KR19990053134A - Electro zinc plating chromate coating method with excellent black resistance - Google Patents
Electro zinc plating chromate coating method with excellent black resistance Download PDFInfo
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- KR19990053134A KR19990053134A KR1019970072725A KR19970072725A KR19990053134A KR 19990053134 A KR19990053134 A KR 19990053134A KR 1019970072725 A KR1019970072725 A KR 1019970072725A KR 19970072725 A KR19970072725 A KR 19970072725A KR 19990053134 A KR19990053134 A KR 19990053134A
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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
- C23C22/24—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 hexavalent chromium compounds
- C23C22/26—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 hexavalent chromium compounds containing also organic compounds
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Abstract
본 발명은 내흑변성이 우수한 전기아연도금 크로메이트 피막처리 방법에 관한 것으로서, 특히 전기 아연 도금강판의 크로메이트 처리피막이 고온 다습한 분위기에 방치할 경우 표면이 검게 변하는 흑변성을 향상시킬 수 있는 내흑변성이 우수한 전기아연도금 크로메이트 피막처리 방법에 관한 것이다The present invention relates to an electrogalvanized chromate coating method having excellent blackening resistance, and particularly, when the chromate treated coating of an electrogalvanized steel sheet is left in a high temperature and high humidity atmosphere, the blackening resistance of the blackened surface may be improved. It relates to a method of electroplating chromate coating
전기아연도금강판에 크로메이트 용액으로 피막처리를 하는 전기아연도금강판의 크로메이트 피막 제조방법에 있어서, 상기 크로메이트 용액에 3메칠5피로졸린을 2∼10g/L 첨가하는 것을 특징으로 하는 내흑변성이 우수한 전기아연도금 크로메이트 피막 제조방법을 요지로 한다.In the method for producing a chromate coating of an electrogalvanized steel sheet in which an electrogalvanized steel sheet is coated with a chromate solution, 2 to 10 g / L of 3 methyl 5 pyrazoline is added to the chromate solution. The manufacturing method of a galvanized chromate coating is made into the summary.
Description
본 발명은 내흑변성이 우수한 전기아연도금 크로메이트 피막처리 방법에 관한 것으로서, 특히 전기 아연 도금강판의 크로메이트 처리피막이 고온 다습한 분위기에 방치할 경우 표면이 검게 변하는 흑변성을 향상시킬수 있는 내흑변성이 우수한 전기아연도금 크로메이트 피막처리 방법에 관한 것이다.The present invention relates to an electrogalvanized chromate coating method having excellent blackening resistance. In particular, when the chromate coated film of an electrogalvanized steel sheet is left in a high temperature and high humidity atmosphere, the blackening resistance of the blackened surface may be improved. The present invention relates to a galvanized chromate coating process.
크로메이트 처리 강판은 전기아연 도금강판 표면에 내식성 확보를 위해 크로메이트 피막처리 강판으로 생산되는 공지의 기술이다. 크로메이트 피막은 용액 및 처리방법에 따라 도포형, 반응형 및 전해형 크로메이트 피막으로 분류되며 반응형 크로메이트 피막은 우수한 표면외관 확보가 가능함으로 여러 제철소에서 공지의 확립된 기술로 사용되고 있다. 이러한 크로메이트 처리강판이 고온 다습한 지역으로 운송 혹은 장시간 보관시 표면이 시간이 지남에 따라 검은 색으로 변색되어 가는 소위 흑변현상이 진행되어 표면외관이 불량해지는 것이 기술적 한계점으로 노출되있다. 이러한 흑변현상은 용융아연도금강판의 크로메이트 피막처리강판에 관한 연구가 주로 진행되었다. 흑변현상은 아연의 산화반응중 산소부족 분에 의한 ZnO1-x의 형성에 의한 것으로 알려져 있다. 일본국 공개특허(59-177,381,52-22618,52-43171)등에서는 흑변현상을 해결하기 위하여 크로메이트 처리 전에 Ni,Co,Fe등을 함유한 용액에 용융아연도금 강판을 침지 석출시키는 기술을 공지하였다. 이러한 침지 석출 기술은 용융아연도금강판의 입계를 따라 Ni,Co,Fe등의 천이금속이 석출하면서 아연산화물로의 반응 진행을 억제하여 흑변성이 개선되는 것으로 보고하였으나 이러한 방법으로 처리시 내흑변성은 개선되나 중금속(Ni,Co,Fe)등이 입계를 따라 아연도금강판 표면에 집중적으로 석출함으로서 불균일 분포가 형성되어 표면외관성은 열위하여지는 것이 문제점으로 지적되었다. 그러나 전기아연도금강판은 용융아연도금 강판과는 달리 입계가 불분명하여 Ni,Co,Fe등이 함유된 크로메이트 용액으로 처리하여도 흑변성이 개선되지는 못하였다. 따라서 전기아연도금 크로메이트 처리피막의 흑변성을 개량하기 위한 크로메이트 용액의 개선이 요망된다.The chromate treated steel sheet is a known technique produced by a chromate coated steel sheet in order to ensure corrosion resistance on the surface of the galvanized steel sheet. The chromate coatings are classified into coating, reactive and electrolytic chromate coatings according to solutions and treatment methods, and the reactive chromate coatings can be secured with excellent surface appearance, and thus are used in various steel mills with well-known techniques. When the chromate-treated steel sheet is transported or stored for a long time in a hot or humid area, a so-called black discoloration phenomenon, in which the surface becomes black as time passes, is exposed as a technical limitation. This blackening phenomenon has been mainly studied the chromate coated steel sheet of hot-dip galvanized steel sheet. It is known that blackening is caused by the formation of ZnO 1-x due to the lack of oxygen during the oxidation of zinc. Japanese Laid-Open Patent Publication (59-177,381,52-22618,52-43171) discloses a technique for immersing and depositing a hot dip galvanized steel sheet in a solution containing Ni, Co, Fe, etc. before chromate treatment in order to solve the blackening phenomenon. It was. The immersion precipitation technique reported that the transition metals such as Ni, Co, Fe, etc. precipitated along the grain boundaries of the hot-dip galvanized steel sheet to suppress the progress of the reaction to zinc oxide, thereby improving black denaturation. Although it is improved, it is pointed out that heavy metals (Ni, Co, Fe), etc. are concentrated on the surface of the galvanized steel sheet along the grain boundary, resulting in inhomogeneous distribution and inferior surface appearance. However, unlike the hot-dip galvanized steel sheet, the electrogalvanized steel sheet did not improve the blackness even when treated with a chromate solution containing Ni, Co, Fe, etc. because the grain boundary is unclear. Therefore, improvement of the chromate solution for improving the blackness of an electrogalvanized chromate treated film is desired.
