TW495559B - Coated steel material having corrosion resistance and improved workability and a method for producing the same - Google Patents

Abstract

This invention relates to coated steel materials having corrosion resistance and improved workability used for structures, bank protection works, fishing nets, fences which are exposed outdoors, and a method for producing the coated steel materials. The present inventive coated steel materials having a coating layer comprising; in terms of wt%, Al: 4 to 20%, Mg: 0.8 to 5%, Fe: less than 2%, and the remainder Zn and unavoidable impurities, and having an alloying layer comprising Fe-Zn-Al-Mg of a thickness of less than 20 μm between the coating layer and the base steel. Furthermore, the present inventive coated steel materials having a coating layer comprising; in terms of wt%, Al: 4 to 20%, Mg: 0.8 to 5%, Si: 0.01 to 2%, Fe: less than 2%, and the remainder Zn and unavoidable impurities, and containing dispersed Mg2Si in the coating layer, and having an inner alloying layer comprising Fe-Zn-Al-Mg-Si of a thickness of less than 5 μm and an outer alloying layer comprising Fe-Zn-Al-Mg-Si of a thickness of less than 30 μm between the coating layer and the base steel. The above coating layer optionally contains one or more elements selected from the group consisting of a, b, c, d. a: one or more of Ti, Li, Be, Na, K, Ca, Cu, La, Hf in an amount of 0.01 to 1.0%; b: one or more of Mo, W, Nb, Ta in an amount of 0.01 to 0.2%; c: one or more of Pb, Bi in an amount of 0.01 to 0.2%; d: one or more of Sr, V, Cr, Mn, Sn in an amount of 0.01 to 0.5%.

Description

495559

The present invention relates to a plated steel and a method for manufacturing the same. The present invention relates to the survivability of steel materials exposed outside buildings, embankments, fishnets, and fences, and their manufacturing methods. Improved workability. The plated steel is plated steel wire such as iron wire for gold mesh, fiber for concrete reinforcement, bridge wire, pWS wire, PC steel wire, ROPE, etc., structural steel for H-beams, steel plates, screws, Mechanical parts for screw cups, springs, steel products such as steel plates. Qianshi steel, especially plated steel wire, uses galvanized steel wire and zinc-aluminum alloy plated steel wire which is superior in corrosion resistance to the galvanized steel. The zinc-aluminum alloy plated steel wire is generally manufactured by the following methods, that is, cleaning and degreasing the steel wire by washing, degreasing, etc., and then performing FLUX treatment, and then implementing zinc as the main body in the first stage. Melt plating, and then in the second stage, use Zn—A1 alloy bath with 10% A1 addition amount to perform molten plating, or directly use 211-18 alloy bath with 10% A1 addition amount, followed by plating The bath is pulled up vertically, and the coiler is wound after cooling. The zinc-aluminum alloy plated steel wire has good corrosion resistance, but in order to further improve its corrosion resistance, a method of increasing the plating thickness is adopted. One method to ensure the required plating thickness is to increase the moving speed (wire speed) of the steel wire. 'The steel wire is pulled out of the ore bath at two speeds, and the viscosity of the plating alloy is dissolved to increase the The amount of plating alloy attached to the steel wire. However, in this method, due to the high speed, unevenness in the thickness of the ore deposits is prone to occur on the section along the length of the plated steel line at right angles, which has its limits on the plating equipment. Therefore, with the current galvanization of the plating equipment and the fusion plating by Zn-A1 alloy, the corrosion resistance is hardly sufficient. Under the circumstances that the demand for the longevity of the plated steel wire is increasing, there are The problem of not being able to fully meet this demand exists. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) 丨 .Ί. ------- Order --------- Line contention «(Please read the note on the back first (Fill in this page again) 4 495559 A7

%% Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (2) In order to solve this problem, the Zn-Al-Mg alloy-based plating composition system in which Mg is added to the plating bath to improve corrosion resistance is disclosed at Japanese Patent Publication No. 10-226865. The plating method based on this plating composition is based on the premise of thin plating for steel plates, and the method is used for thick plating steel wires mainly exposed to steel wires used outdoors such as buildings, embankments, fishnets, fences, etc. , There is a problem of cracking in the ore coating during the processing of the plated steel wire. Furthermore, Japanese Patent Application Laid-Open No. 7-2 07421 discloses a method for thickening a Zn-Al-Mg alloy ore deposit. However, when this method is used for the ore deposit of a steel wire in its original state, Fe- The Zn alloy layer becomes thicker, and problems such as cracking and peeling of the alloy layer during plating steel wire processing occur. The present invention has been made in view of the various problems described above, and aims at providing a plated steel material provided with molten zinc alloy plating and a manufacturing method thereof. In particular, a plated steel wire has excellent corrosion resistance and is processed in the plated steel wire. In this case, the plated layer and / or the plated alloy layer are excellent in workability without causing cracking and peeling, and a method for manufacturing the same. The present inventors have conducted various reviews on methods that can solve the above-mentioned problems, and as a result, have completed the present inventors. The outline is as follows. (1) A money-applied steel with southern surname resistance and excellent processability, characterized in that the plated steel has an alloy layer with a thickness of 20 μm or less at the interface between the plating layer and the iron, and the alloy layer system Contained: In terms of mass%, Fe: 25% or less, A1: 30% or less, Mg ·· 5% or less, and the remainder Zn. (2) —A kind of plated steel with high corrosion resistance and excellent processability, which is characterized in that: The plated steel has a paper size on the interface between the plating layer and the iron, which is applicable to the Chinese National Standard (CNS) A4 specifications (21〇X 297 public love) ^ ---- I --- Order --------- (Please read the notes on the back before filling out this page} 495559 A7 A B7 V. Description of the invention (3) An alloy layer having a degree of 20 μm or less, the alloy layer contains: when expressed in mass%, Fe: 25% or less, A1: 30% or less, Mg: 5% or less, and the remaining Zn; and the foregoing alloy layer The upper system has a plating layer, and when its average composition is expressed in mass%, it contains A1: 4-20%, Mg: 0.8-5%, Fe: 2% or less, and the remaining portion of Zn. (3)-species A key-coated steel with high remanence and excellent workability is characterized in that the plated steel has an inner layer of an alloy of 5 μm or less and an outer layer of an alloy of 30 μm or less at the interface between the plating layer and the iron. Alloy layer, the alloy inner layer contains: when expressed in mass%, Fe: 15% or more, A1: 20% or more, Si: 2% or more, Mg: 5% or more And the remaining part of Zn; the alloy outer layer contains: when expressed in mass%, Fe: 25% or less, A1: 30% or less, Si: 2% or more, Mg: 5% or less, and the remaining Zn. Printed by the Consumer Cooperative of the Ministry of Intellectual Property Bureau (4) A plated steel with high corrosion resistance and excellent processability, characterized in that the plated steel has a thickness of 5 μm or less on the plating layer-quality iron interface. An alloy layer composed of an alloy inner layer and an alloy outer layer having a thickness of 30 μτη or less. The alloy inner layer contains, when expressed in mass%, Fe: 15 0/0 or more, A1: 20% or more, Si: 2% or more, Mg: 5% or less, and the remaining portion 211; the outer layer of the alloy contains:? 6: 25% or less, 8: 30/0 or less, Si: 2% or more, Mg: 5% or less, and the remaining portion of Zn And the above-mentioned alloy has a plating layer on the outer layer, and when its average composition is expressed in mass%, it contains A1: 4-20%, Mg: 0.8-5%, Si: 〇.〇1_2%, Fe: 2 % And the remaining part of Zn, there are those dispersed Mg2Si in the plating layer. This paper size is applicable to China National Standard (CNS) A 4 Specifications (210 X 297 public love) 495559 • A7 ____B7 5. Description of the invention (4

