λ point weldability and adhesion. Please read 1 | Method of steel sheet 〇Read back | © I So Fe -N i-〇 The film has a film that contains at least Ni and Fe metal Note 1 I means 1 1 and the microstructure and form of the mixture of oxides of Ni and Fe, regardless of the combination of if! | 1 and the combination of the elements into a thin film can meet the requirements. 0 Fill 1 Specific writing The method of manufacturing a galvanized steel sheet in Example 1 is characterized in that it includes K page S ^ / 1 | The galvanized steel sheet is used as a cathode for electrolysis in a 1 1 aqueous solution containing 1 臬 sulfuric acid, ferrous sulfate, and iron sulfate, and thus galvanized The surface of the electric ore layer of the steel plate is shaped! 1 The step of forming a thin film, in which the Fe-N 1-0 thin film is made through the nickel sulfate 1 in the 1 1 Λ total concentration of ferrous sulfate and iron sulfate. The ratio of the concentration of F e 3+ (1 ο 1 / ϋ) in the range of '3 to 2 · 0 m 〇1 / 对 to the total concentration of Fe 2 及 and F e 3+ is 1 1 1 from 0.5 to In the range below 1.0M, M and P are electrolyzed in an aqueous solution 1 of 1.0 to 2.0 to produce 0. The galvanized layer of this galvanized steel sheet may have a range of 7 to 15 W t.%. The alloy is impregnated with iron content. The plating of this galvanized steel sheet! | The layer can be a zinc plating layer or a zinc dip coating layer. In the present invention, nickel sulfate, ferrous sulfate, and iron sulfate are used as The composition of Fe-N i--0 film under the aqueous solution 1 1 on the surface of galvanized steel plate is abbreviated as "-electricity selection solution"), because M galvanized steel plate is used as cathode 1 1 to make F The electrolysis of e-^ i--0 film formed on it is suitable for efficient ί 111} 1 I into a film containing F e ^ N and 0. 1 I Total concentration of sulfuric acid-bound ferrous sulfate and sulfuric acid m, based on κ under Reason »1 1 I Should be in the range of 0 3 to 2.0 mol / A. 0 I 1 This paper size is applicable to the Chinese National Standard (CNS) A4 size (210X 297 mm). Standard (CNS) A4 specification (210 × 297 mm) A7 B7 V. Description of the invention (12) If the total concentration of the three chemical components is below 0.3 tno [/ Λ K, the low conductivity of this electrolytic cell will produce a relatively low High electrolytic voltage. Therefore, even with low current density, electroplating scorch (P 1 atingbur η) will proceed too much, and the oxygen content in the Fe-Ni-O film will exceed 10wtJ, which will easily cause spot weldability. On the other hand, if the total concentration of such ingredients exceeds 2.0 mol / il, at low temperatures, nickel sulfate and / or ferrous sulfate will reach the solubility limit, which will cause nickel sulfate and / or sulfuric acid. Precipitation of ferrous iron. For reasons of M, an aqueous solution with p Η in the range of 1.0 to 2.0 is used as the electrolyte. Electrolyte at pH 1.0M * Hydrogenation plays a major role in the cathode reaction during electrolysis Role, resulting in significantly reduced current efficiency. On the other hand, in electrolytes with p Η exceeding 2, there will be precipitation of iron hydroxide. The ratio of the concentration of F e 3+ (mo 1 / A) to the sum of the concentrations of F e 2+ and F e 3+ (mo 1 / λ) in the electrolyte is limited to 0.5 based on the reason of K. 5 To a range of down to 1.0 M. In my opinion, the oxygen in the F e -1U -0 film mainly contains oxygen existing in the oxide of eutectic iron. In order to make the content of oxygen in the film at least a specified value, it is preferable to increase the concentration ratio of Fe3 +, which is lower than that of Fe2 +, with respect to the concentration ratio of Fe2 +. In order to reach an oxygen content of at least 0.5 wt% in the Fe-H i-O film, the concentration of F e 3+ is U 〇 / A) to the concentration of F e 2+ and F e 3+ (m ο 1 / A) The ratio of the sum must be at least 0.5. A higher Fe 3+ concentration (m ο 1 / 殳) ratio will result in a higher efficiency of achieving eutectic iron oxide in the Fe-Ηί-0 film. F e 3+ produces hydroxides at p 较 lower than F e 2+ (for example, -15-. Rapture. Girl (please read the precautions on the back before filling this page) 470783 Central Standard of the Ministry of Economic Affairs A7 B7 printed by the Bureau ’s Consumer Cooperative Fifth, the description of the invention (13) The concentration of 0.1 m ο 1 / A, respectively equivalent to 2.2 and 7.5 p Η), is caused by electrolysis on the surface P Η increases, making it ribbed to eutectic precipitation of the oxide. The temperature of the electrolytic cell need not be limited to a specific range. However, at temperatures below 30 ° C, the conductivity of the electrolytic weight will become lower, resulting in a higher electrolytic voltage. On the other hand, at a temperature of 70 ° CK, there is an increase in the amount of vapor in the electrolyte, which makes it difficult to control the concentration of nickel and iron ions. Therefore, the temperature is preferably in the range of 30 to 70 t :. There are no special restrictions on the current density of electrolytic plating. However, at a current density of 1A / dni2M, a significant decrease in current efficiency occurs because hydrogenation plays a major role in the cathode reaction. On the other hand, the current density at 150A / dm2 K will produce matte precipitates, which will cause many nickel and iron hydroxides to sink, resulting in lower weldability. Therefore, the current density should be limited to the range of 1 to 150 A / dm2. In the present invention, in the ore-zinc steel sheet used to form a F eN i -0 film on its surface, the surface of its plating layer should include an alloy immersion plating layer, plating layer, or immersion coating having an iron content of 7 to 15 wt.%. Plating is preferred. The reason for this is that the galvanized steel sheet * having any of these electroplated layers is inferior in workability, or especially press-formability, and cold-rolled steel sheet or zinc-nickel-plated steel sheet with weak point weldability. Forming a Fe-Nί-0 film on the aforementioned electroplated layer has a significant improvement effect on press formability and spot weldability. The electrolytic solution may include cations of metals such as Z η, C ο, Μ η, Μ 〇, A 1, T i, S η, W, S i, P b, N b, and T a, which are included in In the galvanized layer1 The vapors and hydroxides of these gold tinctures, as well as the anion apart from chlorine cations. The paper size applies the Chinese National Standard (CNS) Λ4 specification (210X 297 mm) —.----- -c Order, please (please read the notes on the back before filling this page) 16 470783 Α7 Β7 Printed by the Consumers' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (14) 1 1 Ι Sub 0 1 1 The galvanized steel sheet used is a steel with a galvanized layer formed on the surface by any method such as the dipping S 1 1 plating method and the steam plating method. Please read 1 sheet. This galvanized layer is in addition to pure zinc. In addition, it also includes a single layer or a plurality of notes containing one or read back 1 & I, such as F e ^ Ni, Co, M η Λ Cr A 1 Λ Mo, Ti > S ί, W, S η Note 1 I means 1 1 Λ Pb% Nb Ta (S i also seen as a metal) of a metal or its oxide, or event 1 j 1 1 then m has a tear substance plating layer. The electroplated layer may further include particles C such as S⑷ and ϊ 1 copybook A 1 2 03. The galvanized layer may include a plurality of layers each having the same composition but different contents of page 1. In addition, the galvanized layer may Contains a number of layers that each contain the same 1 1 I component 9 but whose content changes continuously in the thickness direction, which is referred to as “fun C ti ο na 1 gracient P 1 at ί ng 1 ay er S ) ". 1 The 1 1 Fe -N 1-0 film formed on the surface of the galvanized layer of the galvanized steel plate under the stated restrictions can eliminate the 1 I adhesion between the steel plate and the mold during the press forming process, reduce the sliding resistance, Improve the smoothness of entering the mold and suppress the formation of a brittle alloy layer between the steel plate and the copper electrode during the spot melting 1 I 1 bonding process. Therefore, the continuous spot welding performance is improved by 1 wire, and the oxides containing Fe The film is used 1 to improve the adhesion. The coating weight of the Fe-N i-0 film (the total converted weight of the metal elements in the film) of the Fe-N i-0 film at 10 in g / m 2 Μ cannot obtain the effect of improving the formability of 1 I compression. On the other hand, the effect of improving the press formability at 1 1 1 coating weight at 1,500 0 ir 8 / m 2 Μ has reached saturation 0, so 1 1 Fe-\ 1-• 0 film wrap The covering weight (total converted weight of the metal elements in the film 1 1) should preferably be in the range of 0 to 1,50C mg / m 2. 1 1 Such as the ratio of the Fe content in the film F e-bi-〇 wt.%) To the sum of the Fe content and t 1 ί content-fs 1 I (wt * S!) (F'e / < (F e + N i)) 0. 0 5 Κ down i 1 This paper size is applicable to China National Standard (CNS) A4 (210 × 297 mm) -17-A7 B7 Off-line Consumer Cooperatives, Central Standards Bureau, Ministry of Economic Affairs Printing V. Description of the invention (15) 1 1 1 can not obtain the improvement effect of adhesion 0 and the other 9 when thin. 1 1 F e / (Fe + Ν ί) in the film exceeds 0.9 > The reduction of the Ni content in the film leads to a reduction in the proportion of the high melting point Zn-Ni alloy produced during the welding process ^ -N 1 |. This will cause β ί to be charged. Please read 1 pole and cause more serious degradation > The item that hinders the improvement effect of the point fusion property is achieved on the back surface 1 to reach 0 1 | Italy I. Therefore, the Fe / (Fe + Ni) ratio in the film should be between 0.5 and 0.9. The range is better than the matter 1 and 1 I is better »or from 0.1 to 0.5 is better 0 4 The best range of oxygen content in the 1-pack Fe-N i-0 film is 0.5 to 10 wt.% 〇In the oxygen content of page 1 I 0. 5 wt., The metal β of the film becomes more prominent 1 1 | Therefore, the improvement effect of reducing the press formability 0 Another aspect is 10 W t Λ > × Oxygen content on 1 9 The amount of oxide becomes too large > causes an increase in the surface resistance1 Order-, reduces the weldability, and suppresses the generation of phosphate crystals > causes 1 1 the degradation of the chemical treatment 〇1 I Example 1 1 I Any of electroplating types GA-GI and EG under galvanized steel sheet line 1 before electrolysis by the method of the present invention or a comparison method are generated thereon: 1 i GA: generated by Contains 10 wt. Ge of Fe and sufficient amount of Z η 9 and two surfaces Alloy dip coating t 1 IGI with a coating weight of 60 in g / in 2 on each 1 1 surface: \ 1 I immersion coating with a coating weight of 90 g / m3 is formed on each of the two surfaces t 1 1 EG: On each of the two surfaces, t is formed with a coating weight of 40 g / m Σ-of 1 1 plating layer 0 1 1 with galvanized steel as the cathode > in a sulfuric acid mirror containing a specified concentration, sulfuric acid 1 1 m and ferric sulfate in a mixed solution for electrolytic treatment) Therefore, in the forged steel 1 1 this paper size applies Chinese National Standard (CNS) A4 specifications (2 丨 OX 29? mm) -18-470783 Μ 5. Description of the invention ( 1G) A film of F e-Ni-0 is formed on the surface of the plate, and a sample is prepared. However, for some samples, the electrolytic treatment is omitted. Table 1 shows Examples 1 to 20, K and electrolysis under conditions within the scope of the present invention and comparative cell examples 2, 3, and 5 where electrolysis was performed under conditions in which at least one of the conditions is not within the scope of the present invention. Electrolytic conditions. Regarding Comparative Examples 1, 4, and 6 in Table 1, the treatment was limited to immersion in the electrolytic solution, and no electrolytic treatment was performed. Table 1 also shows the type of plating, the chemical composition of the electrolyte, ρ Η, temperature, current density, and time before the electrolytic treatment. . ^ 纟 定 纟 (please read the precautions on the back before filling this page) Printed by the Central Consumers Bureau of the Ministry of Economic Affairs, Consumer Cooperatives This paper is sized for the Chinese National Standard (CNS) A4 (210 X 297 mm) 19 470783 A7 B7 V. 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10 ID i 昆 湿 w «--改 遐 w 镒 qq Magic Bandit 5SSM Inch K 捶 K 捶 ssw lsffiw ε Kuangyaw®- -ssw USSM 01 囷 倕 91 SE Bu M s ^ ®9 * Bu Tu Bu 》 2 菡 捶 脒 ®- iiEffiKB- 91 Ji Jin Yi Yi--Ε $ Μ *--Bandit **-萑 bury »?!-9 菡 遛: w®- 03 玄 里 w 6- 众 街》 This paper scale applies Chinese National Standard (CNS) Λ4 specification (210X297 mm) 20 470783 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (18) Concentration of ferrous sulfate to ferric sulfate in the electrolyte The ratio is controlled by adjusting the concentration of the added chemical. However, when the ratio of ferrous sulfate to iron sulfate changes with the progress of the electrolysis, the ratio is determined by using an oxidizing agent such as hydrogen peroxide. When added to the electrolyte, M oxidizes ferrous ions to iron ions, or controls M by contacting iron ions with metallic iron to reduce them to ferrous ions. Regarding the formation on each of the samples treated by electrolysis described above Fe-Hi-0 film, measure the coating weight of this film (the total converted weight of metal elements in the film), film according to the method under K The Fe content (wtj) U t of Fe and Ni content.% Ratio) of the sum, Μ and oxygen content of the film. [Measurement of coating weight of film (total conversion weight of metal elements in film) and F e / (F e + Ν 丨) in film] Regarding samples of plating type GI and EG, the Fe-lU-〇 film The coating weight (total conversion weight of the metal elements in the film) and chemical composition are obtained by dissolving the F e-Ni-0 film M and its electroplated layer (zinc plating layer; the same applies hereinafter) through the dilute hydrochloric acid. , To cause peeling, and K IC P method (abbreviation of Inductively Coupled Plasma Spectroscopic method) quantitative measurement of Fe and Ni and measured. The Fe / (Fe + Ni) ratio in the film was then calculated. Regarding the sample of electroplating type GA, since the lower plating layer contains the constituent elements of the F e-Ni-0 film, it is difficult to make the constituent elements in the upper F e-Ni-0 film and the lower plating layer by ICP method. The constituent elements are completely separated. Therefore, only the component elements of the F e-M i-0 thin film not included in the underlying plating layer were quantitatively analyzed by the I C P method. In addition, after Ar ion spattering, the paper size is -21-this paper size applies the Chinese National Standard (CNS) Λ4 specification (210X297 male f): -1 ordering (please read the precautions on the back before filling this page) 470783 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (19) Abbreviation for M XPS method (X-ray P h 〇t 0 e 1 ectr ο η Spectroscopic method) ), Starting from the surface of the film, repeatedly measuring each component element of the Fe-Ni-O film, and measuring the chemical composition distribution of each component element in the Fe-Nί-〇 film to the depth of the plating layer. In this measurement, the distance between the maximum concentration of the constituent elements of the Fe-N i -0 film that is not contained in the underlying plating layer and the position equal to one and a half depths where the other element can no longer be detected, Considered the thickness of the Fe-Ni-O film. The coating weight (total conversion weight of metal elements in the film) and chemical composition of the Fe-Ni -0 film are calculated from the results of the IC P method and the XPS method. Then calculate the FeWFe + NU ratio. [Measurement of Oxygen Content in Thin Film] The oxygen content in the thin film is determined by the analysis result in the depth direction according to AES, Au electron electron spectroscopy. Table 2 shows each of the samples obtained from the cell examples 1 to 20 and comparative examples 1 to 7, namely, the sample No. 1 of the present invention No. 1 to 20 and the comparative sample No. 0.1 to 7-Fe-Ni -0 The measurement result of the coating weight of the film (the total conversion weight of the metal elements in the film), the F e (F e + H i) ratio in the film, and the oxygen content in the film. ----------- Installation ------ ir ------ i (Please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) Μ specifications (210X297 mm) -22-470783 A7B7 V. Description of invention (20)

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Is®10®- ° KffiKSSSK ^ sffiwεκ®MSS? K-in mw 2tKffiw hs, 8w olEffiw 6 encirclement rights: issw SM-'^ S, -11 2E buried w »qq-^^^-9iE buried w» --sffiwaq: j -zhongjie 軚 bismuth- 9kunli tt2f- inch 菡 swffi- 0? 玄 bury 51 2SSK u " s-9-pendulum®- This paper size applies to China National Standard (CNS) Λ4 specifications ( 210X 297 mm) -2 3 470783 A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (£ 1) Next, the measurement of the friction coefficient in the spot welding and the continuous points are as follows: Weldability test and adhesion test, M evaluated the press formability, spot weldability and adhesion of samples Nos. 1 to 20 and comparative samples Nos. 1 to 7 of the present invention. [Measurement of Friction Coefficient] FIG. 1 is a schematic front view illustrating a friction coefficient measuring device. As shown in FIG. 1, the friction coefficient measurement sample 1 taken from the sample is fixed on the sample holder 2, and the sample holder 2 is fixed on the upper surface of the horizontal movable sliding table 3. The lower surface of this slide table 3 is provided with a vertically movable slide table support 5 having a roller 4 in contact with the lower surface. The first force gauge 7 for measuring the pressure load N on the friction coefficient of the sample 1 by pushing the sliding table support 5 upward by the edge 6 cell is mounted on the sliding table support S3. Under the action of this pressing force, one end of the sliding table 3 in the horizontal moving direction is connected to a second force measuring device 8 for measuring the sliding resistance F of the sliding table 3 horizontally. The coefficient of friction w between the sample and the rounded edge is calculated by the formula: "= F / Ν. In this calculation, the pressure load N is 400 kgf, and the pulling speed of the sample (the horizontal moving speed of the slide table 3) is 100 cm / minute. The edges used are of two sizes and shapes under M. Fig. 2 is a schematic perspective view illustrating the shape and size of the first type of rounded edge (hereinafter referred to as "rounded edge type A"). Among them, the lower surface of the K-circle edge 6 is slid against the surface of the sample 1. As shown in Figure 2, its lower surface has a width of 10mra and a plane with a length of 3mπm in the sliding direction, > and 1/4 cylindrical surfaces with a radius of curvature of 4.5 mm, which are connected to the front surface and the rear The boundaries of 10 in nt width on the surface are in contact. ---------- ^ ------, 玎 ------ line (please read the precautions on the back before filling this page) The paper size applies to China National Standard (CNS) A4 Specifications (210X 297 mm) 470783 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (22) 1 1 I Figure 3 illustrates the second type of direct M (U hereinafter referred to as "gap; Shape Β. &Quot;) Shape 1 | Shape and Dimensional Perspective View 0 In the round edge type B, the length of the sliding side 1 of the slayer 'I increases from 3 mm r in the round edge type A to 60 mm 1 Please read 1 for the rest. Same as round edge type A. Read back 1 Side 1 Among the two types of A and B »Μ N i ho η Per rkeriz in g Co Lt d. Note 1 I Meaning 1 1 NOX RUST 550 ΗN manufactured as a lubricating phase is applied to samples s 3 1 The above matters! I and 1 I On the surface, measure and test the friction coefficient of K. Guide 1 Mabenz [continuous point weld test] Page 1 I Two samples of the same number 9 Μ. S one way above> 1 1 Placed between one pair of electrode welding machines of the spot welding machine »Power on the stacked samples 1 1 * At the same time, apply pressure, so the centralized welding current is connected to the resistance of M Welding, that is, point welding under the conditions of M 1 I * Electrode crystal: Dome-type crystal with a diameter of δΐϊΐϊπ 1 1 I * Compression force: 250kgf 1 1 * Welding time: 12 cycles (6 0 Η z) 1 wire * Welding current: 11. 0ΚΑ 1 1 * Welding speed: 1 point / second 1 1 Μ During the point welding process, 1 1 | of the molten and solidified metal portion (hereinafter referred to as 'point welding block') produced in the welding area between two overlapping samples "), the straight I 1 diameter becomes less than 1 IU of 4 X (t: thickness of the sample), and the number of consecutive 1 1 point weldings is performed. This point is referred to as the point where the weldability of the joint mine is 0 Μ It is 1 1 ”, the life of the psychic pole ". 1 I adhesion test] 1 1 | Adhesive test specimens under M prepared from each sample 〇1 1 This paper size applies to China National Standard (CNS) Λ4 specification (210X2W (Mm) 470783 A7 B7 V. Description of the invention (23) Figure 4 is a schematic perspective view illustrating this combination method. As shown in FIG. 4 ′, the test piece 13 is obtained by placing one of two samples 10 with a width of 25 mm and a length of 200 mm on the other, and a spacer 11 having a diameter of 0.1 5 mm therebetween. The adhesive 12 has a thickness of 0.15 ni in, and is prepared by bonding the two samples. The test piece thus prepared was dried at 150 ° C for 10 minutes. The test specimen thus prepared was folded into a T-shape as shown in FIG. 5, and a tensile test was performed at a speed of 200 mra / min by a tensile tester, and the average peel strength (η = 3). The peel strength is calculated from the work load diagram of the tensile load curve obtained when peeling is performed, the average load is determined, and the result is expressed as k g f / 2 5 mm. In Figure 5, P is the tensile load. For the adhesive, a semi-flange (h e m f 1 a n g e) adhesive was used. Even the ground and the display number are erasable ’Mo Zhi products. The test results are described in the test results before the results show the degree of determination Λί · strong separation. The following table shows the following points: -II-nm n. 'ITm: m (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs The obligatory formation of the compulsory serial number and the intention to issue the full number of my order to clear and resolve the power 0 ^ m ^ a 0 ^ ^ »^ ® gi purpose low order, the current display on the W display are all 1¾¾ product_this ρ δκ 1I and Ε sample 丨 In 1 there is 0 ′ bb PB jf sample is as small as 6 or 4 and as small as the current exhibit sample 1-any sample is better than the original sample . The longevity of the life of the pole is relatively strong and its strength is strong. The number of people who are lacking is the number of products. The strength of the strength is small and the number is within the range. The best of this continuity is that the paper size of the paper is applicable to the Chinese National Standard (CNS) Λ4 (210 X 297 mm 26 470783 A7 B7 Consumer Cooperatives of the Ministry of Economic Affairs) Fifth, the description of the invention (24) and at least any one of the press formability, point weldability and adhesion is insufficient. According to the present invention, the structure formed on the surface of the galvanized steel sheet has the structure as described above. Fe-Ni-O film has higher hardness and melting point than zinc or zinc alloy plating layer. The existence of an appropriate amount of this film can reduce the surface area between the plating layer and the stamper during the press forming process of the galvanized steel sheet. The sliding resistance makes the galvanized steel plate easy to flow into the mold. This high-melting F e-Ni-0 film can improve the continuous point weldability. The oxide of Fe existing in the Fe-H ί -0 film can ML Improved Peeling of Adhesive Substrate In addition, since the oxygen content K in the film can be adjusted to prevent it from exceeding a certain limit, it is possible to obtain an ore-zinc steel sheet having excellent chemical treatment properties. Therefore, according to the present invention, it provides press formability, spot fusion, and adhesion The galvanized steel sheet with excellent strength provides industrially very useful effects. Specific Example 2 The present inventor has devoted research to solve the aforementioned problems. As a result, the inventor found that the press formability, spot weldability, And the adhesive force can be significantly improved by forming an appropriate Fe-N ί-O film on its surface. According to the findings of the present inventors, an appropriate F e-Ni-0 film satisfies the following conditions. 1) The coating weight based on the total weight of gold tincture in the M film is in the range of 10 to 1500 mg / m2. (2) Fe content (weight percentage) to Fe content and N ί content in the film ( The ratio of the sum of the weight percentages) is in the range of 0.05 to 0.9, and M is preferably in the range of 0.1 to 0.5. [This ratio may be referred to as the F e Paper size applies Chinese National Standard (CNS) Λ4 specification (210X297 male f) — -27- (Please read the precautions on the back before filling out this page) 470783 A7 B7 Printed by the Consumer Consumption Cooperation of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the Invention (25) 1 1 Ratio > And expressed as Fe / (Fe + N i)] 0 1 (3) ii The oxygen content in the film i is within the range of 0.5 to 10 weight percent. 0 1 1 The galvanized steel sheet has a colder press formability. The reason why the rolled steel sheet is poor can be attributed to fS. Please read 1 1 before the increase in sliding resistance due to the adhesion between the mold and the low melting point zinc at high surface pressure, 0 to prevent this from happening. Method * To produce __ »on the surface of the plated 1 I zinc steel plate. It is harder than zinc or zinc alloy plating layer and has a higher melting point. 0 This can reduce the plating items in the press forming process. Then fill in 1 1 layer surface Sliding resistance with the stamper »makes the galvanized steel sheet easy to flow into the stamper and write this page | f Therefore, the press formability is improved 0 1 I Simultaneously > The galvanized steel sheet has more continuous point weldability during the spot welding process Cold rolled 1 1 1 The reason why the steel sheet is poor »can be attributed to the rapid unordering of the electrode caused by the formation of a brittle alloy layer on the electrode due to contact during fusion welding with the electrode copper during the welding process 1 1 0 here It has been found that the formation of high melting point on the surface of galvanized steel sheet | thin film can effectively improve the wall-to-wall spot weldability. The inventors have conducted research on various layers 1 1 K Improved point weldability of galvanized steel plate N i I 1 wire metal is found to be particularly effective 0 Although the mechanism by which it is effective has not been fully understood> 1, it may be due to the high melting point and high conductivity of the Ni metal 0 1 1 Although the fact that the adhesion properties of galvanized steel sheet is worse than that of cold heading steel sheet is known 1 | *, the reason is not clear yet 0 In this case f The inventor studied its cause »I conducted a research 0琨 The adhesion is controlled by the sister of the oxide film on the surface of the steel sheet. 1 In cold-rolled steel sheet »The oxide film on the surface of the steel sheet is mainly composed of 1 1 Ft i oxide. On the contrary, it is on galvanized steel sheet. The main component is the oxide of 1 1 Zr 1. The difference in adhesion is determined by the composition of the oxide film. The adhesion of the oxide of η 1 | is worse than that of the oxide of 3. 0 Therefore »踱 Zn Steel plate 1 1 This paper size is applicable to China National Standard (CNS) 8 4 specifications (210X 297 mm) 470783 A7 B7 Printed by Zhengong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the adhesive force of the invention (26) 1 1 1 The improvement t has been modified by the method 9 of the present invention. 1 1 | A thin film containing Fe oxide is formed on the surface to achieve 0 1 I As stated previously, 9 Fe -N 1-〇i ί The oxygen content in the film should basically be 0.5 to 10 Please M 1 Within the range of 1 | wt.% 0 The inventor has met the basic requirements on M »Also obtained the discovery under II II 0 Note 1 I Meaning 1 IF e -N i-0 film mainly contains a total of # r % ί formed in the gaseous substance of iron 1 and 1 I oxygen 0 is the oxide of the eutectic iron obtained by cathode electrolysis t should be Fe -N ί- Fill in this page V- · 1 Fill 0? 1 f The deposition rate of the film is accelerated, and the diffusion rate of the metal ions cannot keep up with 1 I. At t, the so-called • inr Μ state of glossy precipitates should be produced. 0 Specifically, the base 1 1 should have a current density that exceeds the limit current. Electrolysis 9 This limit current 1 1 is based on the composition of the electrolytic plating bath and the electrolytic conditions. The present invention has been completed based on the findings described above. It provides a method for forming a Fe -N 1-0 film M 1 I on the surface of an electroplated layer of a galvanized steel sheet through 1 I to obtain press formability. 1 1 1 method of galvanized steel sheet with excellent point welding% and excellent adhesion. The method will be described in the next 0 1 line. Here is the micro-texture of Fe -N 1 _ 〇 film and the formation of 1 element of the film. Combined conditions and • far limit f as long as the film includes a mixture of at least N i 1 1 and Fe 鼷 and N i and Fe oxides 0 1 1 A method for manufacturing a galvanized steel sheet according to specific example 2 Including the use of galvanized steel 1 1 plate as the cathode »Electrolysis in an electro 1 1 plating solution including an aqueous solution containing sulfuric acid wire and ferrous sulfate to form a thin film 1 1 on the surface of the galvanized steel sheet Electrolysis under the following conditions The total concentration of nickel sulfate and ferrous sulfate in the plating solution of Fe i--0 1 I · * is in the range of 0.1 to 2. 0 1 | mol /, A »and M is 0 1 To 0.: Im 〇 1 / is better; 1 1 This paper size applies Chinese National Standard (CNS) A4 (210X 297 mm) 29-470783 A 7 B7 V. Description of the solution In the range of 1.0 to 3.0; M and the total concentration of ions and ferrous ions in the plating solution, M (raol / il), the average flow rate of the plating solution, U (m / s), and electrolysis The relationship between the current density, IUA / dm 2) satisfies the equation (1) under M. 11 ^ (11 ^^ 0 = 50 to 150 ...... (1) The plating layer on the surface of the steel plate may be an alloy zinc-dip coating layer containing iron in the range of 7 to 15 wt.%. In addition, The electroplated layer on the surface of the steel plate may be a zinc electroplated layer or a zinc dip-plated layer. In this patent specification, the Fe-Ni-O film formed as an upper layer on the surface of the hafnium layer is sometimes referred to simply as a "film", M is different from the zinc or wrought zinc layer referred to as the "plating layer" as the lower layer. Next, the reason for restricting the manufacturing conditions of the present invention will be explained. In the present invention, nickel sulfate and ferrous sulfate are used as the zinc plating The composition of the electroplated layer of the Fe-H i-0 thin film on the surface of the plated layer of the steel plate, because when the galvanized steel plate to be formed of the Fe-Ni-0 film is used as the cathode, these sulfates are suitable for effectively converting Fe, Ni and 0 are introduced into the film to be formed. Under M, the total concentration of nickel sulfate and ferrous sulfate is designated as 0.1 to 2.0. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the note on the back first) Please fill in this page again) Raol / A, and M0.1 to 0.5mol / Jl is the better basis. When the total concentration is low At 0.1 m ο 1 / 殳, due to the lower conductivity of the plating bath, the voltage used for power supply will be higher, so a rectifier that can be used for higher voltages is needed. Therefore, such a low concentration is not appropriate. On the one hand, a total concentration exceeding 2.0 mol / il > sulfuric acid and / or ferrous sulfate will precipitate at a lower temperature due to its concentration reaching the upper limit of the solubility of nickel sulfate and / or ferrous sulphate. , Its limit current density This paper size applies the Chinese National Standard (CNS) Λ4 specification (210 × 297 mm), Λ 470783 A7 B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. The invention description (28) will become larger, so The system is electrolyzed at a relatively high K current density, otherwise the state of matte precipitates cannot be achieved. Moreover, in this case, the electrolysis time to obtain the optimal coating weight of the Fe-N i-O film will be greatly shortened At 1 sM, this kind of electrolysis will be difficult to control. From such a viewpoint, the total concentration should be set at 2.0mol / AM, and M0. 5mol / il or lower is preferred. In addition, the electrolyte may contain a shoulder g is included in the present invention Cations, hydroxides, and / or oxides such as Zn, Co, Mn, Mo, Al, Ti, Sn, W, Si, Pb, Nb, and Ta in the electroplated layer on a zinc steel sheet, and This solution may contain anions that do not affect the electrolytic reaction and are non-chlorine, fluoride, bromide, or iodide. Below K is the reason for using an electrolyte with a pp value in the range of 1.0 to 3.0. For electrolytes with a ρ Η value of 1.0 M, hydrogen will be the main product of the electrolytic reaction of the cathode, and the current efficiency will be greatly reduced. On the other hand, for electrolytes with a pH value above 3, iron hydroxide will precipitate. The temperature of the electroplating bath can be avoided. However, at temperatures below 30 ° C, the conductivity of the plating bath will be lower, so the power supply voltage will be higher. In this case, the oxygen content in the Fe-N i-0 film tends to be higher. On the other hand, if the temperature exceeds 70 ° C, the amount of evaporation of the electrolyte will increase, and it will be difficult to control the concentration of nickel ions and ferrous ions. Therefore, the temperature of the plating bath should preferably be 30 to 70 ° C. Generally speaking, the limit current density I M is the limit at which matte precipitates cannot occur, and it is related to the constituent metals by the following equation (2), which is proportional to the diffusion coefficient of the metal to be deposited D and ion M, but inversely proportional to the thickness δ of the diffusion layer formed on the surface of the steel sheet. This paper size applies to Chinese National Standard (CNS) Α4 specification (210 × 297 mm) I --------- Ε ------ ΐτ ------ ii (Please read the precautions on the back first (Fill in this page again) -31 470783 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (29) Ikd = nFD (Μ / δ) .. (2) on K In the equation, η is the valence of the metal ion; F is the Faraday constant; D is the diffusion coefficient of the metal ion; and M is the ion concentration of the metal to be deposited. In contrast, the present inventors studied the relationship among the limiting current density I k d, the ion concentration M of the metal to be deposited, the average flow rate U of the plating solution, and the temperature of the plating bath. As a result, the hairpin limit current density I k d is proportional to the square root of the ion concentration M of the metal to be deposited, and the average flow rate U of the electrolyzed fluid. Specifically, the relationship represented by equation (3) under M has been found. Ikd = K (U ^ M) ........ (3) Ikd: limiting current density (A / dm2) U: average flow rate of electric ore liquid U / s) Μ: Sum of ion concentration (mo 1 / il) K: Equation (4) under constant M is obtained by modifying equation (3). Ikd = (U ^ H) = K ........ (4) As a result of further research, the present inventors have found that it is 0.5 Wt.% Or higher in the 卩 e -N ί -0 film For the oxygen content, the constant k should be 50 or more: and to reach the oxygen content of ~ t.% Or less, the constant k should be 150 or less. Therefore, in order to limit the oxygen content in the F e-Ni-0 film to a range of 0.5 to 10 wt.%, The sum of the ion concentrations of all metals in the plating solution M (m ο 1 / A), plating The average flow rate U (m / s) of the liquid and the current density Ik (A / din2) in the electrolysis should satisfy the relationship expressed by the following equation (1). IW (UV2M) = 50 to 150 ...... (1) -.-------- Yi Yi Yi Λ ^. (Please read the precautions on the back before filling this page) This paper size applies China National Standard (CNS) Λ4 specification (210 × 297 mm) 32 470783 A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention: 30) 1 1 1 Here »The average flow rate of the plating solution is expressed The average value of the flow rate between the anode and the cathode at the midpoint 1 1 1 0 1 I Accompanying most of the metals used for deposition in the plating tank in the present invention, please read 1 1 1 Ferrous ions 9 K and other than iron ions basically do not read the back 1 I surface I will affect the finding of Fe i-0 film: imprint] ions. Since the iron ion will decrease according to ξ F e-note i I meaning 1 i N i -0 thin film deposition efficiency and cause degradation of galvanized steel sheet f Therefore the concentration of iron ion matter I j 1 I should be limited to 0. 09 m 〇1 / Λ or lower 〇4 This is a galvanized sheet for forming Fe-N 1-0 film on its surface in the present invention, and the plating layer on the surface of y 1 I steel sheet should include 7 to 15 w t% of iron alloys 1 1 Zinc dip galvanized zinc plating layer or zinc dip galvanized layer is preferred. Z 1 1 has such plating layer in terms of workability, especially press formability and accessibility or class 1 The cold-rolled steel sheet and galvanized-i 臬 -alloyed steel sheet are different in order from the nature. Therefore, 9 1 I will be formed from Fe-N i 1 I -0 on the surface of the aforementioned electroplated layer. Film and greatly improve its press formability and Spot weldability 0 1 1 1 The state of the galvanized steel sheet used in the present invention before it forms F e -N 1-01 * 1 wire film is that its surface is deposited by immersion plating vapor deposition 1 etc. In addition to pure zinc, the composition of this galvanized layer is not equal to pure zinc, such as 有 N i Co Μ Cr Cr A 1 Μ 〇, T i Λ S i Λ y, i I Sn Pb, And Ts of the metal (where S ί is also regarded as a metal) or its oxide t 1 1 or this plating layer may include a single or a plurality of organic materials containing 1 or more. 1 1 layer 0 In addition, the aforementioned plating layer may include If such as S 0 particles and A 2 0 3 1 1 fine particles of particles 0 The galvanized layer may include a plurality of layers each containing the same composition but containing 1 1 different amounts. In addition, the galvanized layer may include a plurality of layers each containing the same The layer r which becomes 1 Ι 1 but whose content is continuously changed in the thickness direction is called " Nengdi degree 1 1 This paper size is applicable to Chinese National Standard (CNS) Λ4 specification (210X 297 mm) 470783 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (31) 1 1 I Plating layer " 0 1 1 1 When the Fe-N i — Of? Film is formed on the surface of the galvanized steel /-N 1 I plated plating layer according to the specified conditions of the former household / the above, f can reach Μ The following advantages or effects * Please read 1 1 first. In the press forming process 9 there will be no adhesion between the steel plate and the mold f so sliding read back 1 [surface I resistance will be reduced > and therefore 1 steel plate will easily flow into the mold Medium > 1 I means 1 i 9 can be suppressed due to the formation of a brittle alloy layer between the steel plate and the electrode copper during the point welding 9 due to the matter 1 I 1 1 This will improve the m-point welding; and Thin oxide filling 1 ¥% Effect of film > Adhesion can be improved. Page 1 I Fe-N i-0 film on the 1 1 1 surface of galvanized steel sheet produced under the specified conditions as described above can produce M The following advantages and effects will not occur during the pressing 1 1 forming process. The adhesion between the steel plate and the mold will not be reduced. Therefore, the sliding resistance will be reduced by 1. The steel plate will easily flow into the mold. During the point welding process, the formation of the II brittle alloy layer between the copper and the electrode. Suppressed and improved continuous-point weldability M 1 I and adhesive force are improved by the action of the oxide containing Fe 0 m vm 1 1 1 and 9 when the coating weight of the Fe -N * 0 film is 1 0 Below mg / m 2, the wire formability cannot be improved when pressed 1. On the other hand, coatings that exceed 1500 mg / It I2 are weighted. t The improvement effect of the press formability is saturated to 0, so t Fe -N i-0 1 The coating weight of the film should be between 1C to 150C) in 8 / ΪΓ 2 is preferred in the range of 0 1 1 | When the Fe content in Fe i--0 film (weight percentage) versus Fe content and N i I 1 content (weight percent soil) The sum of the ratios—that is, Fe (Fe · f 卜 i) in the film — 1 1 is lower than 0 05. f cannot exert the effect of improving the adhesion. On the other hand, when 1 1 Fe / (F 3 + N i) Ultra] I 0. ≪ 3 hours) 1 is formed in the welding process f and has a higher melting point due to the reduction of the content of Ν ί 1 | 1 present in the film. I Zt 1-1 Η Gold spoon Home Rule II will cost 5 $. At the end of the installation, the electrode will speed up ti ib 1 1 This paper size is applicable to the Chinese National Standard (CNS) Λ4 specification (2 丨 0 '乂 297 mm) 34 470783 A7 B7 Member of the Central Standards Bureau of the Ministry of Economic Affairs. Printing 5 、 Explanation of the invention (32) 1 I | The improvement effect of point fusion cannot be exerted 〇1 | Therefore, F e / (F e + 1Π) in 9 film should be in the range of 0.05 to 0.9 > 1 I and μ 0. 1 to 0.5 is better. Please read 1 1 I Fe-N i-or? 1 The oxygen content in the film should be in the range of 0.5 to 10 wt. 〇 Oxygen content lower than 0.5 wt *%. The film's metal quality will become significant * Note 1 1 1 1 Therefore, the effect of improving the press formability is very small. Another --- aspect > more than 10 W t.% event 1 I 1 I oxygen content 9 too many oxides generated as a result t resistance will increase port 1 In addition, the fusibility will be degraded in addition to the writing book. In addition, the chemical processability will be degraded due to the inhibition of the formation of the phosphate sheet '-1 I crystal Wfgf body. 1 1 Example 1 1 GAGI with each M, or EG-type galvanized steel 1 plated as electroplated 1 I zinc steel plate 0 1 IGA which is electrolytically treated in accordance with the method of the present invention or a comparative method. It contains 10 wt.% F e and sufficient Z on both surfaces. η alloy zinc 1 1 dip coating and the coating weight on each surface is 60 g / ra 2 C 1 line GI forms a bell dip coating on both surfaces and the coating weight on each surface 1 丨 is 90 g / ΙΠ 2 1 1 EG forms an electroplated layer on both surfaces and the covering weight of each surface is 1 1 4 0 g / m 2 0 1 1 The plate was set to the cathode 9 for electrolytic treatment in a mixture of a nickel sulfate solution and a ferrous acid solution with a predetermined concentration of 1 1 1 and 1 1 to form a Fe- \ i-0 film on the surface of the i-plated steel plate. Here, some zinc-zinc 1 I steel plates are only immersed in the electrolyte f without electrolytic treatment. 0 1 1 | Tables 3 and 4 show the actual electrolytic treatment under the conditions of the present invention. Applicable to China National Standards (CNS) 8-4 specifications (210X 297 mm) -35 470783 A7 B7 V. Description of the invention (33) The conditions for S solution treatment in Examples 1 to 30; each of which has at least one electrolytic treatment Comparative cell examples 2 to 1 where conditions are not within the scope of the present invention: 2, 1, 4, 15, 5, 7, and 18; K and comparative examples 1, 1, 3, and 16 without electrolysis Immersion conditions. This table also shows the type of plating layer on the steel plate to be subjected to electrolytic treatment, 'component content, ρ Η value, and temperature of the electrolyte; and plating conditions. As can be clearly seen from Tables 3 and 4, the content of the electrolyte components and the ί value of both the examples and the comparative examples are within the scope of the present invention. However, in all the comparative examples, one condition of the present invention is not satisfied, that is, the following equation (1). I k Η II from M) = 50 to 150 batch order (please read the precautions on the back before filling this page) Printed by the Central Consumers Bureau of the Ministry of Economic Affairs, Consumer Cooperatives The paper dimensions are applicable to Chinese national standards (CNS ) Λ4 specification (210 × 29? Mm) 36 470783 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 _____B7 V. Description of the invention (34) Table 3

