TWI239357B - Galvannealed steel sheet and method for manufacturing the same - Google Patents

Abstract

The present invention relates to a galvannealed steel sheet having an oxide layer of 10 nm or more thickness on the convex surface of coating flattened by temper rolling. The use of the galvannealed steel sheet causes little powdering and lowers the sliding resistance at press forming. Especially, it is more preferable when the areal ratio of the convex surface of coating flattened by temper rolling is 20-80%, that the coating consists of a single phase of delta1, or that the delta1 contains a zeta phase.

Description

1239357 V. Description of the invention (1) [Technical Field] The present invention relates to alloyed molten 埶 _ which has good sliding properties during press forming. [Background Art] Γ zinc steel plate and manufacturing method thereof. σ 1 smelting hot-dip galvanized steel sheet, combined with p% & steel sheet system has a better weldability or paintability than #% τ Gang plate σ to fused hot-dip galvanized earth A? j: Bu, the use of the car body as the center of the center, each * you ☆ taxi u here, in the car plated steel plate. As a result, Likou Meng Huaxuan melts hot dip, u 疋 In stamping and forming, for example, on the part where the mold and the washer ea $ == the grip and the sliding resistance is quite large, the humanized hot-dip galvanized steel sheet and It is not easy to flow into the mold, that is, the alloyed hot-dip galvanized steel sheet system does not have good sliding properties, and it is easier to break than the ordinary cold-rolled steel sheet. In the alloyed hot-dip galvanized steel sheet, Fe (iron) in the steel sheet and Zη (zinc) in the dip coating layer are diffused by the heat treatment after the dip plating, so as to form the Fe_Zn alloy phase. The Fe-Zn alloy phase is generally composed of the r phase, the 51 phase, and the t phase, and the Fe (iron) concentration decreases in the order of the Γ phase-5 1 phase θ Γ phase, and the The hardness or melting point of the F e-Z η alloy phase tends to decrease. Therefore, from the standpoint of sliding properties during press forming, forming an alloy phase with a high Fe (iron) concentration with high hardness, high melting point, and less prone to coagulation can greatly contribute to press forming. Of sliding. However, when forming an alloy phase with a high Fe (iron) concentration, it is easy to form a rather hard and brittle Γ phase at the interface between the dip coating and the steel sheet, so that it is easy to peel off the dip coating from the interface during forming. Phenomenon

90101265.ptd Page 8 1239357 —— V. Description of the invention (2) Yi Shesheng's so-called powdering phenomenon method is based on: Specialized :: A method that has both sliding and powdering resistance '利特凯 平 & quot No. 1966i, it is proposed that the following two sounds be formed on the other layer, and the hard iron-based alloy as the flute layer is formed by an electroplating method or the like. ~ F Θ fF is the first place where the plating is performed m. After the hot-dip galvanizing treatment, the cost is significantly increased. -The operation becomes complicated, and at the same time, it will lead to a method-like problem:: r! To improve the stamping formability of hot-dip galvanized steel sheet:! The problem of coating failure due to poor degreasing is caused by deoiling (oi 1-thrower) during ash stamping. Problems such as unstable moldability occur. Therefore, in Japanese Patent Laid-Open No. 53-603 32 or Japanese Patent Laid-Open No. ^ -1 90483, the following methods have been proposed:] Specially on the surface of the immersion ore layer of the hot / fork galvanized steel sheet , Apply electrolytic treatment / and / shell treatment coating oxidation treatment and heat treatment, etc., and form

ZnO (zinc oxide) is the main oxide film in order to improve its press formability or weldability. In addition, in Japanese Patent Laid-Open No. 4-88196, the following method is proposed: A hot-dip galvanized steel sheet is impregnated with sodium phosphate containing 5 to 60 g / 1 sodium phosphate and a pH value of 2 to 6 An aqueous solution, in which an electrolytic treatment is performed, or

Page 9 90101265.ptd 1239357 V. Description of the invention (3) It is formed on the steel plate by phosphorus pressing or forming. In addition, the method is as follows: Ni is formed by hot leaching and immersion treatment. (Nickel) Reason. However, on the surface of the hair layer, a good sliding shape [the disclosure of the invention of the present invention is a phenomenon of pulverization of heat> a fork bell steel plate is passed through and has a thick zinc steel plate so that in addition, it can also be hot-dip ore Zinc steel sheet For the steel sheet, the aforementioned layer is heated to form an oxide on the surface of the alloy, and the oxide can be treated. The patented zinc-plated steel and the coating oxide are applied to make people understand the aforementioned properties. ], Is to obtain and manufacture the quenched and tempered rolling degree of 1 Onm to apply this aqueous solution to the melt melting and hot dipping treatment with the wrong manufacturer before the completion, and the surface of the dip coating is mainly oxidized In order to improve its punching, Kaiping No. 3 -1 9 1 009 is proposed to apply electrolytic treatment, coating oxidation treatment, and heat treatment to the surface of the immersion plating layer of the following plate in order to improve its press formability. Or when forming an oxide film such as leaching of an alloyed molten hot-dip zinc steel sheet, it may not be possible to obtain an alloying fusion method with good sliding properties when stamping is formed. For the purpose of flattening the convex portions on the surface of the immersion plating layer. Hot-dip galvanizing: the following method of operation, in order to facilitate the 4th visit, +, 4 ^ ^ number, ^ other mentioned steel plate: hot galvanizing operation; the zinc-treated steel plate, And its operations; and,

90101265.ptd Page 10 1239357 V. Description of the invention (4) The above-mentioned alloyed molten hot-dip galvanized steel sheet is subjected to quenching and tempering; and, the alloying and melting after the aforementioned tempering and rolling The operation of forming a zinc-based oxide layer on the surface of the hot-dip galvanized steel sheet. [Embodiment of the invention] The present inventors are in a state of alloyed hot-dip galvanized steel sheet. Even if an oxide layer is formed on the surface of the dip bell layer, stable and good sliding properties cannot be obtained. The reasons are reviewed in detail. As a result, it was clearly found that the reason for the foregoing phenomenon occurred due to: °

Because of the uneven presence of A 丨 (aluminum) oxide, the reactivity of the surface is deteriorated; and the unevenness of μ-yiqu is large. That is to say, the reactivity on the surface of A1 (aluminum) oxide-rich parts is low. Therefore, it is not easy to achieve a large thickness by ordinary electrolytic treatment, immersion, coating oxidation treatment and heating treatment. Oxygen: Concavo-convex; None :: As :: An oxide layer. In addition, since =: face :: 部: 时 在 ::; ::: two directly contact the steel

Therefore:: Causes rupture. If the thickness of the material layer is the same, the cracking phenomenon that occurs when the thickness of the object layer is formed during the forming process ii: J 2: Stop at the punch to adjust the temporary dissatisfaction shown in Figure 1 ^ The results are clearly found: On the convex portion 20, a surface oxide layer of an immersion plating layer having a thickness j treatment and being flattened is formed. With ===, the thickness is preferably 2 or more, let alone the thickness of the oxide layer of the attack type, with 1239357 V. Description of the invention (5) Even in the stamping process, the oxide layer wears to the oxide layer , It will not cause the phenomenon of its sliding properties to decrease. On the other hand, although the upper limit of the thickness of the oxide layer is not specifically set, when the thickness of the oxide layer exceeds 200, the surface reactivity is extremely reduced, and it is not easy to form the chemical conversion treatment film. Therefore, the thickness of the oxide layer is preferably 200 nm or less. In addition, there is a measurement of the thickness of the oxide layer. For example, the thickness of the oxide layer can be obtained by Auger electron spectrometry (aes) combined with (argon) ion sputtering. In other words, when plating to a certain depth is Wei L: Spectral intensity of each element of the measurement object, the relative composition of the depth is obtained by relative ^ positive, and it is contained at 0%, made; Hi The depth 1 that is reduced to become a sum of a certain value 1 at first is the thickness of the lice compound layer. The area ratio of the convex portion on the surface of the immersion plating layer that is flattened is the figure below. The area ratio of the convex portion on the surface of the immersion plating layer that is flattened to less than 20r: m is the graph. The other parts are also large, and the contact area between the concave part and the mold shown in 70 of No. 21 of 1 becomes 2 so that the flattened convexity of the thickness of the oxide layer can be reliably controlled. The concave = rate becomes smaller, so that The effect of improving the sliding properties becomes small. In addition, because the system has the function of retaining the embossed oil A 卩 at the time of press forming, the area ratio of the recess is less than 20%, that is, it is flat. When the area ratio exceeds 80%, degreasing is easy to occur (oil_thrower is said to be flat, so that the improvement effect of its press formability is reduced. In addition, the area ratio of the convex portion of the surface of the immersion coating is determined by Optical microscopy

90101265.ptd Page 12 1239357

V. Description of the invention (β)

Mirror or scanning electron microscope (SEM), etc., observe the immersion plating layer and use image analysis to determine the ratio of the flat portion to the guilt-respecting surface. In the field, the flat surface of the immersion plating layer is a part that is in contact with the mold during grounding. Therefore, there must be a hard and high melting point to prevent the phenomenon of condensation with the mold. As for the substance, from the viewpoint of sliding property, as a result, the surface of the immersed ore layer that is flattened ^ '' is a secondary forging layer of 51 single phase ', which can obtain good sliding property quite effectively. .