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (5) The key-coated steel with Nancai's surname and excellent processability as described in item 2 above, characterized in that the solidified structure of the plating layer is a granular crystal structure Or columnar crystal structure. (6) The plated steel with high corrosion resistance and excellent workability as described in item 2 or 4 above, characterized in that: each of the plating layer structure has an α phase containing A1_Zn as a main component, and Zn or The cold phase composed of the Mg-Zn alloy layer and the Zn-Al-Mg ternary eutectic phase exist. (7) The mineralized steel with high surname resistance and excellent processability according to item 6 above, characterized in that the volume fraction of the stone phase existing in the structure of the plating layer is 20% or less. (8) The plated steel with high corrosion resistance and excellent workability as described in item 2 or 4 above, wherein the plating layer comprises one or more of the following groups a, b, c, and d One or more elements in the group; a: each containing one or most elements of Ti, Li, Be, Na, K, Ca, Cu, La, Hf 0.01-1.0% by mass; 1 >: each containing] \ 4 〇, Boundary, > ^, D 3 or one or more elements 0.01-0.2% by mass; c: each containing Pb, Bi or one or most elements 〇〇〇〇_2 · 2% by mass; d: each contains One or most of Sr, V, Cr, Mn, and Sn are 0.01 to 0% by mass. (9) The plated steel with high corrosion resistance and excellent workability as in any one of the above items 1 to 8, characterized in that the plating layer is formed with one of a coating coating and a heavy-resistance coating Covered. (10) Coating 5 with high corrosion resistance and excellent processability as in item 9 above ^ ----------------- (Please read the precautions on the back before filling (This page) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 public love) ----- 7 495559 A7 --------- B7 V. Description of the invention (5) Laminating steel It is characterized in that the heavy-duty coating is a polymer compound selected from at least one kind of vinyl chloride, polyethylene, polyurea, and fluororesin. (11) The plated steel with high corrosion resistance and excellent workability as in any one of the above items 1 to 10, wherein the plated steel is a plated steel wire. (12) — A method for manufacturing a plated steel material with high corrosion resistance and excellent workability, characterized in that the steel material is implemented in the first stage to contain A1: 3% or less and Mg: 0.5% The following molten zinc plating is then carried out in the second stage. The average composition includes A1: 4-20% when expressed in mass%, Mg: 0.8-5%, Fe: 2% or less, and the remainder of Zn. "Plating" is formed on the interface between the mineral deposit and the ferrous iron. The thickness of Fe is 25% or less, A1 is 30% or less, Mg is 5% or less, and the remaining portion of Zn is formed at a thickness of 20 μm or less. The alloy layer is then further cooled at a cooling rate of 300 ° C / sec or less, so that the solidified structure of the plating layer forms a granular crystal structure, or cooled at a cooling rate of 300 ° c / sec or more, so that the plating layer The solidified structure forms a columnar crystal structure. Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (13) — A method for manufacturing plated steel with high corrosion resistance and excellent processability, which is characterized in that the first phase A1: Fused zinc plating of 3% or less and Mg: 0.5% or less. Next, the average composition is carried out in the second stage. The average composition includes A1: 4-20%, Mg: 0.8-5%, Si: 0.01-2%, Fe: 2% or less and the remaining portion of Zn is a molten alloy ore deposit, and is formed on the plating layer-quality iron interface via Fe: 15% or more when expressed in mass%, A1: 20% or more , Si: 2% or more, Mg: 5% or less and the thickness of the remaining part 211 and the thickness This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy 495559 Α7 Β7 V. Description of the invention (6) Inner layer of alloy below 5μηι, and Fe: 25% or more, A1: 30% or less ", Si: 2% or more, Mg: 5% or less and the remaining part made of Zn and the thickness • Alloy layer made of alloy outer layer below 30μπι, and then further at 300 ° C Cooling at a cooling rate of less than / sec to make the solidified structure of the plating layer form a granular crystal structure, or cooling at a cooling rate of 300 ° C / sec or more to form a columnar crystal structure of the solidified structure of the plating layer . (14) The method for manufacturing a plated steel material with high corrosion resistance and excellent processability as described in item 12 or 13 above, characterized in that the second phase of the molten gold deposit includes the following a, One or more elements in one or more of the b, c, and d groups; a: Each containing one or most of the elements Ti, Li, Be, Na, K, Ca, Cu, La, Hf 0.01-1 0% by mass; b: each containing one or most elements of Mo, W, Nb, and Ta 0.01-0.2% by mass; c: each containing one or most elements of Pb, Bi 〇〇〇_ 〇 2 mass 〇 / 0; _ (1: each containing 31- ¥, (^,] ^ 11, 811 or most of the elements 0.01-0.5 _ mass%. (15) If the scope of patent application is 12 or 13 The method for manufacturing key-coated steel with high surname resistance and excellent processability is characterized in that: the first-stage molten zinc plating is performed with a plating immersion time of less than 20 seconds, and secondly, the aforementioned second The molten zinc alloy plating at the stage is to perform a plating immersion time of less than 20 seconds, and the part of the mineralized steel drawn from the first and second stage money deposit baths is cleaned with nitrogen, and Prevent the oxidation of the surface of the plating bath and the mineralized steel. The paper size is based on the family standard (CNS) A4 specification (21 公 χ 297 public love) "--9----------- ----------- ^ --------- ^ (Please read the notes on the back before filling this page) 495559 A7 ____B7 _______ V. Description of the invention (7) (16) If The method for manufacturing a plated steel material with high corrosion resistance and excellent processability according to item 12 or 13 above, characterized in that the molten alloy zinc plating is performed in the second stage, and after the plated steel material is pulled out of the plating bath, , Immediately cooling by one of the f water, air water spray or water flow, so that the alloy is solidified. (17) Manufacture of forged steel with high corrosion resistance and excellent workability as described in item 12 or 13 above. Method 'characterized in that the cooling start temperature of the aforementioned key-coated steel material during cooling is set to the melting point of the plating alloy + 20 t or less. (18) Local residual resistance and excellent processing as described in item 12 or 17 above. A method for producing a flexible plated steel material is characterized in that the plated steel material is a plated steel wire. Brief Description of Drawings Figure 1 (a) shows The invention is a plating structure to which Fe-Zn-Al-Mg alloy plating is applied, and Fig. 1 (b) shows the plating structure to which Fe-Zn-Al-Mg-Si alloy plating is applied according to the present invention. Fig. 2 is a diagram showing the relationship between the thickness of the outer layer of the plating alloy and the number of cracks in the winding test when the Fe-Zn-Al-Mg-Si alloy plating is applied according to the present invention. Fig. 3 (a) is used to show the plating Diagrams of the plating structure with columnar crystal structure in the coated steel wire; Figures 3 (b) and 3 (c) show the plating structure with granular crystal structure in the plated steel wire; Section 3 (d) The figure shows a plating layer having a granular crystal structure with an alloy layer of an inner layer and an outer layer of Fig. 1 (b). Figure 4 is for the size of coated paper coated with Fe-Zn-Al-Mg_ (Si) alloy. Applicable to China National Standard (CNS) A4 (2) 0 X 297 mm. (Please read the back first Please pay attention to this page before filling in this page) Order --------- 'Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 10 495559 V. Description of the invention (8 steel-covered wire, by number) Have you compared the surface cracks during the winding test (% Description of the symbols in the printed figure of the employee's consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1 ... · Quality iron 2 ···· Inner alloy layer 3 ···· Inner alloy layer 4 · ... Alloy Outer layer 5. The plated layer is used to implement the best form of the present invention. The plated steel wire of the present invention, in which the average composition of the plated layer is expressed in mass%, contains A1: 4_2% , Mg: 0.8%, 5% or less: 2% or less, and the remaining portion 211, and further, an alloy layer having a thickness of 20 μm or less is provided on the aforementioned plating layer_quality iron interface, and the alloy layer contains: When expressed in%, Fe: 25% or less, A1 · 30% or less, Mg: 5% or less, and the remaining portion of Zn, and the present invention In the plated steel wire, an alloy layer having a thickness of 20 μm or less is provided at the interface between the plating layer and the ferrous iron. The alloy layer contains Fe: 25% or less, A1: 30% or less when expressed in mass%, Mg: 5% or less and the remaining 211. In addition, the average composition of the plating layer is in addition to A1: 4-20%, Mg: 0.8-5%, and Fe: 2% or less when expressed in terms of mass%. It can be formed by adding one or more of the elements for improving the corrosion resistance, the element for increasing the hardness of the plating, the element for refining the plating structure, and the element for improving the plating processability, and the remaining part of Zn. The plated steel according to the present invention The average composition of the line contains ... The average composition of this paper applies the Chinese National Standard (CNS) A4 specification (210 X 297 public love) at this paper scale. M -------- Order --------- (Please read the precautions on the back before filling this page) 11 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 495559 A7 -----___ V. Description of the invention (9) Except for A1: 4_20% , Mg: 〇8_5%, Si: 〇〇1_2%, Fe · 2% or less, can also add elements to improve corrosion resistance, plating hardness of South One or more elements of the bonding structure micronization element and the plating processability improving element are formed with the remaining part of Zn and have a plating layer in which MgzSi is dispersed in the layer, and the plating layer -An alloy layer composed of an inner alloy layer having a thickness of 5 μm or less and an outer alloy layer having a thickness of 30 μm or less is provided on the interface of the ferrous iron, and the inner layer of the alloy contains: when expressed in mass%, Fe: 15% or more, A1: 20 % Or more, Si: 2% or more, Mg: 5% or less, and the remainder of Zn; the alloy outer layer contains: when expressed in mass%, Fe: 20% or less, A1: 30% or less, Si ·· 2% Above, Mg: 5% or less, and the remainder zn. First, the role and content of the plating layer and the alloying elements used to form the plating layer-quality iron interface will be described. An alloy layer mainly composed of Fe-Zn is formed on the interface of the mirror coating layer and the quality iron. Strictly speaking, the structure of the Fe-Zn alloy layer is an alloy layer composed of ^: 25% or less, A1: 30% or less, Mg: 5% or less, and the remaining portion of Zn when expressed in mass%. Its thickness is 20 μηχ or less. Moreover, in the steel-coated steel wire according to the present invention, an alloy layer composed of Mg-Si is formed on the above-mentioned plating layer-quality iron interface, and the alloy layer is an inner layer of an alloy having a thickness of 5 μm or less (No. 3 in the figure). And, an alloy layer composed of an outer alloy layer (No. 4 in the figure) having a thickness of 30 μm or less, the inner layer of the alloy contains: when expressed in mass%, Fe: 15% or more, A1: 20% or more, and Si: 2% or more , Mg: less than 50 / 〇 'and the rest of Zn; the outer layer of the alloy contains: when expressed in mass%, Fe: 25% or less, A1: 30% or less, Si: 2% or more, Mg ·· I paper Standards: Standards in the Compensator (〇sjs) A4 (21ϋ X 297 public love) '" "--12-(Please read the precautions on the back before filling this page) -— II — I ϋ ϋ ϋ · I ϋ I Βϋ emf I # Printed clothing for employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 495559 A7 B7 V. Description of the invention (10) Less than 5% and the remaining part of Zn. First, an alloy layer composed of Fe-Zn-Al-Mg will be described. As shown in Fig. 1 (a), an Fe-Zn alloy layer 2 is formed on the interface between the plating layer 5 and the iron 1. The Fe-Zn alloy layer has the function of connecting the bond to the high-quality iron, which can be attached to the plating. At the same time, the high-quality iron can absorb the plating alloy when it is deformed by elastic deformation or plastic deformation. The difference from the deformation rate caused by the difference in elasticity or deformation resistance of the quality iron can prevent the plating and coating from peeling. On the other hand, the Fe-Zn alloy layer system is brittle. When Fe exceeds 25%, the alloy layer cracks during processing, causing plating peeling, so the upper limit is 25%. The optimal amount of Fe is 2-25%. When A1 is present in the alloy layer, the alloy layer can obtain ductility, but when it exceeds 30%, a hardening phase occurs and the workability is reduced, so the upper limit is 30%. The best addition of A1 is 2-30%. Mg has the effect of improving the corrosion resistance of the alloy layer, and at the same time, it causes embrittlement of the alloy layer. Therefore, the upper limit without causing embrittlement is 5%, and the upper limit is 5%. When the alloy layer is very thick, the alloy layer is cracked, and the interface between the alloy B layer and the ferrous iron or the alloy layer and the plating interface is easily cracked. When the thickness of the plating alloy layer exceeds 20 μτη, the number of cracks increases, which makes the interface easy to crack. For the plating, it cannot bear it on the practical side. The alloy layer is originally inferior to the corrosion resistance, so it is better to have a smaller thickness, preferably 10 μm or less, especially 3 μm or less. From the above reasons, it is understood that the upper limit of the thickness of the alloy layer above the non-destructive workability is 20 µm, and therefore the thickness of the Fe_Zn alloy layer is 20 µm or less. In the present invention, the inner and outer layers of the alloy layer when Si is contained in the alloy layer will be described. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ------------- Installation -------- Order -------- -Line (Please read the precautions on the back before filling this page) 13 495559 A7 B7 Printed by the Consumers' Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of invention (11) When the alloy layer contains Si, as shown in Figure 1 (b) As shown, the structure of the alloy layer formed on the interface between the plating layer 5 and the iron 1 has a different alloy composition and structure from that of the alloy layer, and there are thin layers with a thickness of about 5 μm or less (inner alloy layer: 1 (b) (3), and it is found that the steel wire with the thin layer has extremely excellent corrosion resistance compared with the steel wire without the thin layer. The reason that the existence of the aforementioned alloy inner layer can greatly improve the corrosion resistance is that although it is not clear at present, it can be speculated that the layer has a function of blocking the progress of corrosion. The thickness of the aforementioned alloy inner layer is less than 5 μm. A thickness of more than 5 μm hinders the adhesion between the high-quality iron and the alloy layer on the outside, and reduces the workability of the plated steel wire. In addition, the thickness of the above-mentioned alloy inner layer is in order to obtain a desired corrosion resistance, and it is preferably at least 0.05 μm. The Mg of the aforementioned alloy inner layer is the same as that of Mg in the plating layer, and is set to 5% or less. In the alloy inner layer, when Fe is less than 15%, Ai20% is less than, or Si 2% is less, Increasing the content of any element will cause phase separation, the alloy layer cannot be stable, and the desired corrosion resistance cannot be obtained. Therefore, in the above alloy inner layer, Fe, Al, and Si must contain Fe: 15% or more, A1: 20% or more, Si: 2% or more. Next, the outer alloy layer (No. 4 in 1 (b)) is formed on the outer side of the inner layer of the alloy and is expressed by mass%. Fe: 25% or less, A1: 30% or less, Si: 2% or more, Mg : 5% or less, and the remaining part of Zn, and the thickness of 30μm or less. The above alloy outer layer is formed by mixing several alloy structures. It is brittle. When Fe— exceeds 25%, the alloy outer layer cracks during processing, causing plating peeling ---------- (Please read the back first (Please note this page before filling out this page) Order --------- Line Thai 14 9 5