No Test sample Composition, content, pH, and temperature of plating type electrolyte Current plating density: Ik (A / dm2) Plating solution 'flow rate: U (ra / S) Ik Plating time (s) u1 / 2m 1 Compare Example 1 GA Nickel sulfate: 0'.08mol / i Ferrous sulfate: 0.02mol / l pH: 2 Temperature: 50 ° C----2 (± Compared with running tree 2 GA 4 1 40 1 3-Implementation of MΓ GA 5 1 50 1 4: Implementation 2 GA 8 1 80 1 5 Example 3 GA 10 1 100 1 6 Example 4 GA 12 1 120 1 7. Example 5 GA 15. 1 150 1 8 Comparison Ning Example 3 GA 17 1 170 1 9 Comparative example 4_ GA Sulfuric acid_: 0.16mol / A 'Ferrous sulphate: 0.04mol / A pH: 2 Temperature: 50 ° C 8 1 40 1 10. Implementation of 钶 6 GA 10 1 50 1 11 Example 7. GA 16 1 80 1 12 'Example 8' GA 20 1 100 1 13 Implementation 洌 9 ^ GA 24 1 120 1 14 Example 10 GA 30 1 150 1 15 Comparative Example 5 GA 34 1 170 1 16 Solid pickled rice 6 GA Sulfate line: 0,4mol / il Ferrous sulfate: O.lraol / Moxa pH: 2 Temperature: 50 ° C 20 1 .4d 1 17 Example 11 GA 25 1 50 * 1 18 Example 12 : GA 40 1 80 1 19 Cell example 13 GA 50 1 100 1 20 Example U GA 60 1 120 1 21 15 · GA 75 1 150 1 22 Comparative Example T GA 85 1 170 1 (Read precautions to fill out the back of the page) Note M: sum of Ni ion concentration and the concentration of ferrous ions (mol / il)

、 1T line The size of this paper is applicable to Chinese National Standard (CNS) Λ4 specification (210 × 297). -37-470783 A7 B7 Printed by the Employees' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (35) Table 4

No Test sample Composition, content, pH, and temperature of electroplating type Electroplating strip 牛 Now current density ^ * Ik (A / dm2) Plating solution: Flow rate U (m / S) Ik Plating time (s) u1 / 2m 23 Comparative Example 8 GA Nickel sulfate: 0.16mol / A subsulfate _: 0.04ιηο1 / 1 pH: 1.5 Temperature: 5 (TC 12 2 42 ^ 0.5 24 Example 16 GA 15 2 53 0.5 25 Implement "17 GA 20 2 71 0.5 26 Implementation 洌 18 GA 25 2 88 0.5 27 Example 19 GA 30 2 106 0.5 28 Example 20. GA 40 2 141 0.5 29 Comparative Example 9 GA 50 2 178 0.5 30 'Zhuang Comparative Example 10 GA sulfuric acid _ '1.76mol / Jl Ferrous sulfate: 0.44mol / il pH: 2 Temperature: 50¾ 50 2 16' 0.5 31 Comparative Example 11. GA 100 2 32 0.5 32 Comparative Example 12 GA 150 2 48 0.5 33 》 Example 13 EG Nickel sulfate: 0.16mol / il Ferrous sulfate: 0.04πκ > 1 / Λ pH: 2.δ Temperature: 50t:----34 U compared to Example 14. EG 12 2 42 0.5 35 Example 21 EG 15 2 53 0.5 36, Example 22 EG 20 2 71 0.5 37. Example 23. EG 25 2 88 0.5 38. Example 24 EG 30 2 106 0.5 39: Example 25. EG 40 2 141 0.5 40 Comparison Example 15 EG 50 2 178 0.5 41 Comparative implementation @ 16 GI Sulfuric acid mirror: 0.16mol / il Ferrous sulfate: 0.04raol / l pH: 2.8 Temperature: 50¾----42 Comparative Example 17 GI 8 1 40 ^ 1 43 Examples of real cells 2S GI 10 1 50 1 44 Example 27 GI 16 1 80 1 45 Mass teacher 28 GI 20 1 100 1 46 Implementation ^ 129. GI 24 1 120 1 47 Example of mass cells 30! GI 30 1 150 1 48 Comparative cell example 18 GI 34 1 170 1 Note Μ: Sum of Νί ion concentration and sulfonium ion concentration ------------ • -install ------ order ---- --Line (please read the precautions on the back before filling this page) _ This paper size is applicable to Chinese National Standard (CNS) Λ4 specification (2 丨 0X297) 婊 470783 A7 B7 V. Description of the invention (3G) The F e-Ν -0 thin film of each sample obtained in the cell example and the comparative example was measured for its coating weight (total weight of the metal in the K film),

The ratio of the Fe content (weight percentage) to the sum of the Fe content (weight percentage) and the Hi content (weight percentage), and the oxygen content. Tables 5 and 6 show the measurement results of the samples obtained in Examples 1 to 30 and Comparative Examples 1 to 18 described above. I batch of clothes -n I — ... order I (please read the precautions on the back before filling this page) The consumer cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs Du printed this paper The size of the paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 (Mm) 470783 Α7Β7 V. Description of the invention (37) Lonely ^ na 53 {— ^ ε / ^ β ^} wing adaptation Jie fl *-88 8 · 9 CN CN ο νη

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CN This paper size applies Chinese National Standard (CNS) Λ4 specification (210X297 mm) 41 470783 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 11 V. Description of the invention (M) Next, rub the above samples Measurement of coefficients, 'continuous point weldability and adhesion test', M evaluates press formability, point weldability, and adhesion. The results are also shown in Tables 5 and 6. The results are shown in Tables 5 and 6 at various points. Here, MX replaces the left side of the equation 1-Ik / (U ^ M) = 50 to 150 —. Specifically, X = Ik / (ϋ ^ M) .. (5) As previously mentioned, in the comparative example, only the value of X is outside the scope of the present invention, and: (1) in In each of Comparative Examples 2, 4, 6, 8, 10 to 12, 14, and 17 having an X value of less than 50, the oxygen content in the Fe-Ni-O film was less than 0.5 wt.%, However, the oxygen content of each case was in the range of 0.1 to 10 wt.%. In addition, regardless of the type of the plating layer, the adhesion of these comparative examples is inferior to that of the cell examples according to the present invention. In addition, the press formability of the comparative examples is inferior to that of the examples according to the present invention having the same type of plating layer; (2) In each of the comparative examples 3, 5, 7, 9, and 9 having an X value exceeding 150 15 and 18, the oxygen content in the Fe-Nί-Ο film is greater than 10wt.%. The point weldability of these comparative cell examples is worse than that of the embodiment according to the present invention with the same type of plating layer: and (3) it is manufactured only by immersion in the electrolyte, without F e-N i-0 All of the comparative examples 1, 13 and 16 of the film, regardless of the type of the plating layer, all of their press formability, spot weldability, and adhesion were inferior to those of the examples according to the present invention. -4 2 A paper size is applicable to the Chinese National Standard (CNS) Λ4 specification (210 × 297 mm) -------------------, 1T ------ ^ (Please read the precautions on the back before filling this page) 470783 A7 B7 V. Description of the invention (4G) As can be clearly seen in Tables 5 and 6, the press formability, spot weldability, and adhesion of galvanized steel The standard of the characteristic value is dispersed in a product which has not been subjected to the electrolytic treatment according to the present invention. Taking this into consideration, the characteristic values in Examples 1, 13, and 16 that have not been subjected to the electrolytic treatment according to the present invention are regarded as standards for the characteristic values of products having galvanized layers of the GA type, EG type, and GI type, respectively value. Next, a ratio of each characteristic value of each embodiment according to the present invention to other comparative examples to the standard value thus obtained is calculated and defined as an improvement index of each characteristic. Tables 7 and 8 show the improvement index of press formability, spot weldability, and adhesion in Examples and Comparative Examples of the type classification of the M plating layer. Approved by the farmer Λ ^. (Please read the notes on the back before filling in this page) Printed by the Central Consumers Bureau of the Ministry of Economic Affairs of the Consumer Cooperatives This paper is sized to the Chinese National Standard (CNS) Α4 (210 X 297 mm) 43 470783 A7 B7 V. Description of the invention (41) Table 7 S15, 6m 000- τ ^ ^ Μ »r〇CO Ch 〇 > vd in ro oo co t-ί rH * -H r- < inch 0 > 0 > inch ΓΛ σ \ r- o cn in BU CO CO 00 (N 00 00 CN BU m ΓΟ ro co σν in co

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卜卜 rH cn < r > in vo ^ UD KO m S9S.0 ΟΟΟΉ ίι®. Η Π H 卜 rH ro m ro ro η t-ί rH CN f—ί f〇 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs s νϋ v ° iEsw8qq vu vu VD VD v ° V0 νϋ inch dizziness Kffi- · νϋ νυ νυ γϋ νϋ 0 £ ^ Μ 6SSK °° Buried peptide H CN ΓΠ T— < ri * ~ 4 This paper size applies the Chinese National Standard (CNS) Λ4 specification (210 X 297 mm) vu vs ν ° VI. — VD ν ° νϋ ν ° -Yeya Peptide Buttons-Bi Kun Tan Twist®-. Vo LK pinch 85-'sl buried wl -Kun buried " · nEs " · -ES5W · US 胂 胂 Γ' »CO CTi O »H r-4 rH ii 04 Oi. --Football- 匡 遐 遐 镒 镒-Crane-^ Ether Tao-uio-s-OJ Berry 07 Bialdehyde transported to ride 叵-Outline 匡 遐 _ wind || Aluminium Your sister 44 470783 A7B7 V. Description of the invention (42) Table 8

No 脃 肜 肜 肜 肜 改良 改良 改良 改良 改良 馆 馆 馆 梭 性 性 改良 改良 改良 改良 Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ:: 样品 样品:::::::::: 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 样品 样品 样品 样品 H 1 A 1 1 ¾ B times inhibition !! / Tooth. 23 七 b 鲛 f Example 8GA 0.847 0.651 1.793 1.000 24 Example 16 GA 0.708 0.557 1.793 1.662 25 17 GA 0.708 0.557 1.759 1.688 26 / '18 GA GA 0.713 0.573 1.793 1.688 27 u 19 0.702 0.557 1.759 1.688 28 " 20 GA 0.719 0.568 1.759 1.675 29 Comparison run 9 GA 0.731 0.568 1.103 1.714 30 " 10 GA 0.901 0.682 1.793 1.294 31 〃 11 GA 0.895 0.675 1.759 1.324 32 " 12 GA 0.889 0.671 1.759 1.250 33 " 13 EG 1.000 1.000 1.000 34 " 14 EG 0.656 0.546 2.158 1.429 3b Example 21 EG 0.567 0.477 2.211 2.179 3 6 " 22 EG 0.558 0.474 2.211 2.179 37 " 23 EG 0.558 0.471 2.211 2,179 39 r 24 EG 0.554 0.474 '2.15δ 2.214 39 " 25 EG 0.554 0.477 2.211 2.214 40 Comparative Example 15 EG 0.558 0.480 1.315 2.250 41 // 16 GX 1.000 1.000 1.000 1.000 42 .// 17 GI 0.705 0.528 3.889 2.000 43-Night example 26 GI 0.595 0.466 4.111 3.395 44 jf 27 GX 0.595 0.466 4.222 3.395 45.; / 28 GI 0.600 0.459 4.222 3.395 46, / 29 GI 0.600 0.459 4.444 3.289 47 ”30 GI 0.610 0.459 4.444 3.263 48 Compare? f Shiwang 18 GI 0.614 0.466 1.667 3 263 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) Note: Various improvement indexes of press formability, point fusion, or adhesive properties It is the ratio of each characteristic observed in the example to the characteristics of the same type of deposits as the example, but without the Fe-Ni-O type surface layer of the corresponding comparative example. This paper size applies to the national standard (CNS) Λ4 specification (210X29? Mm) 45 470783 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (43) 1 1 | As shown in Tables 7 and 8 It is obvious from the results 9 that when the press formability, point weldability Λ, and adhesion I | are evaluated in each group of the M plating layer type 1 1 classification, 5 according to all embodiments of the present invention > Each characteristic is more realistic. Please read 1 first. There are many improvements in the examples. The back surface 1 is the surface of the galvanized steel plate. Fe -N i-0 film on the surface, compared with zinc or alloy zinc plating 1 matters Ϊ re 1 | higher hardness and higher melting point 〇 in the presence of an appropriate amount of film > Copybook i The sliding resistance between the surface of the plating layer and the stamper during the press forming process will reduce the sheet S '1 I f. Therefore, the galvanized steel sheet can easily flow into the mold. Also, > Fe-N with a higher melting point I 1 I The presence of a thin film improves the continuous spot welding of the spot welding process. 1 1 Properties 0 In addition, the presence of Fe oxide in the Fe-N i-〇 film can improve the peel strength of the laminated steel sheet. The present invention can provide a press-coated steel sheet with excellent shape weldability and adhesion, which is excellent in shape. This is the industry's first | Viewpoint The present invention can produce quite good results. 0 1 1 | Specific example 3 1 line The present invention provides a A method for producing a galvanized steel sheet with excellent press formability, spot weldability, and adhesion by forming a Fe -N i-0 film on the surface of the galvanized layer of the galvanized steel sheet appropriately. 1 1 System Method 9 of galvanized steel sheet includes immersing the galvanized steel sheet in an aqueous solution containing at least one of ferrous sulfate and ferrous nitrate and at least one of nickel sulfate and nitric acid II 1 1 The step of forming a thin film on the surface of the electroplated layer of the steel plate, wherein the sum of the iron content (mo / A and nickel 1 1 content (m 0 / A)) in the aqueous solution is in the range of 0 1 to 3.0 mol / A Λ Iron content in water-soluble 1 I solution (mo 1 / il to m content (m 〇 / fl. And m content (η 〇 / 1 1) This paper size applies to China National Standard (CNS) A4 specifications (210X 297 mm) -46-470783 A7 V. Description of the invention (44) A) The ratio of the sum is in the range of 0.4 to 0.9, p Η is in the range of 3.5, M and temperature are in 2 In the range of 0 to 70 ° C, the rhenium-plated steel sheet is immersed in an aqueous solution to form Fe-N i -0 thin. In the present invention, the upper layer of Fe is formed on the surface of the electroplated layer of the galvanized steel sheet of the present invention. -fH -0 film, because of its relationship It referred to as "film"; the other hand, as a lower layer of zinc or zinc coating will be referred to as "plating layer", [mu] funded difference. The reason why the manufacturing conditions of the present invention are limited is explained below. In the present invention, the galvanized steel sheet is impregnated with at least one of F e S 0 4 and F e (H 0 3) ζ and at least one of N i S 0 4 and N i (Ν 0 3) 2 In the aqueous solution, Μ forms a F e-Ν-0 film on the surface of the plating layer of the galvanized steel sheet. The reason is that F e ions and N i ions can be added to the solution in any different form of salt, but should be added in the form of sulfate and / or nitrate. Because of its sufficient solubility, limited equipment corrosion problems, Minor adverse health effects and good economic benefits. In order to form F e-N i-0 film, spray method of aqueous film-forming solution, or roller coating -------- batch coating ------ ΐτ ------ I. Read the back Note for refilling this page) The results of the printed results of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs of the People's Republic of China appear to be in the form of immersion and immersion. The film can be thin d) Ho ho et et m Health η system 10 methods atM 1C electricity: two P, ap and 1-Ran excellent adhesion and formation of pressure is difficult to make it is very difficult to make the film thinner than 1 suitable for Dafa electroplating steaming or method Electroplating ο thin film thin film production costs caused by the cost of conversion "-· · · Mai Gao and the amount of equipment required is large. Its high content contains the iron content of the range. 0 solution of water to the content. Under nickel, such as-it should be combined with the total meaning

Below M A 7 4 This paper size applies the Chinese National Standard (CNS) Λ4 specification (210 × 21) 7 mm) 470783 A7 B7 Printed by the Consumer Cooperatives of the Central Standardization Bureau of the Ministry of Economic Affairs 5. Description of the invention (45) 1 1 I Sum The reduction of the precipitation rate of Hi and Fe results in lower productivity. In addition, __. 1 1 I * total profit above 3.0], the concentration of metal salt reaches J .; And the precipitation of metal salts. In addition, the Fe content in the aqueous solution (please M 1 1 1 mo 1 / il) is the sum of the Fe content (mo 1 / il) and the N i content (mol / A). Than read back 1 | Surface I should be in the range of 0. 0 0 4 to 0.9. 0 The reason is that F e / Note II at 0 '004M 1 I 1 (F e + N ί) ratio < fra: m method to obtain the improvement effect of the adhesive force; and if the item exceeds 0.9, 1 I and 1 I ratio of 1 will limit the improvement effect of point fusion. Fill 1 Write a package \ A. Describe the water-soluble 'liquid should have a pH in the range of 1.0 to 3.5 0 at a pH of 1 · 0M Page 1 |, there will be hydrogenation ― extreme increase in S and Causes precipitation of Ni and Fe 1 1. Reduced efficiency. Under the conditions including constant salt concentration and impregnation time, the coating weight of 9 Ni and 1 Fe is very small, resulting in lower productivity. In addition, this The thin film 1 mainly contains Ν ί and Fe metal, which makes it impossible to obtain the press-formability 1! Λ point improvement of the weldability and adhesive strength 〇 p 上 film at 3.5M 1 | The oxygen content increases Causes lower improvement effects and chemical properties of weldability. 1 1 The chemical processability 0 1 The temperature of the aqueous solution should be in the range of 2C to 70 ° C. 0 1 ° C at 20 ° C At temperature > low reaction rate > it takes a long time to get Enough coating weight of Ν ί and Fe required to improve thin 1 I film properties > resulting in 1 1 I reduction of productivity 0 In addition-at the temperature above 70 ° C, the rationality of the aqueous solution 1 1 Accelerated degradation > Equipment and energy required to maintain high temperature increase the manufacturing cost of 1 1 1 The electrolyte may be contained in the plating layer 1 I or the like of the galvanized steel sheet used in the present invention Znη, Co, Μ η Λ Mo, A1 'T 1., Sr 1' W 1 IP b, Nb and Ti cations Λ hydroxide and oxide 9 and chlorine ion removal 1 1 This paper size applies to China National Standard Twin (CNS) A4 specifications (210X 297 mm) 1 4 8 470783 A7 B7 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (4-6) 1 1 Anion outside the 〇〇 I I In the present invention > For forming Fe -N i on its surface -0 thin film plating / ^ s 1 I steel plate J is a steel plate with a plating layer formed by a method such as dip plating, steam plating, and the like in the first place. In terms of composition 9 this readback | surface I galvanized layer in addition to pure zinc f also includes a single or a plurality of notes containing one or more of 1 1 meaning 1 I such as Fe Ni, Co Μ Λ Cr Λ Α1% Mo Τ ί Si W, S η, P b, Matter 1 I Re 1 1 Metals of Nb and Ta (S i is also regarded as a metal) or its oxide or organic 1 Substance writing plating layer 0 This plating layer may be In addition, it contains pages such as Si 0 2 and A 1 2 〇1 I fine particles 0 As for this galvanized steel sheet K can be used with different chemical composition of electric 1 1 multi-layer galvanized steel sheet or functionally graded galvanized steel sheet 0 1 11 Fe-N i-0 film formed on the surface of the galvanized layer of the galvanized steel plate under limited conditions can eliminate 1 1 adhesion between the steel plate and the mold during the press forming process, reduce sliding resistance, improve the smoothness of entering the mold, Λ inhibit The formation of a brittle alloy layer between the steel plate and the copper electrode during the spot welding 1 1 1 process therefore improved the continuous spot weldability, Μ, and improved adhesion when used as a 1-line film of an oxide film containing Fe. Force 〇1 1 In this case > Μ Fe 1 IN i-C film coating weight based on the total conversion weight of metal elements in the film should be within the range of 10 to 1, 500 mg / m 2 than 1 1 I good 0 The total conversion weight below 10 mg / ΙΪ1 2 can not obtain the improvement effect of press formability 1 1 9 and the total conversion weight above 1, 50 0 in g / B12 will make 1 1 into chemical treatment The degradation of 0 1 I is to cover The amount is adjusted within this preferred range »then the aqueous solution with a fixed salt concentration of 1 I is adjusted» the immersion time 1 is adjusted and when the immersion time is limited by the equipment 1 1 1 system »such as the capacity limit 9 needs to be maintained at a fixed level When the value is i, adjust the salinity. Salinity I 1 1 This paper size is applicable to the Chinese National Standard (CNS) Λ4 specification (210x 297 mm) 470783 A7 B7 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of invention (p) or Fine adjustment of p Η and temperature is sufficient. A preferred range of the oxygen content in the Fe-Ηί-Ο film is 0.5 to 10 wt.%. With an oxygen content of 0.5 vit.% Or less, the metallic properties of the film become clearer, thereby reducing the improvement effect of press formability. On the other hand, the oxygen content at 10wt.% Μ, the amount of oxide becomes too large, which results in an increase in surface resistance, a decrease in weldability, and inhibits the generation of phosphate crystals, leading to chemical treatment Its degradation. The ratio of the Fe content (wt.%) In the film to the sum of the Fe content and the Hi content (wt.%) (M is abbreviated as "Fe ratio in the film" and is expressed as "Fe / (F e + Νί) "), should be preferably in the range of 0.004 to 0.9 > or more preferably 0.1 to 0.5. Although the presence of F e in the film can improve the adhesion, but the F e / (F e + Ni) ratio in the film at 0.04M cannot obtain the effect of improving the adhesion. On the other hand, if the Fe / (Fe + Ni) ratio in the thin film exceeds 0.9, the reduction of the Hi content in the thin film will cause a reduction in the proportion of the Z η-Ni alloy with a high melting point formed during the welding process. As a result, the electrode is more severely degraded, thereby reducing the improvement effect of the spot weldability. EXAMPLES Before the dip plating by the method of the present invention or the comparative method, any galvanized type GA, GI, EG, Zn-Fe, Zn-Ni, Zn-Cr, and Zn- A BU · GA: An alloy zinc impregnated coating containing 10 wt.iCPe and a sufficient amount of Zn and a coating weight of 60 S / ra 2 on each of the two surfaces is generated; (Π: on each of the two surfaces, Generated with zinc coating with a coating weight of 90 g / m 2; -5 0-This paper size is applicable to the Chinese National Standard (CNS) Λ4 specification (210X2517 mm) --------- ^- ---- tT ------ (Please read the precautions on the back before filling out this page) 470783 A7 B7 V. Description of the invention (48) EG: On each of the two surfaces, the coating weight is generated as 40g / m2 electroplated layer; Zn-Fe: On each of the two surfaces, a Zn-Fe alloy electroplated layer containing 15 ",% Fe and coated with a weight of 40g / ra2 is generated; Zn-Hi: in two On each side of the surface, a Zn-Ni alloy plating layer containing 12wtjNi and a coating weight of 30g / m2 was generated; Zn-Cr: On each of the two surfaces, 4wt.% Cr and a coating weight were generated 20g / m2 Zn-Cr alloy plating layer; Zn-A l: On each of the two surfaces, a Zn-A1 alloy plating layer containing 5Wt.5Ul and a coating weight of 60g / m2 was generated. The above-mentioned galvanized steel sheet was treated in Tables 9 and 10 Examples 1 to 3 5 are processed under manufacturing conditions within the scope of the present invention, or are processed under manufacturing conditions outside the scope of the present invention, and the examples and comparative examples of the present invention are performed. The processing conditions (processing numbers 1 to 3 5 ) And any galvanized type of galvanized steel (7 types as above), the sample number is assigned to the sample. This sample includes Example Numbers 1 to 7 5 and Comparative Example Numbers 1 to 31 ° (Please read first Note on the back, please fill in this page again.) The Central Bureau of Standards of the Ministry of Economic Affairs and the Consumer Cooperatives printed this paper in accordance with the Chinese National Standard (CNS) Λ4 specification (2 丨 0 X 297 cm) -51- 470783 A7 B7 V. Description of the invention (4fJ) Table 9 Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Consumer Cooperatives, 菡 埕 m 、---->-mm Axis 1 1 ¾ .m -1 ο ο ο ο ο Γ ~ 4 σ σ σ Ο τ ~ \ σ ο Ο t—i 迚 • H, S Φ + (u (V Ua 1 ο ο ο ο η ο ο inch ο ο ο ο ο ο ιη σ ο ο Τ-Ι ο ο ο σ η ο σ S σ ο ο ο ο S ο ο (N σ \ ο Ο ο τ— < .y State 1 1/1 ιη ΙΤ) ιτ »in in ιη ιη ιη ιη ιη ιη ιη ιη ιη ιη ιη ιη ΙΓ) ιη ιη ιη U1 LD ιη rt 0»! m η m Μ »n 04 ι ι ιη ιη Μ ιη η > Λ < N ιη ΓΊ m Οϊ ΓΊ to Οί a „5 1 1 σ σ σ ο σ Ο ο ο ο o 〇o 〇 ο ο ο σ ο σ ο ο ο ο σ ο σ σ σ ο Ο ο σ Ο ο ο Ο Ο ο ο ο ο ο σ ο ο σ Ο ο ο inch HrH Ο \ cn η • Η 0 ί σ σ S Η ιη ιη σ \ inch? Η? σ > inch r-1 ο ιη C0 inch rH S CN inch rH ο ιη Γ〇ιΗ ο ο σ CN η σ σ ιη Η ο S Γ 'ο ο S ο ο ι η ο ο σ CM ο σ ο ο Cm 1 〇 Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο 〇 Ο ο ο ο ο Ο Ο Ο Ο Ο ο σ Ο Ο Ο Ο ο ο ο ο ο ο ο ο σ ο ο ο ο σ ο ο ο σ ο ο ο σ σ ο σ ο Inch Ο Ο SC / ϊ fi Φ 0 ο e 1 Ο Ο Ο ο ιη ο ο S ο ο ο S γΊ σ ο S σ Ο ιτ > Ο σ ο η ο ο ιη inch ο ο S Γ > ο ο S ο τΗ ο S m rH ο 00 ΓΟ 〇ο S rH ^ 0 r- \ < Ν m ιη C0 σ > ο ri γΗ CN m inch ( Please read the notes on the back before filling out this page) • The binding paper size is applicable to the Chinese National Standard (CNS) Λ4 specification (21 × 297 mm) 2 5 470783 A7B7 V. Description of the invention (50)标准 m brook 1 M V. -v, V. buried 1 · *. Η 1 Kuang m η Retain OJ V IS 埕 W m 〇! 0) .® 一 σ t-ί 〇O oo 〇rH o σ 〇〇oo rH ο τ-Η ο γΗ ο τΗ Ο ο ο ο ο ο Ο Γ Η Η Φ + U | < D ο CN Ο 〇oosoosooso 〇σ o CN 〇o S o 〇 (N 〇〇soo (N 〇Ο Ο Ο Ο Ο Ο Ο ο dal ο ο ο ο S ο Ο Ο ο Μ ο ο s ο oso _ P Μ m in in in in in in in in ir > in IP \ n in m IT) in in in in SSS ο τΉ g in in in aa in o σ > o O 1— < in «—1 O CS rH ΓΊ 〇m tr > nm O ττ in in (N ιη < Ν ιη cm ιη CN ιη Μ η tn ιη CN m οι m (N n — o 2 50 benefits 5 〇ooo 〇〇o 〇oo 〇〇o 〇O oo 〇ooo 〇〇〇o 〇σ oo OOoo OO oo σσ ο Ο σ ο σ σ ο ο ο ο ο ο ο ο ο Ο Ο σ ο ο ο ο ο ο ο ο ο 0 1 ooos H 〇 ^ ¢ /) ^ • rl 〇oo CN t—I os rH oo fNJ rH 0 1 oo CN rH o rH o tH 0 1 T ~ 4 0 1 rH 0 1 rH σ 1 τ-1 ο rH ο 1 ι-Η ο 1 γΗ ο 1 ι-Η ο 1 rH ο γΗ ο rH ο ο (Ν ιΗ 0 1 ooooo W o 5〇 \ oooo 〇OOo 〇ooo 〇oo 〇〇oo 〇ooooo σ σ σ 〇ooo ο ο ο σ Ο ο ο ο ο Ο ο ο ο ο ο ο ο ο ο ο σ σ ο 〇 ο ο ο ο Ο Ο Ο Ο Ο Ο Ο Ο σ os rH ooomo Tf r ~ io, .07 f- \ Φ 0 tu B ooomoo 〇ooo fO oo Q amo 0 1 〇oo σ tremor οο σ 0 1 ooo ο 1 σ σ ο Also ο ο ο η ο § σ ΓΟ ο ο ο ο σ ο ο ο η ο ο ο ο ο σ η ο os rH ooooo ® 0 η 2 in rH v〇rH Γ 'rH 00 rH σ \ rH rH CN Οί (Νί m CN inch (N ιη CN νο OJ r- CN 00 (Ν cn (Ν ο m rH Γ〇 < Ν m η m 邙 m in m ------------ install ------ subscription (please read the precautions on the back before filling this page) ) This paper size applies the Chinese National Standard (CNS) Λ4 specification (210X297 mm) 470783 A7 B7 V. Description of the invention (5i) Above the 0-fruit fruit samples, the 15-sample-to-sample display of the test results is obvious. 11 Thin film of each form and test state ο Appropriate sewing thread (please read the precautions on the back before filling this page) Printed on the paper standard printed by the China National Standards Administration (CMS) A4 specifications (210X29 "? Mm) 54 5. Invention description (52) τΉ Table 1 A7 B7 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs I ... Comparison of spring examples. II i I. Implementation 洌 | _v mm 镒 [Chemical treatment oooooo 〇〇〇〇〇〇〇o 〇〇 'Adhesion peel strength (kgf / 25mm) U) tn o 3 〇o tH in oo rH rH 0 01 κη ro in m rH ir > m in ΓΟ iH in m in fO in ro aDidi Iron, I SDOO | i 7000 | | 7000 | | 7000 | | 7000 I | 6750 | | 6750 I | 6500 II 6500 II 6000 | I 5500 II 5000 I 丨 3500 1 1 3000, 1 Press formability 'friction coefficient I 0.160 | | 0.143 | I 0.143 | I 0.141 | I0 ^ .40 II 0.138] I 0.136 II 0.132 I | 0.134 II 0.137! | 0.138 | I 0.139 I [0.140 1 I 0.143 | Fe-Ni-〇 film | I o in IT) o Tj * in m tTJ CN o (N σ iH o rH in rH ID CN in noo in Fe ; Feb Fe / (Fe + ^ Ii) I i 0.000. | I ο_〇ΰ ^ !, II o I 0.010 I | 0.050 | I o.ioo Π | 0.200 | | 0.300] | 0.500 | | 0.700 | BO 〆 < = > / c4 < Ts, 〇I l.ooo | Coating weight i (mg / m2) 〇220 I! 220 II 220 | I 220 I i 220 | I 220 | i 220 II 220! I 220 | 220 | 220 ί 1..220 1 | 220:! Ί I plating type I i GA I o < < 〇 < 〇 | GA I < a! GA I GA I GA i GA _GA_I < o 1 GA | Sample S No. < <λ; < rt: < < < < <-< »—4 cs Γ0 in vo 00 mo OJ m inch« Η. Long skimming _ pay 鲥 黯 贼 S thieves know the vine collar _ _ unloading () Approval of clothing thread (please read the precautions on the back before filling this page) This paper size applies Chinese National Standard (CNS) A4 specifications ( 210X297 mm) 5 V. Description of the invention (53) 2 1X Table 1 A7 B7 Printed by the Consumers ’Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 捶 U 镒 • ν " W m favor)« V * ·· »m street in 镒jj 1; 1 I m pendulum bait '• v.],-~ m 捶 η iridium jj-m pinch m Lin £ 3 〇ο ο ο Ο Ο ο ο XX Ο 〇 〇〇〇〇〇〇〇〇〇 • R狈 S Φ 亲 ί MS W 〇〇 \ ιη ·. 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Cn of—io 00 ο Ο (Ν ΓΟ% η ο 〇S γΗ 勐 刺 '' Hello! < Ο ο < ο < Ο ο < ο < ϋ Ο < Ο ϋ < ϋ ο < ϋ < ο ϋ < Ο < ϋ < 〇 < ο 〇S o < < < < < < < < < < < < < < < < < < < ιη rH bu00 ο \ CN (Ν m < Ν CN ιη CN νο 04 CO cm σ \ (ΝCN mmm ra ιη rn. Long move_ _ »s < Ms« IR _ ^-NB-sfi > r # willKIP3 (ffi) I batch of clothes ------ ir-- ---- ^ (Please read the notes on the back before filling this page) This paper size applies to Chinese National Standards (CNS) A4 specifications (2ί〇χ297 public registration) 56 470783 A7 B7 V. Description of the invention (54) 3 1 × Table Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs m uu 龆 jj 鹿 m 、-i 'm yaSK 镒 JJ 鹿 i-m 捶 u & aj m • ν.-JJ' Kuang mw U Hu •胡 JJ Sfl O o O ο ο 〇〇o 〇o 〇 〇 〇 〇〇 〇〇〇〇〇〇〇〇〇ίίΐ • R 如 杂 ίϊ ^ ms, -— · σΐ Οί cn in rH ο σ > One inch CN CN CN cs CN inchcs ϊ-ί CN ι-Η CS σ \ σ \ ιη σ \ ο σ \ rH CN inch CJ CN CN CN 04 t—I CN rH CN ka 琅 朗 m. 唆 a · .s1 m. 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Description of the invention (5ί3) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 4 τ-Η Table-Comparative Implementation Example: 1, 1 1 ... Example ",--m Street-U 1 Example 1 m 捶 镒 jj 1 1 buttercup application I, V.-m« 镒 |. 罝 施 钶 1 chemical treatment ο oo 〇o 〇〇〇oo 〇o 〇O o 〇〇oo 〇 oooo |-·. Adhesion * Peel strength (kgt / iismnw in rH σ »o rH CN ΟΊ rH vo m rH VO Γ0 rH v om rH vo ΓΟ V £ > rH m ro iH fO CO Γ 'in rH 〇rH CN 1C m K〇ro rH VO mm rH vo m rH vo n 〇) m * H m ro rH; @) a 1 ^ 3 mm m. 1¾ μ · > Spot '4000 1 8000 | 8000 | 7750 | 7500 | 7500 I 7000. | i 6500 | 1 6000 I | 4500 | | 7500 | [7500 I 1 8000 I 1 100QQ // | 10000 1 10000 " I 10000 ir _ 1 10000 if 1 10000-". | 10000 μ-| 9000 1 i10000 | 10000 ", compacted ^ friction coefficient 0.155 1 0.137 | 0.135 | 0-132 | 0.128 | 0.130 | 0.134 | i 0.136 | 1 0.135 I | 0.137 | | 0.129 | 1 0-130 1 1 0.155 I | 0.137 I 丨 0.134 I \ 0.132 I \ 0.128 I 1 0.130 II 0.133 1 I 0.135 I 1 0.136 1 1 0.137 1 I 0.129 1 1 0.130 Fe-Ni-〇ri membrane | 1 o in oo CN o rH o rH in rH tn cs in moo rH oo in oo CN o rH 〇tH in rH in IT) ro oo rH o rH Fe: fc ... Fe / (Fe + Ni) 1 | 0.000 | | 0.004 | 1 o.ioo 1! 0.200 I 0.300 1 0.500 | 0.700 | 0.900 I 1 0.920— | 1 0.200 | 1 0.200 I 1 | 0.000 i 1 0.004! I o.ioo I 0.200 i 1 0.300 j 1 0.500 I 1 0.700_I I 0.900 II 0.920 | I 0.200 | 0.200 | Package Sifi 1 1 | 220 | I 220 II 220 _I 220 I 220 I 220 | 220 I i 220 II 220 I 1 200 1 | 180 I 1 1 220 i I 220 | I 220 1 I 220 I 220 1 220 1 220 | 220 ·! 丨 220! I 200 180 i Flute plating type 'Zn-Fe | Zn-Fe | Zn-Fe I Zn-Fe I Zn-Fe I Zn-Fe I Zn-Fe I Zn- Fe II 2n.—Fe | 1 Zn-Fe I 1 Zn-Fe II Zn-Fe I • H z 1 C 1 Zn-Ni I • H 1 CN • H 53 1 S • rt 25 1 C CO • H 1 C • H 2: 1 CN • H 2 1 S • rH 1 CN • Η \ c M • H zic • H z 1 CM K m m. No. a QQQQQQQQQQQQ ω M ω w ω CO CO W w ω H CN BU 00 σ \ o rH H (N m »—4 inch m in rH CN inch 00 σ \ σ H CN n inch in 哏 _ _» 鍫 sis old tank collar INfrMitvir _ _ΚΙ53 (ΪΙ) batch thread (please read first Note on the back page, please fill in this page again) This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) 58 470783 A7 B7 V. Description of the invention (56) Table 15 = _d ^ lit: mmmmm lsg, w__I lgl5g, wlmq ~ ^ " ~: " h Ί1 Ί I-'1 7ϊ 75 1 I Marina 捶 g '~ ^ I tels 胂 咨询 ωιΊ Τι ^ ~ J —1 ^ 1 街 peptide —-Ti ~ „1 ^ li 0 Ο ο ο Ο ο ο ο ο ο ο ο ο ο ο ο ο 0 《una ^^ / w ^ so 趔 bury 趄 il * '• • s-8 · ° τ ετ ετ £ Τ ετ ετ ετ ετ ετ ε · ετ 6 · 10 inches · οτ 6 · ττ Μτ ετ ρ Η τ · ετ