However, in this state, an alloying treatment must be applied in order to increase the F e (iron) concentration in the dip coating layer. Therefore, it is easy to form a rather hard and brittle Γ phase at the interface between the dip coating layer and the steel sheet. A powdering phenomenon occurs, and as a result, it is preferably composed of (51 phases) and contains: a phase of the immersion dream layer 0. In particular, at least on the surface sound of the immersion coating on the single side of the steel plate It can reduce the r phase, and it is quite effective. =: = Seeing the occurrence of the phenomenon. In addition, when it exists on the surface layer of the dip coating (in the case of phase, it can improve the reactivity of the surface, so it can be flat The oxide layer is formed quite effectively on the convex portion of the surface of the immersion plating layer. In order to ensure the existence of the Γ phase on the surface layer of the immersion coating layer, the Γ phase in the immersion coating layer and (51-phase X-ray winding The peak ratio (: 5) of the radio wave is preferably 0.2 or more 'or the surface area ratio of the immersion coating layer (the phase area ratio becomes greater than or equal to%. Here, it corresponds to the lattice interval d = 190A (: phase) and d = 1 · 9 9 0 A (51 phase) X-ray diffraction peak intensity, subtracted View (a dagger a c k

1239357 V. Description of the invention (7) ground), and the ratio of Γ phase and λ 1 4 peak. In addition, the ratio of the two items is determined by the X-ray diffraction electron microscope) and the observation of the area ratio of the immersion plating layer is taken as S £ M (scanning crystals occupy 9 surfaces of the observation field. T-phase diffracted peak peak ratio (: / ratio. In addition, in the state where X is 10%, it is less than 0.2, or in the state where the r-phase area ratio is absent. It is considered to be at least on the surface of the immersion layer, and then connected to 'light-dip hot-dip galvanizing treatment followed by lamp-heating, so that the immersion plating layer enters the aluminization place J', after the calendering process, read: In addition, after the adjustment, it is convenient to manufacture the rolled sheet layer of the present invention, and the steel sheet is plated with σ-melt-melting hot-melt hot sub-plating. After i :; Next, oxygen is formed and the surface becomes an activated compound layer. -4 :: == ::::: = is more uniform. In the case of an oxygen compound layer, it is possible to remove lice formed by 7 ^ β ^ Du Duo Zhoubei's post-treatment residual hydrogen formed non-uniform reaction. In order to remove the quenching and tempering == 'd *' therefore 'may The mechanical method using grinding, etc., is a chemical method of spraying alkaline solution in alkaline solution to form an oxide layer. Therefore, various methods shown below can be applied. Oxygen: square it, ζ; (zinc) is easy to form emulsions by contacting neutral solution, and the reaction can be performed as quickly as possible under the condition of "South temperature" 90101265.ptd Page 14 1239357 —— V. Description of the invention (8) It should, therefore, be able to ^ require the oxide layer in a short time. Forming the edge of the South required for its sliding properties 2. The gas with an oxygen concentration of 20% or more * 3. Contact the oxidant-containing water ;: The method of heating. In this method, the ratio = liquid method can be used. Layer. Seasonal low temperature room temperature, the formation of oxides 4 · Repeated contact with water, the formation mechanism of the oxide layer is particularly 2 The method of drying and processing. Then ...: and promote :; the formation of oxides, and 'when the degree of oxidation of the oxide becomes 50 ° C or more' can further promote the formation of compounds, and shorten their Contact time: Where: No; d times of contact within ± The oxide layer is more uniformly formed when drying η is performed immediately. 5. The method of washing with water after contact with an acidic solution. The structure of the lower Si: layer is not clear, but it is considered that the same as m ^疋 5, when the alloyed hot-dip galvanized steel sheet is in contact, acid = liquid: when 1 is on the surface of the dip coating, zn dissolves; when two or two, 逖 generates hydrogen, so the pH value of the surface of the dip coating It rises, and it is easy to generate Zn hydroxide. Then, by washing with water, it promotes the generation of the Zn lice emulsion to facilitate the formation of an oxide layer. When the pH value of the acidic solution becomes above! It is easier to form oxides. In addition, when the Qiu value of the acidic solution is too high, the reaction speed of Zn pyrolysis will be reduced. Therefore, the Qiu value of the acidic solution is 90101265.ptd Page 15 1239357 V. DESCRIPTION OF THE INVENTION (9) is preferably 5 or less. At the same time, when the liquid temperature is above 50 ° C, the > cleavage of z η and the generation of oxides can be further promoted. = Water temperature during washing, preferably 50 ° C or higher. After contacting the acidic solution, leaving it for 1 · 0 ~ 3 0 · 0 seconds and then 'washing it with water can promote the growth of the hydroxide of Zn j > Oxide layer. When the adhesion amount of the contacted acidic solution is “p” called υ u 5 日 守 ”for each steel plate, it can further promote the generation of hydroxide of Z η and form an oxide layer. In addition, rollers can be used by drawing. & Air friction contact, etc., and when adjusting the adhesion amount of the acidic solution, Fe and / or Zn ions are contained in the solution, the unevenness of the friction coefficient after the treatment can be reduced. In addition, due to the components contained in the front layer, even if this is to be used as a Paleo F / coat layer, it will not cause adverse effects. ‘The acidic solution of Fe 2 and f, ZnΐΊ ions can use iron-zinc-like it Ϊ cooling1. In particular, the same effect can be obtained by using an electroless plating line on a non-conductive f steel plate. Dream liquid, a1: The steel plate is in contact with the dipping of the aforementioned iron-zinc dip-plating bath which dilutes the above-mentioned structure: "Object: to help form an oxide layer. Regarding the formation of the oxide layer, the structure is not clear, but it can be considered that as described below, the molten alloy A is impregnated by the iron-dip immersion bath and passed through the helmet as follows: -Zinc leaching; when galvanized steel sheet is used,

90101265.ptd Page 16 1239357 V. Description of the invention (10) Zn dissolves on the surface. At the same time, hydrogen is also generated. Therefore, the pH value of the surface of the immersion plating layer rises, and Zn hydroxide is easily formed. In the state of contact with a common iron-zinc immersion plating bath, the pH value is low. Therefore, in order to prevent the excessive plating of the fork plating from occurring, as a result, the remaining immersion bond solution must be removed, or more Raise the pH value of the surface in order to promote the formation of hydroxides, but under the condition of contact with the dilute immersion bath; the pH value surface, so 'don't have to worry about the surface of the leaching layer Excessive engraving occurs, and even if a small amount of Zn is dissolved, the pH value on the surface of the immersion plating layer can be relatively easily increased, and as a result, an oxide layer can be formed relatively easily. From the viewpoint of preventing the occurrence of over-etching, the dilution rate of the immersion bath must be more than 1000 times. However, when it is over-diluted, the dissolution reaction of Zn is not easily generated. Therefore, It is preferable that the dilution rate of the immersion bath is 10,000 times or less. As an acidic solution containing Fe and / or Z η ions, one or two or more kinds of sulfates, nitrates, and chlorides containing Fe and / or Zn can be used. In this state, the pH value of the solution can be within the aforementioned range, and the concentration of the solution is not particularly limited. The oxide layer as stated is composed of more than one oxide and / or hydroxide of Z n (zinc), F 、 (iron), A1 (aluminum) and other metal elements. Of the body. In order to manufacture the alloyed hot-dip galvanized steel sheet of the present invention, it is necessary to 'add A1' in the dipping bath. However, Pb (wrong), Sb (record), and Si (stone) other than " Evening), Sn (tin) Mn