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ________B7__ Invention Description (l2) ’Therefore, the upper limit of Fe is 25%. The optimal amount of Fe is 2-20%. When A1 is present in the outer layer of the alloy, ductility can be imparted to the outer layer of the alloy. When A1 is more than 30%, a hardened phase occurs and the workability is reduced, so the upper limit of 丨 is 30%. The optimal amount of A1 is 2-25%. In the above-mentioned alloy outer layer, when Si is less than 2%, the desired corrosion resistance cannot be achieved, so Si is 2% or more. However, when there is too much Si, the alloy outer layer tends to harden and become brittle. Therefore, the Si content is preferably about 15% or less.

Mg has the effect of improving the corrosion resistance of the alloy layer, and also causes embrittlement. Therefore, the upper limit of Mg is 50/0 which does not cause an embrittlement upper limit. The optimal amount of Mg is 0.5-5%. When the outer layer of the alloy is very thick, the alloy layer will be cracked, or the interface between the alloy layer and the ferrous iron or the alloy layer and the plating interface will be easily cracked. Figure 2 shows the following relationship. In the form of zn-11% A1-l% Mg-0.1% Si alloy, the relationship between the thickness of the outer layer of the alloy and the cracks (number) during the winding test is used to show the relationship of the outer layer of the alloy. Plating adhesion. As can be seen from the second figure, when the thickness of the outer layer of the alloy exceeds 30 μη ^^, the number of cracks increases remarkably, making it unsuitable for practical use during plating. The corrosion resistance of the outer layer of the alloy is originally inferior to that of the plated layer. Therefore, it is desirable that the thickness of the outer layer is thinner, preferably 15 µm or less, and particularly preferably 5 µx or less. Ideally, it is preferable that the outer layer of the alloy is absent. For the above reasons, the upper limit of the thickness of the alloy outer layer and the non-destructive workability is 30 µm. Therefore, the thickness of the Fe-A1-Si-Zη alloy outer layer is set to 3 or less than 111. Secondly, according to the role and content of alloying elements in the plating layer, the paper size is applicable to the Chinese National Standard (CNS) A4 specification (21G X 297 public love) ^ -------- ^ ---- ----- (Please read the notes on the back before filling out this page) -15 495559 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (l3). A1 can improve the corrosion resistance or prevent the oxidation of another element in the plating layer, but when it is added to less than 4%, the effect of preventing the oxidation of Mg in the plating bath cannot be obtained. In addition, when more than 20% is added, the formed plating layer becomes hard and brittle, making processing impossible. Therefore, the range of the amount of A1 added to the plating layer is set to 4.20%. When the steel wire is plated, it is preferably 9-14% for thick coating. Within this range, a stable plating layer can be obtained.

Mg has the effect of uniformly generating the corrosion products of the plating. For corrosion products containing Mg, it can hinder the progress of corrosion. Therefore, Mg has the effect of improving the corrosion resistance of the plating alloy. However, when the addition is less than 0.8%, the effect of improving the corrosion resistance cannot be obtained. On the other hand, when the addition is more than 5%, it is easy to generate oxides on the surface of the plating bath, and a large amount of scum occurs, making the plating operation difficult. . In order to balance the corrosion resistance and the amount of scum generation, the range of the Mg addition amount is 0.8-5%.