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Tfcz d ο ϋ ο ϋ ϋ ο ϋ ο ο ο 0 οοε τν 丨 cz ϋ 00 ^ -0 ΟΔΕ: τν 丨 cz ο οτ τι ρ οτ ττ ετ yang _ S thief " '鼷 ¥ ^ 仵 鹚 驾 >遂 __ ^ 邱 (^) ------------. Install ------ 1Τ ------ ^ (Please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210X297 mm) 59 470783 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 _ ^ __ V. Description of the invention (57) Fe- fU-O thin film state test ', ratio of coating weight Ug / m2 converted to total metal weight), Fe content Ut.% in film) to Fe content Ut.%) and Ni content Ut.%) Sum ( FeWFe + Ni)) and the oxygen content U t.! S) in the film are measured as follows. [Measurement of film coating weight converted to total metal weight in film and Fe / (Fe + Ni)] For samples of plating type GI, EG, Zn-Cr, and Zn-Al, it is converted into The coating weight and chemical composition of the Fe-Ni-O film based on the total weight of the metal elements are obtained by dissolving the F e-1Π-0 film, M and the surface zinc plating layer M of dilute hydrochloric acid, and then peeling it off. Quantitative analysis of Fe and Ni by ICP method. Then calculate the ratio of F e / (F e + Ni) in the film. For the samples of electroplated GA, Zn-Fe and Zn-Ni, it is difficult to make the components in the upper Fe-Ni-O film by the ICP method because the lower electro-mineral layer contains the constituent elements of the F e-Ν-0 film. The elements are completely separated from the constituent elements in the lower plating layer. Therefore, only the constituent elements of the F e-Ni-0 film not included in the underlying plating layer were quantitatively analyzed by the ICP method. In addition, after the Ar ion sputtering > starting from the film surface by the XPS method, each component element of the F e-Ni-0 film was repeatedly measured, and each component element in the F e -N i -0 film was measured. The chemical composition distribution of the depth of the plating layer. In this measurement, the distance between the maximum concentration of the constituent elements of the Fe-N i -0 film that is not contained in the underlying plating layer and the position equal to one and a half depths where the other element can no longer be detected, As the thickness of the Fe-Ni-O film. The coating weight and chemical composition of the Fe-Ni-O thin film converted to the total weight of gold element in the film are calculated from the results of the I C P method and the X P S method. Then calculate F e / (F e + Ν ί) This paper size applies the Chinese National Standard (CNS) A4 specification (2 丨 〇 × 297 mm). Λ -6 0 1 ---------- (Quote please read the notes on the back before filling out this page) 470783 A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, V. Invention (Explanation (58) 1 1 I). 1 1 1 [Measurement of oxygen content in thin film by white J] 1 I The oxygen content in the thin film is determined by the results of the analysis in the direction of 1 degree according to Austrian Electron Spectroscopy (AES) 1 τδ 1 Next »Notes on the press-formability, continuous-point fusion, adhesive force, and chemistry Division 1 I 1 I Rationality test t Sexual matters of each sample as an example and comparative example 1 I re 1 1 Quality test 0 Fill in 1 Descriptive book [Chemical treatment] Page 1 I Perform test under Μ to evaluate chemical treatment 〇1 1 1 Dilute each sample under normal conditions 1 Use dip for automotive paint primer 1 1 Destroy Treatment with zinc sulfate solution (N ih on Perker ΐ z 1 ng C 0. L tc.) 1 Order to form sulfur on its surface Acid IΦ thin film 〇 Observing the crystals of the zinc sulfate thin film formed through a scanning electron microscope 1 | (S Ε Μ) > As a result, the normal formation of the zinc sulfate 1 I thin film was marked as 0, and the zinc sulfate thin film was not formed or was 1 1 I When there are gaps in the crystal, it is marked as X 0 1 Line. The above-mentioned friction coefficient continuous point weld peeling strength and chemical treatment 1 1 The results of the property test are shown in Tables 11 to 1 5 〇1 | Tables 11 to 1E show The following findings: The properties of the samples (press formability, spot welding, and adhesion) were performed from 1 to 1 and the comparison with the comparative examples shows the facts under M. Comparison of all the aforementioned properties of i in Example 1 1 with no F e-^ i--ϋ film formation on it 1 1 Example of cell (Yangpin number A; 1 B; 1C; 1 D; 1 E; * LF Compared with LG), all I | have an effective improvement * and a comparative example (2A '3 Λ' 1 η) with a Fe-N i- -0 film with 1 I formed under conditions outside the scope of the present invention 1 4A '1 5 A λ 1 1 This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 6 1 470783 A7 B7 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (59) 1 1 1 16 A, 23 A 24A ^ 25A 26 A; 2B, 1 3B; 2C 13C; 2D '1 3D 1 1 1 2E 13E; 2F, 1 3F 2G, 1 3 G) compared to 9 at least one of the properties 1 I There are improvements, which show that the examples are generally and have better properties. Please read 1 I. Comparison of actual temperature of the aqueous treatment solution higher than the scope of the present invention. (32A, 33/0 9) Although its properties are excellent f, the manufacturing cost is increased. Note 1 I Note I According to the present invention, the electrical matters generated on the galvanized steel sheet have the structure as described above 1 and 1 I coating surface The Fe -N i-0 film on the film has higher hardness and melting point than the zinc or zinc alloy plating layer. The existence of this film can reduce the surface of the galvanized layer on the galvanized steel sheet. 1 1 Sliding resistance with the mold ϊ The galvanized 1 1 I steel sheet Ge flows into the mold P, which improves the press formability. This local melting point is 1! Fe -N i-0 film can improve continuous point weldability = exists in F e — Ν ί -0 Film 1 Ordered oxide of Fe 1 can improve the peel strength of the adhesive substrate. Therefore) 1 1 According to the present invention, it provides excellent press formability, point weldability and adhesion 1 1 of Galvanized steel, s this Provides industrially very useful effects. 0 1 1 I Specific example 4 1 line The inventors found that by forming an appropriate 1 1 Fe-N 1 10 thin film I on the surface of the plated layer of a hafnium-plated steel sheet and forming a film F e Ν ί -0 of the film ¾..¾. 刖 9 The zinc-plated 1 1 steel plate is subjected to alkaline treatment in an alkaline solution with a pH of at least 1 1 for 2 to 30 seconds for 1 1 time t can be greatly improved Press-formability Λ point weldability and adhesion. 1 1 | The galvanized steel sheet has lower press formability than cold heading steel sheet »because under high surface 1 1 pressure» zinc with low melting point will adhere to the mold and cause sliding resistance 1 1 increase the force 0 to avoid this Inconvenience > An effective method is to form a thin film with higher hardness and higher melting point than zinc or zinc alloy plating layer on the surface of electroplated 1 1 layer of hafnium-plated steel plate »It will reduce the electroplating during the press forming process. Layer surface and pressure 1 This paper size is applicable to China National Tomb Standard (CNS) Λ4 specification (210X 297 mm)-62 _ 470783 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of invention ⑽) 1 1 | The sliding resistance f between them makes the galvanized steel sheet flow into the die more easily. J is therefore changed to 1 1 I Good press formability 0 1 | The flail point weldability of the galvanized steel sheet is worse than that of the cold rolled steel sheet 9 because 1 1 Process > The molten zinc comes into contact with the copper electrode y— * brittle alloy layer > its reading back 1 1 will cause the electrode to be more severely degraded 0 and formed on the surface of the electroplated layer— »face 1 note 1 with high melting point Method 9 for thin films It is believed that continuous point weldability can be effectively improved 1 | 〇 is to improve the point weldability of hafnium-plated steel sheet. In the present invention, due to the results of research on various thin films Φ-1, 9 the formation of Fe -N i- 0 Thin film is particularly effective c Although it is not yet %% installed on this page 1 Understand the reason t, but it may be due to the high melting point I Zn η i alloy produced by the reaction of Ni and Zn, the high melting point of the oxide of Η i The high conductivity of 1 and N i oxides due to their semiconductor-like properties. 0 1 1 Although the adhesion of galvanized steel is worse than that of cold-rolled steel, the reason is unclear. Study of the Causes of Inferiority The inventors have demonstrated that the adhesion is dominated by the chemical composition of the oxide film on the surface of the steel sheet. More specifically, 1 1 Although the oxide film on the surface of the cold-rolled steel sheet mainly contains Fe The oxide on 1 1> The thin film on the surface of galvanized steel is mainly composed of the lines of Z r I The oxide 0 The adhesion force varies with the chemical composition of the oxide film The oxide of Fe is worse than 0 1 1 so that the adhesion can be improved by forming 1 I on the surface of the galvanized steel sheet 1 as in the present invention to improve the adhesion 0 1 | The present invention iii Introduce ~ y hair development based on > and the method of manufacturing I 1 galvanized steel sheet according to the present invention > includes subjecting the galvanized steel sheet to alkaline 1 1 treatment in an alkaline solution for a period of 2 to 30 seconds, Next to base 1 After the treatment, it will be treated with Ⅰ or 1 I film 9 Μ to form F (ί-Ν ί--ϋ film on the surface of the galvanized layer of the galvanized steel sheet, 1 1 1 1 This paper size applies to Chinese national standards ( CNS) A4 size (210 X 297 mm) 63 470783 A7 B7 Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (S1) 1 1 I The steps to improve the quality. 1 1 1 A preferred method for manufacturing a wrought zinc steel sheet according to the present invention »includes an alkali-treated 1 1 galvanized steel sheet containing ferrous chloride and thallium chloride, and having a range between 2.0 and 3.5. 1 The pH, M in the range of 1 and the m-degree aqueous solution in the range of 20 to 70 are treated with back surface I and surface I to form a Fe-N 1-0 film. Note 1 1 Note 1 I A better method for producing a galvanized steel sheet according to the present invention f includes matters that have been treated with an alkali 1 I 1 | Galvanized steel sheet is treated in an aqueous solution containing ferrous chloride and nickel chloride, | The ratio of the iron content (wt.%) In the aqueous solution to the iron I 1 I content (wt · V) and the nickel content (V / t. 50) is found in the Fe-N 1-0 film. In the range of 1 1 1 from 0.004 to 0.9, p Η is in the range of 2.0 to 3.5 and the temperature is in the range of 20 to 70 ¾ 1 I. Ordered in the present invention for the forging in the present invention The surface of the galvanized layer of the zinc steel plate is shaped as 1 | The Fe-N 1-0 film that becomes the upper layer will be referred to as "film" for its relationship; 1 I On the other hand, the zinc or galvanized layer as the lower layer will be referred to as "plating" The layer ", 1 1 1 is not a "film" M. 1 line will limit the invention The reasons for the manufacturing conditions are explained below. 1 1 Galvanized steel sheet is treated in a test solution for 2 to 30 seconds of E Shima, and then 1 | Fe i--0 film is formed on the surface of the galvanized steel sheet. The reason is 1 | Galvanized steel sheet with Fe -W i-0 film is better than case 1 without alkali treatment 1 1 »Has better press formability. 1 1 Figure 6 shows that it is carried out in comparison with E Temple Alkali treatment and Zhu 3 Alkali treatment 1 1 Ni coating weight on the surface of galvanized steel sheet galvanized steel sheet and 1 | Friction coefficient observed in the press formability test of galvanized steel sheet The figure of the interval 1 [, is shown in Figure 0. It can be clearly seen from FIG. 6 that the package m of f \ i is constant when the weight dimension is constant. 1 1 This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm). ) -64-470783 kl B7 Printed by the Consumers' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (62 1 1 9 Compared with the case without processing t There are treatments in an alkaline solution. 1 1 | Case > Small friction coefficient value is available > and excellent press formability 〇1 I About this test solution > Can be used or a variety of alkaline chemistry Product 1 For example, please read I 1 | Na 0H Κ0Η, Na a 2 so 4, Na a P0 4, L ίΟΗ and Μ g 0 水溶液 aqueous solution. Iti means that the alkali concentration of the aqueous solution on the back side and the back side should have a pH of at least 10 and the pH should be adjusted to at least 11. Note 1 I means 1 is better 0 In this case, the concentration is generally set to about 5 to 50 g / meaning Enough matters 1 ί 1 1 Enough. Fill in this package. When the Fe -N i-0 film is processed on a galvanized steel sheet in an acid solution, it will be shaped as' W ^ 1 I. Slightly improved 9 However, the obtained steel sheet 1 1 has press-formability, point weldability and adhesion compared to that in an alkaline solution 1 1 is poorer than 0. This is due to the formation of galvanized steel sheet after treatment in an alkaline solution 1 Improvement of the adhesion of Fe-N 1-0 film > Treatment in acidic solubility 1 1 caused an unavoidable increase in the amount of oxide film on the surface of galvanized steel sheet 1 1 I > The foregoing effect cannot be obtained. 0 1 1 In this case, the Fe -N 1-0 film is a mixture of Fe metal F e oxide N helium and N ί oxide. There is no method for forming a thin film. 1 1 Special limitation: It is enough to treat the steel sheet in a water 1 I solution containing iron ions, nickel ions and oxidants. The applicable methods include immersion method in aqueous solution 1 1 | spraying of aqueous solution Method and electroplating method 0 In addition > 1 1 laser CVD, photo-CVL, vacuum deposition, sputtering vapor deposition or other vapors 1 1 electroplating method 0 1 1 The aforementioned aqueous solution for film formation may sometimes include Zr Ϊ 'C (), Mr Me), ATS η 1 1 I, W,' Pb, N b and T a, which are contained in the plating layer of the galvanized steel sheet used in the present invention, Hydrogen and oxygen are not positive and 1 1 a 6 5 — This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 470783 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (S3) 1 1 | Anion 0 1 1 is an improved zinc plating Alkali treatment of steel plates »Surfactants or U 1 I-like substances can be added to alkaline solutions in the form of 0, /, and v. Adding an oxidant will form oxidation on the surface of galvanized steel sheet. And the degradation of the adhesion of Fe -N i-0 film. Read back 1 Side I So it is not desirable to add oxidants and their analogs 0 Note 1 I Mean I When forming a Fe -N i-0 film, you can use F e C 1 2 and N i C 1 2 1 1 and 1 I aqueous solution. 0 For the supply of iron ions and nickel ions. 9 Filling this 1 with a metal salt of chloride can produce high precipitation efficiency. Therefore, compared with nitrate and sulfate, the same as page 1 I Under the salt concentration and treatment time of 9, a larger package of Ni and Fe can be obtained. 1 1 Cover weight J. Therefore, productivity can be improved. 0 1 1 Figure 7 illustrates the immersion in a chloride bath in a galvanized steel sheet system. 2. In the case of a sulfate bath 1 as a nitrate bath as a treatment solution for forming a Fe -N 1-0 film, the difference in coating weight between 1 IN i and the ratio of Ni to F e in the treatment solution is 1. I is 90:10, and the total concentration is 100g / A 1 1 | For film formation The solution should have a 1-line pH in the range of 2.0 to 3.5. The reason is as follows: 0 1 1 ρ 下 at 2.0M, the amount of hydrogenation from the cathode becomes excessively large, resulting in a ratio of 1 I Low precipitation efficiency > At the same salt concentration and processing time, Ν ί and F e 1 1 I coating weight is reduced > resulting in lower productivity 0 and this film becomes main 1! Contains Ν and F e Metal 1 cannot improve the press formability, spot weldability, and adhesion 1 1. On the other hand, ρ 3 on 3 5 κ, the oxidation of F 1; in the aqueous solution becomes fierce f, and the soft sludge Will cause defects on the surface of the steel plate. 0 1 1 Figure 8 says that the temperature of the moon is 5 0 < C, the ratio of 1 I to F * 3 concentration in the treatment tank is 20: 80, and the total concentration A condition of 100 g / A r 1 1 This paper size applies the Chinese National Standard (CNS) Λ4 size (210X 297 mm) 66-470783 A7 B7 Employees of the Central Bureau of Standards, Ministry of Economic Affairs Printed by the cooperative V. Description of the invention (64) 1 1 | t Figure of an example of the coating weight of N i with respect to the impregnation time 1 1 1 when p 变化 changes from 2.0 to 3.5 S 1 | The temperature of this aqueous solution should be in the range of 20 to 70 ¾ 0 Please read 1 first. I have a low reaction rate at a solution temperature of 20 ° CK. Sufficient coating weight of N i and Fe required to improve film properties Note 1 I means I reduce productivity 0 On the other hand t At temperatures exceeding 70 ° C t Matter 1 I then 1 I Accelerated processing degradation > The equipment required to maintain high temperatures and the ability to fill in this source increase manufacturing costs. Page 1 I Fe content in aqueous solution (W t *%) vs. Fe content (wt, SO The ratio of the sum of the N i content 1 1 I (wt.%) (F e / (F e + Ν i)) should preferably be in the range of 1 1 from 0.004 to 0.9. The reason is as follows: 1 The ratio of F e / (F e + Bu η in an aqueous solution set below 0. 0 0 4 can not obtain the improvement effect of 1 I adhesion. 0 In addition-the aspect i exceeds 0.9. The improvement of the weldability 1 1 The effect will be reduced. 0 1 1 I The galvanized steel sheet used in the present invention is only required to be a steel sheet having a plating layer 1 1 formed on the substrate by the immersion plating method, the steam plating method, and the like. Enough 0 Μ for chemical composition. 9 This plating layer leaves pure zinc. 1 I In addition »It also includes a single or multiple containing one or more such as Fe, Ni i Λ Co, 1 1 M r Cr, A 1 M c, Ti. S ί Λ W, S η, Pb, Nb and Ί, the metal Si 1 1 is also considered as metal), or its oxide, or the layering of organic matter ΰ J) t 1 1 layering In addition square containing fine particles such as S 2 and the A 1 2C 3. As for the galvanized steel 1 1 plate, a galvanized steel plate with a large number of layers can be used »or a functionally graded galvanized steel plate with a plating layer of a different chemical 1 I composition. 0 1 I is formed on the galvanized steel plate under the restrictions described above. 1 1 on the surface of the layer This paper size is in accordance with Chinese National Standard (CNS) A4 (210X 297 mm) -67 470783 A7 B7 V. Description of the invention (65) The horizontal cross section and the plate steel are formed in the process of pressing In addition to the elimination of thin film melting point in the mold to suppress the smooth flow of the mold into the good to change the force to prevent sliding down, sticking b due to the change, the next layer of thin film made of raw materials together. Β sex F There are some brittle inclusions between the electrode and the electrode, copper, and the steel connected to the plate, and they are melted at the point. Continued to change the process, and then apply the good degree of adhesion E,, D, IC film, 0B ο I, ♦ Ti Art -N Type Θ Proof. The F-type electroplating method is better than the ratio of M or any method. The method of forming hair is based on the fact that the plate is made of steel.

The surface and surface of the F surface are double-wrapped and the surface surface is double-wrapped. ¾ is the weight of 10 '' heavy-bearing layer. The ore bag is impregnated with gold and grown together, and each of the two faces / m each Og 之 Π ZO Measure and dip (please read the notes on the back before filling this page)

.1T layer is the quantity of the surface covering the adult surface. The layer of the surface is W 5 τ-Η. The surface containing the surface of the growing surface is the surface. Printed with double-layer plating Electroplated metal alloy printed by the Consumer Standards of the Central Standards Bureau of the Ministry of Economic Affairs 2 11 Including the surface with each surface covered with two layers of double-layered plating and metal plating t tf 4 Including the surface with the surface of the growth surface, the surface is double-coated, and the layer is plated with gold t W 5 Including the surface with the surface, the surface is covered with the metal layer, t W 5 The description of the front A, the inner L, the inner circumference Π12, the range of 8/60, is the hair volume, the weight is overwrapped, and the paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm). Η Z Enough and measuring enough 68 470783 A7 B7 V. Description of the invention M and 'M0 Examples of test and implementation of the comparative example of the practical application of the application than the film of the implementation of the implementation of the law did not go beyond the scope of the internal application . Make it clear that this example is under way The unreal number is C and the code is Fe. The test has a fixed K. The tester contains a firmware display system. The type of fine liquid plating is detailed. ί 専 理 验 of Office Examination 1-Going forward I for Fe work, change the law, change the confession, and so on. — Membrane thin strip-0 of liquid soluble water (please read the precautions on the back before filling this page). Packing-1T Printed by the Central Standards Bureau, Ministry of Economic Affairs, Consumer Cooperatives. This paper is printed in accordance with Chinese national standards ( CNS) Λ4 specification (210X297 mm) 9 6 470783 A7 B7 V. Description of invention ($ 7) Table 1 6

No Test plating type Alkali treatment conditions Fe-f 丨 ί-O thin film solution treatment temperature (0 * »time (sec) presence or absence of film formation chemistry pH 1 comparison case 1 A------X-2 Comparative implementation 洌 2 A NaOH 12.0 impregnation 50 5 X-3 Comparative cell example 3 A-----0 impregnation 4 Comparative example 4: A NaOH 9.5 impregnation 50 5 0 impregnation 5 Example 1 A NaOH 10.5 Impregnation 50 5 0 Impregnation 2 A NaOH 11.0 Impregnation 50 5 0 Impregnation 7 Cell example 3 A NaOH 11.5 Impregnation 50 5 0 Impregnation 8 Solid 4 A NaOH 12.0 Impregnation 50 5 0 Impregnation 9 Example 5 A NaOH 13.0 impregnated 50 5 0 impregnated 10 Example 6 λ NaOH 14.0 impregnated 50 5 0 impregnated 11 Comparative cell example 5 A. H2S04 2.0 impregnated 50 5 0 impregnated 12 A HC1 2.0 impregnated 50 5 0 Impregnation Comparative Example 6 13 Congratulations Example 7 A NaOH .12.0 Spray 50 50 0 Soak 14 Example 8 A KOH 12.0 Soak 50 50 0 Soak 15 Implement 9 A, Na2Si〇4 12.0 Soak 50 5 0 impregnated 16 cell examples 10 A Mg (OH) 2 12.0 mm 50 5 0 impregnated 17 cell cells 11 A LiOH 12.0 mm 50 5 0 impregnated. 18 cell examples 12 A Na? P〇4 12.0 Stain 50 5 0. Impregnation · 19 case examples 13 A 12.0 dipping 50 5 0 dipping 20 Example 14 A 12.0 dipping 50 5 0 decomposing 21. Example 15 A NaOH 12.0 dipping 50 5 0 steam deposition 〇: With Fe-Hi-〇 film X: Without Fe-Ni_〇 film booking (please read the precautions on the back before filling out this page) Printed on the paper by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs The paper standards are applicable to Chinese national standards (CNS) A4 specification (210X297 mm) 7〇470783 A7 B7 V. Description of the invention

In the trial, the G and F of the zinc plating of sheet steel were applied, and the mK treatment was performed before the Jit treatment. The implementation of the case was not included. fTHl rml after alkali treatment at the place where the film has been applied ΓΜ- treatment with alkali treatment is better than the example of the application, and the example is more effective than ο 0 case W rzhi of rml tTT11 Edit test with. The test solution is shown in the same phase as the dissolved phase. The strip is made of ¾ film for thin film formation. 9 The detailed strip is 9 3 to the same phase of the group (please read the precautions on the back before filling this page). Ministry of Economic Affairs Printed by the Central Bureau of Standards Consumer Cooperatives This paper is sized to the Chinese National Standard (CNS) A4 (210'X 297 mm) 71 470783

A

7 B Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of Invention (Rg) Table 17

No Test Electric Wolf Type Alkali Treatment Conditions Pe-Ni-〇f # Membrane Solution Treatment Temperature _ (V) Time (sec) Existence and S Film Formation Chemical Composition pH 22 Comparative Example 7 B-----X-23 Cell example 8 B NaOH 12.0 impregnated 50 5 X-24 Cell example 16 B NaOH 12.0. Impregnated 50 5 0 Impregnated 25 Comparing cell example 9 C-----X-26 Comparing cell puncture 10 C NaOH 12.0 Dip m 50 5 X-27 Example 17 C NaOH 12.0 Dip 50 5 0 Dip 28 Comparative Example 11 D-----X-29 Comparative implementation D 12 D NaOH I 12.0 Dip 50 5 X-30 Dip Example 18 D NaOH 12.0 impregnated 50 5 0 impregnated 31 Comparative Example 13 E-----X-32 Comparative Example 14 E NaOH 12.0 impregnated 50 5 X-33 Example 19 E 'NaOH 12.0 impregnated 50 5 0 Dip 34 Comparative Example 15 F-----X-35 Comparative S Application 16 F NaOH 12.0 Dip 50 5 X-36 • Cell Example 20 F NaOH 12.0 Dip 50 50 0 mm 37 Comparative Dye 17 G -j---X-38 Comparative cell example 18 G NaOH 12.0 impregnated 50 5 X-39 M21 G NaOH 12.0 impregnated 50 5 0 0 waves: with Fe-Hi-OM film X: without Pe-N Bu 0 film-¾ clothing- -(Please read the notes on the back before filling this page)