90101265.ptd Page 17 1239357 V. Description of the invention (11) (manganese), Ni (nickel), Ti (titanium), Li (li), Cu (copper), etc., without impairing the effect of the present invention. In addition, even if the processing liquid used in the oxidation treatment and the like contains impurities, it is convenient to add S (sulfur), N (nitrogen), p (phosphorus), β (boron), ci to the oxide layer. (Chlorine), Na (sodium), Mn (manganese), Ca (l $), Mg (鎭), Ba (barium), Sr (ming), Si (shixi), etc., without damaging the present invention The effect. Example 1

On a cold-rolled steel sheet with a plate thickness of 0 · 8mm, by a common alloying and hot dipping method, a dip-coating layer with a certain iFe concentration and a deposition amount of 60 g is formed, and after the quenching and tempering treatment, Next, on the surface of the steel plate, the oxide layers stomach of different thicknesses were formed by treating A and β as shown below to facilitate the production of samples n 0 · 1 to 2 0. At this time, the reduction load of the quenched and tempered treatment is changed, and the area ratio of the convex portion on the surface of the money dipping layer which is flattened by the quenched and tempered treatment is changed. i) Treating A, a to, 4 hot-dip iron-zinc steel plates, immersed in a hydrogen peroxide aqueous solution of sulfuric acid with a value of 3 and a temperature of 5 and a hydrogen peroxide concentration of different

ii) Treatment B The alloyed molten hot-dip galvanized steel sheet is immersed in a sulfuric acid solution of pH 2 at a temperature of A 5 0 C, and an aqueous solution of sodium nitrate I of ^ ^ ^ 11 is used to change the current. Density and energization time while performing cathode electrolysis. Measure the Fe concentration, flatness, and lice compound layer thickness in the immersion plating layer, and the area ratio of the convex portions that are to be press-formable, uniformity & flaws! Clothing

90101265.ptd Page 18 1239357 V. Measurement of friction coefficient V of the heart standard of the invention (12). Here, the measurement of friction coefficient and friction coefficient are as follows. ”Carry out the measurement of the thickness of the oxide layer

1) The thickness of the oxide layer is measured as described above. After borrowing Ar (argon) from A, remove the table material of Table = τ3 = # 作 M 备 处, the contamination layer on the surface of the tongue The thickness of the oxide layer was determined as the maximum value of the content ratio of 0 and the subsequent average value at three locations. The ice degree of 2 ^ is determined from this 2) Measurement of friction coefficient Figure 2 shows the friction coefficient measurement device used in this test. It means that the sample 1 is fixed on the sample table 2 provided on the slide base 3, and the moving base 3 is moved horizontally on the roller 4 on the support base 5 for the slide base which can move up and down freely. Squeeze the support base 5 for the slide base, and squeeze the sample 1 to the upper bead 6 at the same position, while moving the sample 1 in the horizontal direction. Next, the load for pressing the sample 1 to the bead 6 was measured by using a load cell (100ad-ce 1 1) 7 provided on 7 sliding supports for '5. N, and a load cell (1 oad-ce 1 1) 8 provided on the slide base 3 is used to measure the sliding resistance F which causes the sample j to move in the horizontal direction, so as to obtain the friction coefficient. # = F / N At this time, "N0X-LAST 55 (product name)" manufactured by PARKERIZING Co., Ltd., Japan, which is used as a lubricant, is applied on the surface of sample 1 to carry out 卞

90101265.ptd 1239357 V. Description of the invention (13). In Figs. 3 and 4, the shape and dimensions of the beaci used are shown. The bead in FIG. 3 has a width of 10 mbar, the length in the sliding direction of the sample is 12mm, the curvature of the lower part of the two ends in the sliding direction is 4., and 'the bead used to squeeze the sample Below, it has a width of 10 mm and a plane with a length of 3 mm in the sliding direction. In FIG. 4 washer (bead), the width is 1 Omm, the length in the sliding direction of the sample is 69mm, the curvature of the lower part of both ends of the sliding direction is 4.5 mmR, and the washer (bead) used to squeeze the sample ) Below, a plane with a width of 10 mm and a length of 60 mm in the sliding direction. In any state, the surface of the sample 1 is pressed against the surface of the sample 1 under the gasket (b e a d), and the sample 1 is slid. The test conditions were performed under two conditions shown below. Condition 1: the bead of FIG. 3, the pressing load n: 400 kgf, and the horizontal movement speed of the sample: 100 cm / min. Condition 2 · The bead in Fig. 4, the pressing load n: 400 kgf, and the horizontal movement speed of the sample: 20 cm / min. In addition, the measurement of the thickness of the oxide layer and the measurement of the coefficient of friction in the following examples were also performed by the aforementioned methods. Table 1 shows the measurement results. In the sample of the present invention, Ν ο · 1 ~ 1 7 'Under condition 1, its friction coefficient # is reduced to below 0 · 160, and under condition 2, its friction coefficient v is reduced to below 0.190, and has Good sliding properties. Especially sample No. 4 ~ 7,

\\ 312 \ 2d-code \ 90-04 \ 90l0l265.ptd Page 20 1239357 V. Description of the invention (14)

No. 10 ~ 15, because the flat immersion plating layer is 20 ~ 80%, therefore, the area ratio of the friction convex portion of the condition 2 is reduced to less than 0.1 7 0, and it has a better saying =, system Significantly, in other respects, this does not impose temperament and delay. Sample No. 18 of the comparative example, the oxide layer to be formed under the quenching and tempering pressure: two samples: the sample No. 9 of the comparative example of the layer forming process, and the oxide layer = at least 1〇ηπ ^ the sample of the comparative example No. · 20, whose coefficient of friction is "white grape" and does not have good sliding properties.

90101265.ptd Page 21 1239357 V. Description of the invention (15)

[Table 1] Sample No. Fe concentration (wt%) in oxide layer forming treatment Dipping layer thickness (nm) Area ratio (%) of flattened protrusions Friction coefficient # Remarks Condition 1 Condition 2 1 A 10.3 16 2 0.153 0.183 Invention Example 2 A 10.5 3 5 6 0.135 0.181 Invention Example 3 A 10.2 2 8 10 0.135 0.181 Invention Example 4 A 9.4 2 9 2 2 0.134 0.168 Invention Example 5 A 11.2 22 3 8 0.136 0.168 Invention Example 6 A 11.6 40 5 9 0.133 0.160 Invention Example 7 A 10.8 16 8 0 0.150 0.159 Invention Example 8 A 8.9 18 8 5 0.153 0.181 Invention Example 9 A 13.0 2 6 10 0 0.138 0.187 Invention Example 10 A 11.9 13 60 0.158 0.169 Invention Example 11 A 9.0 14 5 5 0.153 0.165 Invention Example 12 B 8.2 22 5 0 0.138 0.161 Invention Example 13 B 10.6 6 8 5 5 0.133 0.162 Invention Example 14 B 10.4 12 0 4 5 0.132 0.161 Invention Example 15 B 12.5 2 2 0 5 0 0.132 0.162 Invention Example 90101265.ptd Page 22 1239357 V. Description of the Invention (16) Table 1 Cap 16; B 12.4 11 8 5 0.154 0.184 Invention Example 17 B 11.0 13 14 0.155 0.181 Invention Example 18 No Treatment 11.8 — No Tempering 0.184 0.245 Comparison Normal pressure Process 19 No process 11.5 7 4 5 0.178 0.226 Comparative Example 2 0 A 9.8 9 4 2 0.171 0.214 Comparative Example \\ 312 \ 2d-code \ 90-04 \ 90101265.ptd Page 23 1239357 V. Description of the invention (17) f Shi Hej adjusted an alloyed molten hot-dip galvanized steel sheet having a thickness of 0.8 mm by changing the alloying conditions to a thickness ratio of 0.8 mm, and adjusted it in an aqueous solution of sodium oxychloride having a value of 12 to remove the alloy. = 、 After the oxide layer generated by Mori, then, through the aforementioned processing A 1 ~ 3! The sample No. t is produced on the surface of the steel plate to form an oxide layer. No. Kefan is the same as the implementation Example 1: Change the reduction surface of the quenched and tempered treatment:; Si is flattened by the quenched and tempered treatment, and the leaching rate is U = meaning: that. Measurement of content rate, Γ ”value,“ mesh area ”and friction coefficient. The thickness f of the product layer is shown in Tables 2 and 3. The sample N0 q ~ ^ ^ /. Of the example of the present invention is quite high, even in the case of * spread, 八 ζ 5 value, and r-phase area ratio, under conditions! The surface layer of the lower friction surface ^ clearly exists (in the state of phase, especially the oxide " sound 〃 " is relatively low, and has good sliding properties ~ 24, 2% at the stoppage ^^ degrees The sample No. U of the present invention example above 20 coffee is good = the friction other than this, the number " system is also quite low ... Within the range, it is flattened: the thickness of the oxide layer is within the range of the present invention. 5 ~ 8, although the coefficient of friction of the coefficient of friction of the sample 2 with a small area ratio of the convex portion on the surface of the stripe layer is relatively low, the fruit is small. "And ..., reduced, therefore, the sliding property Comparative Examples of Improved Effective Oxide Layer Thickness Outside the Scope of the Invention

90101265.ptd Page 24 1239357 V. Description of the invention (18) Sample No. 1 ~ 4, its friction coefficient // is quite high, and does not have good sliding properties.