Fe is in the form of being precipitated from steel during plating or in the form of impurities and being present in plated texture metal. However, if it exceeds 2%, the corrosion resistance will be lowered. Therefore, the upper limit is set to 2%. In addition, the lower limit of the Fe addition amount is not particularly limited, and Fe may not be added depending on the circumstances.

Si is an element that is added to the plating layer to generate Mg:? Si, and to improve corrosion resistance. The size of Mgji is about the same, and it is evenly and finely dispersed in the plating layer, which can increase the corrosion resistance. When the content is less than 0.01%, Mg2Si cannot be generated in an amount sufficient to improve the corrosion resistance, and the desired effect of improving the resistance cannot be obtained. The more Si can be added in A1 and the paper size applies the Chinese National Standard (CNS) A4 specification (210x297 public love) —.1 A ------- ^ --------- (Please (Please read the notes on the back before filling this page) 16 495559 A7 Description of Invention (M) The more effective it is, the maximum amount of Si added is 2% when A1 is added to A2G%. Therefore, the amount of Si added is in the range of 001_2%. In addition, in the present invention, in addition to A1, Mg described above, one or more quaternions selected from the following groups a, b, c, and d may be contained. a: each containing one or most of Ti, Li, Be, Na, K, Ca, Cu, La, Hf 0. 0M. 0 mass 0/0;

b: each containing one or most of Mo, W, Nb, Ta, or 0.001% by mass; c: each containing one or most of Pb, Bi, or most of the element, 〇1_〇2 mass 0 / 〇; d: each of which contains one or most of Sr, V, Cr, Mn, and Sn is 0.0015% by mass. Threading Ti has the effect of improving the corrosion resistance. The elements with the same effect are Li, Be, Na, K, Ca, Cu'La, and Hf. By adding 0.01 to 0.5 mass% of one or more of these elements, the corrosion resistance can be improved. If it is less than 0.001%, the effect cannot be exhibited, and when it exceeds 1.0%, there is a possibility that phase separation may occur when the plating is solidified. Therefore, the range is in the range of 0.001-0050 / 〇 . It has the effect of increasing the hardness of the plating layer and being difficult to damage. The elements having the same effect are W, Nb, and Ta. By adding one or most of the elements in the range of 0.01-0.2% by mass, the plating layer can be improved. Hard and difficult to damage.

Pb and Bι have the effect of crystallizing the plating surface into a fine state. On a plated steel such as a plate or shaped steel with a large plated surface, the plated alloy greatly grows on the plated surface, so that the appearance can be seen. In order to avoid this phenomenon ', Pb or Bi that is not solid-solved with Zn and Fe can be added. During the plating, solidified nuclei are formed to promote the growth of fine crystals without appearance. The paper size can be obtained according to CNS A4 specification (21 · ό · x 297 Public Love -17-495559 A7 B7 V. Description of the invention (15) The scope of this effect lies in 〇e〇le〇. 2 mass 0/0.

Sr, V, Cr, Mn, and Sn are effective in improving workability. However, if it is less than 0.01%, the effect cannot be displayed. On the other hand, if it is more than 5%, segregation is noticeable and cracking is easy to occur when processing plated steel. Therefore, it is within the range of 0.01-0.5%. An alloy layer mainly composed of Fe-Zn is formed on the interface of the first layer of iron in the bell layer. Strictly speaking, the structure of the Fe-Zn alloy layer is an alloy layer composed of Fe: 25% or less, A1: 30% or less, Mg: 5% or less and the remainder when expressed in mass%, and its thickness is within 20μπι or less. The Fe_Zn alloy layer is brittle. When Fe exceeds 25%, the alloy layer will crack during processing and cause plating to peel off. Therefore, the upper limit is set to 25%. The optimal amount of Fe added is 2-25%. The presence of A1 in this alloy layer can make the alloy layer ductile, but when it exceeds 30%, a hardening phase occurs and the workability is reduced, so the upper limit is set to 300/0. The best addition of A1 is 2-30%. Although Mg has the effect of improving the corrosion resistance of the alloy layer, it also causes embrittlement of the alloy layer. Therefore, the upper limit without causing embrittlement is 5%, and 5% is set as the upper limit. The optimal amount of Mg is 0.5-5%. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Furthermore, in the plated steel of the present invention, A1 and Mg are used as the main component 'so it is cooled after forging'. Phases formed by a single phase of Zη or an Mg-Zn alloy layer, and a ternary eutectic phase of zn / Al / Zn-Mg coexist in a plating alloy layer outside the alloy layer existing at the money-quality iron interface ( Plating)). Among them, by the existence of the Zn / Al / Zn-Mg ternary eutectic phase, the uniform formation of corrosion products and the effect of preventing corrosion progress of corrosion products can be obtained. In addition, the / 3 series is compared with others. The paper size is in accordance with the Chinese National Standard (CNS) A4 specification (210 X 297 mm). 18 495559 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention It shows that (16) is poor, and it is easy to cause partial corruption. In addition, if the volume ratio of the / 3 phase exceeds 20%, the corrosion resistance will decrease, so the volume ratio is set to 20% or less. In the present invention, a cooling treatment is performed after plating, and the cooling may be performed by slow cooling or rapid cooling. That is, in the form of slow cooling, the plated solidified structure forms a granular crystal structure, and when rapidly cooled, the structure forms a columnar crystal structure. If it is a plated steel material that requires both corrosion resistance and workability, the solidified structure is preferably a granular crystal structure. Even if a small amount of workability is sacrificed, a columnar crystal structure can be formed when only the residual resistance is required. The aforementioned cooling rate is preferably in the range of 100-400 ° C / sec. The purpose of crystallizing the solidified structure of the plated layer is to add not only the residual resistance to the mineralized steel but also the workability. After the granular crystal structure is subjected to molten zinc plating, further molten zinc alloy plating treatment is performed, followed by cooling treatment at a cooling rate of 300 ° C / sec or less, and the solidified structure of the plating layer can be obtained. Grained crystallizers. The purpose of crystallizing the solidified structure of the plated layer into a columnar shape is to provide corrosion resistance to the plated steel. The columnar crystal structure is subjected to molten zinc plating, and then further subjected to molten zinc alloy plating treatment, followed by cooling treatment at a cooling rate of 300 ° C / sec or more, so that the solidified structure of the plating layer can be obtained. Columnar crystallizers. -Figure 3 is a schematic diagram showing the structure of the mineral deposit. The bonding cooling rates are (a) 350 ° C / sec; (b), (c) 150 ° C / sec. Fig. 1 (a) shows the solidified structure of the columnar crystal money coating. During the solidification, similar fine-grained grains were generated between the developed dendritic structures. The solidified structure of the mineral coating obtained by the present invention in Fig. 3 (a) is the solidified structure of the columnar crystal plated coating. At the time of solidification, the Chinese national standard (CNS) A4 specification (Q χ tear public love) applies to this paper scale. --------------------- Order ------- --Line (please read the ii idea on the back before filling this page) 19 495559 A7 B7

I. Explanation of the invention (There is a fine granular crystal structure between the well-developed dendritic structure. Due to the discontinuity of the structure due to the thinning of the structure and the low corrosion resistance, it is difficult to start the corrosion from the surface layer, and its corrosion resistance is high. Figures 3 (b) and 3 (C) show a granular crystal structure. The solidified structure of the plating layer obtained by the present invention shown in Figures 3 (b) and 3 (c) shows a completely granular crystal structure. In the form of a coated steel wire, when the strength reduction is more than 60% during wire drawing, the granular soft tissue can be stretched between columnar hard tissues, so no cracks occur. Figure 3 (d) shows that if the alloy layer contains a morphology with a cooling rate of 15 ° C / sec, the inner and outer layers of the alloy layer show a granular crystal structure. The manufacturing method for manufacturing the plated steel of the present invention is a two-stage plating method. In the first stage, molten zinc plating with zinc as the main body is applied to form a Fe-Zn alloy layer, and then the second stage is applied. It can be efficiently plated with molten zinc alloy having an average composition prescribed by the present invention The plated steel of the present invention is obtained. In the first stage, the zinc used in molten zinc plating can be pure Zn, or a small amount of rare earth metal can be added to Zn for the purpose of preventing oxidation of the plating bath or improving fluidity. For alloy baths mainly containing zinc, Si, Pb, etc., or for the growth of mineralized alloy layers, molten zinc alloys containing A1: 3% or less and Mg: 0.5% or less when expressed in mass% may also be used. When a Fe-Zn alloy layer is obtained by applying the first-stage molten zinc ore, when the Fe-Zn alloy layer contains Al and Mg, Al and Mg can be easily entered into the plating alloy. The manufacturing method of the coated steel sheet is to clean the part of the plated steel sheet drawn out from the plating bath by nitrogen to prevent oxidation of the surface of the plating bath and the plated steel sheet, thereby improving the workability. Oxidation is generated immediately after plating When the formed oxide is adhered to the surface of the plating bath, the Chinese National Standard (CNS) A4 specification (210 X 297 public love) applies to the paper size of the plating. 20 B7 B7