1. The paper size of the 1T line is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) 72 470783 A7 B7 V. Description of the invention (* 70) Example 3 Pretreatment of the same alkaline treatment conditions as the fixed plating type code AK Experiments were performed by changing the chemical composition of the F e-Ν -0 film-forming solution. This aqueous solution contains F e C 1 2 and N i C 1 2. The concentrations of F e C 1 2 and Ni C 1 2 were changed. Change the ratio of Fe content (wt.%) To the sum of Fe content UtD and Ni content UtJ). Other conditions remain the same. Table 18 shows the detailed conditions for test numbers 40 to 58. I Batch ordering (please read the precautions on the back before filling this page) Printed by the Consumers' Cooperative of the China Standards Bureau of the Ministry of Economic Affairs, the paper size applies to Chinese National Standard (CNS) A4 specifications (2 丨 0 > < 297 (Centimeters) 73 470783 A7 B7 7 / i \ Instruction issued '5 8 ii Table ° τ

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KoflN s Kuang According to the age of thief-δς -74-470783 A7 B7 V. Description of the invention (72) For the galvanized steel sheet and samples prepared in the cell example and the comparative example, the press formability, spot weldability, Evaluation test of adhesion and chemical treatment. The point weldability is evaluated by K consecutive point welds. Adhesion is the evaluation of peel strength after MM adhesion. Chemical treatment was evaluated by the crystal state of the zinc phosphate film. Tables 19, 20 and 21 show the results of tests, 2 and 3, respectively. (Please read the notes on the back before filling this page) The printed paper size of the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs applies to the Chinese National Standard (CNS) A4 specification (210 × 297 mm)-'75 470783 A7 __B7 V. Description of the invention (73) Table 19 Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs

No. Test press moldability friction pseudo-number (-) point weldability continuous point weldability adhesion strength (kgf / cm ^) chemical treatment of phosphate palmitate film condition 1 comparative example 1 0.150 2500 β.〇 2 2 Comparative Example 2 0.145 2500 10.0 2 3 Comparative S Application 3 0.125 5000 12.0 0 4 Comparative Cell Example 4 0.125 5000 12.0 0 5 Cell Example 1 0.120 5500 12.0 0 6 Cell 2 2 0.115 5500 12.5 0 7 Implementation Example 3 0.110 5500 12.5 0 8 Cell Example 4 0.110 5500 12.5 0 9 Example 5 0.105 5500 12.5 0 10 Implementation of M6 0.105 5500 12.5 0 11 Comparative Example 5 0.130 5000 12.5 0 12 Comparative Example 6 0.130 5000 12.5 0 13 Cell phone 7 0.110 5300 12.5 0 14 Example 8 0.110 5500 12.5 0 15 Example 9 0.110 5500 12.5 0 16 Cell phone 10 0.110 5500 12.5 0 17 Application Shi 11 0.110 5500 12.5 0 18 Cell phone 12 12 10 10 5500 12.5 0 19 Implementation 洌 13 0.110 5500 12.5 0 20 Cell example 14 0.110 5500 12.5 0 21 Implementation 洌 15 0.110 5500 12.5 0 22 Comparative Example 7 0.180 1500 5.0 0 23 Comparative implementation 洌 8 0.175 1500 6.0 0 24 Cell stab 16 0.130 4000 12.5 0 25 Compare Example 9 0.180 2500 6.0 0 26 Comparative® Example 10 0.175 250 7.0 0 27 Example Π 0.130 5000 12.5 0 (Please read the precautions on the back before filling this page) This paper size applies the Chinese National Standard (CNS) Λ4 specification (210X 297mm) -76-470783 A7 B7 V. Description of the invention (74) Table 2 0

No. Test E Molding Friction Coefficient (-) Point Welding Flail Point Welding Adhesive Peel Strength (kgf / cm2) Status of Chemical Property Mmmim 28 Comparative Case Example 11 0.150 3000 8.0 0 29 Comparison 寊Application Example 12 0.145 .3000 10.0 0 30 Example 13 0.115 6000 12.0 0 31 Comparative Example 13 0.150 8000 6.0 0 32 Comparative Example 14 0.145 8000 7.0 0 33 Quality Example 19 0.115 10000 12.5 0 34 Comparative Example] 5 0.150 3000 6.0 0 35 Comparative example 16 0.145 3000 7.0 0 36 Example 20 0.115 6000 12.5 0 37 Comparative example 17 0.180 1500 5.0 0 38 Comparative quality 18 0.175 1500 7.0 0 39 Example 21 0.130 4000 12.5 0 (Please read the notes on the back before filling out this page) The printed paper produced by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs is fully compliant with the Chinese National Standard (CNS) Λ4 specification (210X297 male f) 77 470783 A7 B7 Central Standard of the Ministry of Economic Affairs Printed by the Bureau's Consumer Cooperatives V. Description of Invention (75) Table 2 1,

No. Test cavity forming moldability coefficient (-) Point-weldability Consecutive-point-weldness Adhesion Peel strength (kgf / cm ^) Chemical treatment mmtmm Status 40 Comparison Example 19 0.135 5500 6.0 0 41 Example 22 0.130 5500 11.0 0 42 Quality application 23 0.120 5500 12.0 0 43 Cell example 24 0.110 5500 12.5 0 44 Implementation 25 25 0.110 5500 12.5 0 45 Cell M26 0.110 5500 12.5 0 46 Blister example 27 0.110 5000 12.5 0 47 Example 28 0.110 5000 12.5 0 48 Asset Example 29 0.110 5500 12.5 0 49 Example 30 0.110 5500 12.5 0 50 Congratulation Example 31 0.110 5500 12.5 0 51 Example 32 0.110 5500 12.5 0 52 Cell Example 33 0.110 5500 12.5 0 53 Example 34 0.110 5500 12.5 0 54 寊 Example 35 0.110 5000 12.5 0 55. Example 36. 0.120 4500 12.5 0 56 Example 37 0.120 4000 12.5 0 57 Example 38 ο.α3〇3500 12.5 0 58 Comparison Cell example 20 0.135 2500 12.5 0 I ---------- install ------ II ------ ^ (Please read the precautions on the back before filling this page) This paper size Applicable to China National Standard (CNS) A4 specification (210X297 mm) -7 8 470783 A7 B7 V. Description of the invention (7 6) Printed by the Consumer Standards Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs. Test result 1 From the results shown in il9, the following facts can be clearly seen. When the plating type is fixed to the code A (alloy immersion plating), at least one of the properties of the comparative example is inferior to that of the example. More specifically, (1) Comparative Example 1 in which no F e -1Π -0 film was produced without alkali treatment, and M and F e-Ν-0 thin 4 film with alkali treatment In Example 2, all the press-formability, spot-weldability, adhesion, and chemical treatment properties were inferior to those of the example. (2) Comparative Example 3 in which an Fe-N i-O thin film was formed but was not subjected to an alkali treatment was inferior in press formability compared to the example. (3) The steel plate is treated in an aqueous solution having an alkali concentration of P Η: 9.5 which is lower than the alkali treatment concentration commonly used for comparison, and then a comparative implementation of F e -N i -0 film is performed. Example 4, its press formability is inferior to that of the example. C (4) Fe-N i-O thin film was formed, but the pretreatments were performed in an acidic solution. Comparative Examples 5 and 6, its press formability was better than the example. Is bad. Test result 2, the results shown in Table 20, suggest the facts under M. (1) Regarding the primary plating type code D, E, or F, even if the alkali treatment is not performed and the F e-Ni-0 film is formed, or the alkali treatment is not performed but the F e-Ni-0 film is formed, its properties are The performance values are almost the same as those of the plating type code A under the same conditions. However, in the case of the codes B, C and G, Comparative Examples 7, 9 and 1 7 without the alkali treatment nor the formation of F e -1Π -0 film, K and the alkali treatment without the formation of F e- (Comparative Examples 8, 10, and 18 of Π-0 film, any of press-formability, point-weldability, and adhesion, batch order. 衣 (Please read the precautions on the back before filling this page ) This paper size applies to Chinese National Standard (CNS) A4 (210 X M7 mm) 79 470783 A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (77) 1 1 or even better under the same conditions The following electroplating type codes are A. Comparative Examples 1 1 1 and 2 are inferior. I (2) In the case of any primary electroplating type codes BC, D, Ε, F, and G, please refer to 1 first and 1 in t. Comparative Examples 7 to 18 have at least one of the press formability, point weldability, and adhesion of reading 1 being inferior. The ratios of Cell Examples 17 to 21 to the same electro-forged back 1 1 type 1 Compared with the examples, it shows improved properties. Note 1 1 Things 1 Test results 3 items and 1 1 From the results shown in 'Table 2 1', you can clearly see that the type of plating under M is filled in with this code A Page 1 1 (1) Galvanized steel sheet is in an aqueous solution containing N i C 1 2 but without F e Cl 2 1 is subjected to 1 I alkali treatment and then a thin film is formed. Comparative Example 20 treated in an aqueous solution containing 1 1 1 Fe C 1 2 but without N ί C 1 2 t 1 of them were respectively pressed into a swell. K and pressure K and press-formability and spot weldability 1 1 Poor 〇1 I (2) Example 2 within the scope of the present invention 2 to 3 8 relatively show all 1 I improvements in press formability, spot weldability, adhesion, and chemical treatment 0 This 1-line improvement is in Fe The ratio of F e (wt.%) / (F e (wt 1 Ν ί (W t *%)) in the -N i-Ο thin film treatment solution is between 0.004 and 0 · S. It is especially significant in the range of 0 1 1 even in the case of plating type code B, CD 'EF and G »Similarly 1 1 can obtain a result similar to the plating type code A 0 1 1 According to the present invention, it has the same as before The F e-丨 i-O film formed on the surface of the galvanized steel sheet of the I 1 coating described above has a higher hardness and melting point than the zinc or zinc alloy plating layer of 1 1. The existence of this film can reduce the sliding resistance between the galvanized layer surface and the stamper during the pressing of the galvanized steel sheet during the forming process, and make the galvanized 1 I steel sheet slide easily into the mold, so i good i μ formability 0 1 of this high melting point 1 This paper size is applicable to Chinese National Standard (CNS) A4 specifications (210X297 mm) -80-470783 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of invention (7S) 1 II Fe -N i-〇 The film can be a: good continuous 黒 i welding method: 〇 The oxide of Fe existing in Fe-N i. -0 film 1 1 1 can improve the adhesive base. The peel strength of the material is 0 1 I According to the present invention 9 It provides a method for manufacturing press-formability Λ point weldability and adhesion. Please refer to 1 1 I method for galvanized steel sheet with excellent strength. 9 Therefore, it is very useful in X industry. 0 Note 1 1 Meaning 1 I Specific example 5 Matters 1 I and 1 I have been filled in. Forming an island or mosaic on the surface of the galvanized layer of the galvanized steel sheet. Fill in the Fe-N i-0 film, which can be used for β β, good press formability, point welding β, and adhesion. force. Page 1 I The conventional press-formability of galvanized steel sheet is worse than that of cold-rolled steel sheet. This is because 1 1 1 low-melting-point zinc adheres to the die t and increases sliding resistance. The effective method is to produce a thinner film with higher hardness and higher melting point than zinc or zinc on the surface of galvanized steel. Because of the high hardness and high melting point of the Fe -N 1-1 | 〇 film, Therefore, the formation of 1 | island-shaped or mosaic-shaped Fe -N 1 — 0 films on the surface of galvanized steel sheet can reduce the sliding resistance between the surface of the deposit and the die in the press forming process 1 1 1 and promote the galvanized steel sheet. No. 1 line slides into the die, thus improving the press formability. 1 1 The conventional point-welding process of the galvanized steel sheet is worse than that of the cold-rolled steel 1 I sheet. This is due to the fact that the zinc Melting and contacting the electric 1 I pole Copper produces a brittle alloy layer 9 and thus seriously degrades the electrode 0 Therefore »1 1 In the present invention, due to the formation of island-like or mosaic Fe i-• 0 film f 1 1 1 The copper electrode and zinc are welded at the point The contact area is reduced in the medium and the 1 1-point weldability is improved. I I also believe that the effective method for improving the continuous m «•• Λ-point weldability of galvanized steel sheet is to produce a high melting point film on the surface of the plating layer. 0 Various papers are used for improved plating. 1 This paper size is in accordance with Chinese National Standards (CNS) 8 4 specifications (210X 297 mm) 8 1 470783 A7 B7 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (79) 1 1 | As a result of the research on the point weldability of zinc steel sheet, the inventors have found that the thin film of ΝΝ ί or Ν ί oxygen 1 I is particularly effective. 0 Although the reason is not obvious, 9 but the possible cause 1 I is due to Ni and Zn η reaction For high melting point Z η -N i alloys, please refer to 4 1 1 I oxides have very high melting points > and Ni oxides have semiconductor properties 1 | > Film with high conductivity 0 side Note 1 | Although the adhesion of the conventional galvanized steel sheet is known to be worse than that of the cold rolled steel sheet > Matter 1 1 The reason is not obvious 0 therefore 9 The result t The hair adhesion of human hair is dominated by the composition of the oxide film on the surface of the steel sheet. 0% This page is installed on the page 1, that is, although the oxide film on the surface of the cold-rolled steel sheet mainly contains the oxide of Fe. The oxide film on the hafnium-plated steel plate mainly contains the oxide of Z η. 0 1 | Adhesion depends on the composition of the oxide film. The oxidation adhesion of Z η is worse than that of Fe 1 1 oxide. 〇Thus as in the present invention on the surface of the hafnium plated steel sheet The formation of a film containing Fe oxide can improve the adhesion. The conventional chemically treated steel sheet is inferior to the cold-rolled steel sheet. The reason is 1 1] Due to the high content of Zn in the surface of the galvanized steel sheet, The crystal structure of the resulting phosphate thin 1 1 film is coarse and non-uniform f and the phosphate thin film line I on the galvanized steel sheet has a crystal structure and composition different from those of the thin film of the cold-rolled steel sheet. Danggang 1 | When the content of Z ΙΊ in the surface of the plate is high, the phosphate crystal mainly contains phosphazite i 1 1 and the secondary adhesion of hot water after painting is poor. The reason is that the phosphate content of the thin 1 1 film is low. 9 The adhesion of the chemically treated film to the steel plate is lost due to the condensation of the film after exposure to the wet environment after being painted! 1 1 | To prevent the chemically treated film from regaining the lost water > the effective method is 1 1 Phosphate crystals contain metals such as F (ί or N 1. In the present invention, the formation of F e-1 1 K i -0 thin film makes Η and F (i arrested during chemical treatment 1 1 1 This paper size applies to the China National Standards for Family (CNS) A4 specification (2 丨 〇'〇297 mm)-82 470783 A7 B7 V. Description of invention (ao) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs The salt crystal forms a chemically treated film with good adhesion. Fe-Nί-Ο films with island-like or mosaic distribution are formed *, so the film is not covered. The entire galvanized layer. Therefore, a direct reaction between the chemical treatment film and the galvanized layer occurs simultaneously, thereby ensuring the adhesion of the galvanized layer itself. As mentioned earlier, it has been found that when a thin film having an island-like or mosaic distribution and containing Ni and Fe metal and its oxide, that is, F e-Mi-0 film, is formed on the surface of a galvanized steel sheet, The steel sheet is excellent in all press formability, spot weldability, adhesion and chemical treatment. The present invention has been completed based on the foregoing findings, and the galvanized steel sheet of the present invention includes an Fe-Ni-O film formed on at least one electroplated layer > wherein the Fe-lU-O film has an island-like or mosaic distribution, Coating weight of Fe-Ni-O film Μ The total weight of metal elements in Pe-Ni-〇 film is in the range of 10 to 1500 g / ni2, and the surface coating rate of Fe-Ni-O film Within the range of 30 to 90¾ In this galvanized steel sheet, the ratio of the Fe content (wt.JS) of the Fe-Ni-O film to the sum of the Fe content (wtD and Ni content Utj) is in the range of 0.004 to 0.9 Preferably, the oxygen content of the Fe-N i-0 film is in the range of 0.5 to 10 wt.%. A method for manufacturing the galvanized steel sheet of the present invention comprises spraying a spray solution containing Fe ion and Ni ion and having pΗ in the range of 1 to 3.5 on at least one of the galvanized steel sheets. On the galvanized layer; leaving the galvanized steel sheet at a temperature in the range of 20 to 70 ° C for 1 second, and then heating the galvanized steel sheet to form a coating weight based on the total weight of the metal element on the galvanized layer It is in the range of 10 to 15 0 mg / m 2, the coating ratio is in the range of 30 to 90%, and 1 is for clothes. Order. I line (Please read the precautions on the back before filling (This page) This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) 83 470783 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention ('81') Fe island-shaped or mosaic-shaped Fe- N i-0 film. In this method of manufacturing a galvanized steel sheet, the ratio of the Fe content U / Ai in the spray solution to the sum of the Fe content (g / il) and the Ni content (g / il) is in the range of 0.004 to 0.9. Inside. In this method for manufacturing a hafnium-plated steel sheet, a Fe-H i -0 film is formed by heat-treating a galvanized steel sheet at a temperature of 80 to 500 ° C. Another method of manufacturing the galvanized steel sheet of the present invention is explained below. Its important features are the island-shaped or mosaic Fe-Ni-O thin film formed on the plating layer of a predetermined galvanized steel sheet, and a method for forming the same. In order to properly generate island-shaped or mosaic Fe-N i -0 thin films, the galvanized steel sheet is pre-treated as described below, and M is formed on the electroplated layer to form minute portions of Fe-N i -0 thin films and Fe- N i -0 thin film is a small part which is not easily formed. Next, Fe-N thin film was formed on a galvanized steel sheet with such a small portion formed on the surface. This method for forming a thin film is characterized in that the coating weight based on the total weight of the M metal elements is in the range of 10 to 15 0 m s / m 2, and the coating ratio is in the range of 30 to 90 ¾. The pre-treatment methods of the galvanized steel sheet include the following methods: (1) Forming fine irregularities on the surface of the electroplated layer by temper rolling the galvanized steel sheet. (2) A new surface is formed on the surface of the electroplated layer by temper-rolling the galvanized steel sheet. (3) By immersing the galvanized steel sheet in an acidic solution or performing anodic electrolysis in an acidic solution, the air oxide film existing on the surface of the electroforged layer is partially dissolved, and M forms active and inactive on the surface of the electroplated layer Part of it. This paper size applies to Chinese National Standard (CNS) Λ4 specification (210 × 297 mm) Lining order (please read the precautions on the back before filling this page) 84 470783 A7 B7 Explanation of the invention (82) 1 1 | (4) The zinc-plated steel phase i is immersed in an alkaline solution via I, or anodized in an alkaline solution 1 1 I. Existing on the surface of the plating layer The above air oxide film 1 | partially dissolves to form active and inactive parts on the surface of the plating layer. Please M 1 | In the method of manufacturing galvanized steel readback 1 | face I plate according to any one of the foregoing pre-processing methods (4), the cathode electrolytic method should be used as the Fe-N i-Ο film Note 1 1 means 1 I method is better, and the electrolyte used should satisfy the total content of 0.3 to 1 |-1 I 2. 0 ία 〇1 / A range of nickel sulfate, sulfuric acid Ferrous and ferric sulfate, and P Η series is better to be installed in the range of 1 to 2. Page 1 I In this method of manufacturing galvanized steel sheet 4 The electrolyte used meets Fe 1 1 content ( g / il) to the sum of the Fe content (g / A) and the Ni content (g / l) is in the range of 1 1 0. 0 0 4 to 0.9 and iron sulfate (m ο 1/1 ) Molar ratio to the sum of ferrous sulfate (mol 1 / A) and ferric sulfate (m 〇 1 / il) is a condition within the range of 0.5 to less than 1.0 1 1 〇 1 | In the method for manufacturing a galvanized steel 1 1 1 sheet according to any one of the foregoing pretreatment methods (1) to (4), an aqueous solution is used to form a F e -N i-0 film, and the 1-line aqueous solution contains F e C 1 Z and hi [: 12 > and it satisfies the conditions that P Η is in the range of 1 1 in the range of 2, 0 to 3.5 and t and the temperature is in the range of 20 to 70 ° C. 1 I In this method of manufacturing galvanized steel sheet 9 1 Aqueous solution for forming F e ~ Π-0 thin film »Satisfies Fe" content (g / A) to Fe content (g / A) and Ni content ( 8 / I 1 A) -D: b is a bar in the range of C >. 0 0 4 to 0 9 1 1 Figure 9 illustrates the specific example according to the present invention. A schematic diagram of a longitudinal section 1 1 of a galvanized steel sheet. As shown by a circle, the galvanized steel sheet of the present invention includes a steel sheet 2 1 ′ 1 | a plating layer 22 formed on at least one surface of the steel sheet 21-and formed on the plating 1 | F ϊ-Ν i-Oi 1 film on the surface of the zinc layer 22 with island-like or mosaic distribution 1 1 This paper size applies to the Chinese National Standard (CNS) Λ4 specification (210X297 mm) 85 470783 A7 B7 5 Explanation of the invention (83) 23 〇 The reason for restricting the F e-Ni-0 film of the hafnium-plated steel sheet as described above will be described below. The coating weight of the Fe-Ni-0 film is defined as a metal element. The reason why the total weight is 10 to 1500 mg / m2 is as follows. If the coating weight is less than 10 mg / m2, the pressure cannot be obtained. The improvement effect of formability, spot weldability and adhesion. However, if the coating weight exceeds 1500rag / m2, not only the improvement effect has reached saturation, but the formation of phosphate crystals is inhibited by the presence of an oxide film, which makes the chemical treatment Degradation. The coating ratio of Fe-Ni-0 film 23 covering the surface of galvanized layer 22 with island-like or mosaic distribution should be limited to the range of 30 to 909 per steel plate as follows. For example, Fe -The coating ratio of -tU-O film 23 is lower than 30¾ per steel plate, the improvement effect of press formability and spot weldability cannot be obtained. However, if the coating ratio of F e-N i -0 film 2 3 exceeds 90% of the surface steel plate, the area where the phosphate crystals and the galvanized steel plate directly react is reduced, thereby deteriorating the adhesion to the galvanized layer 22. The printing is printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, F e-Νί- 0 The film has an island-like or Marbucks distribution, which is a basic requirement. The reason is as follows. So the film covers the entire surface of the galvanized layer, and when the chemically treated film is formed thereon, the treated film will not interact with the galvanized layer. Reacted, so no The adhesion between the chemically treated film and the galvanized layer itself is ensured, so the adhesion between the chemically treated film and the galvanized layer itself is degraded. In the Fe-Ni-O thin film 23, the Fe ratio of the film (FeMFe + Ni) ) M is preferably in the range of 0.04 to 0.9. The reason is as follows. F e / 8 6 below 0. 0 0 4 (Please read the notes on the back before filling in this page) This paper size applies to China National Standard (CNS) A4 (210X297 mm) 470783 A7 B7 Central Ministry of Economic Affairs Printed by the Consumer Bureau of the Standards Bureau. V. Invention Description (84) 1 1 | (F e -f N ί) The adhesive effect is lower than 9; however, if the ratio exceeds 0.9, 1 1 1 is point-weldable. The improvement effect is low. The oxygen content K of the 0 1 1 Fe -N i-0 film is preferably in the range of 0.5 to 10%. Please read 1 1 first. The reason is as follows: oxygen content is less than 0.5 wt%. Due to the metal nature of the film, read back | Surface I is improved, so the improvement of press formability is low, but more than 10 wt. Note 1 1 Meaning I 1% oxygen content The generation of phosphate crystals is inhibited by the presence of oxide film 1 | 1 more I > thus causing the tendency of chemical degradation of rationality 0 Fill in 1 This book contains the galvanized steel sheet used in the present invention The steel sheets, which are attached to the surface 1 and the surface 9 of the copper plate as a base material, each have a plating layer formed by a method such as a dip plating method, an electroplating method, a vapor phase plating method, and the like. This bell plating layer includes single or most of the 11 layers containing pure zinc and such as Fe ^ Ni, C〇 ^ ΜηCr A 1, Mo-1 Ti Si% S η, Pb, Nb '• Ta, etc. Delamination of a metal or its oxide or a composition of at least one organic substance. This plating layer may include Jffl grains of Si02, 1 1 1 A 1 20 3, etc. > Multi-layer electrical 1 1 plated steel plate and functional gradient plated steel plate with changed composition may also be used as plated steel plate 0 1 wire bonding A method for manufacturing a galvanized steel sheet according to the first aspect of the present invention 1 1 0 In the first to the * aspects, f is a 1 1 spray solution in which p Η is 1 to 3.5 and contains Fe and Ni ions 9 Spray on the surface of the galvanized layer on at least one side of the mineral zinc steel plate. After the 1 1 I steel plate is left at 2C to 70 ° C for 1 second, it is heated β on the surface and surface of the plating 1 1 layer to form an island shape or a Marbuck distribution 9 Μ. The total weight of the metal elements is 1 1 The F e--N -C film with a coating weight of 1C > to 1 500 m 8 / in 2 and a coating ratio of 30 to 1 1 90¾ 〇 1 I P of the m-shaped solution The reason that the eye is in the range of 1 to: i. 5 is that the pH exceeds 1 I. In this range, i will not occur when the solution adheres to the surface of the plated steel plate. 1 This paper size applies the Chinese national standard (CNS ) A4 size (210X297 mm) 470783 A7 B7 Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (R5) 1 1 1 Take V Λ generation deposition reaction > 4 1 to form the metal Ni and 1 1 1 1 re spray the steel plate on it at a temperature of 20 to 7 0T; stop at a temperature of ~~, please read 1 1 1 for 1 second To ensure that all the hair has enough room so that Φ [ί provision substitution reaction occurs, the read back | N i plane I and the capture and Fe in Fe -N i - 0 films. 1Η :: The spray solution should have the following: Note 1 I! 1 High substitution deposition efficiency. Chloride bath is preferred. Any other solution can ensure that the 1 I 1 1 generation reaction occurs, such as a sulfate bath. Nitrate baths, etc. can also be used to fill 1 with 0 to improve the efficiency of the deposition. 9 Add additives such as oxidants, surfactants, I agents, etc. to f Μ to promote the decomposition of the salt during heating. 1 1 In order to form the total metal element, the coating weight is in the range of 10 to 1500 ffl g / m 2 1 1 »and the coating ratio is in the range of 30 to 90¾. F e-N i -0 film can be adjusted 1 order The size of the sprayed mist particles and the concentration of M. in or solution. The reason why the heating temperature of 1 I galvanized steel sheet sprayed with 4 mist solution is limited to 80 to 1 1 1 5 0 0 ° C is as follows: > Salt is less than 8 0 ° C 1 Decomposition, the -fm * Μ method appropriately forms Fe -N i-0 thin film. However, at temperatures higher than 50 0 1 line ° C, the properties of the steel plate and the plating layer may be adversely changed. 1 1 Problem 〇1 I The following describes a method for manufacturing a galvanized steel sheet according to the second aspect of the present invention. 1 1 1 0 In the second aspect, 1 1 is formed on the surface of a fresh layer through tempering and rolling into a fine shape. Regularize the dream and process 11 lines on the surface of the plating layer on at least one side of the steel plate to generate Fe i-〇 film, and ϋ fS to form islands or 禺 secco points 1 1 cloth > M total weight of metal elements Fe- -N i -C film with coating weight of 1C to 150C) mg / π t2 »1 I and coating ratio of 3 (> to 90¾ 0 1 I Tempering and rolling of galvanized steel sheet is used to correct the shape and smooth the surface t 1 1 This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 8 8-470783 A7 B7 Employees of the Central Standards Bureau of the Ministry of Economic Affairs Printed by the Consumer Cooperative 5. The invention description ("6") was carried out using a roller with fine irregularities formed on its heart. Figure 1 0 shows the use of a roller with fine irregularities formed on its surface. Schematic illustration of the cross-section of a tempered rolled galvanized steel sheet. As shown in the figure, there are fine convex and concave portions 2 2 a and 2 2 b in the surface of the galvanized layer 22 of the steel sheet 21. Forming. Then, the surface of the galvanized steel sheet with fine irregularities formed thereon is subjected to a process of forming a Fe-fU-O film, and only a Fe-Ni-O film is formed on the protruding portion 22a. As a result, an island shape is formed. Or mosaic-like Fe-H i-O film. This is due to the fact that the formation reactivity of the Fe-N i-O film in the convex part is higher than that in the concave part. When Fe-Ni-Ο When the thin film is formed by the electrolytic method, the electrolytic current is concentrated on the protruding portion . In the aqueous solution immersion method, the protruding and recessed portions show different diffusion behaviors of the reactive ions in the solution. A method for manufacturing a hafnium-plated steel sheet according to a third aspect is described below. In the third aspect, a new surface is formed on the surface of the electroplated layer by temper rolling and galvanizing a steel sheet, and then a process of forming a Fe-Ni-O film is performed on the surface of the electro-galvanized layer on at least one side thereof. An Fe-1Π-0 film with an island-like or mosaic distribution, a coating weight of 10 to 1500 mg / in2 based on the total weight of K metal elements, and a coating ratio of 30 to 90¾ is formed. Temper rolling of galvanized steel sheet is used to modify the shape and smooth the surface, and it is performed using a rolling roll having a relatively smooth surface. Fig. 11 is a schematic diagram illustrating a cross section of a galvanized steel sheet which is tempered by a rolling roll having a relatively smooth surface. As shown in the figure, the fine irregular protrusions that originally existed on the surface of the galvanized layer 22 of the steel plate 21 were in contact with the roller, and the protrusions 2 2 a appearing on the new surface were formed, and not-- -------- Gutter (please read the notes on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 89 A7 B7 Central Bureau of Standards, Ministry of Economic Affairs Printed by the employee consumer cooperative V. Description of the invention (R 7) 1 1 I Concave part exposed on the new surface 22b ° Then generate Fe on the surface of the galvanized steel sheet with the new surface coming out of the convex 1 I part- Treatment of N i-0 thin film 1 1 T and only F e — N i -0 thin film is formed on the new surface of the protruding portion 22 a. Please 阋 1 1 | Then, form an island or mosaic Fe -N i -0 films. JH;: It is due to the fact that the Fe-N i-0 film in the 1 I surface 1 point of the convex part reads back is higher than that in the concave part Note 1 I meaning 1 I Fe-N i-0 The electrolytic current system matters in the electrolytic method of the thin film 1 I and 1 I focus on the convex part ♦ In the aqueous solution impregnation method, the convex and concave part of t is filled with 1 Table 1 shows the diffusion of different reactive ions in the solution. Page 1 I Behavior 0 I 1 I The method of manufacturing a galvanized steel sheet according to the fourth aspect is described below. In the fourth 11 aspect, it is formed by immersing a galvanized steel sheet in an acidic solution or anodic electrolysis in an acidic 1 solution, and partially dissolving the air 1 | oxide film present on the surface of the plating layer. Active and inactive parts. Then I 1 is processed to form Fe _ H i-0 thin film | to produce island-like or mosaic distribution 1 1 Ϊ > coating weight based on total weight of metal element is 10 to 1500fflg / m 2 and 1 wire coating ratio It is a film of F e -N -0 from 30 to 90¾. 1 1 Figure 1 2 is formed on the surface of the plating layer by immersing the galvanized steel sheet in an acidic solution, or by anodic electrolysis in an acidic solution 1 | JK. A schematic cross-sectional view of a galvanized steel sheet 1 1 with active and inactive parts. As shown in the figure> On the surface of the galvanized layer 22 is formed an inactive part 24 with an air oxide film 1-and a thin layer The 1 1 active part of the air oxide film 2 5 〇 Then the treatment of forming Fc i--〇 film on the galvanized 1 I steel plate with the above active and inactive parts was performed, F ίί only on the active part 1 | forming F (3-Bu 1 i--0 film 23. Result is 7 F e--N i 1 1 in the form of Sugishima or Marbok. This paper size applies the Chinese National Standard (CNS) A4 specification (2 丨 0X297 mm)- 90-470783 Μ B7 Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention m) 1 1 | -0 Film 0 This is due to the fact that the Fe -N 1-0 film in the active part has a higher 1 1 1 reactivity. 0 In the electrolytic method of forming a Fe -N i ~ 0 film /-V 1 I 1 The electrolytic current is focused on the active part. In the aqueous solution immersion method, please read 1 1 1 The active part has high activity. 0 Read back 1 1 Side 1 »Μ The following describes the manufacture of plated 鉾 based on the fifth aspect. Method of steel plate. In the fifth note 1 I means 1! In the aspect t, the alkaline solution M is used instead of the acid used in the fourth aspect 1 1 and 1 1 The sexual solution t can obtain the same result. Filling the surface of the galvanized layer with the air oxide film of Maben. By immersing the galvanized steel plate in an alkaline solution, or by performing anodic electrolysis in the alkaline solution of page '— ^ 1 I, the solution is partially and actively formed. 1 1 Part 1 of 0 > ,,, and then the Fe-N ί-0 film is processed to produce a 1 1 island or mosaic distribution M. The coating weight based on the total weight of the metal element is 10 1 Order to 1500 rag / m 2 Fe-Ni-0 film with a coating ratio of 30 to 90% 〇1 | When the air oxide film existing on the surface of the plating layer is immersed in an alkaline solution or an alkaline solution by dipping the galvanized steel sheet 1 I Anode electrolysis in solution and partial dissolution 1 1 | Μ When the active and inactive parts are formed, the steel sheet has the same cross-sectional shape as the line 1 in Figure 12 0. Then, the treatment of forming Fe-N i -0 1 1 film on the galvanized steel sheet 9 is performed, and only the active part A thin film of Fe-Hi-0 was formed on it. Results 1 I formed Fe-Ν 0 films in the shape of island or Marseille. This is due to the fact that the Fe i-〇 film in the active part 1 I has a high reactivity. 1 1 1 In the electrolytic method for forming a Fe i-0 film, the electrolytic current is concentrated on the active 1 1 part), and in the aqueous solution impregnation method, the 1 active part has high activity, such as 1 1 is the same as the fourth aspect. 1 I In the treatment of Fe-\ i-• 0 thin film, it is possible to use sulfuric acid with p Η from 1 to 2 and containing 1 I with a total amount of 0.3 to 2. () fll C > 1/1 Nickel, Ferrous Sulfate and Ferric Sulfate 1 1 This paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) 470783 Printed by the Consumer Cooperatives of the Central Standardization Bureau of the Ministry of Economic Affairs A7 B7 5. Description of the invention (only 9) The electrolytic solution forms a Fe-Ni-O thin film through cathode electrolysis. The ratio of the Fe content (g / il) to the sum of the Pe content U / JI) and the Ni content (g / meaning) in the electrolyte is controlled within the range of 0.004 to 0.9, and the ratio of ferrous sulfate (mol / il) to It is also preferable that the molar ratio of the sum of ferrous sulfate (mol / il) and ferric sulfate Uol / A) is controlled in a range of 0.5 to less than 1.0. The reason why these conditions are preferred is as follows. If the F e ratio (F e / (P e + N i)) of the electrolyte is lower than 0.04, the F e content of the F e-N i -0 film is reduced, and the effect of improving the adhesion is therefore reduced. reduce. However, if the F e ratio exceeds 0.9, the F e content of the F e-Ni-0 film increases, and the improvement effect of the spot weldability is reduced accordingly. The molar ratio of ferric sulfate (ferric sulfate / ferrous sulfate + ferric sulfate) with M below 0.5, the oxygen content of the Fe-N i -0 film is reduced. On the other hand, the higher the molar ratio, the easier the iron oxide is captured in the Fe-H i -0 film, and the higher the oxygen content becomes. However, electrolytes containing only ferric sulfate are not good because they can yellow during electroplating. In the process of forming the Fe-N film, the Fe-H i-0 film should preferably be passed through an aqueous solution containing "6 (: 12 and (: 12, pH 2.0 to 3.5, and temperature 20 to 70 ° C). It is better to be processed. The ratio of the Fe content (g / il) to the sum of the Fe content (g / ϋ) and the Ni content U / A) is controlled to be 0.004 to 0.9. The examples are described below as examples of real cells that fall within the scope of the present invention and comparative examples that do not fall within the scope of the present invention. Regarding the galvanized steel sheets used in the examples and comparative examples, according to the plating method and composition And covering weight, and the appropriate selection of M code A to G means the following seven types of steel plates. _ This paper size applies to China National Standard (CNS) A4 specifications (210X297 mm). Non-clothing I " Order (Please read the precautions on the back before filling this page) -92-A7 B7 V. Description of the invention (90) A: Alloy drop-dip forged steel plate (10wt% Fe, sufficient Zn), both sides. 60 g / m2 Cover weight: B: Zinc-plated steel sheet with 90s / m2 coating weight on both sides. C: Zinc plated steel sheet with 40g / m2 coating weight on both sides. D: Zn-Fe alloy plated steel plate (15wt% Fe), with a coating weight of 40g / m2 on both sides. E: Zn-Ni alloy plated steel plate (12wt% Ni), with a coating of 30s / ffl2 on both sides. Weight: F: Zn-Cr alloy plated steel plate (UwU Cr), with a coating weight of 20g / m2 on both sides. G: Zn-A1 alloy plated steel (5wt% A1), with a coating weight of 60g / m2 on both sides. In the embodiment of the present invention, island-like or mosaic elements are formed on the plating layers of the foregoing types of galvanized steel sheets through the following methods I) to V). -Install ------ 1T (Please read the notes on the back before filling this page) 470783 A7 B7 V. Description of the invention (91.) Heating time: 1 minute I) Μ The second aspect of the invention is Basically, manufacture galvanized steel sheet with F e-Ni-0 film with island shape or mosaic distribution. Tempering and rolling galvanized steel sheet to form fine irregularities on the surface of galvanized layer (irregularity: 50 Up to 300 Wm), and then through the cathode electrolysis method 1 or the aqueous solution impregnation method 2 under K to perform the process of forming F e-Ni-0 thin film < Solution concentration of the solution of nickel acid, ferrous sulfate and ferric sulfate: 0.3 to 2.0 m / 1 / A (total concentration of ingredients) pH: 1 to 2 Fe ratio (Fe / (Fe + Mi)): 0.004 to 0.9 t Moore ratio of ferric sulfate (ferric sulfate / ferrous sulfate + ferric sulfate): 0.5 to 1.0 2. Aqueous solution impregnation method and component content: Central Standard of Ministry of Economic Affairs Printed by the Bureau's Consumer Cooperative (please read the precautions on the back before filling out this page) Nickel Chloride = 1 2 0 g / il Ferrous Chloride = Varying Concentration p Η: 2.5 to 3 '5 Fe Ratio of Aqueous Solution (Fe / (Fe + Νί)): 0.004 to 0.9 Immersion time: 1 to 30 seconds I) Based on the third aspect of the present invention, the Fe-N i -0 film with island shape or mosaic distribution is manufactured Galvanized steel.

