KR960009197B1 - Cold rolled steel sheets with an excellent phosphating galvanized surface and the method therefor - Google Patents
Cold rolled steel sheets with an excellent phosphating galvanized surface and the method therefor Download PDFInfo
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- KR960009197B1 KR960009197B1 KR1019930031046A KR930031046A KR960009197B1 KR 960009197 B1 KR960009197 B1 KR 960009197B1 KR 1019930031046 A KR1019930031046 A KR 1019930031046A KR 930031046 A KR930031046 A KR 930031046A KR 960009197 B1 KR960009197 B1 KR 960009197B1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0278—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving a particular surface treatment
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
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Abstract
Description
제1도는 종래의 냉간압연강판 소둔처리 공정 및 본 발명에 의한 소둔처리 공정도.1 is a conventional cold rolled steel sheet annealing step and the annealing step according to the present invention.
제2도는 종래의 냉간압연강판 및 본 발명에 의해 처리된 냉간압연강판의 인산염조직에 대한 확대조직사진.2 is an enlarged texture photograph of a conventional cold rolled steel sheet and a phosphate structure of a cold rolled steel sheet treated by the present invention.
본 발명은 자동차 내·외판 및 가전제품용으로 사용되는 냉간압연강판을 제조하는 방법에 관한 것으로써, 보다 상세하게는, 강판면의 인산염 핵생성을 조밀하게 하여 치밀한 인산염피막을 형성시킬 수 있는 인산염 처리성이 우수한 냉간압연강판(이하, 냉연강판이라칭함) 및 그 제조방법에 관한 것이다.The present invention relates to a method for manufacturing a cold rolled steel sheet used for automobile interior and exterior and home appliances, more specifically, a phosphate that can form a dense phosphate coating by densifying the phosphate nucleation of the steel sheet surface The present invention relates to a cold rolled steel sheet (hereinafter referred to as a cold rolled steel sheet) having excellent processability and a method of manufacturing the same.
냉연강판표면은 제조방법, 강판표면 편석성분, 조도, 산화피막의 상태등에 의해 달라질 수 있다. 이와같이 다른 강판표면 상태는 인산염핵생성처의 밀도를 변화시키게 되며, 이는 인산염결정의 크기 및 피막 기공도를 지배하는 중요한 인자가 된다. 따라서 종래에는 냉연강판 표면에 인산염핵생성처를 증가시키기 위하여 니켈, 코발트, 구리, 티타늄 등을 전기도금 및 환원제를 첨가한 무전해도금법으로 냉연강판표면에 약 0.3-10mg/m2정도 부착시켜 인산염처리성을 증가시키는 방법이 일본 특허공개 (소)56-116883호 및 (소)56-116887호 등에 제시되어 있다.The cold rolled steel surface may vary depending on the manufacturing method, the steel sheet surface segregation component, roughness, and the state of the oxide film. These different steel surface conditions change the density of phosphate nucleation sites, which are important factors that govern the size and film porosity of phosphate crystals. Therefore, in order to increase the phosphate nucleation on the surface of the cold rolled steel sheet, nickel, cobalt, copper, titanium, etc. are attached to the surface of the cold rolled steel sheet by an electroless plating method with electroplating and a reducing agent, about 0.3-10 mg / m 2 Japanese Patent Laid-Open Nos. 56-116883 and 56-116887 are disclosed in a method for increasing the treatment.
그러나, 장기한 종래의 전기도금법은 기존의 생산설비에 설치하기가 어려우며 또한, 설비비용이 많이 소요되는 문제점이 있고, 상기한 종래의 무전해도금법은 환원제에 관한 비용이 소요되고, 용액이 불안정하여 관리가 어려운 문제점이 있다.However, the long-term conventional electroplating method is difficult to install in the existing production equipment, there is a problem that requires a lot of equipment costs, the conventional electroless plating method is expensive for the reducing agent, the solution is unstable There is a problem that is difficult to manage.
이에, 본 발명자들은 상기한 종래방법들의 제반문제점을 해결하기 위하여 연구와 실험을 행하고, 그 결과에 근거하여 본 발명을 제안하게 된 것으로서, 본 발명은 냉연강판에 구리를 미량(부분) 부착시키므로써 인산염처리성이 우수한 냉연강판 및 그 제조방법을 제공하고자 하는데, 그 목적이 있다.Accordingly, the present inventors have conducted research and experiments to solve the above-mentioned problems of the conventional methods, and based on the results, the present invention proposes a small amount (part) of copper on a cold rolled steel sheet. It is an object of the present invention to provide a cold rolled steel sheet having excellent phosphate treatment and a method of manufacturing the same.