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (18)% The oxide is the core and the plating is cracked. Therefore, the oxidation prevention of the pull-out ^ becomes an important task. In order to prevent oxidation, in addition to nitrogen, inert gases such as argon and helium can be used. From the cost point of view, nitrogen is the best. Fig. 4 is a comparative winding test for the plated steel composition (Zn • Jump A!], Ζη-ιο% Α1 · 3% Μ ^ 0 · 1% Μ) of the plating alloy of the present invention, with or without gas interruption When the surface cracks (number). When the air supply is not interrupted, the number of cracks on the surface exceeds the allowable limit. When the plating steel is obtained by the two-stage plating method in the present invention, in order to properly grow the plating alloy, in the first stage, the molten zinc bond with zinc as the main body must be immersed in a plating bath for less than 20 seconds. Then, in the second stage, the molten zinc alloy boat was subjected to a bath immersion time of 20 seconds or less. This is because when the plating is performed for a long time, the alloy layer will be thicker than 20 μm. Therefore, it is necessary to perform a plating bath immersion time of less than 20 seconds in the zinc-based melt plating in the first stage. Next, in the second stage, the molten zinc alloy plating is performed for a bath immersion time of 20 seconds or less. The first stage is performed in a plating bath for 20 seconds or less. Even in the state where the alloy layer is growing, the thickness of the alloy layer in the second stage of molten zinc alloy plating is increased by the plating alloy immersion time for 20 seconds. In the following cases, it is rare, and the thickness of the alloy layer can be maintained below 20 μm. In the present invention, the specific cooling method for performing the cooling treatment after the plating treatment is to adopt the following method, that is, after the second stage of molten zinc alloy plating, the plated steel wire is subjected to the aforementioned molten zinc alloy plating bath After being pulled up, the air will be cut off by one of the methods of water spray, water spray, or water flow. The paper size applies the Chinese National Standard (CNS) A4 (210 X 297 mm) 21 (Please read the back first Note: Please fill in this page again.) 495559 A7 B7 V. Description of the invention (l9 tube's direct cooling 'to solidify the plating alloy, which should be sprayed with water or gas water spray' to make the cooling start temperature in the aforementioned cooling is greater than the plating alloy A melting point of 20 ° c 'can obtain a stable plating layer. Figure 1 shows the relationship between the presence or absence of air supply interruption by the aforementioned gas interrupter and the number of cracks in the coil or steel wire during the winding test. Using a plating bath of the same composition, and performing plating under the same conditions as the presence or absence of a gas-breaker, a coiling test was performed on the coated steel wire, and the number of cracks on the surface was compared. From the results, it can be seen that the gas-cut Significant effect. In addition, the composition of the plated steel used in the present invention is applicable to steels of low carbon steel, of which the representative is expressed by mass%, which is C: 0.02-0.25%, Si: 1% or less, Mn: 0.6% or less, P: 0.04% or less, S · 0.04% or less, the steel formed by the remaining Fe and unavoidable impurities is particularly preferred. Also in the present invention, at the end, Applying a coating coating on the surface of the plated steel wire, or applying a heavy-duty corrosion protection coating of a polymer compound coating of vaporized ethylene, polyethylene, polyurea, or fluororesin, can further improve the surname. 0 Ministry of Economic Affairs Printed by the Intellectual Property Bureau's Consumer Cooperatives The present invention is described with reference to mineral-coated steel, especially steel wires, and it goes without saying that it can be applied to steel plates and steel pipes up to steel structures. Examples < Example 1 > On the steel wire with a diameter of 4mm caliber coated with pure 211 on the surface of the steel wire JIS G 3505 SWRM6, Zn_A1_Mg -22-495559 printed on the conditions of the conditions shown in Table 1 printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 Five Note (20) is evaluated after zinc alloy plating. Comparative examples are similarly evaluated by changing the plating composition and the shape of the Fe-Zn alloy layer. All gas interrupters are used, and the internal gas interruption is used for flooding. Nitrogen and fluorine are used for cleaning. The observation of the plating structure is the C-section of the abrasive plating line, which is observed by EPMA. The composition analysis of the alloy layer is based on a quantitative analysis of the molecular beam diameter of 2 μm. The continuous salt water spraying is based on the weight difference before and after the test, and the amount of plating corrosion per unit area is the reduction of residue. In this test, a pass of less than 20 g / m2 is set to determine the pass or fail. The evaluation of the workability was performed by winding the plated wire around a 6-in.-caliber steel wire 6 times, and visually observing the surface, and judged with or without cracks. In addition, after the crack was judged, an adhesive tape was affixed to the sample, and the presence or absence of plating peeling at the time of tearing was observed. The condition is that the number of cracks is 1 or less and no peeling is acceptable. Table 1 shows the relationship between the plating composition, the composition and thickness of the alloy layer, the plating structure and the / 5 phase volume ratio, the residual resistance, the processability, and the scum formation in the mineral bath. Each of the embodiments of the present invention shows good corrosion resistance and workability, and few scums are formed. Comparative Examples 1 to 5 refer to those in which the composition of the plated alloy is outside the range prescribed by the present invention. In Comparative Examples 1 and 2, the amount of A1 or Mg was lower than the lower limit, and the corrosion resistance was poor. In Comparative Examples 3-5, the amount of A1 or Mg was higher than the upper limit, and the corrosion resistance was also poor. Comparative examples 6, 7 and 7 refer to those in which the thickness of the plated alloy layer is outside the range prescribed by the present invention, and results in which the workability is poor are obtained. Comparative Examples 8-10 refer to those in which the cold phase in the plating structure is outside the range of the present invention and the corrosion resistance is poor. This paper size is in accordance with Chinese National Standards (CNs) A4 (210 X 297 mm) ϋ n »ϋ ϋ n ϋ I nl ϋ ϋ I · n ϋ n II— II-σ4I ϋ an ϋ · ϋ I 11 I ( (Please read the notes on the back before filling out this page) 23 495559 A7B7 V. Description of the invention (21) 000000000000000000X00000000000000000000000000. 〇〇〇〇〇χ 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 〇 〇〇〇〇 B '—bo as a 〇m inch ^ -4 > nt ^ oo〇tnrfmO (N 〇o inch (N inch mm —— inch Orn xxxxx xxx 0/0 〇 b inch mm mmmi «« H 4 ^ -H f—Η V—4

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V. Description of the invention (22)

Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs <Example 2> The steel wire JIS G 3505 SWRM6 is coated with a pure 4 mm diameter steel wire on the surface of the steel wire, as shown in Tables 2 and 3. The conditions were evaluated after Zn-Al-Mg-based zinc alloy plating. The comparative example was modified in the composition of barley and the shape of the Fe-Zn alloy layer, and evaluated in the same manner. All of them were used gas blowers, and the interior of the gas blowers was purged with nitrogen. The observation of the plating structure is the C-section of the lapping line, which is observed by EPMA. The composition analysis of the alloy layer was carried out with a molecular beam diameter of 2 μm for quantitative analysis. Corrosion resistance is based on 250 hours of continuous salt water spray. The weight difference between before and after the test is calculated. In this test, a pass of less than 20 g / m2 is set to determine the pass or fail. The evaluation of processability was performed by winding the plated wire on a 6-mm-diameter steel wire 6 times after making it, and visually observing the surface to determine whether there were cracks. In addition, after the crack was judged, an adhesive tape was affixed to the sample, and the presence or absence of plating peeling at the time of tearing was observed. The condition is that the number of cracks is 1 or less and no peeling is acceptable. Tables 2 and 3 show the relationships between the composition of the ore deposit, the composition and thickness of the alloy layer, the plating structure and phase volume ratio, corrosion resistance, processability, and scum formation in the plating bath. Each of the examples of the present invention shows good corrosion resistance and workability, and few blemishes are generated. Comparative Examples 11 to 15 refer to those in which the composition of the plating alloy is outside the range prescribed by the present invention. The amounts of A1 or Mg in Comparative Examples 11 and 12 were lower than the lower limit, and the corrosion resistance was poor. In Comparative Examples 13-15, the amount of A1 or Mg was higher than the upper limit, and the corrosion resistance was also poor. Comparative Examples 6 and 7 refer to those in which the thickness of the plated alloy layer is outside the range specified in the present invention, and results in poor workability. Comparative Examples 18-20 refer to plated tissue. The paper size is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) ^ ----------------- ^ (Please Read the precautions on the back before filling this page) 25 495559 A7 B7 V. Description of the invention (Three of the / 3 phases in 23 are outside the scope of the present invention, and the corrosion resistance is 9 · inch ετι inch · inch eo- 9 · 6. Inch 'Inch · Ι- τ τ e-si1VO1CO%% ΰβΙΛΙ sound ^^