After tempering and rolling the galvanized steel sheet, a new surface is formed on the galvanized layer (the pitch of the new surface (P itch): 10 to 50 0 ϋ in), and then F e-N is generated. This paper size is applicable China National Standard (CNS) A4 specification (210X297 mm) 94 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (92) 丨 1 I -0 Film processing 0 1 1 This film is made by M In I) 4 丨 said: the aqueous solution of the Ming impregnation method 2 formed. 1 I IV) K The third aspect of the present invention is based on i. To manufacture an island-like or horse-like galvanized steel sheet with Fe-N i-0 film distributed by Sec. Read back I side 1 By immersing the galvanized steel sheet in the sulfuric acid solution of PH3 for 2 to 5 seconds, the note 1 I means 1 I lies in the galvanized layer. The air oxide film on the surface is partially dissolved in 9 and is deposited on the surface of the electroplated layer. Matter 1 I The active and inactive parts are formed on the I surface, and then Fe -N i-0 4 1 is formed. The thin film is installed on the a page, ○ 1 I This film is prepared by the cathode electrode method 1 and an aqueous solution. 1 1 to 001 1 V) Μ according to any of the immersion method 2) The fifth aspect is based on the manufacture of a galvanized steel sheet with a Fe-N i-0 film having an island-like or mosaic distribution. 1 I is immersed in a galvanized steel sheet in a Na 0H alkaline solution of pH 12 for 2 to 5 seconds) 1 1 I The air oxide film existing on the surface of the galvanized layer is partially dissolved to be electroplated 1 1 • Layer surface The active and inactive parts are formed on the surface, and then the process of forming 1-line Fe -N 1-0 thin film is performed after the formation of the thin film) 1 1 This thin film is formed by any of the cathode electrolytic method 1 and the aqueous solution impregnation method 2 1 I becomes 0 1 1 1 On the other hand) In the comparative example, the forged zinc steel sheet is formed by forming Fe-N i-Ο thin film under the conditions beyond the scope of the present invention, or without forming thin film 1 1 film was prepared by the method of processing. 0 1 1 Tables! To 2ί > Shows the types of plating layers (indicated by 1 | code) and coating weight of galvanized layers for each example and comparative example, and generates fe-- N -C > Method 1 of thin film (represented by code), total weight of M metal element Wrapping weight and coating 1 1 Narrow Chinese national standard (_Α4 size (breast coffee men_ 95-470783 A7 B7) V. Description of the invention (93) and 5 卄 2 Θ Table (F / ο Θ ratio (F ratio The example of thin film is more oxygen-rich than that of the example, and the examples are more oxygen-containing ----------- install-(Please read the precautions on the back before filling this page)

1, 1T line Ministry of Economics Central Bureau of Standards printed by the consumer consumer cooperatives Paper size applicable to Chinese National Standards (CNS) A4 specifications (2H) X'297 mm) 470783 A7 _____B7 V. Description of invention (¢ ^) Table 22 Central Ministry of Economic Affairs Printed by Standards Bureau Consumer Cooperatives

m 1® 〇〇〇〇〇 Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο o < o Chemical treatment < 1 〇〇ο ο Ο Ο Ο < 〇 ο Ο ο Ο ο ooom to welcome ^ 3000 5000 Above points i 5000 points KK on 5000 points KK on 5000 points κ on 5000 points KK on 5000 points KK on 5000 points or more 4000 5000 points KK on 5000 points Μ on 5000 points or more 5,000 points κ on 5000 points κ on 5000 points or more 5000 From above: _______1 More than 5000 points and more than 5000 points. Press-formability. Friction pseudo-number 0.165 1 0.145 0.135 0.125 0.140 0.130 0.140 0.130 0.155 0.140 0.135 0.132 0.155 0.142 0.132 0.125 0.125 0.125 0.120 丨 Fe-Ni-〇 film. 1 Coating ratio ( %) 〇S ο σι ο ο 5 ο r * ο ο ο r * ο Γ- ο r * ο CN ss 100 o Cover weight (mg / m2) 〇 200 200 200 1 200 1 200 200 200 in ο S 100 200 200 200 200 200 400 Generation method 1 1 \ I Η Μ CN < Ν CN < Ν CN (N < Ν CN CN (N cs 1 Η Η Η Η Η Η Μ Η W Η Η XII III ΙΙΙΙ III III III III hi! _1 III III 1 lower layer 1 coating weight ig / m2i 〇SSSSSSSSS ο S S sso < 〇ss type < < < Λ: < < < < < < < < < < < < < < comparative example Comparison of examples of buttercup examples, examples of examples, examples of examples, examples of comparison, examples, examples, examples, spring cells, '_1 comparison, examples, examples, rH CN U1) ν〇r * 00 σ > ο fH rH CN m r4 m H \ 〇pH CO rH (Please read the notes on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210X297 mm) -9 7-470783 A7 B7 V. Description of the invention (95) Table 23 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs ^ < D m ^ m gff ^ m 〇〇〇 Ο Ο Ο Ο Ο Ο Ο oo 〇 〇 〇 〇 〇 〇 〇 〇〇〇 X Ο ο Ο ο Ο Ο oo < Ο Ο < Ο om to π ^ m 5000 points on 5000 K and above 5000 points and above 5000 points and above 5000 points and above 5000 points and above 5000 points 5000 points or more, 5000 points, K or more, 5000 points or more, 2000 i or more, 5000 points or more, 5000 points or κ, 4000, 15,000, or KK, SOOO or £ 5K. : Friction coefficient I_ 0.120 _I_! 0.115 0.115 0.115 ί 0.140 0.130 0.140 0.130 0.140 0.130 0.140 0.130 0.180 0.145 0.135 0.165 0.135 0.125 fe-Hi-O film: 1 coating ratio (%) 〇〇ο ο r * ο ο ο ο ο ο ο Γ- ο ο Γ ~ oor * o ο m ο Γ * »ο o Cover weight (mg / m2) 700 1000 1500 1600 200 200 200 200 200 j 200 200 200 o 200 200 ί 1 ο 200 200 (N < N < Ν (Ν Η Η οι (Ν Η CM CN 1 ίΝ (Ν 1 CN Oi III III XII > > δ > > > > > > 1 III 工 11 丨 1 III III 1 lower layer 1 | coating weight (g / m2) S ο Ο SSSS Ο ν〇S s KO os ο < Γ »Ο σ \ ο ο o type < < rf: < < < & lt < < < < (Q Ρ3 CQ ο Ο o Example! The example embodiment is more than S5 examples of buttercup examples, examples of spring examples, examples of buttercup examples. Example Comparative Example Example Implementation 洌 Comparison Example of Implementation Example < Ν Η (ΝCN (Ν CN < N CM ΙΛ < N ΓΊ CN CO < N fN om Η m CN m η m Μ * η in \ 〇ro (please first Read the notes on the reverse side and fill out this page.) The paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 98 470783

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Company 7 9 2 X 9 9 470783 A7 B7 V. Description of the invention (970 5 2 Table Printed Chemical Non-Responsibility of Employees Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs < 〇 〇 〇 〇 〇 〇 〇oooo 〇〇 adhesion, Peel strength I (kgf / 25mmJ ο 00 〇〇〇 〇 «Η γ4 U1 τΗ ο CN« Η m < N in CN rH m CN in ΓΊ t—l in CN in CN H in < N rH in < N in cs rH in CN rH m to ππ 3000 8000 ί 8000 1 1 8000 1 1 8000 1 1 8000 1 | 8000 | | 8000 | | 8000 | I 8000 I 1 8000 1 1 7000 1 | 6000 | | 5000 1 | 4000 1 3000 1 Ε Made of friction coefficient i 0.165 0.130 0.130 1 0.130 ι 0.130 1! 0.130 1 I 0.130 | 1 0.130 | I 0.130 | | 0.130 I | 0.130 | | 0.130 1 | 0.135 | 0.140 I | 0.140! 0.140 | Fe-IU-〇 Film oxygen containing fi. (%) Ι η Γ * > cn mmmnnm cn cn Fe / 1 (Fe + Ni) 1 〇0.003 1 ί 0.004 1 1 0.010 1 ι 0.050 1 1 o.ioo | i 0.150 | | 0.200 | I 0.250 | | 0.300 ι i 0.500 1 | 0.700 | | 0.900 | | 0.920 1 tl sm ratio t%) t 〇ο ο r 'ο r * ο ο Γ- O r- o r- oor * o r- oo r- o P- o Γ »o Bag weight 1 200 1 200 1 1 200 1 1 200 1 1 200 I | 200 | | 200 | | 200 | | 200 | | 200 | | 200 | | 200 | I 200] 1 200! CN < N < N CN CN CN CN < N CN CN CN (N CN cs CN 1 III ΓΙΗ) i IIlJ ΓΗ3 III Packing weight M (g / m2)} S ο νο 2 2 s SS so VO s S o V〇sss 1 Type 1 < < < < < < < < < < < < < < < 1 Comparison Yin 1 1- . Compare SSS 洌 1 Ming Shi 阏 II Buy Shi 洌 1 1 Butternet I 1 Jiashi Example 1 Tribute Case I Buy Case I I 眛 1 Temple Case 1 i Shibei II Case II I Temple Case 1 Tribute examples | | Spring temple example 1 Comparison 萁 网 〇 > 〇cn • Η CN in m in in ui VO in CQ σ > s rH (N U9 m K £ 3 (Please read the precautions on the back first) (Fill in this page again) This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) 100 470783 A7 B7 V. Description of the invention (9 valleys) 6 2 Chemical processing properties οο ο ο Ο Ο ο < adhesion (Kgf / 25mm) 〇CO ο τΗ ο CN m OJ Η ιη < N rH m Η tn CN rH m (N rH m pin ΰ £ 8000 1 8000 1! 8000 1; 8000 1 ι 8000 1 8000 1! 8000 1 i 8000 | Cavity forming friction protection j 0.155 1 0.145 1 1 0.130 1 ί 0.130 1 1 0.125 ι 1 0.125 1! 0.125 I | 0.125 | Fe-Ni-〇 Film oxygen contains fi .ί% ϊ ο rp Ο in ο rH tn ο iH H Fe / (Fe + Ni) < Ν Ο CN Ο < N ο (Ν Ο (Ν Ο CN Ο CN ο cs σ) Outgoing ratio (%) Ο Is * Ο r- ο r- Ο Γ * 'Ο Γ- Ο Bu ο Γ ** σ r- coating weight tnig / m2) | 200 1 200 1 1 200 1 200 1 200 1 200 1 200 1 200 1 Formation method ^ CN 1 ( Ν (Ν < Ν CN CN III hi 1 UxiJ -lliJ -IIlJ; hi! Lower saMfi (g / m2) ο νο ο U5 s SS s SO VO 1 type < < < < < < & lt < Comparison page Example ι Butter Example ι 1 萁 施 萁 1 1 荄 防 荄 · 1 1 萁 Example 1 萁 Example I 1 萁 Example 1 Shopping m VO VO 5 00 (Τ \ ο rH r * < N r * (Please read the notes on the back before filling out this page) This paper size is applicable to China National Standard (CNS) A4 (210 '/ 297 mm) ), A, a 101 470783 Α7 Β7 a five invention is described in (99)

The coating weight, coating ratio, e ratio and oxygen content of the Pe-Ni-O film are printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs and measured by the following method. [Measurement of coating weight of film and F e / (F e + Νί) ratio] Samples in immersion-plated steel, electroplated steel, Z n -C r alloy plated steel, and Z η-A 1 alloy plated steel Among them, they are M code B, C, F and G respectively. The Fe-N i -0 film is dissolved in dilute hydrochloric acid and is on the surface of the lower plating layer (equivalent to the Zn-based plating layer below) The layers were peeled together, and the coating weight and composition of the Fe-fU-O film were measured through the ICPS analysis of Fe, Ni, and metal. The F e / (F e + N i) ratio of the film was calculated. In the test samples of alloy freshly immersed ore steel, Zn-Fe alloy electric ore steel, and Zn-Ni alloy electric total steel, they are represented by M code A, D, and E, respectively, because the lower plating layer contains Fe and -N i-0 film has the same constituent elements, so the constituent elements of the upper F e-N film can not be easily separated from the constituent elements of the lower plating layer by KICP method, so only Fe that is not included in the lower plating layer Quantitative analysis was performed by elemental M ICP method of -N i-O thin film. After needle ion sputtering, the component elements of the F e-Ni-0 film were repeatedly measured from the surface by the MX Ps method, and the composition distribution of each component element in the depth direction of the plating layer was measured. In this measurement, the depth at which the elements of the F e-H i-0 film that are not included in the underlying plating appear to have the maximum content, and the distance between the center and the surface of the depth where no other element can be detected are regarded as F e -N i -0 film thickness. The coating weight and composition of the F e -N i -0 film were calculated from the results of the I C P method and the X P S method. Then calculate the F e / (F e + Ν ί) ratio of the film. [Measurement of coating ratio] The coating ratio of F e-Ν ί-0 film distributed in the form of island or mosaic is customized., Line (please read the precautions on the back before filling this page) This paper size applies to China Standard (CNS) Λ4 specification (210 × 297 mm) 102 470783 A7 V. Description of the invention | fi〇) Measured by the following method. · M AES analysis (Austrian Electron Spectroscopy) or EPMA analysis, mapping analysis is performed on the surface on which the Fe-Ni-0 film is formed, and N i, F e and 0 on the surface are measured. Distribution status. The point where the strength of the table 琨 is the coating weight of the Fe-Ni-0 film showing the total weight of M metal elements at 10 mg / m2 Μ is regarded as the coating point, and the total halo is measured by measuring the coating point. The ratio of dots is used to calculate the coating ratio. [Measurement of oxygen content of thin film] The oxygen content of the thin film is determined by the results of AES analysis in the depth direction of 0. The press-formability and spot welding of the samples (Nos. 1 to 72) of the Examples and Comparative Examples were evaluated. And chemical treatment, re-evaluate the adhesion between the sample numbers 1 to 48 and the galvanized layer itself, and re-evaluate the adhesion to the adhesive of the sample numbers 49 to 72. [|| Adhesion test of chemically treated film] Sample K was treated as an impregnated zinc phosphate treatment agent for automobile primer, and then coated with & P with a thickness of 20 «m. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page). As shown in Figure 13, two samples 35 with a size of 10x25mm are used to have a size of 0.15mm. Adhesive 3 7 with a thickness and a bonding area of 2 5 X 1 0 mm was bonded, and there was a spacer 16 of 0.15 mm therebetween, and a test sample was prepared, and then dried at 1 0 ° C for 3 0 minute. The adhesive used is an epoxy adhesive for structural applications. Although various steel plates with a thickness of 0.8 m «1 are used as specimens, since some materials have the possibility of damage to the substrate due to low strength in the tensile test, 2 mm is used for each specimen. The thickness of the steel paper is applicable to the Chinese National Standard (CNS) A4 specification (210XM7 mm) 103 470783 A7 _ B7 _ ^ __ V. Description of the invention (101) The plate is used as a reinforcing plate 3 9 to form a test sample. The test specimen thus formed was pulled using a tensile machine at a speed of Μ200 m / min, and the average peel strength at the time of peeling was measured, and the peeled surface was observed with a scanning electron microscope (SEM). Peeling occurs at the location with the lowest strength. In the case where GA (code A) is used, peeling occurs at the interface between the GA deposit and the steel plate, and peel strength represents the interface peel strength between the GA film and the steel plate. When using GI (code B), EG (code C), Zn-F e (code D), Z η -N i (code E), Z η-C r (code F), and Z η-A In the case of 1 (code G), the aggregate in the adhesive is broken, so the peel strength represents the strength of the adhesive itself. If the film of the present invention covers the entire galvanized layer, the adhesion between the chemically treated film and the galvanized layer itself cannot be ensured, thereby reducing the peeling strength. The peel strength K 0 is the same as that of the untreated sample, and the peel strength K X is lower than the untreated sample. This paper size applies Chinese National Standard (CNS) Λ4 specification (210X297 mm) ------ 1 ---- ^ 1 clothing H-order n (read the precautions on the back before filling this page) Θ The two islands 22 and 22 have a good U because of the test. Try 'Yu Liang II's connection with the small one and the 11-phase reduction of the number of melted fruit CDs. Wipe-N strips are trying to get rid of Fe He. Department of Yuqimo. Good sex, low quality, good connection with good crystals. Yes-change the test when the amount is normal. The results of the supplementary test with unexplained examples indicate that the coverage rate of each package in this report is based on the actual cost of the package, and the zinc obtained in the test results in the upper acid test κ, The enclosing example is shown by the dish method at its application point. The quantitative display range is especially helpful on the 00 test. There are 50 cases of isochronous race watches on the surface, which are even more practical before the application. In process or plated in fruit. Printed on 26 system. Printed by the Central Consumers' Bureau of the Ministry of Economic Affairs. Printed by the Consumer Cooperative Cooperative-104 470783 A7 B7 Printed by the Consumer ’s Cooperatives of the Ministry of Economic Affairs. Good 〇1 1 About the adhesion between the chemically treated film and the galvanized layer > When the F e -N 1-〇 film is coated ^ 1 I to cover b- galvanized layers > Between the chemically treated film and the galvanized layer Μ method In order to obtain adhesion, kj 1 to 1 force 9 and thus reduced peel strength. In Comparative Example No. 17 in which the ratio of being covered with Fe-N 1-0 film is 1 and the back is 1 100%, adhesion cannot be obtained. RAN Coins-In the above Note 1 I Note 1 In some examples > Adhesion can be obtained ○ Matters 1 I and 1 I In most embodiments, the peel strength is 12 kg f / 25 mm Μ due to 4 I The installation is good. Page 1 1 The friction coefficient, continuous spot melting of the comparative examples outside the range of the present invention r ^ FTt 1 1 Any of the adhesiveness and chemical treatment-bad 0 1 1 Due to the structure in the present invention, the Fe-N ί-0 film formed on the surface of the galvanized steel 1 plating layer as described in ^ Λ. 具有 has improved properties compared to zinc or zinc alloy 1 | Hardness and melting point and island-like or mosaic-like distribution 1 I Therefore, the sliding resistance between the plating layer surface and the stamper 1 1 I is significantly reduced during the press forming process, and the galvanized steel sheet can accommodate The ground flows into the die, thereby improving the forming properties of the press line. 0 Continuous M in the spot welding process. &Quot; Steam point weldability is also 1 1 improved due to the presence of a high melting point Fe 1 — 0 film. 3 F e ~ N i -0 1 I Presence of Fe oxide in the film} Increases the peel strength of the bonded board > 1 I Therefore improves the adhesive strength 0 The chemical processability is also due to the characteristics of M and thin 1 1 I The island-like or mosaic distribution of the film is more improved. Therefore, the present invention has the ability to provide 1 1 with excellent press formability, point weldability, and excellent adhesion and chemical treatment. I Specific Example 6 1 I First, the special feature of the method for manufacturing galvanized steel sheet is to make the galvanized steel sheet apply the Chinese National Standard (CNS) A4 specification (210X297 mm) at 1 1 paper size 105 470783 Employees of the Central Standards Bureau of the Ministry of Economic Affairs Printed by Fei Cooperative A7 B7 V. Description of the invention Tempering and rolling in an elongation range of 0.3 to 5.0%, alkaline treatment of galvanized steel in an alkaline solution having a ρ 以上 of 10 or more 2 Within 30 seconds, F e-Ν-0 thin film was then formed on the surface of the electroplated layer of the galvanized steel sheet which had been subjected to alkali treatment. Second, the method of manufacturing a galvanized steel sheet is characterized by subjecting the galvanized steel sheet to an alkali treatment in an aqueous solution having P Η on 10 M for a period of 2 to 30 seconds, so that the alkali-treated plating is performed / performed in another way. The zinc steel sheet is temper-rolled in an elongation range of 0.3 to 5.0%, and then, a Fe-Nί-0 film is formed on the surface of the plating layer of the galvanized steel sheet thus temper-rolled. The method for forming the Fe-Ni-O thin film can be completed by treating a galvanized steel sheet in an aqueous solution having a ρ Η range of 2.0 to 3.5 at a temperature of 20 to 70 υ. This aqueous solution contains F e C 1 2 and N i CU. The formation of the Fe-N i -0 film is completed by subjecting the galvanized steel sheet to an aqueous solution having P 2 of 2.0 to 3.5 at a temperature of 20 to 70 ° C. This aqueous solution contains ? The content ratio of 6 (: 12 and "(: 12, and Fe content Ut.%) To the sum of Pe content t (wt.%) And Ni content (wtj) is in the range of 0.004 to 0.9. In this patent application In the case, it should be noted that in the case of the F e-Ν-0 film formed on the surface of the galvanized layer of the galvanized steel plate for the upper layer, it is referred to as a "film"; and in the case of the zinc plating for the lower layer In the case of a layer, it is referred to as a "plated layer", rather than a "film". The following description explains the reasons for limiting the manufacturing conditions of the present invention as described above. In the present invention, the galvanized steel sheet is presumed to have Processed in alkaline solution of ρ 上 on 10 Κ for 2 to 30 seconds, and then formed on the surface of 綷 plated steel plate. ^ Clothing thread (please read the precautions on the back before filling this hundred 〇 This paper size applies the Chinese National Standard (CNS) Λ4 specification (210 × 297 mm) 106 470783 Μ B7 Printed by the Bayer Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention 1 I | Fe -N i-0 film , Galvanized steel is in the alkali β: case of 1 1 1 treatment in solution) and The galvanized steel sheet is not treated in an alkaline solution, that is, the case of 1 I forming Fe -W i — 0 thin film. Compared with ft, its compression into Le M is significant. Please refer to 1 1 I Excellent. In addition, J will describe The reason is that a galvanized steel sheet with improved adhesion can be obtained on the back surface 1 1 1 and exhibits excellent press formability. Since Fe-N i-0 is thin, it is noted that the film is attached to the zinc steel sheet at 0. Tempering and rolling in the range of elongation from 3¾ to 5. 0¾ 1 I Re 1 1 Forming after pressing and tempering rolling is written before it is processed in the test solution. The surface of the steel sheet was tempered and flattened, and the oxide film with deteriorated adhesion of the sheet 1-Fe -N ί-0 was removed. C 1 1 | Fig. 1 shows the alkaline solution treatment. And tempering case 1 1 > λ and not treated In the case, the coating weight of ni on the galvanized steel sheet is shown in Figure 1. The relationship between the coating surface is shown in the figure. According to the chart, the coating weight of nickel is the same as that of the nickel coating. The value of the friction coefficient becomes smaller than the case where the treatment is not carried out. 1 Here, > A test chemical containing 1 1 1 or 2 M can be used, such as N a 0H Λ Κ0Η N az An aqueous solution of S0 4 \ 1 wire Li 0H, Na -2 P 0 4 Mg 0H, etc. is used as an alkaline solution. The test concentration of this water 1 1 solution must have a pH of 10M, and this test solution is prepared 1 | An alkaline concentration with a pH of 1 1K is more preferred. 0 In this case > an alkaline solution with a concentration in the range of 5 1 1 to 50 g / il is generally acceptable. 0 1 1 | Relatively t at Fe i- -0 Thin Film System Sugasei in the case where the galvanized steel sheet is treated in an acidic solution 1 1 } Slight changes in press formability 1 1 good f, but the press formability, point weldability, and adhesion are worse than those of zinc-based steel plates when processed in alkaline II solutions. This can be attributed The adhesive force on the Fe-N i- 1 I 0 film was obtained on the galvanized steel sheet in the alkaline solution. 1 1 This paper size is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) -107- V. Description of the invention ((D5) On the surface of the improvement, there is a certain method of processing Ni and oxygen on the surface, such as Zr A7 B7, which has no effect on lightning. In fact, the foregoing effect is known when the hafnium-plated steel plate is acidic. · It is not available in solution in time, because the amount of oxide film inevitably formed on galvanized steel sheet will increase with acidic solution. , Fe-Ni-O thin film is a mixture of 6 metals, oxides of Fe, Ni metals, and compounds, and the method of forming a thin film is not particularly limited. It can contain Fe ion, N ion and oxidant In aqueous solution, an aqueous solution dipping method, an aqueous solution spraying method, a coating method, and the like can also be used. In addition, a vapor phase plating method, radiation CVD, photo CVD, vacuum deposition, sputtering deposition, and the like can be used. Avoidably included in the electroplated layer Mn'M 'of the galvanized steel sheet used to practice the invention

Si, Pb, Nb, T; positive ions, hydroxides, and oxides printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, etc., are contained in the aqueous solution forming the thin film. In addition, the plating layer may include negative ions. In addition, in order to improve the alkali treatment properties of the hafnium-plated steel sheet, a surfactant may be additionally contained in the alkaline solution. However, when an oxidant is added to an alkaline solution, an oxide is formed on the surface of the galvanized steel sheet, and the adhesion of the F e-Ni-0 film is degraded. Therefore, it is not desirable to include the surfactant K in another way. Assuming that the factors that hinder the coating weight of the F e-Ni-0 film are removed, the tempering and pressing and alkali treatment can be performed before the Fe-Nί-〇 film forming treatment, regardless of the order of the two treatments | Have the same effect. Therefore, the order of the above two removal factors can be appropriately selected according to the type of galvanized steel. Regarding the elongation rate of temper rolling, it is sufficient if the factors hindering the adhesion of the F e-Ni-0 film can be removed. For this purpose, from 0.31 ¾ to 5.0% Fan I-binding (please read the precautions on the back before filling this page) This paper size applies the Chinese National Standard (CNS) Α4 size (2 丨 OXW7 mm ) 108 _ 1 Λ Q-A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of Invention 1 The elongation within the range of 1 is acceptable. When the same elongation is used, the larger 1 1 I The compressive load provides a greater effect on the same elongation. When the elongation is lower than 1 1 to 0.32 »The leveling effect is small. J So that the satisfactory press formability cannot be obtained, please read 1 1 first. On the other hand, when When the elongation exceeds 5. 0¾ > Degradation of the material is bad 0 Read back 1 Face 1 Use water containing Fe C 1 2 and N iC 1 2 to dissolve in the note 1 generated in the present invention I I 1 1 Fe -N The reason for the i-0 film is that when a metal salt of chloride is used Tip 1 I -k 1 1 When divalent iron ions and nickel ions are supplied, t can obtain a high precipitation efficiency. Therefore, writing 1 can improve the productivity of the present invention. 0 At the same salt concentration and the same processing time. Page 1 | In the case of t Ν ί and Fei, the coating weight is 1 1 more than that in the case of nitrate and sulfate. Figure 1 5 shows the type and coating of the processing tank for the production of Fe -N ί-0 film. 1 Diagram of the relationship between ΊΤ weight 0 This figure shows the case where the concentration of N i to Fe in the treatment tank 1 is 90 10 and the total concentration in the stationary tank is 100 g / y 1 1 1 Compared with sulfate bath and nitrate bath. 9 The chloride bath exhibited 1 1 high efficiency. 0 1 The pH of the aqueous solution used for film production is more in the range of 20 to 5.5. 1 1 is appropriate. 0 Reason. Under 0 1 I When p Η is lower than 2 '0, the amount of hydrogen produced by the cathode and the anode increases excessively-adding > I 1 I reduces the f precipitation efficiency at the same salt concentration and the same processing time, and N i 1 1 The coating weight of Fe and Fe is reduced and the productivity of this method is reduced. In addition, 1 1 »This film is mainly composed of metal f including N and Ff) and cannot be formed by pressing. 1 1 Effect of improving adhesion 0 On the other hand »When P Η exceeds 1 I 3 5, 'e in aqueous solution 1 is violently oxidized > fn ® plate surface in the presence of Penny 1 I slurry -V Crack 0 1 1 This paper size is in accordance with Chinese National Standard (CNS) 8-4 specification (210X297 mm) 109 470783 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of inventions 1 1 Figure 1 6 series Example shows the change in pH white 2.0 to 3.5 in the case of 1 I. ≫ Ni i coating weight versus impregnation Time graph. This graph shows that the processing tank has a temperature of 1 I 50 ° C, and the concentration ratio of H i to F e in the processing tank is 80: 2 0, and the concentration should be 1 1 first. The total degree is 100 g / The situation of A; it can be found from the figure that when P 肩 lifts the shoulder-, the precipitation reads back | I the efficiency is satisfactory 〇 1 I 1 1 The temperature of the aqueous solution for the film formation Μ is in the range of 20 ° c to 70 ° C The internal affairs if 1 I and 1 are more appropriate. The reasons are explained as follows. 1. Fill in the speed section and write when the temperature of the aqueous solution is lower than 20 X: When the reflectance becomes slower, it takes-Page 1 for a long time to maintain improved film properties. The required coating weight of Ni and Fe is 0. Another 1 1 On the one hand, when the temperature of the aqueous solution exceeds 70, the degradation of the properties of the aqueous solution is accelerated, and equipment and heat to maintain it at high temperature are required. Energy, which leads to an increase in the cost of producing 1 1 D 0 1 I Fe content 1 1 (W t.%) Vs. Fe content (W t %) And the sum of the Ni content (W t ·%) (the following 1 1 Fe ratio Fe / (Fe + Η ί)) is defined within the range of 0 04 to 0.9! The reason is that > When the Fe ratio is lower than 0, 0 0 4 the adhesion cannot be improved 1 I »and when it exceeds 0.9, the properties of the point weldability are only improved to some extent 1 I good 0 I 1 which A steel sheet t having a galvanized layer formed by a method such as a zinc dip plating method, a vapor plating method, and the like is acceptable as the 1 1 galvanized steel sheet used for practicing the present invention. The composition of the plating layer, in addition to pure rhenium, 1 I 1 may include, for example, Fe, N., 1 IC (), Mr 1, Cr, A , M (), T 1, SW, S η, Pb, N b and T a gold 1 1 I belongs to (in this case, the si pseudo wave 丨 see as metal oxide > into one or two 1 1 copies Paper size applies to China National Standards (CNS) A4 (210X297 mm) 470783 Α7 Β7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention Uns) K Organic substances. In addition, the plating layer may contain fine particles of S i 0 2 and A 1 2 0 3. In addition, as the ore fresh steel sheet, a multilayer electric steel sheet and a function inclined plated steel sheet having a composition change of a plating layer can be used. A kind of adhesion phenomenon between a steel plate and a forming die during press forming, which disappears due to the existence of the F e-Ni-0 film formed on the surface of the galvanized layer of the galvanized steel plate under the aforementioned restrictions, thereby reducing the sliding resistance . Therefore, the sliding profit of the steel sheet in the forming mold is improved, and the formation of a brittle alloy layer between the copper electrodes during spot welding is suppressed, resulting in improved continuous spot welding. In addition, the adhesion is due to the presence of F e The effect of thin lotus root was improved. Example The galvanized steel sheet obtained by electroplating a cold-rolled sheet steel with a conventional method is used, which represents a method defined in the scope of the present invention according to Example 1, and M and which are not according to Comparative Example 1 A method within a defined range to produce a predetermined galvanized steel sheet. The plating type of the galvanized steel sheet is selected from the types represented by the letters A, B ·, C, D, E, F, and G under M. A: It is an alloy zinc impregnated layer including an alloy of 10 w t.% Fe and a sufficient amount of Z η, and the coating weight of the alloy on both surfaces is defined as 60 g / m 2. B: Zinc-plated coating is formed, and the coating weight of the two surfaces is defined as 90 g / κι 2 ° C: Zinc-plated coating is formed, and the coating weight of the alloy on both surfaces is limited to 40g / m2 . D: It forms a zinc electro-galvanized layer of 15 W t.% Fe and a sufficient amount of Z η, and the two paper surfaces are in accordance with the Chinese National Standard (CNS) A4 specification (210 × 297 mm). Each booklet (please read the precautions on the back before filling this page) 470783 A7 B7 _ ^ __ V. The coating weight of the alloy of the invention description (! 〇9) is limited to 40 g / in 2. E: Forms an alloy plating layer of 12 w t% Ni and a sufficient amount of Z ri, and the coating weight of the alloy on both surfaces is limited to 30 g / m 2. F: Forms an alloy plating layer such as t.% C r and a sufficient amount of Z η, and the coating weight of the alloy on both surfaces is defined as 20 g / m 2. G: It forms an alloy immersion coating layer of 5 w t.% A 1 and a sufficient amount of Z η, and the coating weight of the alloy on both surfaces is limited to 60 g / m 2. In the following tests 1 and 2 *, the press formability, spot weldability, adhesion, chemical treatment, and mechanical properties of the galvanized steel sheets produced by the methods of the examples and comparative examples were evaluated. Next, Examples and Comparative Examples concerning Tests 1 to 3 will be described. The outline of the content of each test is shown in Table 27. -.-------- Approval of clothes ordering (please read the precautions on the back before filling this page) The paper size printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs applies the Zhongguanjia standard (_ 铁 格 （ 21〇'x gift) 2 _ 470783 A7 V. Description of invention mo) Table 27 Printed by the Consumer Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs

Run m ο ^ IU * 1 II 1 rH i 〇1 1 I 1 in ».» 1 1 1 1 1 om 3: 〇4 1 1 1 1 l < N CNI — Μ Η 在 H (J · Ο -H JJ 4) 2 > Cli + w 1 1 1 1 oo < M chain mm mm side foot m ^ fW sm M 4 ± i Zhao W crucson wins to m to 1m inm to m P ssss m S 癍 mm Sword M Deer X α i ο ΙΟ · • But σ > η ο Η 〇 ° H 〇J o OJ H o C4 H chain κ ο Λ Zn X 〇 < α Zn w ^ m X o < rS X o (ϋ -x 侫 孙 侫 m -w 蜮 蜮 fc ^ ^ η -Ν m Μ 淀 UU • N 鹚 假 呼 一 _ £ £ ρ- «ο r- • o 〇ir · oo bu * o · ≪ < CD 1 m < r— (Η s CM Ν Η CO i Csj 锵 CO (Please read the precautions on the back before filling out this page) This paper size applies the Chinese National Standard (CNS) A4 specification ( 210'X297 mm) 113 470783 A7 B7 V. Description of the invention [Experiment 1] (Experiment 1 to 1) As shown in Table 2 8 describing the test conditions, the plating type < Galvanized steel, before or after the alkali treatment, is subjected to a certain tempering and rolling of 0.7%, and is subjected to It was immersed in an aqueous solution of N a 0 Η in the range of p Η in the range of 9.5 to 14.0. The preliminary treatment was performed at a temperature of 50 ° C. Then, after the preliminary treatment was completed, The zinc steel sheet was immersed in an aqueous solution containing F e C 1 2 and HiCl2 to form a Fe-Ni-O film on the surface. In addition, it showed that no alkali treatment was performed and no Fe-ίΠ-Ο film was formed. Cases, cases where preliminary treatment was performed but no Fe-N i -0 film was formed, and cases where F eN i -0 films were formed without any alkali treatment were taken as comparative examples. —.------- --- Installation ------ Ordering (please read the notes on the back before filling this page) Central Standards of the Ministry of Economic Affairs, Consumer Cooperatives, India This paper size applies to China National Standard (CNS) A4 specifications (210X 297 mm) 114 470783

7 7 A B V. Description of Invention "2) Table 28

Mo. Electroplating type 'Tempering pressure conditions Moth buried conditions Fe-Ni-0 thin film — elongation of test sample% before or after alkali treatment Solution treatment method temperature (° C) time ts) Presence or absence of film formation Method Composition pH 1 A 0.7------X Comparative Example 2 NaOH 12.0 impregnation before λ 0.7 / 50 5 X η 3 A 0.7------0 impregnation " 4 A 0.7 before NaOH 9.5 impregnation 50 5 0 " < 1 5 A 0.7 before NaOH 10.5 Μ 50 5 0 U Specific cell example 6 A 0.7 after NaOH 10.5 Η 50 5 0 " 7 A 0.7 before NaOH 11.0 " 50 5 0 U 1 »After 8 A 0.7 NaOH 11.0 II 50 5 0 Μ 9 A 0.7 before NaOH 11.5, 50 5 0 α 10 A 0.7 after NaOH ll.S Η 50 5 0 II w 11 A 0.7 before NaOH 13.0 " 50 5 0 U " NaOH 13.0 Μ 50 5 0 V after 12 A 0.7 > NaOH 14.0 before 13 A 0.7 " 50 5 0 " 1) NaOH 14.0 after 14 A 0.7 " 50 5 0 π II (Please read the Please fill in this page again for attention) Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economy Quasi (CNS) A4 size (210X297 mm) ~ 115 - 470783 A7 B7 V. invention described Γί 3) the results of the test are shown in Table 29. The facts under M can be found in the table. (1) No F e-Ni-0 film was formed on the test sample, and its compression molding, point weldability, adhesion and chemical treatment were poor (N ο 1 and No 2). Although F e-Ni-0 films were formed, the test samples with p 低于 lower than 10 had slightly poor press formability (N 0 3 and N 0 4). (2) In the specific embodiment, the press formability, spot weldability, adhesion, and chemical treatment properties are improved (N 0 5 to N 4 1). When the solution for the alkali treatment has a large pH, the press formability is greatly improved. These advantageous effects will not change regardless of the order of tempering rolling and alkali treatment in the preliminary treatment. I Order (please read the notes on the back before filling out this page) Printed by the Shell Standard Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 1 16-This paper size applies to China National Standard (CNS) Α4 specification (210X297 mm) 470783 5 Description of the invention (114) Table 29

7 7 A B

No. Friction Steep Welding Coupling® Continuous Welding Times Adhesive Strength Chemical Treatment Test 1 0.150 2500 8.0 Two Comparative Cell Examples Example 2 0.145 2500 10.0 Two " 3 0.125 5000 12.0 0 II 4 0.125 5000 12.5 0 tl 5 0.120 5500 12.0 0 Specific implementation M 6 0.120 5500 12.0 0 tl 7 0.115 5500 12.5 0 " 8 0.115 5500 12.5 0 9 0.110 5500 12.5. 0 10 0.110 5500 12.5 0 ”11 0.105 5500 12.5 0 " 12 0.105 5500 12.5 0 " 13 0.105 5500 12.5 0 14 0.105 5500 12.5 0 Μ (Please read the notes on the back before filling out this page) Printed on the paper by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs The Chinese standard (CNS) Μ specifications (210X297 mm) 470783 A7 B7 V. Description of the invention (Π 5) (Test 1-2) As shown in Table 30, the test conditions are the galvanized steel plate with the symbol A of the plating type M (representing the alloy zinc dip plating) Before or after the alkali treatment, the tempering rolling at an elongation of 5.5 M is performed; the alkali treatment is carried out by immersing it in a Na 2 Η aqueous solution having a fixed ρ 1 of 12.0, and 5 0 ° C for 5 seconds; then, after the preliminary treatment is completed, the galvanized steel sheet is immersed in an aqueous solution containing F e C 12 and Ni Cu, and the surface of each galvanized steel sheet is immersed. Generate Fe-Nί-Ο film. Yi Yi _ _ Preparation (Please read the notes on the back before filling out this page) Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, this paper is printed in accordance with China National Standard (CNS) A4 specifications ( 210X297 mm) One 118_ 470783 A7 B7 V. Description of invention M 6) Table 30

No. Electric tempering type Tempered rolled 嵇 Taurine treatment conditions Fe-Hi-0 film · Test sample i Determination rate% Solution treatment method before or after burying in alkali Temperature_ (° C) Time (si Presence of thin film and method of forming apricots. Ingredients pH 15 A 0.0. Before NaOH 12.0 impregnated 50 5 〇 Comparison of impregnation 洌 17 A 0.2 before NaOH 12.0 If 50 5 0 U " 18 A 0.2 after NaOH 12.0 50 5 0 η 11 19 A 0.3 before NaOH 12.0 50 5 0 Μ Example S After 20 A 0.3 NaOH 12.0 It 50 5 0! μ II 21 A 0.7 before NaOH 12.0 H 50 5 0 I It 22 A 0.7 after NaOH 12.0 " 50 5 0 < 1 Μ 23 A 1.0 before NaOH 12.0 II 50 5 0 .η if 24 A 1.0 after NaOH 12.0 il 50 5 0 «1 U 25 A 3.0 before NaOH 12.0 ,, 50 5 0 tl tt 26 A After 3.0 NaOH 12.0 »1 50 5 0 II " 27 A 5.0 before NaOH 12.0 II 50 5 0 u II 28 A 5.0 After NaOH 12.0 h 50 5 0 " II 29 A 5.5 Before NaOH 12.0 " 50 5 0 " tfc is more practical: after 30 A 5.5 NaOH 12.0 M 50 5 0 II (master) test sample No. 16 is not shown in this table I Thread for clothing (please read the notes on the back before filling this page) Printed by the Central Consumers Bureau of the Ministry of Economic Affairs, Consumer Cooperatives This paper is printed in accordance with Chinese National Standard (CNS) A4 (210X297 mm) 119 470783 A7 B7 Description of the invention (117) The results of the foregoing tests are shown in Table 31. From this table, the following facts can be found. (1) When the preliminary treatment of temper rolling is performed at an elongation lower than 0.3%. Although F e-H i-0 film is formed on the surface of each galvanized steel sheet, the properties of the press formability cannot be improved sufficiently (N ο 1 5 to Ν ο 1 8). When the elongation exceeds 5 At 0%, each galvanized steel sheet is excellent in press formability, spot weldability, adhesion, and chemical treatment, but the mechanical properties of the galvanized steel sheet are poor (N0 2 9 and M 3 0). (2) On the contrary, in the specific embodiment, the properties of press formability, spot weldability, adhesion, and the properties of each galvanized steel sheet were improved (No 19 to M 2 δ). When the return train is performed under a large elongation, the press formability of the galvanized steel sheet is greatly improved. These advantageous effects, regardless of the order of tempering and rolling and alkali treatment, can be obtained invariably in the preliminary treatment of the steel sheet. ^ I ---------- Installation ------ Ordering (please read the notes on the back before filling this page) Printed by the Central Standards Bureau of the Ministry of Economy National Standard (CNS) Α4 Specification (210X297 mm) 120 470783 A7 _____B7 V. Description of Invention ί Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

No. Friction coefficient point weldability Flail point welding times Adhesive strength kg / 25 πτη The nature of the generation treatment is still test test 15 0.130 5500 12.5 0-compare S cell network 17 0.125 5500 '： 12.5 0-" 18 0.125 5500 12.5 0-" 19 0.120, 5500 12.5 0-; 逋 M vesicular cases 20 0.120 5500 12.5 0-II 21 0.110 5500 12.5 0-< 1 22 0.110 '5500 12.5 0-" 23 0.105 5500 12.5 0 -ir 24 • 0.105 5500 12.5 0-〇25 0.100 5500 12.5 0-”26 0.100 5500 '12-5 0-II 27 0.09 5500 12.5 0-• 1 28 0.09 5500 12.5 0-tt 29 0.09 5500 {12.5 0 material degradation ttCompared with real cell 钶 30 0.09 5500 12.5 0 Material degradation II (a) Test sample Ho. 16 is not shown in this table (please read the precautions on the back before filling this page) This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -12 1-470783 A7 B7 _ V. Description of the invention (119) (Test 1 of 3) '' As shown in Table 3 2, the test conditions are such that the type of plating is represented by the symbol A (representing alloy zinc Dip galvanized steel) at a constant elongation of 0.7% Tempering and rolling; Alkali treatment is performed by immersing it in an aqueous solution with a fixed p Η of 12.0 (a part of which is immersed in an acidic solution with ρ 2 2.0), and at 50 ° The temperature was increased for a few seconds at a temperature of C (aqueous solution was sprayed on a part thereof). Then, after the preliminary treatment was completed, the galvanized steel sheet was immersed in an aqueous solution containing F e C 1 2 and Ni C 1 2 In addition, F e-Ni-0 film is formed on the surface of the galvanized steel sheet (a part of the galvanized steel sheet is sprayed with water solution by spraying, electrolysis or vapor deposition). I gutter (please read the note on the back first) Please fill in this page again) Printed by the Central Consumers Bureau of the Ministry of Economic Affairs of the Consumer Cooperatives The paper size applies to the Chinese National Standard (CNS) A4 (210X297 mm) 122 470783 A7 B7 V. Description of the invention (120) Table 32 Tempering and rolling Conditions 鹸 Processing conditions Fe-Ni-O Film No. Plating elongation at the temperature of the alkali treatment solution The temperature of the film formation test before or after the type of film Test method (S) Presence or absence Method% Ingredient pH (r) 31 A 0.7 Before H2SO4 2.0 dip 50 5 0 Impregnation comparative implementation 洌 32 A 0.7 刖 HC1 2.0 Impregnation 50 5 〇 'Immersion Comparative Example 33 A 0.7 NaOH 12.0 Pre-coated' 50 5 0 Immersion specific implementation 34 A 0.7 before KOH 12.0 Impregnation 50 5 0 Impregnation Example 35 A 0.7 before Na2Si〇4 12.0 Impregnation 50 5 0 Impregnation _ Specific Example 36 Mg (OH) 2 12.0 Impregnation before 50 A 0 Specific example S Example 37 LiOH 12.0 before impregnation 50 5 0 impregnation of specific examples Example 38 A 0.7 before Na2P〇4 12,0 impregnation 50 5 0 impregnation specific for implementation of 39 A 0.7 NaOH 12.0 impregnation 50 5 0 Specific examples of spraying before 40 A 0.7: NaOH 12.0 impregnated 50 5 0 Electrolytic concrete (41 A 0.7 before NaOH 12.0 impregnated 50 5 0) Steam specific ranunculus application deposition (please read the precautions on the back before filling in (This page), ye printed by the Central Consumers Bureau of the Ministry of Economic Affairs, Consumer Cooperatives, this paper is printed in accordance with Chinese National Standard (CNS) A4 (210X 297 mm) 123 470783 A7 B7 V. Description of the invention (121) Results of the previous test于 表 33。 In Table 3 3. From this table, the following matters can be found. (1) When the preliminary treatment is performed using an acidic aqueous solution containing an acid component, the properties of the press moldability cannot be sufficiently improved (N 031 and N 032). (2) Conversely, in the examples, the press formability, spot weldability, and adhesion of each galvanized steel sheet were improved (N 033 to N 41). ------------ Sai ------ 1T ------ # (Please read the notes on the back before filling out this page) Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs This paper size applies Chinese National Standard (CNS) M specification (plus thin) — 124 _ 470783 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention 122) Table 3 3 No. Friction point continuous welding Number of spot welding times Adhesive strength · kg / 25 mm Chemical treatment test sample 31 0.130 5000 12.5 〇 Comparative Example 32 0.130 5000 12.5 0 Comparative Example 33 0.110 5500 12.5 0 Specific Example 34 0.110 5500 12.5 〇 Specific Example Example 35 0.110 5500 12.5 0 Specific examples 36 0.110 5500 12.5 〇 Specific examples 37 0.110 5500 12.5 〇 Specific examples 38 0.110 5500 12.5 〇 Specific examples 39 • 0.110 5500 12.5 〇 Specific examples 40 0.110 5500 12.5 〇Examples of specific examples 41 0.110 5500 12.5 〇Examples of specific examples (please read the precautions on the back before filling out this page) This paper size applies Chinese National Standard (CNS) Λ 4 Specifications (210 X 297 mm) —125 470783 A7 B7 V. Description of the invention (123) [Test 2] As shown in Table 3 4, the test conditions are such that the type of plating used in each test is changed to B, C, D, E , F, and G. In a specific embodiment, the temper rolling is performed at an elongation of 0.7% before the alkali treatment; the preliminary treatment is performed by immersing each galvanized steel sheet in N a 0 having p Η of 12.0. Η in an aqueous solution and at a temperature of 50 ° C for 5 seconds; and after the preliminary treatment is completed, the galvanized steel sheet is immersed in an aqueous solution containing F e C 1 2 and N i C 1 2, and A Fe-Ni-O film was formed on the surface. In the comparative examples, all the tempering rolling, alkali treatment and formation of F e-Ν-0 thin film were compared in the comparative test, and there were cases in which alkali treatment was performed but tempering rolling was not performed and formation was performed. In the case of Fe-Ni-O thin films. (Read the precautions on the back before you fill in this page) The paper size printed by the Employees' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs applies to the Chinese National Standard (CNS) A4 (210 X 297 mm) 126 470783 Μ B7 Central Standard Bureau employee consumer cooperatives seals (5) Description of inventions (4) Table 34

No. Electroplating type Tempering and rolling conditions Alkali treatment conditions Fe-Ni-〇 Thin film test sample elongation% Before or after alkali treatment Solution deposition temperature (° C) Time is) Presence or absence of film formation method Ingredients pH 42 B 0.0------X Comparative test application 43 B 0.0-NaOH 12.0 Impregnation 50 5 0 Impregnation comparison implementation 44 44 0.7 Month 11 NaOH 12.0 Impregnation 50 5 〇 Impregnation II II 45 C 0.0------X-Comparative implementation 46 C 0.0-NaOH 12.0 impregnated '50 5 0 impregnated Comparative Example 47 C 0.7 before NaOH 12.0 impregnated 50 50 0 impregnated concrete Example 48 D 0.0 -----X-Comparative 萁 Shi 洌 '49 D 0.0-NaOH 12.0 impregnated 50 5 〇 impregnated compared with the implementation of 50 D 0.7 NaOH 12.0 impregnated 50 5 〇 impregnated with solid case 51 E 0.0 ------X-Comparative implementation 洌 52 E 0.0-NaOH 12.0 impregnated 50 5 〇 impregnated comparative cell case 53 E 0.7 NaOH 12.0 impregnated 50 5 〇 impregnated specific cell case 54 F 0.0--- ---X-Comparative implementation 洌: 55 F 0.0-NaOH 12.0 immersion 50 5 〇 impregnation 'comparison Cell 洌 56 F 0.7 before NaOH 12.0 mm 50 5 〇 impregnation with Niu 洌 implementation 洌 57 G 0.0-----X two comparisons 萁 58 G 0.0-NaOH 12.0 immersion 50 5 0 immersion comparison cell Example 59: NaOH 12.0, impregnated with 50,50, before G 0.7, impregnated with ultra-solid lung M (please read the precautions on the back before filling in this page) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) ) 127 470783 A7 _B7 _ ^ _ V. Description of the invention 〇 25) The results of the foregoing tests are shown in Table 3 5. From this table, the following facts can be found. (1) In the case where all the temper rolling, alkali treatment and formation of F e-Ν-0 films have not been performed, regardless of the type of electroplating, the press formability, point weldability and adhesion of each galvanized steel sheet All were bad (N 0 04, N 0 4 5, N 0 4 8, N 0 51, N 0 5 4 and M 5 7). In the conditions of the present invention, only the temper rolling is not performed, and only the press formability is improved to some extent. Since Fe-Ni-0 film is formed on the surface of the steel sheet, this improvement is not Enough (N 〇 4 3, No 46 'No 49' Νο 52 'Ν ο 5 5 S. No 58) 〇 (2) Conversely, in the specific embodiment, the properties of press formability, point weldability and adhesion are all Improved (No44, No47, No50, No53, No56, and No59) 0 Order 0¾ (Please read the precautions on the back before filling out this page) Printed by the Chengong Consumer Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs Zhang scale is applicable to China National Standard for Scrubbing (CNS) A4 (210X297 mm) 128 470783 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention Table 35 No. Friction coefficient point weldability Number of continuous point welding Adhesive strength kg / 25 mm Chemical treatment test sample 42 0.180 1500 5.0 〇 Comparison s Shi _ 43 0.150 1500 6.0 〇 Comparative cell example 44 0.125 4000 12.5 〇 Case example 45 0.180 2500 6.0 〇 Comparative test冽 46 0.150 250 7.0 〇 Comparison of Ranunculus cellulum-47 0.125 5000 12.5 〇 Example of hip 48 48 0.150 3000 8.0 〇 'Comparison stabbing 49 0.130 3000 10.0 〇 Comparative implementation 洌 50 0.110 6000 12.5 〇 Example of super net cymbal 51 0.150 8000 6.0 〇 Comparison Implementation of spines 52 0.130 8000 7.0 〇Comparison of real cell cases 53 0.110 10000 12.5 〇Large blisters 54 0.150 3000 6.0 〇Comparison S example 55 0.130 3000 7.0 〇Comparative example 56 0.110 6000 12.5 〇S3剌 57 0.180 1500 5.0 〇Compared with real cell 58 0.150 1500 7.0 〇Compared with real cell 0.159 0.125 4000 12.5 0 Ultra-sweet buttercup thorns This paper applies Chinese National Standard (CNS) A4 specifications (2 〖OX 297 mm） -129 470783 A 7 B7 V. Description of the invention (1.7) (Test 3) As shown in Tables 3 6 and 37, the test conditions are such that the type of electroplating is indicated by the symbol A (representing alloy zinc dip plating) The steel sheet is tempered and rolled at an elongation of 0.7% before or after the alkali treatment; the alkali treatment is performed by immersing it in an aqueous solution of Na 0 Η with a fixed p 1 of 12.0, And for 5 seconds at 50 ° C Next, after completion of the preliminary treatment, the galvanized steel sheet was immersed in an aqueous solution containing F e C and 1 z of the N i C h, to generate a Fe-tU-Ο film on the surface of each zinciferous plated steel sheet. Here, the total concentration of FeCl2 and NiCl in the aqueous solution is set at a fixed value of 200 g / A, Fe content (W t.%) Versus Fe content (wt.%), And Ν content (W t %) The ratio of the total sum is changed in the range of 0 to 1, so that the PP of the aqueous solution is set to 2.5, and the temperature of the aqueous solution is maintained at a temperature of 50 ° C. (Please read the notes on the back before filling out this page) The paper size printed by the Employees' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 130 470783 A7 B7 V. Description of the invention (J %) Table 36 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs

The test Yangpin 1 compares S Shiji with a super case with buttercups, with a girl with a buttercup, a girl with a buttercup, a girl with a buttercup, a case with a 趄 钶 κ, a case with a super case, a case with a case, a case with a case.例 例 例 K Example implementation tool 尥 阏 萁 火 HMHMHMSTfisq. With "钶» 施 例 具 女 钶 萁 炮 钶 萁 Niu buttercup application tool Η 例 K Example "例 M钶 例 例 《ms steep 酙 ComparisonΪΓ 拉 洌 水 1 Fe + Ni 〇ι〇η 〇〇〇〇〇〇〇m ο ο ο to CM ο ο in σ ο Η Ο mr ~ i Ο CN O m < somo ο mo κο ο BU〇CO o ο ΙΛ (N (Ti 〇Η immersion mi time 〇〇〇ο γΗ ο ο ο o «Η o» H o ο o ο 〇o ο o rH Ο temperature 〇SSSSSS s S s SSSS s SSS tf) < N 1〇CM U ·) < Ν m OJ ιη < Ν »in eg m ίΝ in l〇 < N m (N \ r >« Ν XT) l〇U ·) 1 〇 < N VO < N m < N m iN U *) < N NiCl2 I (g / D 200.0 a \ σ \ rH σ > σ > rH σ \ ςη »Η ιΛ σ \ · — < Ο σ \ ri ο 00 W o Γ- r-4 〇VO om 〇tH o eg rH oo «—I 2 S 5 S in o FeCl2 (g / D ο ο ο CO ο Ο rH Ο ΙΟ Ο ο ι—1 ο ο CVJ oo Γ0 〇〇oo in 〇o 〇〇 CO ooo rH ο ο CN rH 〇〇rH oo VO rH ο ο 00 «—ί om 00 rH ooo CSJ Fe- Ni-0 formation method mm-----=---Di-alkali treatment conditions? Sf ιο mm ΙΛ in ΙΟ mm l〇lO l〇lO l〇m ΙΟ ml〇ml〇in itemperature〇ο ιο ssssssssssssssss 〇m treatment 'method丨 Immersion-2-=-=? =,-22% ο CN γΗ ο CM »—1 ο eg tH ο« Η Ο eg rH ο CM rH ο γΗ o 04 〇CM rH o rH o ΓΊ H o CM »-4 〇 (N rH ο CNJ rH 〇rH o rH ο CM * Η o rH O fH Solution components! NaOH NaOH NaOH NaOH NaOH NaOH NaOH NaOH NaOH NaOH NaOH NaOH 1 NaOH NaOH NaOH NaOH NaOH NaOH NaOH NaOH NaOH Elongation before or after alkali treatment · »卜 ο 卜 〇 卜 o 卜 ο 卜 ο 卜 ο 卜 ο r- o 卜 〇r * 〇r * · 〇or or o ο r- or * o · b o r- o b o < < < < < < < < rt: < < < < < < < < < is CNJ ΓΟ νχ > in i £ > νο CO U5 mon rH r * CN CO t ^ · m bl * CO (Please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210X297 mm) 470783 A7 B7 Table 37 Comparison of printed test samples printed by employees' cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs With limbs, S cells, ss cases, s examples 丨 + .1 exemples, examples, exemples, example K. With 55,55, 55 examples, 59 cases of artillery, women's cases, pickles, sa »Shi 9 、 Slave sr thin scorpion scorpion sling gun H net K sling gun H case S pickled shou ni shou net K gun case. With M cases S celli) With" example »Comparison 钶Stomach in aqueous solution: Fe + Ni 〇0.0035 ο ο ο 0.005 ΙΟ csj oo ΙΟ oo 〇 in rH Ο cnJ ο m CN ο fO o inch ο lο ο V £ > 〇o CO oa \ ο in σ \ ο rH Impregnation time 〇ο ο ο oo ο Ο σ ο o rH ο Η 〇o rH o S ο 〇 Temperature 'G Ο ir > SSS ol〇SS ο in 〇in s 〇i〇ss S ο ιο S m < Νί m < N m in (N in m ι〇 (Ν m < Ν U ") m cv m < N m (Ν to < s lO < N m < N iN ϋΊ < Ν m < Ν 1 NiCl2I (g / l) ο ο ο σ > ι—1 σ \ σ \ ι-Η cn cn rH ir > 〇 > «Η o σ» rH Ο 00 rH Ο Γ- γΗ o vo rH ο m rH 〇rH 〇 * Η oo HS s 5 ΙΟ »Η ο FeCl2 (g / l) Ο ο Γ *» ο CD 〇 〇rH 〇in Ο ο rH Ο Ο ο ο 00 〇〇〇〇〇lO 〇〇VO Ο 〇 αο ooo » H 〇o OJ rH oo r-4 oo VO rH 〇o CO rH Ο ιΟ CO »~ ι ο ο 〇CN Fe-Ni-0 formation method m-= = ': r di- alkali treatment conditions m ΙΟ ΙΟ m tn ΙΛ ΙΛ ι〇ml〇if) m 4Λ mmml 〇ιη ιη I temperature ο sss SSS ss 〇in ο ΙΛ S ssss S a method chain m = two > = > = / two two-% ο CJ rH ο C4 rH ο ι-Ι 〇04 O CM w ο CV4 «-f Ο Η ο rH 〇 (VJ tH o C4 wo N rH 〇 CM ii 〇r ~ i 〇cq. O CN o rH o« Η ο C4 rH ο < N rH _Solution composition NaOH NaOH NaOH i NaOH NaOH NaOH NaOH NaOH NaOH NaOH NaOH NaOH NaOH 1 NaOH NaOH NaOH NaOH NaOH 1 NaOH Tempered? LK condition before or after alkali treatment-3 1 Secondary growth rate I r · ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο r- ο ο ο ο or ο Oo 卜 o 卜 ο 卜 ο Yue K < < < < < < < < < < < < < < < < <rt; 〇 2 cn s (N CD cn CO CO tn 〇〇i〇03 ε 00 CO < j \ CO s rH σ \ CVJ < J > m σ »σ > in a \ U3 σ \ 5; (Please read the notes on the back first (Fill in this page again.) This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -132 470783 \ Ί 5. Description of the invention θ 3d) The results of the foregoing tests are shown in Tables 3 8 and 39. The facts can be found in this table. (1) In the comparative example, the F e / (F e + N i) ratio in the aqueous solution used to form the F e-N i-0 film is set to 0, and thus Ν ί-0 is generated. In the case of a thin film, the press formability and the properties of each galvanized steel sheet are poor (NO60 and NO79). On the other hand, in the case where FeWFe + Ni) is set to 1, and therefore an Fe-O film is formed, * press formability and spot weldability are poor (N078 and No97). 0 (2) Conversely, in Examples In addition, the press formability, adhesion, and chemical treatment were improved (No61 to No. 77 and No. 80 to No. 96). In particular, when the ratio of Fe / (Fe + Ni) is in the range of 0.4 to 0.9, the aforementioned properties are greatly improved. These advantageous effects will not change regardless of the order of temper rolling and alkali treatment in the preliminary treatment of the steel sheet. ---------- Installation ------ 1T ------- @ (Please read the precautions on the back before filling out this page) Printed copy of the staff consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) 133 470783 A7B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention m) Table 38 No. Friction Coefficient Point Welding Flail Point Welding Number of times of adhesive strength kg / 25 mm Chemical treatment test sample 60 0.135 5500 6.0 〇 Comparative Example 61 0.130 5500 10.0 0 with spores 62 0,120 5500 12.0 〇U 63 0.110 5500 12.5 〇U 64 0.110 5500 12.5 〇U 65 0.110 5500 12.5 〇66 0.110 5000 12.5 〇V) 67 0.110 5000 12.5 0 U 68 0.110 5500 12.5 〇Μ 69 0.110 5500 12.5 0 W 70 0.110 5500 12.5 〇il 71 0.110 5500 12.5 〇 \ ι 72 0.110 5500 12.5 〇w 73 0.110 5500 12.5 mM 74 0.110 5000 12.5 mM 75 0.120 4500 12.5 〇 1 1 76 0.120 4000 12.5 〇 »/ 77 0.130 3000 12.5 0 78 0.135 2500 12.5 〇 Please fill in the meaning of the cell phonetic The paper size on this page applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 134 470783 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (ί 2) Table 39 No. Friction point welding Number of continuous welding points Adhesive strength kg / 25 mm Chemical treatment test product 79 0.135 5500 6.0 〇Comparison cymbal cymbal 80 0.130 5500-10.0 〇 Bile cymbal κ cymbal 81 0.120 5500 12.0 〇 1 82 0.110 5500 12.5 〇U 83 0.110 5500 12.5 0 VJ 84 0.110 5500 12.5 〇W 85 0.110 5000 12.5 0 " 86 0.110 5000 12.5 〇t 87 0.110 5500 12.5 〇 1/88 0.110 5500 12.5 〇W 89 0.110 5500 12.5 〇U 90 0.110 5500 12.5 〇1 t 91 0.110 5500 12.5 〇VI 92 0.110 5500 12.5 〇 (/ 93 0.110 5000 12.5 〇u 94 0.120 4500 12.5 〇w 95 0.120 4000 12.5 〇w 96 0.130 3000 12.5 〇97 0.135 2500 12.5 〇 f Qi first read the notes on the back before filling out this page) This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -135 470783 A7 B7 V. Explanation 1 1 1 Since the method of the present invention is performed in the manner described above > The properties of the Fe -N 1-0 film formed on the surface of the galvanized layer of the galvanized steel sheet 1 1 j have been improved. S 1 I Because Fe -N i-〇 film is harder than zinc or zinc alloy plating layer and has a long melting point 1 1 | high melting point, it is read between the surface of the plating layer and the press molding die during the press forming process. The sliding resistance is reduced, which makes the galvanized steel sheet easy to be accepted in the press forming cross. 1 I means 1 I 9 As a result, the press formability is improved, and in the process of point welding 1 I true 1 1 Continuous point weldability due to Fe -N The improvement of the existence of the i-0 film >> Furthermore, the properties of the steel plate Fe-N 1 10t were changed due to the existence of the F e-N i-0 film 1 I Good 0 Kamiyuki It has been shown that the present invention can provide a method for manufacturing a galvanized steel sheet with excellent press formability and spot weldability and excellent adhesion 1 1 and can obtain very useful industrial results. 1 Order specific example 7 1 I The inventor has carried out continuous research 9 and obtained the following items described as 1 1 I fruit 0 can also be obtained by being located on an alloy zinc-impregnated zinc steel sheet 1 and having or < 5 1 Fe-N 1-〇 thin film was formed on the plating layer of the surface alloy phase of 1 1 phase, and the pressure line 1 470783 A7 B7 was printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (H4) 1 1 About this The problem waiting to be solved is to provide a method which is more effective than the Fe -Z η alloy ft! Film with 1 | higher hardness and higher melting point. 0 -N 1 I Fe -N i-〇 Hardness and high melting point. When coated on an alloy zinc dip-plated sheet of m 1 1 I t, this film can reduce the resistance of such sliding tendencies that occur in the electroplated layer with respect to the back reading 1 I surface I closing pressure > therefore To make the steel plate slip into the mold easily, note 1 I, meaning 1 M, resulting in improved press formability. 0 matter 1 I, then 1 I. In addition, if the phase with low Fe content needs to be placed on the plating layer, fill in 1 copy. Loading t can prevent the generation of brittle ε phase) As a result, the crushing resistance (P 0 W dering page, 〆1 | re si st an ce) is also improved. At the same time, it is desired to form a high F e 1 1 content on the electroforged layer. In the case of δ 1 phase, can it prevent softness and low melting point? ? Phase production 1 1 results in improved flaking resistance (f 1 aking Γ es is tance) and improved at the same time ο 1 order The general use of the alloy zinc-dipped steel sheet compared with the cold-rolled steel sheet in the continuous point 1 1 welding process Poor spot weldability 0 This is because zinc has been melted at the spot weld when 1 1 | when anti-IT * C contact with the copper electrode occurs in a fragile 1 1 sexual alloy layer which will seriously degrade the electrode 0 Line 1 is generally considered to have continuous weldability. ”&Quot; Only point weldability can be formed on the electroplated 1 1 layer of an alloy zinc-dipped steel plate. A high-melting-point thin film 9 is effectively improved. 0 is an improvement point for obtaining steel 1 1 plate. Weldability) The inventors have studied many kinds of thin films. I 1 1 It is found that a thin film derived from oxide of N is particularly suitable for this giant 1 1 0 Although the reason is not fully understood, it is considered N Reaction with Z η produces 1 1 high melting point Zr-N i alloy, and due to its high melting point 4 and due to 1 1 its semiconductor properties > Η develops to a high degree in various films 1 1 Electrical conductivity 0 1 1 I Known that the conventional alloy zinc-impregnated steel sheet has lower adhesion than cold-headed steel sheet »1 1 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 137 470783 A7 B7 Printed by the Consumer Cooperatives of the Central Procurement Bureau of the Ministry of Economic Affairs V. Invention Description (1 1 I but there is very little explanation for the reason 0 due to the research of the inventor. Results $ 1 1 | The sister of the oxide film deposited on the steel plate is dominated by 0 1 I. In short, the oxide film in cold rolled steel is mainly oxide of M Fe »m Please 1 1 1 The film is mainly the oxide of Z η 0 Adhesive read back 1 I The ft I force varies with the composition of each of two different films, and it has been confirmed that the oxide of Zn is inferior to the oxide of Fe in this 1 I, meaning that I I is inferior to Fe oxide. The I 1 force can be improved by forming a thin film of Fe-containing oxide on an alloy zinc-dipped steel sheet. Page 1 '' 1 I The conventional alloy zinc-dipped steel sheet is chemically comparable to cold-rolled steel sheet. It is not enough than 1 1 0 This can be attributed to the fact that the crystals of the phosphate film produced are thick and irregular due to the high concentration of Z η 1 1 present on the steel plate * 1 ordered and used in both steel plates The crystal a® body of the two phosphates is not the same. In the case of cold-rolled 1 1 steel plates, the phosphate crystals are mainly M dizinc phosphate. (1 1 ph 0 SP h 0 fi 1 1 te) (Z η 2 F e (P 0 4) a 4H 2 0) as the basis 3 When the concentration of Zn η of 1 1 on the steel plate is high t Phosphate crystal system Made of zinc phosphate (ph 〇bite) 1 wire (Z η 3 (P0 4) 3 * 4H 2 0), which is twice in warm water after painting 1 1 The adhesion is quite poor 0 The reason is The Fe concentration in the phosphate film is too low. 1 1 Low r. Therefore, when exposed to a wet environment after painting, 9 the chemically treated film will condense 1 and I will cause the steel to lose its adhesion. 0 1 1 To prevent chemical treatment. Film coagulation 1 An effective method is to incorporate metals such as Fe i, 1 1 Η and the like into phosphate crystals 0 As for the thin film of Fe 1 -1 1 i--0 mentioned in the present invention, Η Η fD F e Incorporates into phosphate crystals to produce chemically treated films with excellent adhesion II and produces dense regular phosphate EI m bodies »Due to 1 1 I The secondary adhesion K in water and the corrosion resistance have been improved. 0 1 1 This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 138 470783 A7 B7 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs DESCRIPTION OF THE INVENTION (1%) 1 1 | As mentioned previously, it has been found that alloy zinc-dipped steel sheets can be electroformed on it. The coating 1 1 1 suitably forms at least a metal of Hi and Fe and an oxide of Ni and Fe It is composed of a composite film of 1 I (hereinafter referred to as F e-Ni-0 film), and it is made by press molding. Please kj 1 1 and 1 Λ point weldability. Adhesive force and chemical treatment and deep drawability (dee P means back 1 I dr aw a bi 1 it y) Excellent steel sheet 0 More specifically, a must note of the present invention 1 | Meaning 1 I The condition is that Fe-N on M is provided on the plating layer i-0 film. Item 1 I re 1 | This invention has been completed based on the findings described in the month U. The first aspect of the alloy zinc-filled 1 copybook dip-coated steel sheet includes at least one surface, and includes 6 to 11 pages of vy 1 I wt,% F e and a sufficient amount of Z η and inevitably The electroless 1 1 1 coating of the chemical composition of impurities is characterized in that the electroplated layer has a surface alloy phase 9 of the phase and the electro 1 1 coating has a coating weight of 20 to 100 g / Π.2 and includes 1 Order Fe -N i-0 film 1 | The second aspect of the alloy zinc-dipped steel sheet is characterized in that in the invention stated in the first aspect 1 Fe -N i-0 film has all M contained in Among them, the coating weight based on the total weight of the metal element is 10 -1 5 0 0 in g / m 2 F e ~ N i -0 1 Fe content (wt. X) in the wire film versus Fe -N 1 — The ratio of the sum of Fe content (wt,%) 1 1 and Ni content (t.%) In 0 film is 0.004-0. 9 and F e-H i -0 thin 1 | film Including content 0. 5- • 1C wt.% Oxygen 〇1 I The alloy zinc-dipped steel sheet according to the third aspect includes a surface t disposed on at least one 11 thereof and has a content of 9--1 ^ .W t % F €! And a sufficient amount of Z η K and electroplated layer of the chemical composition of unavoidable 1 1 f is characterized in that the electroplated layer has a surface alloy 1 with δ Π ;; mesh, and Layer has a coating of 2 0--1 0 0 g / π I2 1 | weight »and includes Fe-N ί- -〇 film formed thereon 〇1 1 The fourth aspect of the alloy zinc-dipped steel plate Characterized in the second aspect 1 1 This paper size is applicable to Chinese National Standard (CNS) A4 specifications (210X297 mm) 139 470783 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of invention (13 "/ III The medium 1 Fe -N i-〇 film has all the metals contained in it 丨 the total weight of the element III, the coating weight is 10 -1 5 0 0 mg / ΙΠ 2 F e-F in the Ni-0 filme Contains I | Amount (% by weight) is the ratio of the sum of Fe content (V / 1.%) and Ni content in Fe -N i-0 film to the total content of I (W t.%) At 0. 004-0. 9., And the Fe-N i -0 film includes the read back I side I content of 0.5-10 W t.! Ί Note 1 I means I, the following explanation is made. Explain the implementation of this issue as instructed above 1 1 Re 1 I Tomorrow i The alloy zinc dip coating deposited on the steel plate as a primer, and fill in this 1 Install on the plating layer as the outer film (0 verc oat) Specific restrictions imposed by thin films. Page • — ， 1 I (1) Zinc alloy coating 1 1 1 [when the surface alloy phase is ξ phase] 1 1 Fe content is higher than 6 wt. Conversely, phase formation is effective. Conversely, the Fe 1 1 content M higher than 11 w 1: ·% should be avoided to prevent the formation of an increased thickness of the Γ phase. 0 The Γ phase formed is extremely thick, and 1 I will result in pulverization resistance. Deterioration therefore damages the formability of the house, even in the case where a 1 1 1 Fe -N 1 0 film is formed on the plating layer. Therefore, the Fe content in the alloy zinc coating should be in the range of 6-1 1 w t.%. 1 1 [when the surface alloy phase is δ 1 phase] Fe in the zinc-plated coating of 1 I alloy contains B. Weight exceeds 9 wt.% | Because if it is less than 1 1 of it, δ 1 cannot be formed on the plating layer Phase> Even with δ 1 1 phase on the plating layer ♦ Fe content higher than 14 wt.% Will increase the thickness of the obtained plant phase 1 1 0 so that the Γ phase becomes thick wall > Shatter resistance and therefore adversely affect the formability of pressed 1 1 ί even in the case of 1 1 with Fe-N i-0 film on the electroplated layer 〇 1 I Therefore, the Fe content in the alloy zinc impregnated layer It should be in the range of 9-1 4 wt.%. 1 1 This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) 140 470783 Μ B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention! As) 1 1 I [Covering weight of alloy zinc dip coating] 1 1 Coating weight is limited to the range of 20-1 00g / m2. Below 20g / m 2 will fail to obtain sufficient corrosion resistance for S 1 I; however, if it is higher than 100 g / m 2, the Γ phase will grow excessively during the 1 I alloying step, resulting in large thickness. Among them, Fe system M is higher than I 6 wt on the 11 side of the read back, and the amount is added to the alloy zinc dip coating. In the latter case, there is still a problem that even if the invention is practiced > proper crush resistance cannot be achieved. ○ Item 1 I again 1 | Here, only MF e is used as a representative of the alloy zinc dip coating composition. Ο You can also write a book using various other metals, such as A1 'P b, C d., S η, In, Li, Sb Page 1 1 As Β ί Λ Η g Λ La 、 Ca 、 Ti ^ Z r, Ni ^ Co, Cr, MηPS,! 1I0, etc. as long as they are added to the plating layer in a limited amount, or they are inevitable to invade into the layer. These metals will not have any significant effect on their ordering properties produced by the present invention. For example, regarding A1, this metal has been added to the electroplating bath in an amount of about 0.1wtj in the practice of line 11. Therefore, it will inevitably enter 1I into the plating layer produced. 1 1 I (2) F e-N i -0 film 1 line [F e — Hi -0 coating film coating weight] 1 1 Fe _ 1Ί i-0 film coating weight, such as with all metal elements If the total weight is less than 10 mg / Π! 2, the press formability t cannot be sufficiently improved, and if the height is higher than 1 1500 mg / m 2, the further improvement of these physical properties will not produce more 1 1 I good result 0 1 1 Therefore, the coating weight of the Fe i-ο film * is based on the total weight of all the metals in the plating layer 1 1 -V 1 should be in the range of 10-150〇rag / m2, preferably 0 1 1 The coating weight of the Fe -N 1--0 film is set within that range. When the salt concentration 1 I remains constant in the processing liquid used to form the film, the processing can be adjusted. CNS) Α4 specification (210 X 297 mm) -141-470783 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (1 1 I The length of time, and when the processing time is maintained by the position of the equipment to When the value is 1 1 1, f can adjust the salt concentration in the processing liquid, and control p Η and the temperature bar 1 1 M as an auxiliary 0 Please read 1 [F e-Ni-0 Fe content in the film The ratio of the sum of the Fe and Ni contents] Reading the I side I Fe -N i-0 The proper Fe content in the film can improve the adhesion. The adhesion 1 1 means 1 I is better > the surface position of the metal The higher the energy. F e is the metal with the highest surface potential. 1 I re 1 | 1 1 Therefore, as the Fe content increases, the adhesion will be improved ___.% Of step 1 Improved 0 To improve the adhesion, at least Fe must be substantially present in the film. The Fe content of this giant 1 Fe-N ί-0 film is Ut.%) And the Fe 1 1 1 content (wt. %) And the sum of the Ηί content (W t.%) (Hereinafter referred to as Fe / (Fe + Ν ί) of 1 1 in the film) should be greater than 0. In particular, the Fe 1 order / (Fe + Ni) in the thin film higher than 0.04 is very helpful for improving the adhesion. 1 | On the other hand, Ν ί must be substantially contained in the film 9 and Fe / (Fe + IIN 1) should not exceed 1 0 and less than 0.9 in the film F e / (Fe-f N η 9 more 1 1 I good point weldability can be changed. Therefore, the Fe contained in the Fe-N i-10 film should be between 0.004-0. 9 Fe / 1 1 (F e + N ί). 0 1 | [Fo-Ni -C oxygen content in the film] 1 I Fe -W ί-• 0 The proper oxygen content in the film helps to improve the press forming properties and spot welding properties. Large, at least the oxygen needs to be substantially contained in the thin 1 1 film and the oxygen content should be greater than 0 wt *% ΰ In the F e-Ni -0 film 9 is higher than 1 1 0 5 w L ·% 0¾ oxygen content Contributes to greatly improving the press formability 〇1 | If the oxygen content is less than 1 Owl .5 ί, it will be more significant to improve the puddle weldability and chemical treatment 1 I therefore 0> > Fe-t Η -〇 in the film The oxygen content should be between 0.! .0 wt, 1 1 This paper size applies to China Home Standard (CNS) A4 specification (210X297 mm) 142-470783 A7 B7 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of invention (? 4Ό) 1 1 1% of the limited range P 1 is better. 1 1 Even if the Fe -N i-0 film contains derivable 1 1 existing in the primer or plating layer, such as Z η Λ Co Μη, Mo, A 1 τ i Λ S η W, S i ', Pb' T a Please first 1 1 price and other elements of oxides or M oxides or δ buy back of gold 鼷 itself | the benefits of 1 can still reach 0 successfully Note 1 I meaning 1 1 other than that Outer 9 Fe-N i-0 thin film configured as an outer film according to the present invention, Matter 1 | There are no restrictions on its preparation method. Various methods 9 can be used as appropriate. 9 Such as replacing and refilling. Dipped in an aqueous solution Water-soluble page 1 BOC cathode or anode electrolytic spraying given aqueous solution roller coating (r 〇1 1 1 1 C 0 at in g) etc. Λ laser auxiliary rib CVD photon auxiliary rib CVD vacuum deposition and 1 1 vapor phase plating such as spraying Plating deposition 0 1 Order 1 I The Fe -N i-0 film discussed in the text is formed on a plating layer disposed on at least one surface of an alloy zinc-dipped steel sheet. 1 1 I can be used in a car according to the use of the steel sheet. Processing steps of the body and the area to be formed by this car body> 1 1 and choose to have such a film on any of its surfaces or 1 line with this film on both surfaces 0 1 Example 1 1 The present invention will be further described with reference to the illustrated example. 01 1 A 0.7 mm thick cold-rolled steel sheet M is subjected to zinc dip plating in a known manner, and 1 1 is used to adjust the coating weight and electroplating. Ff content in the layer and table 1 1 parameters of alloy formation expectations »Thus, an alloy 鉾 dip-plated steel sheet was produced. Then, through the following three methods of manufacturing 1 | any one of the preparation methods >, Fe 1-• 0 film was formed on the plating layer 0 1 1 [ Preparation method A] 1 1 1 Dip alloy steel plate with a mixture of ferrous sulfate and sulfuric acid II »1 1 This paper size is applicable to China National Standard (CNS) M specifications (210X297 mm) 143 470783 Central Ministry of Economic Affairs A7 B7 printed by the Bureau of Consumer Standards of the Bureau 5. Cathodic electrolysis in a solution containing an oxidant (Mi) and an oxidant, M forms the desired F e-Ni-0 film on the plating layer. Here, the concentration of ferrous sulfate is changed, while the concentration of nickel sulfate is maintained at a fixed value of 100 g / A. In addition, the p Η and temperature of the mixed solution were maintained at a fixed value of 2.5 and 50 ° C, respectively, and an aqueous hydrogen peroxide solution was used as the oxidant, and the gas content in the film varied with different desired concentrations of the oxidant. [Preparation method B] An aqueous solution containing nickel chloride at a concentration of 120 g / 殳 and ferrous chloride having a desired concentration was spray-coated on an alloy zinc-dipped steel plate. Drying is performed in a mixed atmosphere of air and ozone, and the oxygen content of the F e-Ni-0 film is adjusted, so that a desired F e -N i -0 film is formed on the plating layer. [Preparation method C] The alloy zinc-dipped steel sheet was immersed in nickel chloride containing 120 g / 殳 concentration and ferrous chloride varying the desired concentration *, and having p Η of 2.5-3.5 and 50 ° C in water. The coating weight of the F e-Ni ~ 0 film was changed to a desired level by adjusting the immersion time. The oxygen content in the F e -N i -0 film is adjusted within the desired range through the adjustment of p h. In order to further adjust the oxygen content, a given oxidant can be incorporated into a given aqueous solution, and heating can be completed in a given oxidation environment to form a desired F e -N i-0 film on an alloy zinc-dipped steel plate. . The F e -N i-0 film was formed on the alloy dipped steel plate by the method of preparation on M to prepare a sample according to the present invention and for comparison purposes. These invention and comparative samples were made into two separate groups. The first set of tests Γ cell examples Γ ') are examples related to aspects 1 and 3; and the second set of tests ("This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm), ,, -14 4----------- batch clothes ------, 玎 ------. ^ (Please read the precautions on the back before filling this page) 470783 A7 B7 V. Description of the invention 彳 42) The example of the implementation of the ay_ pattern and the _ —_ system test Γ test?-The group of the implementation of the implementation of the sum of the test shows that the upper layer of the test can be tested and tested. Containing e IF, the first layer of zinc leaching in the middle of the layer, zinc leaching, gold, 41, and 40 samples of the test table are covered in a relatively large proportion, whether the phase and the gold are on the coexisting surface, and the film is thin and prepared. Made of thin film (please read the precautions on the back before filling this page) -pack.

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Ο ο XXX o XXX ο X > <: o XXXX m jacket • N Φ S Ηπ ο X; ο > < J o X oo X ο X 〇X o X 〇X o XI chain 豳 ammonium 雠 绛 ο Χί 〇X o X o X o X ο X 〇X o X 〇X 〇X; m 1¾ 〇〒 fc know ms ® w ο X ο X o X o X o X ο X 〇X 〇X 〇Χί o > <: m + «1g 拗 υ 1 03 1 < 1 a I < 1 υ 1 < 1 o 1 < 1 o 1 mm ΦΦ 普 盈 ίο Zhao 4 If 1 ο U3 s 2 ο VO in inch in cut sg LH inch tn inch m inch in o < T \ so σ \ s S sgo \ 〇 < 1π la ® UJ UJ »to MJ» uJ * JZ CO UJ1 to to UJ · nJ * to Uf * uj > to to Φΐ i Η • Η Η tH Η ιΗ HH fN 04 CN rH (N rH mm rH m «Η Γ0 rH inch rH rH rH rH un lo l / l in 雔 ό Η 之» — ♦ 0S (N (N m (N CN un < N κΩ CN and CN CO < N cn CN 04 ΓΟ rom 邙 r〇in m \ £ imi; CO m σ \ mo 锕 鹚 homing K ^ _M: X system direction Τ 'Plastic S: o ---------- • install ------ 1T ------. ^ (Please read the precautions on the back before filling this page) _ This paper size applies Chinese National Standard (CNS) Α4 specification (210 X 297 mm) 147 470783 A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention 1 1 I Use the method indicated under K 9 to test on M. Kind of press-formability Λ 1 1 1 Crush resistance, spot welding, adhesion and chemical treatment Perform performance evaluation 1 I Please 1 I 〇 Press formability #, according to the friction coefficient K of the sample and the percentage change in the outer diameter of the cup deep drawing test Λ test (see 1 ICUP deep dra wing test) . Read back 1 1 | [Cup deep pull test] Note | I Change the outer diameter of the white-line sample after δ formula 1 double λ ·. / · / Through cup deep pull test m 1 I re 1 I percentage 〇 Fill in this sample and take out a disc with a diameter of 10 mm from each sample. Then use a punch with a diameter of 50 mm and a shoulder radius of 5 mm to form a cylinder with a crimping force of 3 tons. 1 I with a diameter of 5 3 mm and a shoulder radius of 5 m Π1's die f 1 uses N ip P 〇η Par rk er is ί ng 1 1 I Co * »L td. Manufactured Ν 0 X r U st 550HN for lubrication Agent 0 1 Figure 1 7 is a schematic perspective view of the sample after the cup deep pull test. In I 1 in this figure, M 50 represents the system --- flange D series flange outer diameter and 5 1 The crack occurred from 1 I formed in the cylinder. 0 1 I The outer diameter of the flange after deep drawing of the cup is calculated from the equation below M. Change I-line percentage. 1 1 Percentage change of outer diameter U) I 1 = {(11 0--D) / 110} X 100 1) 1 I where D: outer diameter of flange after test (mm) 1 1 | According to pull-ball test (C ra W be ad i, e £ 丨 t) 'Removed from the thin 1 1 film (alloy zinc dip coating and F e-N i-() film) on the steel plate (M is referred to as "film 1" 1 peeling amount "), and evaluated the crush resistance 0 1 1 [pulling test] 1 | Using the method below, the sample is placed on steel 1 by scraping the sample against the edge of the bead» This paper size applies Chinese national standards ( CNS) A4 specification (210X297 mm) -148 470783 A7 B7 V. Description of the invention (1 The film on the board is peeled off so that the peeling amount can be measured. 'Take out a certain shape and size test piece from each sample, Then, by dissolving and degreasing with dilute hydrochloric acid, the electroplated layer and the F e-Ni-0 film on the asymmetric surface were peeled off, and then the weight of the test piece was measured. The test piece thus prepared was set under M Indicated material tests On board. Fig. 18 A schematic cross-sectional view of a bead testing machine used in the 8 series. In this figure, KK 5 indicates a test piece, 5 3 series with a bead edge, and 5 3 a with a bead edge frame. , 5 4 series molds and 5 5 series hydraulic devices. Figure 19 is an enlarged view of Figure 18. As seen in Figure 19, the test piece 5 2 is placed on the bead edge 5 3 and the bead edge frame 5 3 a And the die 5 4 and the test surface (the surface on which the test is performed) of the test piece 52 faces the bead 53. Thereafter, the pressure plate 5 6 is pressed forward by the hydraulic device 5 $. Next, the test piece 5 2M is inserted in a press-fit relationship between the bead frame 5 3 a and the mold 54, and then M is abutted to the tip of the bead 53. The hydraulic pressure P is 50 kgf. With The test surface of the test piece 5 2 is so close to the tip of the bead edge 5 3, and this test piece is squared at a right angle to the longitudinal direction of the bead edge 53 (¾, M 200 mra / min, and the length of UOmin is pulled up. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page). Figure 20 illustrates the shape and size of the bead edge tip. As can be clearly seen from this figure, beads Margin 5 3 is hemisphere Shape, with a tip radius of 1.0 in m and a bead height of 4 m m. The test was performed by coating the test surface with a lubricant Noxrust 550ΗN manufactured by Parkerising Co., Ltd. Secondly, degrease the test piece 5 2 and stick an adhesive tape on the test surface. Then peel off the tape and follow the next step of degreasing, and then measure the weight of the test piece 5 2. The paper size applies the Chinese national standard (CNS ) A4 size (210 X 297 mm) 149 470783 A7 B7 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention P7) 1 1 〇 Calculate the weight difference before and after the test 9 This determines the film peeling amount 0 1 1 | Results 9 shown in Tables 40 and 4 1 reveal the situation under M 0 1 I The alloy zinc-dipped steel plate falling within the scope of the present invention provides a reduction in its film. Please read 1 1 Coefficient while improving deep formability (dee P f 0 rmabi 1 ity) Read Back | I 9 Therefore, it shows a practically acceptable level of press formability 0 Note 1 I Meaning 1 I Films made by wiping film Stripping amount In fact, it is small and can accept things 1 | again 1 I 9 Therefore it has a high resistance to smashing 0 1 The number of points during the spot welding process is actually large. Acceptable 9 because of page 1 I The point weldability is quite satisfactory. 0 1 1 The peel strength after bonding with a resinous adhesive is actually 1 1 at an acceptable level, so it can show a fairly good adhesion. 1 Chemically treated phosphoric acid结晶 The crystalline state provided by the thin film is actually excellent chemical treatment at an acceptable level of 1 I. 0 1 1 I is relative to the steel sheet of the present invention and is outside the scope of the present invention. All its friction coefficient, deep drawing resistance, shatter resistance, point welding 1 linearity, adhesion and chemical treatment Unsatisfactory < €, 〇1 1 [Second set of tests] 1 I The conditions and results of the second set of tests are followed. 0 1 1 I In the second set of tests, 9 Fe-} i--0 films are covered. Cover weight and chemical composition 1 1 Examined under harsher conditions than the first group of tests 0 1 1 Tables i2-47 list the preparation of the invention soil for the second group of tests 1 1 test m of the existing alloy The Fe content in the immersion coating Λ is combined on the surface of the plating layer 1 I Metallographic Λ Electroplating deposits Λ Fe-N i- -0? The preparation method of the film 'Go, film> 1 1 I Weight (film Sum of all metal elements in the conversion • The same i can be adapted to 1 1 This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm), r Λ 1 15 0-470783 A7 B7 V. Description of the invention ( ^ 8) Explain the test results below), F e / (F e + Ν Π) in the film, and oxygen content in the film. I --------- i ------ IT ------. ^ (Please read the notes on the back before filling out this page) Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ^ Paper size applies Chinese National Standard (CNS) Λ4 specification (210X297 mm) 470783 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of inventions PTABLE) Table 42 Sample alloy zinc-dip coating Fe-Η i-〇M Membrane No. Pe content Surface combined electroplating deposition film formation film Fe / Fe + Ni Oxygen content Wt.% Metallurgical deposit Bismuth method Deposit m at 1 fi wt.% 41 9 ζ 60 A 200 0 3.0 Comparison 踅 —42 9 ζ 60 A 200 0.002 3.0 Example 43 9 ξ 60 A 200 0.004 3.0 ι 44 44 ζ 60 A 200 0.01 3.0 U 45 9 ξ 60 A 200 0.02 3.0 If 46 9 ξ 60 A 200 0.04 3.0 U 47 9 ς 60 A 200 0.05 3.0 il 48 9 ζ 60 A 200 0.08 3.0 1, 49 9 e 60 A 200 0.11 3 • 0 It 50 9 e 60 A 200 0.14 3.0 XI 51 9 ζ 60 A 200 0.17 3.0 \ < 52 9 ζ 60 A 200 0.2 3.0 \ l 53 9 ξ 60 A 200 0.23 3.0 、 (54 9 ζ 60 A 200 0.24 3.0 .0 — If 55 9 ξ 60 A 200 0.27 3.0 u 56 9 ξ 60 A 200 0.3 3.0 w 57 9 ί 60 A 200 0.33 3 .0 \\ 58 9 ζ 60 A 200 0.4 3.0 59 9 ξ 60 A 200 0.6 3.0 VJ 60 9 ζ 60 A 200 0.8 3.0 .i \ 9 61 ζ 60 A 200 0.9 3.0 V 62 9 ξ 60 A 200 0.95 3.0 -.11 63 9 ι 60 A 200 1 3.0 Comparative Example 64 9 60 A 200 0.2 0 .0 Comparative Example 65 9 ζ 60 A 200 0.2 0.2 .2 Implementation 66 9 ξ 60 A 200 0.2 0 .4 U 67 9 ζ 60 A 200 0.2 0.5 1 | 68 9 ζ 60 A 200 0.2 1.5 tf 69 9 ζ 60 A 200 0.2 2 • if 70 9 ξ 60 A 200 0.2 4 ', 71 9 δ 60 A 200 0.2 5 Μ 72 9 ξ 60 A 200 0.2 6.. 11 73 9 e 60 A 200 0.2 8 1! 74 9 ζ 60 A 200 0.2 10 Μ 75 9 ζ 60 A 200 0.2 11 II 76 9 ζ 60 A 200 0.2 22… —-------- Order each (please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 specification (210 × 297 mm) 470783 A7 B7 V. Invention Description (15¾ Table 43 Sample No. Alloy Zipping Coating Fe-N i_〇M Film Fe Content Wt.% Surface Alloy Phase Electrodeposition Deposit Bismuth Film Formation Method Film Deposits mjC Fe / Fe + Ni Oxygen Content wt.% 77 9 ξ 60 B 200 0.2 0.0 Example 78 9 ζ 60 B 200 0.2 0.2 Cell example 79 9 e 60 B 200 0.2 0.4 U 80 9 ζ 60 B 200 0.2 0.5 if 81 9 ζ 60 B 200 0.2 1.5 il 82 9 ξ 60 B 200 0.2 2 It 83 9 ξ 60 B 200 0.2 4 .1 84 9 ζ 60 B 200 0.2 .r 5 * u 85 9 ζ 60 B 200 0.2 6 1 (86 9 ς 60 B 200 0.2 8 u 87 9 ζ 60 B 200 0.2 10 \ t 83 9 £ 60 B 200 0.2 11 \ t 89 9 60 B 200 0.2 22 xi ---------- install-(Please read the precautions on the back before filling this page) Order-line · Ministry of Economy Printed by the Central Bureau of Standards Consumer Cooperatives The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) 153 470783 Μ B7 V. Description of the invention (| Ι? Ϋ́) Cooperative Society Printed Sample Alloys: Dip-coated M Fe-Ni-〇 Film No. Fe Contains the Most Surface Electrode Sinking to Fe / Fe + Mi Oxygen Content Wt.% In Metallic Thin Films Method Product 1 content wt.% 90 9 ζ 60 c 0 0.2 1 Comparative Example _ 91 9 e 60 c 5 0.2 1 Example 92 9 ζ 60 c 8 0.2 1 it 93 9 ξ 60 c 10 0.2 1 Μ 94 9 ζ 60 c 30 0.2 1 if 95 9 ξ 60 c 50 0.2 1 u 96 9 ζ 60 c 100 0.2 1 ll 97 9 ξ 60 c 200 0.2 1 * V 98 9 .ξ 60 c 300 0.2 1 " 99 9 ζ 60 c 400 0.2 1 tl 100 9 ζ 60 c 500 0.2 1 101 9 ζ 60 c 600 0.2 1 102 9 ξ 60 c 800 0.2 1 103 9 ξ 60 c 1000 0.2 1 V 104 9 ζ 60 c 1200 0.2 1 \ f 105 9 ξ 60 c 1500 0.2 1. U 106 9 ζ 60 c 1600 0.2 1 \ l 107 9 ξ 60 c 200 0.2 0.0 Comparative philosophy_ 108 9 ξ 60 c 200 0.2 0.2 Cell example 109 9 ζ 60 c 200 0.2 0.4 ti 110 9 ξ 60 c 200 0.2 0.5 U 111 9 ξ 60 c 200 0.2 1.5 if 112 9 ξ 60 c 200 0.2 2 it 113 9 ξ 60 c 200 0.2 4 114 9 ζ 60 c 200 0.2 5-" 115 9 ζ 60 c 200 0.2 6 It 116 9 ζ 60 c 200 0.2 8 ll 117 9 ς 60 c 200 0.2 10 "118 9 ξ 60 c 200 0.2 11 、 l 119 9 ζ 60 c 200 0.2 22 Kt I --------- ^ ------ ir- -----. ^ (Please read the notes on the back before filling in this page) -15 4-This paper size is applicable to the Chinese National Standard (CNS) Λ4 specification (210 X 297 mm) 470783 A7 B7 V. Description of the invention (1% Table 4 5 Sample alloys printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs Dip coating Fe-H iO film No. Fe contains fi Wt.% Surface alloy phase m 踱 Deposits Formation _ Method 洱 Film deposits Fe / Fe + Ni content in 1 film Oxygen content s wt ;.% 120 10 δΐ 60 A 200 0 3.0 Comparison example 121 10 δΐ 60 A 200 0.002 3.0 Cell example 122 10 δΐ 60 A 200 0-.004 3.0 123 10 δΐ 60 A 200 0.01 3.0 124 10 δΐ 60 A 200 0.02 3.0 | {125 10 δι 60 A 200 0.04 3.0 II 126 10 δΐ 60 A 200 0.05 3.0 1 1 127 10 δι 60 A 200 0.08 3.0 • 128 10 δι 60 A 200 0.11 3.0 ((129 10 δι 60 A 200 0.14 3.0 \ | 130 10 δΐ 60 A 200 0.17 3.0 \ 1 131 10 δΐ 60 A 200 0.2 3.0 \ f 132 10 δΐ 60 A 200 0.23 3.0 133 10 δΐ 60 A 200 0.24 3.0 t (134 10 δΐ 60 A 200 0.27 3.0 If 135 10 δΐ 60 A 200 0.3 3.0 W 136 10 δΐ 60 A 200 0.33 3.0 137 10 δΐ 60 A 200 0.4 3.0 \ Γ 138 10 δΐ 60 A 200 〇.β 3.0 w 139 10 δΐ 60 A 200 0.8 3.0 v 140 10 δΐ 60 A 200 0.9 3.0 141 10 δΐ 60 A 200 0.95 3.0 11 142 10 δΐ 60 A 200 1 3.0 Comparison (Example 143 10 δΐ 60 A 200 0.2 0.0 Implementation) 144 10 δΐ 60 A 200 0.2 0.2 Η 145 10 δΐ 60 A 200 0.2 0.4 1/146 10 δι 60 A 200 0.2 0.5 il 147 10 δι 60 A 200 0.2 1.5 η, 148 10 δΐ 60 A 200 0.2 2 l | 149 10 δΐ 60 A 200 0.2 4 150 10 δι 60 A 200 0.2 5 II 151 10 δΐ 60 A 200 0.2 6 ιι 152 10 δι 60 A 200 0.2 8 Μ 153 10 δι 60 A 200 0.2 10 II 154 10 δΐ 60 A 200 0.2 11 155 10 δι 60 A 200 0.2 22 tr (Please read the precautions on the back before filling in this page) The paper size applies to the Chinese National Standard (CNS) Λ4 specification (210X297 mm) 155 470783

A V. Description of the invention (refer to Table 46 Sample No. Alloy zinc dip coating Fe_N ί_〇Γ Edge film Fe content wt.% Surface alloy phase lightning plating deposit Bismuth formation _ Method Film deposit 1V Fe + Hi oxygen content wt.% 156 10 51 60 Β 200 0.2 0.0 Comparative Example 157 10 61 60 Β 200 0.2 0.2 @ 施 钿 158 10 δΐ 60 Β 200 0.2 0.4 1/159 10 δΐ 60 Β 200 0.2 0.5 if 160 10 δΐ 60 Β 200 0.2 1.5 1/161 10 δΐ 60 Β 200 0.2 2-If 162 10 δΐ 60 Β 200 0.2 4 II 163 10 δΐ 60 Β 200 0.2 5 Μ 164 10 δΐ 60 Β 200 0.2 6 u 165 10 δΐ 60 Β 200 0.2 8 .l! 166 10 δΐ 60 Β 200 0.2 10 u 167 10 δΐ 60 Β 200 0.2 11 «168 10 δΐ 60 Β 200 0.2 22 t '(Please read the notes on the back before filling this page) Economy Printed by the Consumer Standards Cooperative of the Ministry of Standards of the People's Republic of China Standards for paper used by China National Standards (CNS) A4 (2 丨 0X 297 mm) 156 470783