이하, 본 발명에 대하여 상세히 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.
본 발명은 통상의 냉연강판에 있어서, 그 표면에 구리(Cu)가 0.2-20mg/m2의 부착량으로 부분 피복되어 있는 인산염처리성이 우수한 냉연강판에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cold rolled steel sheet having excellent phosphate treatment property in which a copper (Cu) is partially coated with a deposition amount of 0.2-20 mg / m 2 on a surface thereof in a common cold rolled steel sheet.
또한, 본 발명은 냉연강판을 탈지한 후 연속소둔한 다음, 수냉, 건조 및 조절압연을 행하며 냉연강판을 제조하는 방법에 있어서, 소둔강판 또는 수냉처리된 소둔강판 표면에 0.2-20mg/m2의 부착량으로 구리(Cu)를 부분피복시켜 인산염처리성이 우수한 냉연강판을 제조하는 방법에 관한 것이다.In addition, the present invention is a method for producing a cold rolled steel sheet by degreasing the cold rolled steel sheet and then continuously annealing, followed by water cooling, drying and controlled rolling, the surface of the annealing steel sheet or water-cooled annealing steel sheet of 0.2-20mg / m 2 The present invention relates to a method for producing a cold rolled steel sheet excellent in phosphate treatment by partially coating copper (Cu) with an adhesion amount.
이하, 본 발명에 대하여 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명은 종래의 연속소둔공정을 나타내는 제1도(가) 및 취환공급법 적용시의 본 발명의 연속소둔공정을 나타내는 제1도(나)에 나타난 바와같이, 통상의 방법으로 냉간압연하여 냉연강판을 제조한 다음, 냉연강판을 탈지처리하고, 연속소둔로에 장입하여 연속소둔을 행한다.The present invention is cold rolled by a conventional method, as shown in FIG. 1 (a) showing a conventional continuous annealing process and FIG. After the steel sheet is produced, the cold rolled steel sheet is degreased, charged into a continuous annealing furnace, and subjected to continuous annealing.
다음에, 상기와 같이 연속소둔된 연속소둔 냉연강판을 수냉처리한 후 수냉처리된 연속소둔 냉연강판의 표면에 구리를 0.2-20mg/m2이 부착량으로 부분 피복시키거나 또는 연속소둔로에서 소둔처리한 후 행하는 수냉처리시 다수개의 수냉탱크 중 물대신에 구리용액으로 채워진 적어도 1개 이상의 탱크에 냉연강판을 침적시켜 냉연강판을 1차 수냉시킴과 동시에 그 표면에 0.2-20mg/m2의 부착량으로 구리를 부분 피복시킨다음, 2차 수냉시킨다.Subsequently, after the continuous annealing cold rolled steel sheet continuously annealed as described above, the surface of the water-annealed continuous annealed cold rolled steel sheet is partially coated with 0.2-20 mg / m 2 of adhesion amount or annealed in a continuous annealing furnace. During the subsequent water cooling process, cold rolled steel sheets are deposited on at least one tank filled with copper solution instead of water among a plurality of water cooling tanks to cool the cold rolled steel sheets first, and at the same time, with a deposition amount of 0.2-20 mg / m 2 . The copper is partially coated, followed by secondary water cooling.
본 발명에 적용될 수 있는 구리피복 방법으로는 전기도금법, 진공증착법, 환원제를 이용한 무전해도금법, 및 치환도금법등을 들 수 있는데, 이중 치환도금법을 제외하고는 기존의 설비에 설치하기가 어렵거나, 설비 비용 및 용액관리에 문제가 있는 반면에, 치환도금범은 설비비용이 저렴하고 용액관리가 용이하므로 가장 적당한 방법이라고 할 수 있다.The copper coating method that can be applied to the present invention includes an electroplating method, a vacuum deposition method, an electroless plating method using a reducing agent, and a substitution plating method, but it is difficult to install in an existing facility except the double substitution plating method, On the other hand, there is a problem in equipment cost and solution management, while the replacement plater is the most suitable method because of the low equipment cost and easy solution management.