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Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. % 〇〇〇〇〇〇〇〇〇〇〇〇XXX 〇〇XX 〇〇〇εε) On »r &gt; 〇 inch 00 inch 00 U U &quot; i inch X 卜 (NX 00 inch X Ο Γ ^ X ir &gt; ΓΟ X inch ^ Η m '〇 inch X CN v〇X OO m X you 0 m m Cs Ό TH m VH CN Ψ &quot; ^ inch rH m r rH ν νο V—Η ΓΝ rH ON m CN VO CM m 饀 SXXX tm- ^ r &lt; mg mg mg tng mg &lt; &lt; mg ton mg mg ® S mg Μ, v? n |, 丨 1 '—,, 1 ”1,, 1, 丨 1' ^,,》 1 ,, 1, 1, 1, 1, 1 u |, 1 A 03. ~ € mg &lt; ®S &lt; &lt; nig tng-----N *-4 M: ε tn (N mf *-^ v〇v〇m inch α m tH VO (N m ON &lt; N »n (N tn (N m inch ο m 〇CN 〇ντ 1 (N (Ν inch 〇〇VO 00 〇o &lt; N 〇fH F—H CN inch fH vH bu00 ▼ -H CN ΓΟ inch V— ^ »T) ^ Η ν〇 卜 oo Os 〇 (N • 4 Yu Yu Road ♦ ^^ 3days / ^ 3:驷 飧 众 趄 -installation (please read the precautions on the back before filling in this page) Order · · · Thread · This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 27 495559 A7 B7

&lt; Example 3 &gt; This steel wire was subjected to Zn_Ai_Mg-based zinc alloy plating under the conditions shown in Table 丨 on a 4mm-diameter steel wire on which the surface of steel wire JIS G 3505 SWRM6 was subjected to pure 211 plating. Various characteristics. In the comparative example, the plating composition and the shape of the Fe-Zn alloy layer were changed, and they were evaluated in the same manner. The observation of the plating structure was a C-section of the abrasive plating line, and the observation was performed by EPMA. The analysis of the composition of the alloy layer was carried out with a molecular beam diameter of 2 µm for quantitative analysis. Corrosion resistance is calculated by applying a continuous salt water spray for 2 to 50 hours, and calculating the amount of bond surname per unit area from the weight difference before and after the test. In this test, a pass of 20 g / m2 or lower is set to pass or fail. Evaluation of processability 'was to wind the money-applied wire after it was made on a 6-mm-diameter steel wire 6 times, and visually observe the surface to determine whether there were cracks. In addition, after the crack was judged, an adhesive tape was affixed to the sample, and then it was torn apart after the sticking was observed. The presence or absence of keying peeling was evaluated as a condition where the number of cracks was 1 or less, and the condition of no peeling was acceptable. Table 4 shows the relationship between the average composition of the plating, the composition and thickness of the inner and outer layers of the alloy, the thickness of the plating layer, the microstructure and the / 3 phase volume ratio, corrosion resistance, processability, and scum formation in the mirror bath. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Each embodiment of the present invention shows good surname resistance and processability, and few scums are generated. Comparative Examples 1 to 7 refer to those in which the composition of the plating alloy is outside the range prescribed by the present invention. The amount of Al, Mg, or Si in Comparative Example 1 to 3 was lower than the lower limit of the range of the present invention 'and the remaining resistance was poor. The amount of Al, Mg or Si in Comparative Example 4-6 is higher than the upper limit of the range of the present invention, the margin resistance is also poor, and the amount of scum generation is large. X 297 mm) 28 495559 V. Description of invention (26) Comparative Examples 8 and 9 are those in which the thickness of the plated alloy layer is outside the range prescribed by the present invention, and results in which the workability is poor. Comparative Example 10-12 means that phase 0 in the plating structure is outside the range of the present invention, and the corrosion resistance is poor.

-------------- Install --- (Please read the precautions on the back before filling out this page) _Line-Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is applicable to China Standard (CNS) A4 specification (210 X 297 public love) 29 495559 A7 B7 V. Description of invention (27 Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs

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OS * 〇〇m 二 * 0000 00 »r &gt; X ((NX &lt; NX oo X om X ro ( NX m X m Ό 呀 X (N v〇X oc m X ϊ | π 〇 ON * 〇- m CN inch m 卜 to 卜 v〇m CN CN m CN X Ό fN X m X 〇§, 05. « 〇§ 、 1 03. — «〇S ,, 1« 〇S, «〇S,,« 〇S »Ί, 〇CL, 〇S, 1« 〇gu! 〇α, «〇S 'Vs, , L, «〇§» «!, Qq.,« ®s Ul, QCL «〇S μ!« Tng,, 1, «〇S 'Ί 〇i,« 〇S,, 1 QQ. «Ton Qi, tag,, 1 «s,,« Dg QQ., 〇S,, 1, «&lt;,, 1,« 〇S &quot; 1, 03. «®s« 〇S 〇§ Μ 〇S # mg-og From®§ 4S 〇S # z £ = L mv〇iN * n CN mm bu Tf m rs ON fN so in (N v〇 * r &gt; CN mm inch om S 〇m (N Γ ^ ϊ S 〇 »no 00 〇S time £ = L ma \ (Ν 〈N rs ro m» n CN ON inch m &lt; N 00 oo inch 00 ya ON bu 00 v〇rn pair 〇s 00 &lt; N ΓΟ bu m &lt; N m to 00 rs CN m X bu 『N ^ f vo m &lt; D (JU — fN 〇oo r〇rs in tt fN ON rN Q) CN mm rn NO v £ &gt; rN iN 00 — 00, m vd 00 00 Tt NO to 00 m ye r4 rn »n &lt; N mo rn * cn (N 卜 CN 00 m 00 (N m CN m inch «N &lt; N ΓΝ 00 &lt; N ΓΟ m fN &lt; N &lt; N &lt; N rs &lt; N v〇 &lt; N rn ri &lt; N r ^ &gt; r- m rN mm Ό m rnrn s〇00 dd two r- CN Tt inch trj b VO ΓΝ m &lt; &lt; ^ o rs m CN (N &lt; NS (NS «Ν &lt; NO) d inch v〇〇 s 00 «Ν inch in ON CN 00 rn &lt; N inch On to wi &lt; N ON m tgm ε a. v〇Tt inch ON inch CN O) do On O Ό fS o 6 OO &lt; N 00 (N 00 &lt; N On d ON m BUΓN BU X Os — inch mm BU £ r〇 »〇 &lt; N ro rs 00 &lt; N BU &lt; N rs &lt; N rN 00» 〇CN 00 CN ra ^ t (N VO (N 5 &lt; N VO 00 &lt; N On fN Ό &lt; N v〇 vs r4 &lt; N BU v〇 卜 s〇CN inch 00 Tf «N — &lt; N Os' O inch m inch NO m 〇mr〇On &lt; N m CN 〇m rN fN CN BU &lt; N mm rsi &lt; N tn m mm Os · mmm &lt; N r4 On &lt; N v〇ΓΛ rn tn &lt; N — mr ^ iv〇r〇 VO 00 d 'O r〇 »〇mmv〇inchrn &lt; N rn 00 ri inch rn &lt; VO (N ro «Ν rs &lt; N &lt; N g (N m (N yi m« η m BU d * 〇 &lt; N NO mv〇CN rn 〇 &lt; N 00 s On rs SO d ro m NO &lt; &gt; &lt; N ST c \ 0 &gt; b (N Os dgd Os Ό d 00 00 d (N d oo bsd On ON »nds〇m \ 〇ό 00 dv〇d * 00 d inch d O) 00 c &gt; o iri l〇00 bb π qd VO b sd On m ON ms〇σ ^ ro dd b O d ON &lt; N 00 d ON &lt; N o ό CN d ON dm b d Μ 50 2 〇〇 &lt; N On d 00 ON d ro two m — · rn do &lt; N m 〇v〇o rn ov〇On dm (N On 6 (N &lt; N rn &lt; o fN v〇00 two m BU ON O fN II &lt; N BU rs rs BO 00 200 00 m ○ inch — &N; N m inch v 0 00 00 O 2 — «N m inch v 0 OOO 〇 2 &lt; N ( Please read first Note on the back, please fill in this page again) ------- ^ ------ 1 ^^ This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 30 495559 Intellectual Property of the Ministry of Economic Affairs Printed by the Consumer Cooperative of the Bureau A7 B7 V. Description of the invention (28) &lt; Example 4 &gt; The 4mm diameter steel wire with pure 211 plating on the surface of the steel wire JIS G 3505 SWRM6, as shown in Table 5. This condition was evaluated after applying Zn-A1_Mg-based zinc alloy deposit under the conditions shown. In the comparative example, the plating composition and the shape of the Fe-Zn alloy layer were changed, and the same evaluation was performed. Observation of the plating structure is the C-section 'of the abrasive forging wire, which is observed by EPMA. The composition analysis of the alloy layer was performed with a molecular beam diameter of 2 m '. The survivability of the surname is based on the continuous salt water spray of 2500 hours, and the weight difference between the front and back of the test is used to calculate the amount of rotten surname per unit area. In this test, a pass of less than 20 g / m2 is set to determine the pass or fail. The evaluation of processability was performed by winding the plated wire on a 6-mm-diameter steel wire 6 times after making it, and visually observing the surface to determine whether there were cracks. In addition, after the crack was judged, an adhesive tape was affixed to the sample, and then it was torn apart after the sticking was observed, and the presence or absence of the peeling was observed, and the number of cracks was 1 or less. Table 5 shows the relationship between the average composition of the plating, the composition and thickness of the inner / outer layer of the alloy, the thickness of the keyed layer, the structure and the volume ratio of the / 5 phase, and the surplus, processability, and scum formation of the keyed bath. Each of the examples of the present invention shows good money resistance and processability, and few scums are formed. Comparative Examples 13 to 19 refer to those in which the composition of the plating alloy is outside the range prescribed by the present invention. The amounts of Al, Mg or Si in Comparative Examples 13-15 were lower than the lower limit of the present invention, and the corrosion resistance was poor. The amounts of Al, Mg, or Si in Comparative Examples 16 to 18 were higher than the upper limit of the range of the present invention. As a result, the processability was poor, and the amount of floating formation in the plating bath was large, which affected the operation. Comparative Examples 20 and 21 refer to the size of the coated paper and the applicable Chinese National Standard (CNS) A4 (210 X 297 mm) ^ -------- ^ --------- ^ ( (Please read the notes on the back before filling this page) 31 495559 A7 V. Description of the Invention (29) The thickness of the gold layer is beyond the range specified in the present invention, and the result is obtained. Comparative Examples 22-24 refer to those outside the range of poor phase processability in the plated structure, resulting in a difference in resistance to creep. . &amp; This invention {Please read the notes on the back before filling out this page) • ------- Order --------- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economics This paper is applicable to paper standards China National Standard (CNS) A4 Specification (210 X 297 mm) '32 495559 A7 B7 V. Description of Invention (30)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