_ 画画 II 90101265.ptd Page 25 1239357 V. Description of the invention (19) [Table 2] Oxidation quenching and tempering dip plating with m m-/ / 5 r surface oxidation flat friction system 尠 Μ Remarks delay The condition for layering convexity in the middle layer of the M layer] Condition 2 No. The thickness of the treatment layer to form the thick part of the oxide (g / η 3) F e (%) removal concentration (η 1 ”) The surface is slightly treated ( wi%) Rate (%) 1 Nowhere 3 3 9.4 8.7 0.389 3 4.8-0 0.194 0.258 Comparative Example 2 Nowhere 4 3.5 8. 9 0.422 3 6.8 6. 2 4 3 0.189 0.244 Comparative Example 3 A No 4 2.2 8.8 0.353 2 6.5 7.5 3 8 0.192 0.230 Comparative Example 4 B None 4 8.8 9. 4 0.390 2 4.8 Ί .9 A 9 0.190 0.239 Comparative Example 5 A Yes 4) .5 8.5 0.304 3 8.8 12.6 10 0.165 0.233 Invention Example 6 B Yes 3 9.6 9. 2 0.362 3 7.3) 9.5 15 0.168 0.244 Invention Example 7 A Yes 4 2.6 7.6 0.637 2 8.8 13.1 8 6 0 · 6 7 0.236 Invention Example 8 B Yes 5 7.4 9.0 0.637 3 6.8 15.5 9 0 0.169 0.241 Invention Example 9 A has 4 6.1 7. .9 0.427 4 0.8 16.5 4 6 0.139 0.231 Invention 11 ΙΙΙΙ 90101265.ptd Page 26 1239357 V. Description of the invention (20) Table 2 i Example 10 A has 4 7.6 8. 4 0.501 3 0 S 15.3 5 2 0.141 0.234 Invention Example 11 A Yes 3 9.1 8.5 0.225 2 2.0 14.7 3 8 0.142 0.229 Invention Example 12 B Yes 4 0.4 8.6 0.418 2 4.5] 3 · 4 5 5 0.141 0.241 Invention Example 13 B Yes 4 3.1 8.4 0.381 18.5 17.1 5 0 0.139 0.237 Invention Example] 4 B has 4 1.0 9.6 0.260 4 1.5 15.4 5 0 0. J 4 0 0.235 Invention Example 15 A has 4 3.5 9.7 0.264 2 7.3 3 0.5 A 6 0.135 0.173 Invention Example 90101265.ptd Page 27 1239357 V. Description of the invention (21) [Table 3] Sample No. Oxide layer formation treatment Oxygen layer after quenching and tempering Removal treatment Dip plating adhesion m (g / 111 :) F in the dip coating ΰ Concentration (wt%) ζ 1 δ Γ Surface tip ratio (%) Thickness of oxide layer (nm) Surface tip ratio of flattened protrusions (%) Friction coefficient preparation condition 1 Condition 2 16 A Yes 5 0.3 9.5 0.224 2 7.3 3 4.3 5 8 0.134 0.172 Invention Example 17 A Yes 4 0. 6 9.0 0.262 2 6.3 3 1.5 5 4 0.128 0.164 Invention Example 1 8 A has 4 0.2 9.5 0.339 3 3.0 3 3.0 5 4 0.124 0.176 Invention Example 19 A has 4 2.4 8.4 0.530 2 4.3 5 1.8 5 0 0.125 0.178 Invention Example 2 0 A Yes 4 6.5 8.2 0.442 3 0.8 8 2.6 4 5 0.125 0.171 Invention Example 2 1 A Yes 4 4.0 8.7 0.428 2 7.0 16 7.5 5 3 0.126 0.165 Invention Example 2 2 Yes 4 7.9 9.4 0.314 2 6.8 4 6.1 4 5 0.124 0.166 Invention Example 2 3 B has 4 4.2 8.8 0.316 3 0.3 5 2.8 5 0 0.125 0.166 Invention Example 2 4 B has 4 0.3 8.4 0.401 19.4 4 4.4 4 9 0.131 0.162 Invention Example 2 5 B has 3 9.9 8.5 0.285 17.9 4 7.8 6 7 0.127 0.166 Invention Example 2 6 B has 4 1.9 9.2 0.315 16.5 8 2.8 5 7 0.133 0.169 Invention Example 2 7 B has 4 3.7 9.4 0.288 2 4.5 112.5 6 0 0.132 0.169 Invention Example 2 8 B has 4 8.8 9.6 0.315 3 2.5 12 6.5 5 4 0.129 0.162 Invention Example 2 9 B has 4 9.3 9. 5 0. 0 1 1.. 8 14.0 5 5 0.140 0.211 Invention Example 3 0 A has 4 8.5 9.6 0.15 2. 8 3 1.5-0.130 0.196 Invention Example 3 1 B There are 4 8.3 9.3 0.07 4. 5 6 8.9 5 1 0.128 0.166 Invention Example ll · 11 \\ 312 \ 2d-code \ 90-04 \ 90101265.ptcl Page 28! 239357 V. Description of the invention (22) 5 After the oxide layer in the sodium hydroxide aqueous solution of 12 is processed by melting the under-recorded steel sheet by ordinary methods, then C and D are processed in order to facilitate The steel sheet layer was used to produce a sample No. under load, and the area ratio of the convex portion on the surface of the coin layer was changed. 1 ii) Treatment C. Water vapor at 100 ° C by alloying and hot dipping. iv) Treatment D at 250 ° C, oxygen concentration 40% For the alloyed hot-dip coating followed by the area ratio of the protrusions and oxides in the dip coating, Tables 4 and 5 show examples of the present invention. Sample No. 6 is relatively low, and the coefficient system of the present invention example having a good 20 nm or more is also relatively low. On the other hand, the plate thickness is 0 without the chemical compound layer and without applying the oxygen method. 8mm alloying melt quenching and tempering, and immersed in the pH value to remove the formation of "alloys formed by the aforementioned treatment A and the surface shown below" during the alloying treatment to form oxides of different thicknesses 3 8. At this time, 'the pressure of the tempering and calendering process is changed. The immersion steel sheet which is flattened by the tempering and calendering process is changed in its processing time, and in the atmosphere of blowing, the process time is changed, and the steel sheet is heated. The Fe concentration, the thickness of the surface layer of the immersion plating layer and the friction coefficient // were measured. The measurement result. ~ 38. Its friction coefficient v under conditions 1 = sliding property. In particular, the thick layer of the oxide sample N ο · 1 5 ~ 3 8. For Ludu 9 πτ and ^ w ^ The friction under condition 2 has better sliding properties. Sample No. 01 for removing the layer formed during the alloying treatment was removed.

1239357 V. Description of the invention (23) The friction coefficient // is quite high, and does not have good sliding properties. In addition, even in samples Nos. 3 to 5 where the oxide layer formation treatment was performed and the oxide layer thickness was outside the scope of the present invention, the friction coefficient was not sufficiently reduced, and it did not have good sliding properties.