상기한 치환도금법에 의해 구리를 피복시키는 경우 바람직한 치환도금은 10-5g/l의 C2+을 함유하는 도금액에서 2-30초동안 행하는 것이다.When copper is coated by the above-described substitution plating method, preferred substitution plating is performed for 2-30 seconds in a plating solution containing 10-5 g / l of C 2+ .
물론, 진공증착법과 같이 구리용액을 사용하지 않는 경우에는 수냉을 위한 물대신에 구리용액으로 대체시킬 필요는 없으며, 이 경우에는 수냉처리한 소둔냉연강판 표면에만 구리를 피복할 수 있게 된다.Of course, when the copper solution is not used, such as vacuum deposition, it is not necessary to replace the copper solution with water for water cooling, and in this case, the copper may be coated only on the surface of the water-annealed cold rolled steel sheet.
한편 구리용액을 사용하여 구리를 피복시키는 경우에는 구리 피복후 수세 및 건조를 시켜야 하며, 건조후 조절압연등을 행하므로써, 구리가 부분적으르 피복된 인산염처리성이 우수한 냉연강판이 제조된다.On the other hand, in the case of coating copper using a copper solution, washing with copper and drying should be performed after copper coating, and by performing controlled rolling after drying, a cold rolled steel sheet excellent in phosphate treatment with a partial coating of copper is produced.
상기와 같이 냉연강판 표면에 피복되는 구리의 량이 너무 많은 경우에는 강판표면을 완전히 피복시키게 되므로써, 강판표면의 전기적 불균일이 형성되지 않아 인산염 처리성 향상효과가 발생하지 않으므로, 구리의 부착량은 강판표면에 구리와 철이 적당하게 분포되어 전기적 불균일이 일어날 수 있는 상태로 제어하는 것이 바람직하며, 본 발명에 있어서, 바람직한 구리부착량은 0.2-20mg/m2이다.As described above, when the amount of copper coated on the surface of the cold rolled steel sheet is too large, the surface of the steel sheet is completely covered, so that the electrical non-uniformity of the surface of the steel sheet is not formed and the effect of improving the phosphate treatment property does not occur. It is preferable to control in a state where copper and iron are properly distributed so that electric nonuniformity can occur, and in the present invention, the preferred amount of copper is 0.2-20 mg / m 2 .
본 발명에 따라 구리를 냉연강판 표면에 피복(석출)시키므로써, 강판표면에 전기적 불균일을 일으켜 인산염처리시 핵생성 위치를 많게 해주어 균일하고 치밀한 인산염피막이 형성되게 되는 것으로서, 이에 대하여 상세히 설명하면 다음과 같다By coating (precipitating) copper on the surface of the cold rolled steel sheet according to the present invention, an electrical nonuniformity occurs on the surface of the steel sheet, thereby increasing the nucleation position during phosphate treatment, thereby forming a uniform and dense phosphate coating. same
인산염결정은 강판표면의 음극부에 핵생성 및 결정성장이 일어나므로 강판표면 편석성분 및 산화피막 상태에 따라 인산염핵생성처의 양이 변하게 된다. 이때 인산염핵생성처의 양이 적은 경우 인산염결정 크기가 조대하고 치밀하지 못한 인산염피막이 형성되게 되며, 인산염핵생성처가 많은 경우에는 인산염결정 크기가 작고 조밀한 인산염 피막이 형성된다.Since phosphate crystals generate nucleation and crystal growth in the negative electrode portion of the steel plate surface, the amount of phosphate nucleation site is changed according to the segregation of the steel plate surface and the oxide film state. In this case, when the amount of phosphate nucleation sites is small, a coarse phosphate film is formed and a dense phosphate film is formed. When there are many phosphate nucleation sites, a small phosphate crystal size and a dense phosphate film are formed.