A. V. Description of the invention 4) Table 47 Sample alloy zinc-dip coating Fe-Hi-O film No. k content Surface combined with Radium immersion film forming film Fe / Fe + Ni oxygen content in the pulse film wt.% Metallographic Deposit Bismuth Method Deposit «in 1 contains the most wt.% 169 10 51 60 C 0 0.2 1 Comparative Example 170 10 δΐ 60 C 5 0.2 1 踅 Example 171 10 δΐ 60 C 8 0 2 1 172 10 δΐ 60 C 10 0.2 1 Μ 10 173 10 δι 60 C 30 0.2 1 if 174 10 δΐ 60 C 50 0.2 1 U 175 10 δι 60 C 100 0.2 1 176 10 δι 60 C 200 0.2 1 • V 177 10 δΐ 60 C 300 0 2 1 w 178 10 δΐ 60 C 400 0 2 1 11 179 10 δι 60 C 500 0.2 1 u 180 10 δι 60 C 600 0 2 1 181 10 δΐ 60 C 800 0 2 1 182 10 δΐ 60 C 1000 0 2 1 li 183 10- δΐ 60 C 1200 0 2 1 u 184 10 δΐ 60 C 1500 0.2 1 u 185 10 δΐ 60 C 1600 0 2 1 186 10 δΐ 60 C 200 0 2 0.0. Comparative Example 187 10 δι 60 C 200 0 2 0.2 Implementation Example 188 10 δΐ 60 C 200 0 2 0.4 w 189 10 δΐ 60 C 200 0.2 0.5 If 190 10 δΐ 60 C 200 0 2 1.5 il 191 10 δι 60 C 200 0 2 2 if, 192 10 δι 60 C 200 0 2 4 U 193 1 0 δΐ 60 C 200 0.2 5 «I 194 10 δι 60 C 200 0.2 6 It 195 10 δΐ 60 C 200 0 2 8 11 196 10 δΐ 60 C 200 0.2 10 M 197 10 δι 60 C 200 0.2 11 (i 198 10 δι 60 C 200 0.2 22 ('(Please read the notes on the back before filling out this page) Printed by the Central Consumers Bureau of the Ministry of Economic Affairs, Consumer Cooperatives This paper is sized for the Chinese National Standard (CNS) A4 (210X297 mm) 157 470783 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (1 C5) 1 1 I About the coating weight of Fe -Hi- Olim, Fe / (Fe + N i) in the film, and 1 I The measurement method of # 中 的 Ｏ 量 content is indicated in the following 'J 1 1 I [F e-Hi -0 film coating weight and F e / (Fe + Ν ί) in the film] Please first 1 1 m in Fe- Quantitative analysis of Ni-0 thin film, ICP method is difficult to make the back of the outer film 1 1 I Fe -N 1-0 thin film k and the other components of the plating layer as a primer 1 | 1 Separation. Therefore, quantitative analysis by ICP method Including matters 1 I In F e -NX-0 film, but not in the primer or plating layer 0 Refill 1 In addition, after Ar ion sputtering, use the XPS method to remove Fe -N i-0 film The surface of the writing page 1 was repeatedly measured for each of the constituent elements, and M determined the composition distribution of the constituent elements with respect to the depth of the electric 1 1 coating. In this measurement method, the thickness of the F eN i-0 thin film 1 1 is defined as (X + (y — X) / 2), which is extended to 1 I Fe -N 1-〇 The depth (defined as X) at the surface where the element in the film but not present in the plating layer has its maximum concentration, and the depth (defined as y) extending from the surface where the element 1 1 I can no longer be detected, and The difference between the depths (X) mentioned earlier (y 1 1 — X) is calculated by adding the sum of the sum divided by 2; more specifically, the definition of line 1 is [(X + y 丨 / 2], which means: Means the average depth of the first mentioned depth (X) 1 I and the last mentioned depth (y). F θ ~ 1 i--0 The coating weight of the film 1 I and its composition are determined by the ICP method Calculated by the two sets of kosher fruit obtained by the XPS method, and then calculate the F e / (F e + N i) in the film 1 1 [Oxygen content in the film] 1 1 The oxygen content in the film is Measured by Austrian Electron Spectroscopy (AES 丨 Thin 1 | Film Depth Analysis) 1 | Next > The sample on M was subjected to press-formability, chipping resistance, spot melting 1 1 I performance evaluation of adhesion Λ adhesion and chemical treatment. Its respective test method 1 1 This paper size applies Chinese national standard (€ ~ 5 > person 4 specifications (210 > < 297 mm) 158 470783 A7 B7 V. Description of the invention (I < Test the first group and the second series of laws ----------- install-(Please read the precautions on the back before filling this page) Order-line _ printed by the staff consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs The paper size of the paper is applicable to the Chinese National Standard (CNS) Λ4 specification (210X297 mm) 159 470783 A7 B7 V. Description of the invention form 48 Kuang 捶 ggl1- Ιί 蜮 琳安 ο ο ο (Please read the notes on the back before filling (This page). • R4U51 s ^ s ° · β ο · οτ 0 · 2τ τ s ρ ετ ρ ετ ετ ετ ρ ετ

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ro6I This paper size applies Chinese National Standard (CNS) A4 (210X297 mm) 169 470783 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention 0 ¢: ¾ 1 1 1 As shown in Tables 48 -57 The results show that 1 can be clearly seen, and various conditions can be issued. 1 I and the same as those obtained in the first group of IS. U 〇 About press formability, resistance to 1 1 1 smashability, point weldability, and adhesion > also It has been confirmed that the sample of the present invention is obviously different from the comparison sample 1 1 I first. 〇 Then proceed to __. To clarify the facts under M. Read back 1 II Fe -N i-0 falling within the scope of the present invention The film β] coating weight, as the package's Note 1 I means 1 I coating weight is close to the upper limit, a higher press formability can be obtained. If it is as matter 1 | Fe Ή 1-0 film of outer film is less than ΙΟπι g / m 2 »Beijing IJ to 3 ί Good press formability refilling effect is not as good as the physical property difference 1 and if it is 1500 ffl g / IR 2 9 On the improvement of this page 1 will produce better results. 0 1 1 The coating weight of the Fe -H i-0 film within the range of EB1 of the present invention will increase as the weight of the coating 1 1 increases. Obtains higher point weldability 0 1 Order 1 I If Fe / (F e + N i) in Fe -N ί-0 film is less than 0.004, sufficient improvement of adhesion cannot be obtained. Conversely, Fe / (Fe + H i) exceeds 0.9 ', 1 1 then the Ni content in the film is not so small as to improve the spot weldability 〇1 1 is lower than 0.5 wt. F e — Hi -0 in the film The oxygen content cannot be properly changed. 1 The good press formability and spot weldability are 0. Above 10 w%, the chemical treatment will be degraded. 0 1 I. Since the present invention is as indicated and described in the text. Fe-N 0 formed on the electroplated layer of 1 1 gold-zinc immersed steel sheet is thinner and harder and has a higher melting point than zinc or zinc alloy 1 1 electroplated layer. This means that when alloy zinc When the dip-plated steel sheet is pressed into a row, the sliding resistance between the electroplated layer and the mating die will be reduced by 1 I > As a result, the steel sheet will easily flow into the die. In addition > As Fe-κ i--0 The existence of 1 I in the special system when the N content is at the specified amount 1 can ensure the high melting point during welding 1 1 1 Zr 1-Ν ί alloy formation 1 The soil rate is maintained at the desired level, 3 which can prevent 1 1 Paper size applies to China National Standard (CNS) A4 (210X297 mm) 470783 A7 B7

, i £. I V. Description of the invention (168) Gross electrode damage. And in the case of point welding, continuous point welding can be improved. It will be more advantageous if it contains a specified amount of Fe * This element can generate a high surface potential energy suitable for improved adhesion, and M can obtain an adhesive-bonded plate with improved peel strength. In addition to the advantages of M, the chemical treatment can promote the N e and Fe of Fe-Ni-0 films to merge into phosphate crystals, and eventually produce high adhesion and form dense, homogeneous phosphate crystals. Therefore, its secondary adhesion in warm water is excellent. As a result, the present invention provides an alloy zinc-dipped steel sheet which is quite satisfactory in terms of press formability, spot weldability, adhesion, and chemical treatment, and which has significant advantages and is quite industrially useful. Explanation of component numbers--! — ^^^ 1 ^^^ 1 — ^ 1 1 H .......... ^ — ^ 1 ^^^ 1 ^ —. 1. — 1J. (Please (Please read the notes on the back before filling this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1 Sample 2 Sample holder 3 Slide table 4 Roller 5 Slide table support 6 Round edge 7 First dynamometer 8 Second Dynamometer 10 sample 11 spacer 12 adhesive 13 test piece 21 steel sheet paper size applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) _ i 7 1-correction page 4 XSIV -in \ w / f Ministry of Economic Affairs Printed by the Intellectual Property Bureau Employee Cooperatives _.H. ..1 ,, -.π, .π-ι. 1 'nm —η 「_ Ί 1 _ I'-" ^ j ^ *** " 5 Description of the invention (169) — one to 22 galvanized layer 22a convex portion 22b concave portion 23 Fe -Η i- 0 film 2 4 .far Μ active portion 25 active portion 35 sample 36 spacer 37 adhesive 39 reinforcement Plate 50 Flange 5 1 Crack 52 Test piece 53 Bead edge 53a Bead edge frame 54 Die 55 Hydraulic device 56 Pressure plate (reading the front side means the back " " Please fill in this page again) This paper is again applicable to China National Standard (CNS) A4 specification (210X297 mm) — correction page

Claims (1)

1. A method of manufacturing a galvanized steel sheet, comprising the following steps: forming a galvanized layer on a steel sheet; forming a Pe-N i -0 film on the galvanized layer; the step package of forming a Pe-Ni-〇 film. The steel plate on which the hafnium plating layer is formed: as a cathode, electrolysis is performed in an aqueous solution containing nickel sulfate, ferrous sulfate, and iron sulfate; the aqueous solution has a total degree of nickel sulfate, ferrous sulfate, and iron sulfate, The ratio of the concentration of F e 3+ (m 0) / 1 to the sum of the concentrations of F e and F s +, and ρ Η, where the total concentration is in the range of 0.3 to 2 m ο 1 / Α, The concentration (® 〇i / 1) ratio is in the range of 0.5 to less than 1.0, and the pH is in the range of 1 to 2. Suyuan Lijin: · Medium film weight C is thinly coated to 0 i -4 1 ί already ο *} one of AO Nο Fe1rs 圜 M ^ ^ yes f yes with s with film ε / film thin off thin ο ο ο 1 5 j ♦ 1 Ti · τ—one Τ to -Η e ο Θ F 1 F should be within the range of the measured weight including Θ F (please read the notes on the back before filling this page) IJ—-I-I n »i-I-n 1» IIII r The present system has t tools (W film volume is thin with -0 (to 5 volumes. Including * 1 N and ί 范 Fan Li Zhuan • 1-please N-string e Π F the 2 ο have and measuring tools M containing system -, T-% of the zinc plating in the oxygen layer and the total range of the total consumption range of the Ministry of Economic Affairs Intellectual Property Bureau employee consumer cooperatives / to the amount of iron contained within the range of iron-containing range Lifanzhuan-, ¾I -T-δ 5 Application r--lJ · If the 〇3 layer is in the plating method, it is UM ~ Please ask Φ if the item is immersed in the plating layer, and the plating is performed. The electroplating layer is immersed in the step M Including its method * The sheet steel is coated with zinc and satin, and it is made of Chinese fir TT / Steel seed steel 5 and M. The paper size is applicable to China National Standard (CNS) A4 (2) 0 X 297 mm ) 470783 IC〇D8 6. The scope of the application for a patent forms a F e-N 丨 -0 film on the galvanized layer. The Fe-! U-0 · film has a total weight of metal elements in the MFe-Hi-〇 film of 10 Coating weight in the range of 150 On! Ε / m2; the Fe-Hi-0 film has an Fe content (w 11) to a Fe content (wt%) in the range of 0.004 to 0.9 Ν ί content U t%); the Fe-Ki-O film has a gas content in the range of 0.5 to 10 WU; the step of forming the Fe-Ni-0 film includes forming a hafnium plating layer thereon The above steel plate is used as a cathode, and electrolysis is performed in a plating solution containing sulfuric acid and ferrous sulfate; the plating solution has a total concentration of nickel sulfate and ferrous sulfate, and a pH, wherein the total concentration is in the range of 0.1 to 2 m ο in the range of 1/1, and the p Η is in the range of 1 to 3; M and the electrolytic system are performed under the condition that the following equations are satisfied: 5 0 ^ Ik / (U ^ · M) S 1 5 0 (Please read the precautions on the back before filling out this page) — -------- Order · --------. Medium irrK Τ-Λ Medium Electroplated Electric Meter Tieya Hezi and i 厶 5 ·· 'printed the even-level liquid-plated electricity meter by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy At 6 degrees and the method of plating, the layer of the French method has a stratified layer / JM -/ 0-+ υ V 5 Ί1 to 7 Among them, the method of the 5th method Fan Li specially asked ΓΓΓ trr layer zinc degree / si Γ'- · Ηπ The method of the 5th method αϋ ί special Please apply the Chinese standard (CNS) A4 specification (210 X 297 male f) 470783 A8 B8 C8 D8 x if the S layer is immersed in this paper size, and apply for the patent scope i® layer. 9. A method of manufacturing a hafnium-plated steel sheet, comprising the steps of: forming a zinc-plated layer on the steel sheet; M and. Forming a Fe-Ni-O thin film on the hafnium-plated layer, the Pe-Ni-O thin film having K The total weight of the metal elements in the Fe-Nί-Ο film is suspended within a range of 10 to 1500 mg / m2; the Pe-Ni-O film has an Fe content (wt%) in the range of 0.004 to 0.9. Fe content U t%) and N Γ content (M t%) of the total straw; the Fe-Ni-O film has an oxygen content of rhenium in the range of 0.5 to 10 w'U; the formation of Fe-H i The step of the -0 film includes immersing a steel plate having a galvanized layer formed thereon in an aqueous solution containing at least one of ferrous sulfate and ferrous nitrate and at least one of nickel sulfate and nitrate lines; The sum of the iron content Uol / A) and the nickel content < ιβ〇1 / Α) is in the range of 0.1 to 3. 0 1 »ο 1 / JI, the iron content in the aqueous solution (m ο I / ϋ ) The ratio of the sum of the iron content (m ο] / ϋ) and the nickel content (m ο] / il) is in the range of 0.4 to 0.9, and p Η is in the range of 1.0 to 3. In the range of 5 and temperature between 20 and 7 (TC Range of meat. 10. A method of manufacturing a forged zinc steel sheet 5 which includes the following steps: forming a galvanized layer on the steel sheet; a steel sheet having the galvanized layer formed thereon, in an alkali having a pH of at least 10 In the solution, the treatment time is in the range of 2 to 30 seconds; a F e-Ni-0 film is formed on the galvanized layer, and the Fe-Nί-Ο film has the total metal element content in the M Fe-丨 U-0 film The weight is within the range of 10 to 15 mg / m. The coating size li Μ is within the fan circle; the size of this paper is applicable to China National Standard (CNS) A4 specification (2) 0 X 297 mm) ------ ----- # 衣 -------- Order --------- # (Please read the notes on the back before filling out this page) ABCD printed by the Employee Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 470783 r. The scope of the patent application The Pe-Μΐ-O film has a ratio of the sum of the Fe content (wt%) in the 0.0 & 4 all 0S garden and the total Fe content and Mi content (wU); the Pe- The ΙΠ-Ο thin film has an oxygen content in the range of 0.5 to 10 wt%; the step of forming the Fe-Ni-0 thin film includes forming a hafnium-plated layer thereon. A lanthanum plate containing? 6 ( : 丨 2 and with (:) 2, and have between 2.0 and 3.5 It is processed in an aqueous solution having a pH in the range and a water content in the range of 20 to 70T. 11. The method as claimed in claim 10, wherein the step of forming a Fe-Hi-0 film includes forming a steel plate 5 having a galvanized layer thereon and containing F e C] 2 and] UC 1 2, and Has p Η in the range of 2.0 to 3.5, temperature in the range of 20 to 70 Ό, and Fe content (ν t%) versus Fe content (v? T%) and H i The ratio of the sum of the contents (vt%) is treated in an aqueous solution in the range of 0.04 to 0.9. 12. A method of manufacturing a galvanized steel sheet, comprising the steps of: forming a zinc-zinc layer on the steel sheet; and forming a F e-1Π-0 film on the galvanized layer, which forms a Fe-N i-0 film The steps include: spraying a dew dew solution containing Fe ion and Ni ion and having p Η of 1 to 3.5, spraying on the surface anise formed on the galvanized layer on the steel plate; ° C for 1 second at Μ; Μ and 邡 hot steel plate; therefore, the amount of cladding shock with a total weight of κ gold 臑 element formed on the galvanized layer is in the range of 0 to 150 0 ntg / m2, The cladding ratio is in the range of 30 to 90¾: Fe-Hi-O thin film in the shape of island or horseshoe. The Fe-lH-0 film has an oxygen content in the range of 0.5 to 0.5. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) I—I—- ----------- * · ------- order · ---- ---- ^ (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 470783 Printed by the Employee Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A8 B8 C8 D8 t, Patent Application Scope 1 3 . The method according to the scope of the patent application] item 2, wherein the mist solution has a ratio of Fe content (g / il) to Fe content (g / il) and the sum of gallium content (g / il). The ratio, the The ratio is from 0.04 to 0.9. 14. The method of claim 12 in the scope of patent application, wherein the galvanometer of the galvanized steel sheet is performed at a temperature of 80 to 500 + ° C. 15. A method of manufacturing a galvanized steel sheet, comprising the steps of: forming a galvanized layer on the steel sheet; and forming a Fe-! H-〇 thin film on the zinc-inlaid layer, which forms F e-1Π-0 The thin film step includes: tempering and rolling a steel sheet with a galvanized layer formed thereon and forming on the hafnium layer. Bundles of micro irregularities; and forming a Fe-Ni-O thin film on the hafnium layer, thus The coating weight based on the total weight of the metal elements formed on the galvanized layer is in the range of 10 to 0.5 mg / m 2 and the oxygen content is in the range of 0.5 to 10 W t%. The coverage ratio is in the range of 30 to 90¾, and F e-Ν-0 thin and thin, which is bird-shaped or mosaic-shaped. 16. The method according to item 15 of the patent application, wherein the Fe-Ni-O thin film is made of nickel sulfate, ferrous sulfate, and iron sulfate with a total content of 0.3 to 2.0 m. An electrolytic solution having a pH of 2 is formed by anodic electrolysis. 17. If the method according to item 16 of the patent scope is claimed, wherein the electrolyte meets the ratio of Fe content (g / Jl) to the sum of F + e content (g / jl) and Ni content (g / A) is 0.00 4 to 0.9 range of meat, and the molar ratio of the sum of ferrous sulfate (βοΙ / Α) to thallium sulfite (mol / A) and ferric sulfate (mo 丨 / 1) is 0.5 to less than] .0 . This paper size is applicable to China National Standard (CNS) A4 specification (2) 0 X 297 MM) ----------------------- ordered ------- -" f · (Please read the precautions on the back before filling out this page) 470783 Employees' Cooperatives of Intellectual Property Bureau of the Ministry of Economic Affairs printed A8 B8 C8 D8 and applied for the scope of patents 18. If you applied for the 15th scope of patents Wherein, the step of forming the Pe-H thin film includes treating a steel plate having a galvanized layer formed thereon with an aqueous solution; this water-soluble solvent contains FeC! 2 and C] 2, and once the p system is 2. 0 to 3, 5 and temperature conditions are 20 to 70. 19. The method according to item 15 of the scope of patent application "wherein the step of forming F e-IU-0 · the film includes the treatment of a steel plate having a galvanized layer formed thereon with an aqueous solution" This aqueous solution contains F e C 丨 2 And H i C 1 2 > and satisfies the ratio of the Fe content (g / 1) to the sum of the Fe content (g / 1) and Ν ί content (g / A) is 0 · 0 0 4 to 0. 9 ′, p Η is a condition of 2.0 to 3.5 +, and the temperature is a condition of 20 to 70 ° C. 20. A method of manufacturing a galvanized steel sheet, comprising the steps of: forming a galvanized layer on the steel sheet; and forming a F e-Ni-0 film on the total fresh layer, which forms a Fe-Ni-0 film The steps include: 'Tempering and rolling a steel plate having a hafnium layer formed thereon to form a new surface on the galvanized layer; K and forming a F e-Ni-0 film on the galvanized layer, and thus the The zinc layer has a coating weight based on the total weight of the metal elements in the range of 10 to 150 mg / m 2, an oxygen content in the range of 0, 5 to 10 wt S5, and a coating ratio. F e-Ν-0 films in the range of 30 to 90¾ and distributed on the island limbs or Marbucks. 21. Such as Shen He patent. Fan Yuan's method of item 20, wherein the Pe-H〗 -0 film is made of nickel sulfate, thulium sulfate and bell sulfate containing a total amount of 0.3 to 2.0 0 ol / il * An electrolytic solution having p Η of 1 to 2 is formed through anode electrolysis. 22. If the method of applying for the scope of the patent No. 20, where the 1 solution meets the Chinese paper standard (CNS) A4 specifications (210 X 297), please read the precautions on the back before filling this page < · IE n I > ^ in II, nn ί I 1 I 6 ABCD 470783 t, patent application scope Fe content (g / l) versus Fe content (ε / 1) and Ni content (ε / Α) The ratio of the sum 侥 is in the range of 0.0 ΰ 4 to 0.9, and the sum of sulfite (m ο) / ϋ to ferrous sulfate (ιβ〇1 / Α) and ferric sulfate (Biol / jl) Morse ratios are 0.5 to less than 1.0. 23. The method according to item 20 of the patent scope *, wherein the step of forming the Fe-Hi-0 film includes treating a steel plate on which galvanized ytterbium is formed, using an aqueous solution containing F e C] 2 and N i Π 2 and satisfy the conditions that p Η is 2.0 to 3.5, and the temperature is 20 to 70 Ό. 24. The method according to item 20 of the patent application park, wherein the step of forming the F e ϋ-0 film includes treating a steel plate having a galvanized layer formed thereon with an aqueous solution, the aqueous solution containing F e C 1 2 and丨 HC] 2 and satisfying the ratio of the Fe content (g / il) to the sum of the Fe content (g / 1) and 含量 ί content U / 1) is from 0.04 to 0.9., Τ > Η system is 2.0 to 3.5 ·, and temperature is 20 to 70 ° C. 2 5. A method for manufacturing a galvanized steel sheet, which includes jy, the following steps: forming a galvanized layer on the steel sheet; and forming a Fe-Ni-O thin film on the galvanized layer, which forms a Fe-N ί -0 thin film The steps include: immersing a steel plate having a chain zinc layer formed thereon in an acidic solution or an alkaline solution, M dissolving an air oxide film existing on the surface of the galvanized layer, and forming an active and Inactive part; K and F e-Ni-0 film formed on the beryllium zinc layer on which the active and inactive parts are formed, thus forming a package having a total weight of gold element on the galvanized layer The covering weight is in the range of 10 to 150 mg / m2, and the covering ratio is in the range of 30 to 90%. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (2) 0 X 297 male f) --- In n I -. I in ί 1-I (^ *! I 11-ϋ n —1 —i 一 DJ. ·) I n ί n 1 I-^ * (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 470783 Bs8 C8 D8 Or the island 1 and the inner range Fan My 专 specially invite Φ Ώ 6 There are useful ΠΜ ~ V is not acid sulfur in the amount of iw to the η, η Ί its method of 0 Poor Η 至 2 to have and NnG. $ Mu ί special-= J = rn CP D ο A term of the method of acid flow and `` rx Recording sulfite formation + '! Xin ^ Tt ·! Ye® I s Extreme Sun by S This Its ΠΑ sulfur and ε / (V'- the amount 01 contains u u θ. Β F 0 pair; δ acid 丨 丨 sulfur and the application please apply for B β ο.. Οο ί s Ν? Η D 契 ί S) · ί. 殳 之 'i / ηΑ He Fang's item 5 2 The first water solution for the water solution includes the film containing the water-soluble rapid dissolution step, the thin plate Θ F and the piece of polyester. The ρ ο 7 to 2 are the temperature and temperature HU He specially invited Φ * Yang iy 9 steps of cb and the total sulfur G pair is Yiqi ear 1il sub 氐 / 1- to (please read the precautions on the back first and then (Fill in this page) Π Shape Haiis. Mouth on top of it. It is in the form of a series of PZ layers with full zinc plating and there are '12 to ο 'items 5 2 φ 'on the steel is coated with zinc on the forming layer I, 1-*-* B is UM for liquid-soluble water, including C, Fe, N1, and liquid — dissolved < g is (this amount, with plate Fe ο equipment · ------- order · --------- ^ and nx '^ J- AV A to / 4 g ο (ο Amount 0. Contains Fe full ratio and He, total 2,] is 5 • Food 3 rhyme to the piece of ° ° ο 7 to ο 2 is the degree of mild steps including the 1 1 \ S square plate and the upper layer of the M layer i (It can be plated into 0 to form M-shaped M-NJS, and the upper Fe zinc solution plate is formed into electroplated steel prototype, which is very important in this step, including thin film coating step Nί. In eM, the solution is soluble in lir or t. The surface of the liquid is soluble in acid on the surface of the paper. The paper size is applicable to the Chinese National Standard (CRS) A4 regulations (2) 0 X 297 male f) 8 A8 B8 CS D8 470783 VI. Application for patent scope * and forming active and inactive parts on the surface of galvanized layer; M and forming Fe- 丨 U-0 film on the galvanized layer on which active and inactive parts are formed, Thus shaped on the galvanized layer Pe-Nί-Ο film with coating weight based on the total weight of M metal elements in the range of 10 to 15 00ws / m2, meat, coating ratio in the range of 30 to, denier-like or horse-like distribution . 31. The method according to claim 30, wherein the Pe-Ki-O film is made of nickel sulfate, ferrous sulfate, and iron sulfate with a total content of 0.3 to 2. Οβιοί / A, and has 1 to 2 The pH electrolyte is formed by anodic decomposition. 3 2. The method according to item 31 of the patent application park, wherein the electrolyte satisfies the ratio of the Fe content (g / A) to the sum of the Fe content (g / ϋ) and the Ni content U / ϋ) The molar ratio is in the range of 0.00 4 to 0.9 and the sum of ferrous sulfate (mol / 1) to ferrous sulfate (κ 〇 丨 / A) and ferric sulfate U ο 1 / A) is 0.5 to Conditions below 1.0. 33. The method of claim 30, wherein the step of forming a Fe-Hi-0 film includes treating a steel plate having a hafnium layer formed thereon with an aqueous solution, the aqueous solution containing F e C 1 2 and Ni CI 2 and satisfies the condition that the pΗ system is 2.0 to 3.5 * and the temperature system is 20 to 70t !. / 3 4. According to the method of claim 30 in the scope of patent application, wherein the step of forming a F e-Ν-0 film includes treating a steel plate having a hafnium layer formed thereon with an aqueous solution, the aqueous solution containing F e C丨 2 and 丨 彳 丨 C 1 2 »and satisfy the ratio of Fe content (g / il) to the sum of Fe content (s / 1) and N ί content (g / 1) is 0.004 to 0.9 , PH is 2.0 to 3,5, and temperature is 20 to? Conditions of 01C. 35. — A method for manufacturing stell-plated steel sheet, which includes the following steps: This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 male f) (Please read the precautions on the back before filling out this page) D · 1111) 11 · 11111111 Printed by A8, B8, C8, D8, 470783, Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 6. The scope of the patent application forms a zinc layer on the steel sheet; and F e-丨 U-0 film is formed on the zinc layer * The step of forming the Fe- 丨 U-0 film includes: tempering rolling at an elongation range of 0.3 to 5.0 μI; 1) a steel plate having a plating layer formed thereon; tempering rolling The steel sheet is subjected to alkaline treatment in an alkaline solution having p Η on 10 Μ * for a period of 2 to 30 seconds; Μ and an Fe-Nί-Ο film is formed on the surface of the 鉾 鉾 coating subjected to the alkali treatment, PF. F g -Ν 丨 -0 film. Xiao i; y, P e _ N i ~ 0 gold in thin fe) S wood cable total weight ii counted in the range of 10 to]. 50 mg / m 2 II weight; the Fe-IU-O film has a ratio of the Fe content (wt%) to the sum of the Fe content (wt%) and the Ni content UU) in the range of 0.0.5 to 0.9; the F e-H i -0 film has 0 5 to 1 0 w t%, the range of oxygen content. 36. The method of claim 35, wherein the step of forming the Fe-Ni-0 film includes treating a steel plate having a galvanized layer formed thereon with an aqueous solution, the aqueous solution containing F e C 1 z and Ni U 2 * and has a p Η of 2.0 to 3, 5 and a temperature of 20 to 70 Ό. 3 7. The method of claim 35, wherein the step of forming the Fe-lH-0 film includes using an aqueous solution. A steel sheet having a galvanized layer formed thereon is processed. This aqueous solution contains F e C 1 2 and 1Ή C 1 2 > and the ratio of Fe content (s / A) 'to the sum of Fe content (g / I) and R 丨 content (g / A) is 0.00 4 to 0.9, and pH is 2.0 to 3.5 The temperature is between 20 and 701. 38. A method for manufacturing a zinc-zinc steel plate, which includes the following steps: forming a sacrificial layer on the steel plate and applying Chinese National Standard (CNS) A4 (210 X 297 mm) to this paper size -1 〇- (please first (Please read the notes on the back and fill in this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 470783 A8 B8 C8 DS 6. The scope of the patent application is in the shape of zinc. In this solution, the upper film tongue is formed by solution plating. .3 It has a shape of 0 layers on top of the package. Zinc enters the fire with a length of 5 to vto— / 1 · above the plate. Θ Alkali travel and pressure on the inner wall. The shape of the plate-back steel is s (旧 β old τ; ... ν The Μ has a gold ΠΓ Γrtmfl thin element (please read the precautions on the back before filling this page) to ο r—i repeat the count The inner range of the package is V / 1 · The amount contains Θ F; The ratio of the total range and range is 9 2 'of ο \), to t% 5 ο ο with a U film, ινϊ thin amount ο ”-content containing fj KP < ^ 1 this 5 ο Form the method of the method in which the inner range of the film contains oxygen. 8 3 The range of UU ΐ Please invite Φ such as 9 3 steel and-Η of P, • J, 5 its. Y ? The forming layer is coated with zinc and there is Z Tt ^-1 ic liquid-soluble water C mesh e piece F is beneficial to include the film containing the solution-containing rapid dissolution step water, thin plate and V to ο temperature To ο 2 Form the legal method of the item 8 3 U 范 UU ί Please ask such as ο Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs should cooperate with Du Duan Steel on the forming layer of zinc-plated liquid-soluble water for iBL Containing the step is liquid soluble water ig this amount > Contains-G plate F and Πχ have 5 3 to ο CZ and A degrees of temperature include the plate steel zinc plating contains e Λ F vulgar foot full And > Total 2.1 pieces I Λ— of P ο 7 to ο 2 are α to plate layered zinc plated paper This paper size applies Chinese National Standard (CNS) A4 specifications (2) 0 X 297 mm 470783 A8 B8 C8 D8 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 6. Fe-Ni-0 thin film formed on the galvanized layer for patent application; The F e-Ni-〇 film has an island-like or mosaic form; the Fe-Ni-〇 film has Fe-Ni-0 The total weight of the metal elements in the film is within a coating weight range of 10 to 15,000 mg / m2; the Fe-Ni-〇 film has a Fe content (wt%) to a Fe content in a range of 0.004 to 0.9 (Wt%) and the sum of Ni content (wt%); the Fe-Ni-〇 film has an oxygen content in the range of 0.5 to 10 wt%; and the Fe-Ni-〇 film has a content of 30 Surface coverage in the range of 90%. 42. A galvanized steel sheet, comprising: a steel sheet; a galvanized layer formed on the steel sheet; a Fe-Ni-0 film formed on the galvanized layer; the galvanized layer is an alloy zinc impregnated layer; the alloy The zinc immersion coating layer contains 6 to 1 lwt.% Fe and a sufficient amount of Zn and unavoidable objects; the alloy zinc immersion coating layer has a surface layer, and the surface layer is essentially composed of a Γ alloy phase; the alloy zinc The dip coating has a coating weight of 20 to 100 g / m2; the Fe-Ni-〇 film has a coating in the range of 10 to 1500 mg / m2 based on the total weight of metal elements in the Fe-Ni-0 film Weight; the Fe-Ni-〇 film has a ratio of the Fe content (wt%) to the sum of the Fe content (wt%) and the Ni content (wt%) in the range of 0.004 to 0.9; and The Fe-Ni-O thin film has an oxygen content in the range of 0.5 to 10 wt%. This paper size applies to China National Standard (CNS) A4 specifications (2) 0 X 297 mm. ------------ -------- Order -------- Taste (please read the precautions on the back before filling this page) 12 470783 A8 B8 C8 D8 VI. Patent application scope 4 3 · A type of galvanized steel sheet, including: steel sheet; galvanized layer formed on the steel sheet; formed on Fe-Ni-O thin film on the galvanized layer; the galvanized layer is an alloy zinc impregnated layer; the alloy zinc impregnated layer contains 9 to 14 wt ·% Fe and a sufficient amount of Zn and unavoidable objects; The alloy zinc immersion plating layer has a surface layer, and the surface layer is substantially composed of 61 alloy phases; the alloy zinc immersion plating layer has a coating weight of 20 to 100 g / m2; the Fe-Ni-〇 film has Fe-Ni -0 The total weight of metal elements in the film is within a coating weight range of 10 to 1,500 mg / m2; the Fe-Ni-〇 film has an Fe content (wt%) in the range of 0.004 to 0.9 The ratio to the sum of the Fe content (wt%) and the Ni content (wt%); and the Fe-Ni-O film has an oxygen content in the range of 0.5 to 10 wt%. (Please read the precautions on the back before filling out this page) Install flu — ^ 1 1 ^ 9 Μ Ν — ^ 1 —β n ^^ 1 Jl6 Printed by the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economic Affairs This paper applies Chinese national standards (CNS) A4 size (210 x 297 mm) 13