90101265.ptd Page 30 1239357 V. Description of the invention (24) [Table 4] Sample No. Oxide layer formation treatment After tempering and rolling oxide layer removal treatment F e concentration (W 1%) oxide in the immersion plating layer Layer thickness (η m) Area ratio of flattened protrusions (%) Friction coefficient A Remarks Condition 1 Condition 2 1 No treatment without 9.9-0 0.18 $ 0.258 Comparative example 2 No treatment without 9.5 6.2 4 3 0.180 0.244 Comparative example 3 C None 11.2 8.1 3 8 0.178 0.230 Comparative Example 4 D None 10.4 7.9 4 9 0.173 0.239 Comparative Example 5 A None 9.8 7.. 4 4 0 0.175 0.233 Comparative Example 6 C Yes 9.9 12.6 10 0.164 0.244 Invention Example 7 D Yes 10.5 19.5 15 0.167 0.236 Invention Example 8 A has 10.6 2 2.4 1 4 0.163 0.24] Invention Example 9 C has 10.1 13.1 8 6 0.163 0.231 Invention Example 1 0 D has 8.9 15.5 9 0 0.166 0.234 Invention Example] 1 A has 9.9 18.3 8 2 0.160 0.229 Invention Example 12 C Yes 11.5 16.5 5 1 0.132 0.241 Invention Example 13 D Yes]]. 6 15.3 5 0 0.133 0.237 Invention Example 1 4 A Yes 10.0) 4.7 5 0 0.130 0.235 Invention Example 1 5 C Yes 9.8 2 5.1 4 6 0.124 0.200 Invention Example 16 D Yes 11.1 2 4.8 5 8 0.132 0.195 Invention Example 17 A 10.6 2 2.4 5 4 0.129 0.193 Invention Example 11 ·! 90101265.ptd Page 31 1239357 V. Description of the invention (25) [Table 5] Sample No. Gas layer formation treatment quenching and tempering F e concentration (wi%) in oxide layer after subsequent oxide layer removal treatment The originality of oxide hafnium (丨 1 m) Surface flatness of flattened protrusions (%) Friction coefficient p Remark condition 1 condition 2】 8 C has 10.9 3 1.0 5 4 0.134 0.176 Invention Example 19 C 10.9 3 2.5 5 0 0.125 0.178 Invention Example 2 0 C has 8.8 4 6.2 4 5 0.136 0.171 Invention Example 2 1 C has 8.6 5 1.3 5 3 0.127 0.165 Invention Example 2 2 C has 9.5 6 2.2 4 5 0.124 0.166 Invention Example 2 3 C has 9.8 8 2.4 5 0 0.125 0. 丨 6 6 Invention Example 2 4 C has 10.4 1 2 5 4 9 0 ·] 3 6 0.162 Invention Example 2 5 D Yes 9.4 3 3.4 6 7 0.127 0.176 Invention Example 2 6 D Yes 10.5 3 0.6 5 7 0.133 0.179 Invention Example 2 7 D 葙 10.4 4 5.9 6 0 0.132 0.169 Invention Example 2 8 D Yes 10.6 5 3.3 5 4 0.129 0.162 Invention Example 2 9 D 宥 10.6 6 8.] 5 8 0. 丨 2 8 0. 丨 6 6 Invention Example 3 0 D has 9.3 8 1.0 5 8 0.131 0.168 Invention Example 3 1 D has 9. 5 1 4 6 6 3 0. 丨 2 9 0.165 Invention Example 3 2 A 10.4 3 8.1 6 5 0.128 0.177 Invention Example 3 3 A Has 9.6 3 4.5 6 4 0.126 0.175 Invention Example 3 AA There are 10.2 4 2.5 3 8 0.131 0.169 Invention Example 90101265.ptd Page 32 1239357 V. Description of Invention (26) Table 5

I 3 5 A has 9.8 5 6.1 6 6 0.) 3) 0.164 Invention Example 3 6 A m 10.2 6 0.3 5 9 0 ·] 2 9 0.170 Invention Example 3 7 A has 9. 6 8 2.7 5 5 0.136 0.171 Invention Example 3 8 A 10.4 13 1 5 6 0.127 0.166 Inventive Example 90101265.ptd Page 33 1239357 V. Description of the Invention (27) Example 4 In the case of a plate thickness of 0.8mm, the alloying fusion heat is produced by a general method. The galvanized steel sheet was dipped and subjected to quenching and tempering treatment, and immersed in an aqueous sodium hydroxide solution having a pH value of 12 to remove the oxygen layer formed during the alloying treatment. After spraying the filtered water at a certain temperature for 5 seconds, the surface of the steel plate is immediately dried to facilitate the formation of oxide layers of different thicknesses on the surface of the steel plate, and samples No. 1 to 40 are manufactured. At this time, the reduction load of the quenched and tempered treatment is changed, and the area ratio of the convex portion on the surface of the immersion plating layer which is flattened by the quenched and tempered treatment is changed. The Fe concentration in the convex iim layer, the flattened surface of the immersion plating layer, the thickness and friction coefficient of the oxide layer, etc. are determined. Table 6 and Table 7 show the measurement results. The sample No. u ~ 4f) of the example of the present invention is relatively low, and has a good coefficient of friction under the condition 1 " 2 a comparison of the upper one = slip ΓΪ. In particular, the thickness of the oxide layer is relatively low, and the coefficient of friction shown under the condition 2 is also better in another person &men; On the other hand, there is no chemical layer, and there is no re-evaluation ', the θ 2 aluminized oxygen generated 2, its friction coefficient / binocular into two water spraying and drying treatment sample N. / Ming In addition, even before the image, it does not have good sliding properties. Samples outside the range No. 3 ~] 〇 & pot treatment and its processing conditions are low in this hair, and do not have good slip ^ = coefficient of rubbing A can not fully drop 90101265.ptd Page 34 1239357 5 Description of the invention (28) [Table 6]

Sample No. Water contact • Drying treatment After tempering and rolling oxide layer removal treatment F e vorticity (W 1%) in immersion plating 1 Thickness of vaporized layer (nm) Planarity of flattened convex portion (% ) Friction coefficient V Remarks Water temperature (r) Number of repetitions Condition 1 Condition 2 I No treatment No 9. 9-0 0.185 0.258 Comparative example 2 No treatment No 9.5 6.2 4 3 0.180 0.244 Comparative example 3 5 0 3 No 11.2 7.6 3 8 0.176 0.234 Comparative Example 4 5 0 5 None 10.4 7.5 4 9 0.171 0.241 Comparative Example 5 5 0 10 None 9. 8 7.6 4 0 0.173 0.231 Comparative Example 6 3 0 3 Yes] !.] 6. 1 5 8 0.169 0.238 Comparative Example 7 3 0 5 Yes M · 5 6. 9 5) 0.175 0.232 Comparative Example 8 3 0 10 Yes] 1. 6 7. 4 5 0 0.174 0.234 Comparative Example 9 5 0 1 Yes 10.0 8.9 5 0 0.166 0.229 Comparative Example] 0 5 0 2 Yes 9. 8 9.6 4 6 0.164 0.236 Comparative Example 1 1 5 0 3 Yes 9.9 13.1 1 0 0.167 0.241 Invention Example 12 5 0 5 Yes 10.5 2 2.5 15 0.164 0.233 Invention Example 1 3 5 0 1 0 Yes 10.6 3 2.2] 4 0.165 0.238 Invention Example 1 4 5 0 3 Yes 10.1 12.6 8 6 0.167 0.233 Invention Example 15 5 0 5 Yes 8.9 18.5 9 0 0.164 0.227 Invention Example 90101265.ptd Page 35 1239357