그러나, 냉연강판 표면에 구리를 소량 부착시켰을 경우, 즉, 강판표면상에 구리를 부분적으로 입혔을 경우, 구리와 철이 불균일한 분포를 이루는 상태가 된다. 이러한 경우 강판표면은 구리와 철간의 전위차가 형성되게 되어 전기적으로 불균일한 상태가 이루어진다. 이때 구리가 부착되어 있는 부위는 음극이 되어 인산염결정 핵생성 및 성장의 기점이 되는 것이다.However, when a small amount of copper is deposited on the surface of the cold rolled steel sheet, that is, when copper is partially coated on the steel sheet surface, copper and iron are in a non-uniform distribution. In this case, the surface of the steel sheet has a potential difference between copper and iron to form an electrically non-uniform state. At this time, the portion to which copper is attached becomes a cathode and becomes a starting point for nucleation and growth of phosphate crystals.
인산염처리는 도장전처리로서 행해지는데, 그 목적은 도장후의 내식성, 강판과 도막과의 밀착성 등을 향상시키는 것이다. 구리가 부착된 냉연강판은 인산염처리성이 향상되기 때문에 전착고장후의 내식성이 기존의 냉연강판 보다 우수해진다.Phosphate treatment is performed as a pre-painting treatment, the purpose of which is to improve the corrosion resistance after coating, adhesion between the steel sheet and the coating film and the like. Since the cold rolled steel sheet with copper is improved in phosphate treatment, the corrosion resistance after electrodeposition failure is superior to that of the existing cold rolled steel sheet.
이하, 실시예를 통하여 본 발명을 보다 구체적으로 설명한다.Hereinafter, the present invention will be described in more detail with reference to Examples.
(실시예)(Example)
통상의 냉연강판 표면에 다음과 같은 조건으로 치환도금법에 의한 구리도금, 인산염처리, 및 양이온 전착도금을 행한 다음, 인산염처리성 및 도장후 내식성을 측정하고, 그 측정결과를 하기 표 1에 나타내었다.After copper plating, phosphate treatment, and cationic electrodeposition plating by the substitution plating method on the surface of a conventional cold rolled steel sheet, phosphate treatment property and corrosion resistance after coating were measured, and the measurement results are shown in Table 1 below. .
한편, 하기 표 1중 비교예(1)과 발명예(5)에 대해서는 도금강판의 인산염 조직에 관한 확대조직을 관찰하고, 그 결과를 비교예(1)는 제2도(가)에, 발명예(5)는 제2도(나)에 각각 나타내었다.On the other hand, in Comparative Example (1) and Inventive Example (5) in Table 1, the expanded structure of the phosphate structure of the plated steel sheet was observed, and the result of Comparative Example (1) is shown in FIG. Honor (5) is shown in Figure 2 (b) respectively.
가. 구리도금end. Copper plating
도금욕 조건 : Cu2+3.5-14.0g/l, pH 1.5, 상온Plating bath conditions: Cu 2+ 3.5-14.0g / l , pH 1.5, room temperature
도금방법 : 치환도금Plating Method: Substitution Plating
도금시간 : 2-30초Plating time: 2-30 seconds
나 : 인산염처리작업(다음의 각 공정에서 3분간 처리)B: Phosphate treatment (3 minutes in each process below)
1) 탈지처리1) Degreasing treatment
용액 : Pyroclean 442(삼양화학(주) 상품)Solution: Pyroclean 442 (Samyang Chemical Co., Ltd. product)
분무 : 50℃ 용액Spray: 50 ℃ Solution
침지 : 45℃ 용액Immersion: 45 ℃ Solution
2) 수세 : 상온의 수도물2) water washing: tap water at room temperature
3) 표면조정3) Surface adjustment
용액 : Parcolene Z(삼양화학(주) 상품)Solution: Parcolene Z (Samyang Chemical)
4) 인산염처리4) Phosphate Treatment
용액 : Bonderite 699D(삼양화학(주) 상품)Solution: Bonderite 699D (Samyang Chemical Co., Ltd. product)
침지 : 5℃ 용액Immersion: 5 ℃ Solution
5) 수세 : 상온의 수도물5) Water washing: tap water at room temperature
6) Cr-처리6) Cr-treated
용액 : Parcolene 86A(삼양화학(주) 상품)Solution: Parcolene 86A (Samyang Chemical)
분무 : 상온용액Spray: Room temperature solution
7) 수세 : 상온 수도물로 분무7) Water washing: sprayed with room temperature tap water
다. 양이온 전착도장작업All. Cationic electrodeposition coating work
1) 전착도장 : 도료 ED1700(고려화학(주) 상품) 전착전압 300V, 전착시간 3분1) Electrodeposition Coating: Paint ED1700 (Korea Chemical Co., Ltd.) Electrodeposition voltage 300V, Electrodeposition time 3 minutes
2) 수성 : 180℃에서 30분2) Aqueous: 30 minutes at 180 ℃
라. 도장후 내식성 실험la. Corrosion Resistance Test after Painting
전착도장된 시편에 X형으로 도막을 절단한 후 JIS Z2371에 의거 800시간 염수분무시험을 행하여 도막절단 편측부위의 도막부풀음 폭을 측정After the coating film was cut into X-type on the electrodeposited coated specimen, the salt spray test was carried out for 800 hours according to JIS Z2371 to measure the coating film swelling width at one side of the cut film.