Plating bath dross formation of 2000000 000 000 000 000 000 5,000 roll reel test stripping 10000 000 000 000 000 000 〇XX 〇〇〇 Crack 〇〇〇〇〇〇〇〇〇〇〇〇XX 〇 × 〇〇〇XX 〇〇X Corrosion loss g / m2 〇 \ 〇 ΓΛ ^ Τί 00 inch 00 Bu x 45 x 27 x 23 x 48 x 30 x 23 m X inch x 46 x 62 x 38 volume fraction of cold phase% 〇 〇 〇 2 〇 〈N m 〔So〕 〈N ON x 23 Ό &lt; NX | x 35 organization α // 5 / Ternary eutectic a / β / Ternary eutectic a // 3 / Ternary eutectic a // 5 / Ternary eutectic a // 3 / Ternary eutectic α / β / Ternary eutectic α / β / Ternary eutectic a // 5 / Ternary eutectic | a /; S / Ternary eutectic | a // 5 / Ternary eutectic cr // 3 / Ternary eutectic a // 5 / Ternary eutectic a /) 9 / Ternary eutectic Ternary eutectic d / No / Ternary eutectic a / Cold / Ternary eutectic 1α / β / Ternary eutectic 1 a / 5/5 Ternary Eutectic a // S / ternary eutectic α / β / ternary eutectic a // 9 / ternary eutectic 1 a / stone / ternary eutectic a // 3 / ternary eutectic cooling structure granular Crystal 2 Granular crystal grains 2 2 Columnar crystals 3 Granular crystal columnar crystal thickness B = L 13.5 16.5 25.2 13.3 34.7 m (N 25.6 25.6 43.3 30.4 g 〇 2 &lt; N &lt; N 〇00 〇 Alloy outer layer thickness B = L 29.3 12.7 13.2 25.3 〇 \ 13.4 18.2 18.6 inch 00 rn 00 v〇14.3 28.9 m 23.3 ro 24.8 &lt; N x 35 12.7 14.4 13.6 φ! 0 &gt; 24.6 11.0 23.8 14.5 29.2 C \ &lt; N rn rn 16.6 27.2 00 00 Yibu · ΓΟ VD 00 οο vd 17.5 OO m 12.4 [15.3 &lt; N inch rn 3.0 «Ν &lt; N Bu fS OO ΓΛ 00 Γ-Ί &lt; N rn ri m ri OO ri rn« Ν ίΝ fN cs VO ri cs SO &lt; N ΡΠ &lt; N in rs 3.6 — (N m fn VO Γ &lt; ί Γ Λ v00 00 π d inch 〇 · 二 卜 — &lt; N — 'n fN ^ Ti ρ d ν〇 &lt; Ν rr rn &lt; 〇 \ νο rs m &lt; N «Ν &lt; Ν tN rs m rs art 10.9 inch vd 28.9 15.4 29.6 Ο m &lt; N 19.4 DO 25.4 〇 \ 11.3 thickness μηι 4.6 leaf 〇 \ ri 0.9 o 0.9 CN 0.03 00 in (N 00 ri 00 ri Os 6 〇 \ cn &lt; N bu X ON — inch ΓΟ ΓΛ bu Un 15.3 23.2 27.8 25.7 22.2 18.5 25.6 00 CN 24.2 27.6 00 rs 〇 \ \ &lt; N 22.4 BU SO 1 21.4 1_ Order 00 νο… Tf (N rs 〇 \ v〇rr r〇ν〇omm pair · Os rs CO &lt; N 〇Ui «Ν« Ν (N ΓΓMM mm &lt; N &lt; N &gt; rj rn BU ON rn m ro fS rsi Os &lt; N VO BU m &lt; n fS m wn v〇m BU rn v〇〇〇d NO r〇mr ^ i rn v〇CN rn 00 &lt; N rn &lt; Ό (N rs rsi &lt; N &lt; N &lt; N (N 15.3 i 30.7 fN 36.5 26.5 20.3 30.8 ON «Ν 30.6 33.4 29.6 average plating composition (mass%)) 5 0.4 0.18 fN d Ο om U 0.05 〇v〇〇0.18 rn o 〇dd 6 Η 0.18 0.92 0.23 0.06 (N 0.45 0.22 0.19 0.77 &lt; N &lt; N m (N cd z 0.23 0.05 0.43 0.88 ΓΛ 0.62 0.48 0.75 0.90 0.02 r〇d 0.04 VD 0.24 0.91 0.43 00 dd-OO d 〇 On OO do Ui 00 dd $ -1 0.7913 0.1725 -1 1.0883! 1 1.6238 0.002 1.5439 〇〇 0.667 s; 1.758 〇o 0.007 〇 &lt; N 00 ο Os 0.002 rN 〇Os or〇 Bud 2.96 00 00 OO m 4.62 «N 3.4 4 B & N 2.79 0.92 3.21 a \ ri 2 6 2.0 rn 〇SO ο rn 〇VO 0.9 1 m rs σ \ d rs &lt; N r〇 &lt; inch On 4.46 7.99 00 17.9 11.8 12.9 &lt; N &lt; N »〇rs (N 0000 — 〇00 m 〇 &lt; N to VO 0000 On iN ΓΜ Inch 40 VO 0000 ON &lt; N IN (N (Please read the notes on the back before filling this page) The paper dimensions Applicable to China National Standard (CNS) A4 specification (210 X 297 public love) 33 495559 A7 _B7_ V. Description of the invention (31) Industrial availability According to the above description, according to the present invention, a kind of high resistance # Zinc-coated steel, especially zinc-bonded steel wire. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is sized to the Chinese National Standard (CNS) A4 (210 X 297 mm) 34