90101265.ptd Page 36 1239357 V. Description of the invention (30) [Table 7] Sample No. Water contact • Drying treatment After quenching and tempering the oxide layer removal treatment F c concentration (w 1%) oxide in the immersion coating Layer thickness (η m) Surface area ratio of flattened protrusions (%) Friction coefficient / i Remarks Water temperature (° C) Rehabilitation times Condition 1 Condition 2 2 1 6 0 3 Yes 9. 6 13.4 3 4 0.138 0.221 Invention Example 2 2 6 0 5 Yes 9.4 2 2.1 6 3 0.137 0.205 Invention Example 2 3 6 0 10 Yes 10.6 3 0.4 4 6 0.136 0: 175 Invention Example 2 4 6 0 2 0 Yes 9. 7 4 2.2 6 0 0.132 0 .] 6 4 Invention Example 2 5 7 0 3 Yes 8. 6 16.7 5 3 0.132 0.221 Invention Example 2 6 7 0 5 Yes 9.5 2 5.9 A 5 0.129 0.205 Invention Example 2 7 7 0] 0 Yes 9. 8 3 7.9 5 0 0.134 0.171 Invention Example 2 8 7 0 2 0 Yes 10.4 4 9.1 4 9 0.125 0.163 Invention Example 2 9 8 0 3 Yes 9. 4 19.) 6 0 0.136 0.209 Invention Example 3 0 8 0 5 Yes 9. 4 2 8.1 5 1 0.129 0.198 Invention Example 3 1 8 0 10 Yes 9.1 3 9.5 5 2 0. 丨 3 I 0.168 Invention Example 3 2 8 0 2 0 Yes 9. 8 4 5.) 4 8 0.129 0 ·] 6 5 Invention Example 3 3 9 0 3 Yes 8.9 2 0.3 6 9 0 .130 0. 丨 9 9 Invention Example 3 4 9 0 5 Yes 9.4 3 0.9 4 9 0.127 0.177 Invention Example 3 5 9 0 10 9. 2 3 9.7 6 2 0.127 0.170 Invention Example 3 6 9 0 2 0 Yes 9. 5 5 0.4 5 4 0.125 0.163 Inventive Example 3 7 1 0 0 3 9. 4 2 6.5 6 7 0.136 0.200 Inventive Example 90101265.ptd Page 37 1239357 V. Description of the Invention (31) (Table 7 3 8 10 0 5 Yes 10.5 3 4.1 5 7 0.127 0.177 Invention Example 3 9 10 0 10 Yes 10.4 4 3.7 6 0 0.124 0.165 Invention Example 4 0 1 0 0 2 0 Yes 10.6 5 5.4 5 4 0.125 0.161 Invention Example 90101265.ptd Page 38 1239357 V. Explanation of the invention (32) Responsiveness ^ = plate thickness manufactured by 1 and 0 method 0 · 8 Yanzhi * Jinhuaxuan = Steel plate 'refined and tempered' and immersed in ㈣ solution of oxygen i and removed in The value of the sulfur core generated during the alloying treatment is, and then, the steel sheet is immersed at a certain temperature and-fixed pH 〇 · Imo: 2〗 Permanent, the valley liquid may contain h 〇m〇1 / 1 In the iron-zinc immersion plating bath of ferrous sulfate and zinc sulfate above 1, in order to facilitate the surface of the steel sheet, the oxide layers of different thicknesses are used to produce samples No. to 51. The pressure of the ink is reduced [and the area ratio of the convex portion on the surface of the dip plating layer is changed by adjusting it. For the adjustment of the pH value of the iron-leaching ore bath, enesulfuric acid was used. The convex surface is measured for the concentration of ^ in the leaching layer, the flatness of the surface of the immersion plating layer, the thickness of the oxide layer, and the coefficient of friction #. Only Tables 8 and 9 show the measurement results. It is = 1 ° ~ 51, and its coefficient of friction under condition 1 " sliding property. In particular, the thickness of the oxide layer thickness part 2 and the surface area of the flat portion of the sample of 20 to 80%, the strip sliding coefficient # is also quite low, and the display has a better quality. The oxygen generated during the alloying treatment was not removed, and the sample m impregnated in the acidic solution was not removed, and its friction was caused by the fact that it was quite round and did not have good sliding properties. In addition, if such a treatment is attempted and its processing conditions are outside the scope of the present invention, 4N0 · 3 ~ 9, its friction coefficient # cannot be sufficiently reduced, but it is not

1239357

90101265.ptd Page 40 1239357

90101265.ptd Page 41 1239357 V. Description of the invention (35) Table 8] S sulfuric acid 2.0 5 0 10 0 10.9 2 3.4 5 0 0.130 0.209 Invention Example 19 sulfuric acid 2.0 7 0 5 0 Yes 8.8 16.4 4 5 0.124 0.231 Invention example 2 0 Sulfuric acid 2.0 7 0 7 0 Yes 9.6 2 5.7 3 4 0.138 0.219 Invention Example 2 1 Sulfuric acid 2.0 7 0] 0 0 9.. 4 3 1.1 6 3 0.] 3 7 0.175 Invention Example 2 2 Sulfuric acid 2.0 8 0 5 0 Yes 10.2 2 8.4 4 6 0.136 0. 2 0 1 Invention Example 2 3 Sulfuric Acid 2.0 8 0 7 0 Yes 9. 7 3 4.8 6 0 0.132 0. 1 6 9 Invention Example 2 4 Sulfuric Acid 2.0 8 0 10 0 Yes 8.6 4 0.7 5 3 0.132 0 ·] 6 4 Examples of invention

Kill 90101265.ptd Page 42 1239357 V. Description of the invention (36) [Table 9] Test for acidic acid i solution treatment water wash quenching and tempering rolling diffuse oxidation flat friction coefficient " Remarks Solution P Η Temperature in the oxide layer after temperature Convexity condition for 丨 Condition 2 No. Kind (t) (r) Processed concentration (nm) of thick part of Fe removed by the material layer (nm) Area (wt%) Rate (%) 2 5 Sulfuric acid 1.0 5 0 5 0 Yes 9.5] 0.6 4 5 0.129 0.238 Invention Example 2 6 Sulfuric acid 1.0 5 0 7 0 There are 9.8 18.4 5 0 0.134 0.220 Invention Example 2 7 Sulfuric acid 1.0 5 0 10 0 There are 10.4 2 2.9 4 9 0.125 0. 2] 3 Invention Example 2 8 Sulfuric acid 1. 0 7 0 5 0 Yes 9.4 15.9 6 0 0.136 0.225 Inventive example 2 9 Sulfuric acid 1. 0 7 0 7 0 Yes 9. 4 2 5.2 5 1 0.129 0.211 Invention Example 3 0 Sulfuric acid 1.0 7 0 10 0 Yes 9. 1 3 0 .6 5 2 0.13] 0.178 Inventive Example 3 1 Sulfuric acid 1. 0 8 0 5 0 There are 9.8 2 7.9 4 8 0.129 0.221 Inventive Example 3 2 Sulfuric acid 1.0 8 0 7 0 Yes 8. 9 3 4.3 6 9 0.130 0.171 Invention Example 3 3 Sulfuric acid 1.0 8 0 10 0 Yes 9. 4 4 0.2 4 9 0.丨 2 7 0. 丨 6 4 Inventive Example 3 4 Sulfuric acid 3.0 5 0 5 0 There is 9. 2 2 4.8 6 2 0.] 2 7 0.205 Inventive Example 3 5 Sulfate 3.0 5 0 7 0 Has 9.5 3 2 .A 5 4 0.125 0.172 Invention Example 3 6 Sulfuric Acid 3.0 7 0 10 0 Yes 9.4 3 9.8 6 7 0.136 0.168 Invention Example 3 7 Sulfuric Acid 3.0 7 0 5 0 Yes 10.5 3 0.) 5 7 0 ·] 2 7 0.176 Invention Example 3 8 Sulfuric Acid 3 0 7 0 7 0 10.4 4 1.3 6 0 0 ·] 2 4 0.164 Inventive Example 3 9 Sulfuric Acid 3. 0 8 0 10 0 葙 10.6 5 0. 9 5 4 0.125 0.161 Inventive Example 40 0 Sulfuric Acid 3. 0 8 0 5 0 Yes 10.2 3 3.8 4 4 0.134 0.] 6 7 Invention Example 4 1 Sulfuric acid 3.0 8 0 7 0 Yes 9.6 4 5.7 4 9 0 · 2 9 0 ·] 6 4 Invention Example mm 90101265.ptd Page 43 1239357 V. Description of Invention (37)

Table 9 4 2 Sulfuric acid 3. 0 8 0 10 0 With S. 9 5 4.6 5 3 0.126 0.162 Inventive Example 4 3 F e-Zn η Dip Bath 2. 0 5 0 5 0 With 9.1 11.9 3 8 0.130 0.221 Inventive Example 4 4 1: c-Zn η dip bath 2.0 5 0 7 0 with 9.2 19.7 4 6 0.129 0.210 Invention Example 4 5 F e-Zn η dip bath 2.0 5 0 1 0 0 with 8.8 2 4.2 6 4 0.138 0.21] Invention Example 4 6 F e-Zn η Dip Bath 2. 0 7 0 5 0 Yes 9. 4 17.2 5 1 0.133 0.209 Invention Example 4 7 F e-Zn η Dip Bath 2.0 7 0 7 0 Yes 10.6 2 6.5 5 8 0.132 0.212 Invention Example 4 8 F e-2 η Dip bath 2.0 7 0] 0 0 12.3 3 1.9 4 6 0.136 0.168 Invention Example 4 9 F c-2 η Drought bath 2.0 8 0 5 0 11.0 2 9.2 6 1 0.130 0.181 Inventive Example 5 0 F e-Zn η 2.0 8 0 7 0 m 10.6 3 5.6 5 2 0.134 0.] 7 6 Inventive Example 90101265.ptd Page 44 1239357 V. Description of the Invention (38)

i Table 9 90101265.ptd Page 45 1239357 V. Description of the Invention (39) Example 6 The alloyed hot-dip galvanized steel sheet having a plate thickness of 0.8 mm manufactured by a general method is quenched and tempered. And immersed in a sodium hydroxide aqueous solution of pH 12 to remove the oxide layer formed during the alloying treatment, and then immersed the steel plate in the containing 丨 · Om〇1 /; [In a solution of ferrous sulfate and 0.1 m 〇1 / 1 zinc sulfate and a dilute iron-zinc immersion bath with a pΗ value of 2 in order to form