[표 1]TABLE 1
*1(양호) 《-도장후 내식성 평가기준-》 5(불량)* 1 (good) << corrosion resistance evaluation standard after coating >> 5 (bad)
상기 표 1 및 제2도에 나타난 바와같이, 구리도금이 안되거나 부착량이 너무 적은 비교예(1-3)의 경우에는 인산염결정크기가 조대하고 불균일하여 도장후 내식성이 떨어지게되며, 또한, 구리부착량이 너무 많은 비교예(4-6)의 경우에는 강판표면의 전기적 불균일이 감소하여 인산염처리성 및 도장후 내식성이 열화됨을 알 수 있다.As shown in Table 1 and FIG. 2, in the case of Comparative Example (1-3) which is not copper plated or the amount of adhesion is too small, the phosphate crystal size is coarse and nonuniform, resulting in poor corrosion resistance after coating. In the case of too many comparative examples (4-6) it can be seen that the electrical non-uniformity of the surface of the steel sheet is reduced to deteriorate the phosphate treatment and corrosion resistance after coating.
그러나, 구리부착량이 0.2-20mg/m2인 발명예(1-7)의 경우에는 강판표면의 전기적 불균일에 의한 인산염 핵생성위치의 증가로 인하여 인산염 결정크기가 미세하고 균일해져 도장후 내식성이 양호함을 알 수 있다.However, in the case of Inventive Example (1-7) having a copper deposition amount of 0.2-20 mg / m 2 , the phosphate crystallization size was fine and uniform due to the increase in the phosphate nucleation position due to the electrical nonuniformity of the surface of the steel sheet, resulting in good corrosion resistance after coating. It can be seen.
상술한 바와같이, 본 발명은 냉연강판 제조시 간단한 치환도금법으로 소량의 구리를 냉연강판위에 부착시키므로서 인산염처리성을 향상시키고 이로써 내식성이 우수한 냉연강판을 제조할 수 있을 뿐만 아니라 냉연강판 수요가의 인산염처리시 탈지용액의 노화등에 의해 탈지가 불량할 때에도 냉연강판 표면에 구리가 석출되어 있어 인산염처리시 강판표면이 일반 냉연강판대비 크게 활성화 되어 있으므로, 인산염 처리불량 발생량을 크게 줄일 수 있는 효과가 있는 것이다.As described above, the present invention improves the phosphate treatment by attaching a small amount of copper on the cold rolled steel sheet by a simple substitution plating method in the production of cold rolled steel sheet, thereby producing a cold rolled steel sheet having excellent corrosion resistance as well as the demand of the cold rolled steel sheet. Even when the degreasing is poor due to aging of the degreasing solution during phosphate treatment, copper is deposited on the surface of the cold rolled steel sheet. will be.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019930031046A KR960009197B1 (en) | 1993-12-29 | 1993-12-29 | Cold rolled steel sheets with an excellent phosphating galvanized surface and the method therefor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019930031046A KR960009197B1 (en) | 1993-12-29 | 1993-12-29 | Cold rolled steel sheets with an excellent phosphating galvanized surface and the method therefor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR950018657A KR950018657A (en) | 1995-07-22 |
| KR960009197B1 true KR960009197B1 (en) | 1996-07-16 |
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| Application Number | Title | Priority Date | Filing Date |
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| KR1019930031046A KR960009197B1 (en) | 1993-12-29 | 1993-12-29 | Cold rolled steel sheets with an excellent phosphating galvanized surface and the method therefor |
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| Country | Link |
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| KR (1) | KR960009197B1 (en) |
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| Publication number | Publication date |
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| KR950018657A (en) | 1995-07-22 |
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