Claims (1)

495559 Announcement name! · BS i C8 i &quot; ·, · ΙΙΙΒ „ΙΙ1Μ 丨 11 丨 &quot;. ,, 1 ___ 1-- --__ D8 VI. Application for Patent Scope No. 90104734 Patent Application Amendment for Patent Scope 91 May 3, 2014 1. A plated steel material, characterized in that the plated steel material has an alloy layer with a thickness of 20 μm or less on the plating layer. The ferrous alloy layer contains a mass of the alloy layer. When expressed, Fe: 25% or less, A1: 30% or less, Mg. 5% or less, and the remainder &amp; 2. A kind of plated steel, characterized in that: An alloy layer with a thickness of 20 μτη or less is provided on the plating layer-quality iron interface, and the alloy layer contains: Fe: 25% or less, Ai ·· 30% or less, Mg: 5% or less when expressed in mass%, and Those with the remaining portion of Zn; and the aforementioned alloy layer has a plating layer, and when its average composition is expressed in mass%, it contains A1 • 4-20 /., Mg • 0.8-5%, Fe: 2% or less, and The remaining part is zn V &quot; 3. A kind of plated steel, which is characterized in that: The interface has an alloy layer composed of an alloy inner layer of 5 μm or less and a thickness of δ to an outer layer of 3 claws or less. The inner layer of the alloy contains: When expressed in mass%, Fe: 15% or more, A1: 20% or more, si: 2% or more, Mg: 5% or less, and the remainder of Zn; the alloy outer layer contains. When expressed in mass%, ^: 25% or less, 8: 30% or less, Si: 2% or more, Mg: 5% or less, and the remaining part of Zn. 4. A plated steel characterized in that the plated steel has an alloy inner layer of 5 μηι or less and a thickness of 3 μm on the plating layer-quality iron interface. | 11111 An alloy layer composed of an outer alloy layer below, the inner layer of the alloy contains: When expressed by mass./0, Fe: 15% or more, A1: 20% or more, Si ·· 2% or more, Mg: 5% or less , And the remaining part of Zn; the outer layer of this alloy applies the Chinese National Standard (CNS) A4 specification (210 X 297 public love) for this paper size (please read the precautions on the back before filling this page) Order--35-495559 A8 B8 C8 D8 The scope of patent application contains: Fe: 25% or less, A 丨: 30% or less, &amp;: 2% or more, Mg: 5% or less, and the rest of Zn; and the foregoing The outer layer of the alloy has a plating layer whose average composition is expressed in terms of mass%, and contains: 4-20%, Mg: 0.8 · 5%, Si 〇1 ~ 2%, Bu: 2% or less, and For the remaining part of Zn, Mg2Si is dispersed in the plating layer. 5. The plated steel material according to item 2 of the patent application, wherein the solidified structure of the plated layer is a granular crystal structure or a columnar crystal structure. 6. The plated steel as claimed in item 2 or 4 of the patent application scope, wherein each of the plated structure has an α-phase containing Al-Zn as a main component, and / 5 is composed of an alloy layer alone or 乂 ^ with an alloy layer. Phase, and Zn-Ai-Mg ternary eutectic phase exists. 7. The plated steel according to item 6 of the scope of application for a patent, wherein the volume ratio of the / 3 phase existing in the above-mentioned plating structure is 20% or less. 8. The plated steel according to item 2 or 4 of the scope of patent application, wherein the plated layer includes one or more elements of one or more of the following a, b, c, and d groups; a · Each contains one or most elements of Ti, Li, Be, Na, K, Ca, Cu, La, Hf 0.01-1. 0 mass%; b: Each contains one or most elements of Mo, W, Nb, Ta 0 〇1-〇2% by mass; c: each containing one or most elements of Pb and Bi 〇〇ι-〇.2% by mass; d: each containing one or more of Sr, V, Cr, Mn, Sn or Most of the elements are in the range of 0.00-0.5 mass%. 9. The plated steel material according to any one of claims 1 to 4, wherein the plated layer is formed with one of a coating coating and a heavy-resistance coating. This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) ---------------------- Loading ...--------- ------ Order ...! .......... Line · (Please read the precautions on the back before filling out this page) -36-495559 'A8 B8 C8 ______ D8 VI. Scope of patent application 10 The plated steel material, wherein the heavy-resistance coating is a south molecular compound far from at least one of gasified ethylene, polyethylene, polyurea, and fluororesin. 1 1 · The plated steel according to any one of claims 1-4, wherein the recorded steel is a steel wire. 12-A method of manufacturing a plated steel material, characterized in that the steel material is included in the first stage of the steel to contain quality. In the case of / 0, molten zinc plating of A1 ·· 30 / 〇 and Mg · 0.5% or less is performed, and the average composition is included in the second stage to include mass. / 〇 means Al: 4-2〇〇 / 0, Mg: 0.8_5〇 / 〇, Fe: 2% or less and the remaining portion of Zn molten metal plating, and formed on the plating layer-quality iron interface There are alloy layers composed of Fe ·· 25% or less, A1 ·· 30% or less, Mg: 5% or less when expressed in mass%, and the remaining portion of Zn and a thickness of 20 μm or less, and then further a3〇 (rc / sec The following cold section speeds are used to cool the solidified structure of the plating layer to form a granular crystal structure, or to cool at a cooling rate of 300 ° C / sec or more to form the columnar crystal structure of the solidified structure of the plating layer. 13. —A method for manufacturing a plated steel, characterized in that: in the first stage, a molten zinc plating containing A1 when expressed in mass% is not more than 3% and is not more than 0.5%, and then The average composition in the second stage includes A1 •• 20% when expressed in mass%, Mg · 0.8-5% mu 2% or less, and the remaining part is fused with gold plating, and the plating In the layer-mass iron interface, Fe: 15% or more, A1: 20% or more, &amp;: 2% or more, and _: 5% when expressed in mass%. The following and the remaining parts are made of the alloy with a thickness of less than this. The paper size is applicable to the Chinese national standard (Norway) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page) Order · 37 A8 B8 C8 D8 I, patent application scope layer, and Fe · 25% or more, A1: 30% or less, si: 2% or more, Mg. 5% or less and the remainder of the composition and thickness The alloy layer composed of the outer layer of the alloy is then further cooled at a cold part speed of 30 (rc / sec or less), so that the solidified structure of the plating layer forms a granular crystal structure, or it is cooled at a cooling rate of 300 C / sec or more. In order to make the solidified structure of the plating layer to form a columnar crystal structure. 14. For example, the method of manufacturing a plated steel of the scope of patent application No. 12 or 13, wherein the second stage of molten alloy coating includes the following a, b, ^, d one or more elements in one or more groups; a: each containing one or more of Ti, Li, Be, Na, K, Ca, Cu, La, Hf 0.01 -1 · 〇 Mass 0 / 〇; D: each containing one or more of ^ / 1〇, ",>, D, 3 or 0.01-0.2% by mass; c: each containing one or most of Pb, Bi Element 〇〇1-〇2 mass%; d: each contains one or most of the elements Sr, V, Cr, Mn, Sn. 0.001-0.5% by mass. 1 5. As claimed The manufacturing method of the plated steel products in the scope of the patent No. 12 or 13, wherein the molten zinc plating at this stage is performed with a plating immersion time of less than 20 seconds, and the second stage of the molten zinc alloy plating is performed at 2 The key immersion time is less than 0 seconds, and the part of the plating steel drawn from the aforementioned first and second stage plating baths is cleaned with nitrogen to prevent oxidation of the surface of the plating bath and the mineralized steel. 16 · 如The method for manufacturing plated steels with the scope of patent application No. 12 or 13, which implements the second stage of molten alloy zinc plating, and applies the Chinese National Standard (CNS) A4 specification (210 X 297) to the paper size of the plated steel Mm) -------------------, installed ------------------ order ------- ----------- Line. (Please read the precautions on the back before filling in this page) 38 495559, A8 B8 C8 D8 VI. After the patent application scope is pulled out from the plating bath, spray water immediately, One of the cooling methods of air-water spray or water flow is to directly cool and solidify the plating alloy. 17. For example, the manufacturing method of the plated steel of item 12 or 13 of the scope of patent application, which The cooling start temperature of the aforementioned plated steel material at the time of cooling is set to the melting point of the plated alloy + 20 ° C or less. 18. For example, the method for manufacturing a plated steel material according to item 12. or 13 of the patent application scope, wherein the plating The steel is plated steel wire. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -------------, ............... ......... Order ... r ......._ n ^ · (Please read the notes on the back before filling in this page) 39