An oxide layer of the same thickness was used to produce a sample No. 1 to 3 g. At this time, the reduction load 'of the quenched and tempered process is changed, and the area ratio of the convex portion of the surface of the immersion plating layer which is flattened by the quenched and tempered process is changed. Next, the Fe concentration in the immersion plating layer, the area ratio of the convex portions on the surface of the immersion plating layer being flattened, the thickness of the oxide layer, and the coefficient of friction # were measured. Tables 10 and 11 show the measurement results. Sample Nos. 12 to 39 of the example of the present invention have a relatively low coefficient of friction under conditions} and have good sliding properties. In particular, the test sample with an oxide size of 20 nm or more and the friction system under condition 2 showed a better sliding property β μ field low chemical layer and did not impregnate the I produced by the dilution 2 treatment 4 i, 2, the sliding coefficient of the zinc immersion bath solution with its friction coefficient ^ is good. In addition, even if a sample like 1_ 目, / is used, but Ya does not have a good condition outside the scope of the present invention, the sample No 3 = Shu Ting-like treatment and its treatment is sufficiently reduced, without having a good pregnancy :, 1. Its friction coefficient is based on the sliding property.

\\ 312 \ 2d-code \ 90-04 \ 90101265.ptd Page 46 1239357 V. Description of the invention (40) [Table 10] Test F e-Z η Dip bath treatment quenching and tempering m immersion lock oxide flattening Coefficient of friction U Remarks Dilution rate Condition of temperature contacting the thick convex part of the F c layer 1 Condition 2 No. (times) (eC) Time oxide concentration (η m) Surface area ratio (second) layer Remove (wt%) (%) Treatment 1---No 9.9-0 0.] 8 5 0. 2 5 8 Comparative Example 2---No 9.5 6.2 4 3 0. 1 8 0 0. 2 4 4 Comparative Example 3 1 0 0 5 0 3 0 None 11.2 7.6 3 8 0.176 0. 2 3 4 Comparative Example 4 1 0 0 7 0 3 0 None 1 0. 4 8.0 4 9 0.171 0. 2 4 1 Comparative Example 5 10 0 0 7 0 3 0 None 9. 8 7. 7 4 0 0. 1 7 3 0. 2 3 1 Comparative Example 6 10 5 0 3 0 Yes 1]. 1 6.4 5 8 0.] 6 9 0. 2 3 8 Comparative Example 7 2 0 5 0 3 0 Yes 11.5 6.8 5] 0. 1 7 5 0. 2 3 2 Comparative Example 8 5 0 5 0 3 0 Yes] I. 6 7.4 5 0 0.174 0. 2 3 4 Comparative Example 9 10 0 2 0 3 0 Yes 1 0 .0 6.9 5 0 0.175 0. 2 2 9 Compare 10 10 0 3 0 3 0 Yes 9.8 7.1 4 6 0.177 0. 2 3 6 Comparative Example 11 1 0 0 4 0 3 0 Yes 9.6 7.3 4 9 0.171 0.24] Comparative Example 12 10 0 5 0 3 0 Yes 9. 9 13.4 10 0.165 0. 2 3 9 Invention Example 1 3] 0 0 5 0 3 0 Yes 10.6 14.4 1 4 0. 1 6 4 0. 2 3 5 Invention Example 14 1 0 0 5 0 3 0 Yes 10.]】 6. 8 8 6 0. 1 6 1 0. 2 3] Invention Example 1 5 1 0 0 5 0 3 0 There are 8.9 15.1 9 0 0. 1 6 5 0. 2 4 0 Invention Example] 6 1 0 0 5 0 10 10 .6 11.1 5 4 0.132 0. 2 2 7 Invention Example ll11.1111III \\ 312 \ 2d-code \ 90-04 \ 90101265.ptd Page 47 1239357 V. Description of the invention (41) Table 1 0 17 1 0 0 5 0 2 0 10.9 15.7 5 4 0.133 0.214 Invention Example 18] 0 0 5 0 3 0 10.9 16.3 5 0 0.130 0.209 Invention Example 1 9 10 0 5 0 6 0 8. 8 2 0.1 4 5 0.124 0.210 Invention Example

I \\ 312 \ 2d-code \ 90-04 \ 90101265.ptd Page 48 1239357 V. Description of the invention (42) [Table 11] Test F e-Zn η dip bath treatment quenching and tempering pressure dipping bond: layer oxide Flattening m; Wiping coefficient β Remarks Conditions for dilution of the F e layer in contact with the elongation at the dilution temperature Condition 1 Condition 2 N 〇 Rate (times) (t) Time oxide concentration (η m) Surface m Rate (seconds) Layer removal (wt%) (%:) Treatment 2 0 10 0 7 0 10 has 9.6 12.7 3 4 〇. 1 3 8 0.22) Invention Example 2 1】 0 0 7 0 2 0 has 9. 4 18.1 6 3 0.137 0. 2 0 4 Invention Example 2 2 10 0 7 0 3 0 Yes 10. 6 2 3. 7 4 6 0. 13 6 0.] 9 9 Invention Example 2 3 10 0 7 0 6 0 Yes 9. 7 3 4.1 6 0 0. 13 2 0. 16 4 Invention Example 2 4 10 0 10 0 10 Yes 8. 6 2 5.1 5 3 0. 13 2 0. 1 9 8 Invention Example 2 5 10 0 1 0 0 2 0 Yes 9.5 2 9. 7 4 5 0. I 2 9 0. 19 9 Invention Example 2 6 10 0 10 0 3 0 Yes 9.8 3 4.1 5 0 0.134 0.】 6 8 Invention Example 2 7 10 0】 0 0 6 0 1 0 .4 A 6. 1 4 9 0.] 2 5 0. 16 5 Example 2 8 10 0 0 5 0 1 0 Yes 9. 4 18.9 6 0 0.136 0. 2 0 4 Invention Example 2 9 10 0 0 5 0 2 0 Yes 9. 4 2 3.5 5] 0. 12 9 0. 2 0 0 Invention Example 3 0 10 0 0 5 0 3 0 Yes 9.1 2 7. 1 5 2 0.131 0. 19 9 Invention Example 3 1 10 0 0 5 0 6 0 Yes 9.8 3 4.5 4 8 0. 1 2 9 0. 】 6 6 Invention Example 3 2] 0 0 0 7 0 1 0 Yes 8.9 2 1.9 6 9 0. 13 0 0. 2 0 4 Invention Example 3 3 10 0 0 7 0 2 0 Yes 9. 4 3 1.3 4 9 0 1 2 7 0. 16 8 Invention Example 3 4] 0 0 0 7 0 3 0 has 9. 2 4 0.1 6 2 0. 12 7 0. 16 4 Invention Example 3 5 10 0 0 7 0 6 0 has 9. 5 5 0.0 5 4 0.125 0.161 Inventive Example 3 6】 0 0 0] 0 0】 0 Yes 9. 4 2 5.7 6 7 0. 13 6 0.201 Inventive Example Picture_Off \\ 312 \ 2d-code \ 90-04 \ 90101265.ptd Page 49 1239357 V. Explanation of the invention (43) Table 1 1 3 7 10 0 0 10 0 2 0 10.5 3 2.4 5 7 0.127 0.165 Invention Example 3 8 10 0 0] 0 0 3 0 There are 10.4 4 1.7 6 0 0.124 0.165 Invention Example 3 9 10 0 0 10 0 6 0-Yes 10.6 5 5.4 5 4 0.125 0.160 Invention Example (lIHii \\ 312 \ 2d-code \ 90-04 \ 90101265.ptd Page 50 1239357 V. Description of the invention (44) Repeat example 7 in The alloyed molten hot-dip galvanized steel sheet having a plate thickness of 0.8 mm produced by a general method is subjected to quenched and tempered treatment, and an oxide layer forming treatment device as shown in FIG. 5 is used to facilitate the On the surface, oxide layers of different thicknesses are formed, and samples Ν ο · 1 to 20 are manufactured. At this time, the reduction load of the quenched and tempered treatment is changed, and the area ratio of the surface protrusion of the immersion plating layer that is flattened by the quenched and tempered treatment is adjusted to 20 to 80 oxides shown in FIG. 5 In the layer forming processing equipment, an alloyed molten hot-dip galvanized steel sheet is immersed in an acid solution tank 11 filled with a sulfuric acid acid solution having a temperature of 50 ° C and a pH value of 5, and then, is pulled by Extend the use of Tiandian 1 2 to adjust the amount of acidic solution on the surface of the steel plate, wash in # 1 washing tank 14, spray with warm water at 50 ° C., and wash. After the summing tank 15, the washing tank 16 is washed in # 2, sprayed with warm water at 50 t, and then washed, and dried by a dryer 17 to form an oxide layer on the surface of the steel plate. . In some samples, the amount of acidic solution on the surface of the steel plate was adjusted by the drawing roller 12 and then washed with a spray-type water washing device 1 3, or after the washing treatment, neutralized The tank 15 'is sprayed with a sodium hydroxide aqueous solution having a pΗ value of 10 to neutralize the residual solution and the acid solution on the surface of the steel plate. At this time, change the adhesion of the acid solution

The amount of time and the time after the acid solution is adhered to the device 13 to start washing by the # 1 washing tank 14 or spray water. Next, the F e concentration in the immersion plating layer, the area ratio of the convexity σ 表面 on the surface of the immersion plating layer which was flattened, the thickness of the oxide layer, and the friction coefficient 进行 were measured. this

\\ 312 \ 2d-code \ 90-04 \ 90101265.ptd 51st stomach 1239357 V. Description of the invention (45) In addition, after the antirust oil is applied, there is no effect of external factors such as dust, etc. The steel plate was placed outside the house, and it was checked whether a little rust occurred after about 6 months (yes (X), no (0)). Table 12 shows the measurement results. 0 至 3 0. 0 秒 All samples, their coefficients of friction // are quite low, and have good sliding properties, but the time after one of the acid solution is attached until the start of washing is 1. 0 ~ 3 0. 0 seconds Or, in the state where the adhesion amount of the acidic solution is 3.0 g / mm2, the friction coefficient // system is also more

\\ 312 \ 2d-cocle \ 90-04 \ 90101265.ptd Page 52 1239357 V. Description of the invention (46)

[Table 12] Sample N 〇. Acid adherence (g / m2) Time after acid contact (seconds) Fe concentration (wt%) in the bath immersion plating layer Thickness (nm) of oxide layer Flatten convex Area ratio (%) Friction coefficient V Presence or absence 1 Condition 2 Spot rust 1 5.0 0 — 9.4 10.2 3 4 0 ·] 7 3 0.231 X 2 5. 0 0.5-10.6 10.8 6 3 0.170 0.229 X 3 5.0 1.0-9.9 11.8 4 6 0.165 0.221 X 4 5.0 2.0 —] 0.9 15.4 6 0 0.158 0.215 X 5 5.0 5.0-10.9 2 0.) 5 3 0.140 0.200 X 6 5.0 10.0 — 10.0 2 1.1 4 5 0.139 0.198 X 7 5.0 2 0.0 -] 0. 6 2 1.8 5 0 0.139 0.200 X 8 5.0 3 0.0 — 10.6 2 2.0 4 9 0.138 0.200 X 9 3.0 1. .0-10.8 13.4 6 0 0.160 0.215 X 1 0 3.0 2.0-10.5 17.7 5 1 0.155 0.210 X 1 1 3.0 5. 0 1] 0. 5 2 2.4 5 2 0.135 0.197 X 12 3.0 10.0-10.7 2 5.1 4 8 0.134 0.195 X 1 3 3. 0 2 0.0-11.1 2 6.4 6 9 0.133 0.196 X 14 3.0 3 0.0 -10.9 2 7.1 4 9 0.] 3 5 0.194 X 1 5] .0] .0 〇]]. 7 14.1 6 2 0.158 0.216 〇16] .0 2. 0 〇] 0. 4] 8. 8 5 4 0.157 0.211 〇17 1. 0 5. 0 〇10.5 2 2.6 6 7 0.134 0.194 〇1 8 1 .0] 0 .0 〇9.9 2 5.9 5 7 0.132 0.191 〇 312 \ 2d-code \ 90-04 \ 90101265.ptd Page 53 1239357 V. Description of the invention (47)] 9]. 0 2 0.0 〇 10.3 2 7.0 6 0 0.133 0.195 〇 2 0]. 0 3 0.0 〇 10.9 2 7.9 5 4 0.133 0.194 〇 [Explanation of element number] F Sliding resistance N Load for extrusion 1 Sample 2 Sample stand 3 Slide base 4 Roller 5 Support base for slide base 6 Bead 7 Load-cell 8 Load cell 9 Track 11 Acid solution tank 12 Rolling roller 13 Spray type Water washing device 14 Washing tank 15 Neutralizing tank 16 Washing tank 17 Dryer

\\ 312 \ 2d-code \ 90-04 \ 90101265.ptd Page 54 1239357 V. Description of the invention (48) 20 Dip coating surface protrusion 21 Dip coating surface depression i Chinese painting_11 \\ 312 \ 2d-code \ 90-04 \ 90101265.ptd Page 55 1239357 Brief description of drawings Figure 1 is a SEM (scanning electron microscope) used to show an example of the convex portion of the surface of the immersion plating layer that is flattened by quenching and tempering. )image. Fig. 2 is a diagram showing an example of the apparatus for measuring the coefficient of friction. Fig. 3 is a diagram showing an example of the shape of the bead for measuring the coefficient of friction. Fig. 4 is a diagram showing another example of the shape of the bead for measuring the coefficient of friction. Fig. 5 is a diagram showing an example of an oxide layer forming processing apparatus.

\\ 312 \ 2d-code \ 90-04 \ 90101265.ptcl Page 56

Claims (1)

1239357 Scope of patent application Hot line, formation of compound layer. For example, the manufacturing method of Figure 1Q in the patent section of the Qing dynasty, one of the alloyed molten hot-dip galvanized steel sheets is subjected to gas-filling. The contact is formed by contacting the aqueous solution containing the oxidant, and the formation of the butyl emulsion layer. . Promote 18 · If the method of patent application, in the bean, the alloyed hot-dip galvanized steel sheet is treated for easy entry; in oxide J: dry place immediately after contact with water 19 such as by ^ Formation of $ layer. 9 • Manufacturing method as claimed in Patent Scope ，, beans φ _, alloys 仫 molten hot-dip zinc steel sheet α · For manufacturing methods on patent scope 篦, beans, I,-q M alloying and melting Dry treatment of hot-dip galvanized steel sheet. After the contact with water for more than 3 times, immediately carry out .t ^ ^ ^ ^ ^ ^ ^ ^ drying treatment. The manufacturing method is carried out immediately after hard contact with water for more than 3 times, wherein the formation of an oxide layer is performed on a junction of a biochemical fused hot-dip galvanized steel sheet. Go ahead first, go ahead 23. If you apply for the manufacturing method in the scope of patent application No. 22, where acidic dissolving: of: dichemical? Hot-galvanized steel sheet over 50 t. The pH value of the combined liquid is above 1 and the temperature is 24. As in the manufacturing method in the scope of patent application No. 22, wherein each member of the steel plate has a single surface of 3.0 g / m2 or less. Inside 1239357 VI. Scope of patent application 2 5 · The manufacturing method of alloyed hot-dip galvanized steel sheet as described in item 22 of the patent application scope, in which the water is washed with warm water above 50 ° C. 26. The method for manufacturing an alloyed hot-dip galvanized steel sheet according to item 22 of the scope of the patent application, wherein after being contacted with an acidic solution, it is left for 1 · 0 ~ 30.0 seconds, and then washed with water. System · Shishen. The method for manufacturing an alloyed molten hot-dip galvanized steel sheet according to item 25 of the monthly patent “wherein, after washing with water, a neutralization treatment is performed. 28. For example, the method of alloying and melting, Shengshi, t, Ganshan, etc. of the scope of application for patent No. 22, and the galvanized steel sheet coating method, in which the acid solution contains Fe (iron) is / + 7η ( Zinc ions. ν iron) and / or Zη 2 9 · The method of alloying melting according to item 28 of the patent application, wherein, in g containing Fe and / or Zη ions, 2. containing Fe and / or Z η Sulfate, nitrate, H 2 or more. 1 of 1 dagger or \\ 312 \ 2d-code \ 90-04 \ 90101265.ptd Page 60