본 발명은 상술한 문제점을 해결하기 위한 것으로서, 전기아연도금 크로메이트 처리피막 제조방법에 있어서, 전기아연도금 처리후 크로메이트 처리용액에 3메칠5피로졸린을 내흑변성 개선 첨가제로서 투입하는 방법을 제공함으로서 달성된다. 바람직하게는 3메칠5피로졸린을 크로메이트 용액에 1-10g/L의 비율로 첨가하여 처리온도 40-60℃의 조건에서 침지혹은 스프레이 방법으로 크로메이트 피막을 형성함으로서 3메칠5피로졸린이 함유된 크로메이트 피막을 형성함으로서 흑변성을 개선시킨다.SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, in the method of producing an electrogalvanized chromate treated film, which is achieved by providing a method of adding 3 methyl5 pyrazoline as a blackening resistance improving additive to a chromate treated solution after the electrogalvanized treatment. do. Preferably, 3 methyl 5 pyrozoline is added to the chromate solution at a rate of 1-10 g / L to form a chromate film by dipping or spraying at a treatment temperature of 40-60 ° C. By forming a film, black degeneration is improved.
3메칠5피로졸린은 강한 소수성 물질로서 금속의 부식반응에 필요한 용존산소의 활성화 에너지를 높여 산소의 침투를 억제함으로서 금속의 부식을 방지하는 첨가제로서 상용화되어 사용되어 진다. 크로메이트 층으로 침투되는 외부부식 인자(H20,O2)와 아연층의 산화반응에 의한 ZnO 혹은 ZnO1-x층의 형성으로 크로메이트 피막이 검게 보이는 흑변현상이 진행된다. 따라서 이러한 흑변현상을 개선하기 위해서는 이러한 외부부식인자 특히 산소 침투를 억제하는 3메칠5피로졸린을 크로메이트 피막에 형성하여 산소의 침투를 억제함으로서 전기아연도금 크로메이트 피막의 흑변성을 개선할수 있는 것이다.3Methyl 5 pyrozoline is a strong hydrophobic material and is commercially used as an additive to prevent metal corrosion by increasing the activation energy of dissolved oxygen necessary for metal corrosion reaction and inhibiting oxygen penetration. The formation of a ZnO or ZnO 1-x layer by the oxidation reaction of the zinc layer and the external corrosion factors (H20, O2) that penetrates into the chromate layer leads to a blackening phenomenon in which the chromate film appears black. Therefore, in order to improve the blackening phenomenon, it is possible to improve the blackness of the electrogalvanized chromate coating by forming an external corrosion factor, in particular, 3 methyl5 pyrazoline, which inhibits oxygen penetration, by inhibiting oxygen infiltration.
이하 본 발명에 대하여 상세히 설명한다.Hereinafter, the present invention will be described in detail.
아연 부착량이 20g/m2인 전기아연 도금강판을 기판으로 사용하여 3매칠5필로졸린이 함유된 크로메이트 처리용액으로 크로메이트 피막처리를 실시후 수세건조 하였다. 크로메이트 처리용액은 상용화된 용액(T-Cr+6:0.1∼3.0g/L, FA: 4∼6pt)을 사용하였다. 이러한 크로메이트 용액에 3메칠5피로졸린을 1∼15g/L 투입하여 처리온도 40℃, 처리시간 40초의 조건에서 침지하였다. 내흑변성 평가는 항온항습기를 이용하여 60℃, 상대습도 80% 조건에서 120 시간까지 나판상태로 보관한 후 백색도를 측정하여 원판과의 백색도 차이를 평가하였다. 내흑변성 평가 전후의 백색도 차이가 클수록 흑변이 심하게 진행되는 것으로 판단할 수 있으며 통상적으로 백색도 차이를 2이하인 경우 내흑변성이 우수한 것으로 판단할 수 있다. 크로메이트 피막 부착량은 중량감량법으로 측정하였다.An electrogalvanized steel sheet having a zinc adhesion of 20 g / m 2 was used as a substrate, followed by washing with a chromate coating with a chromate treatment solution containing 3 methyl 5-pilozoline, followed by washing with water. As the chromate treatment solution, a commercially available solution (T-Cr + 6: 0.1 to 3.0 g / L, FA: 4 to 6 pt) was used. 1-15 g / L of 3 methyl 5-pyrazoline was added to this chromate solution, and it immersed on 40 degreeC of processing temperature, and 40 second processing time. The blackness resistance evaluation was measured using a thermo-hygrostat at 120 ° C for 60 hours at 80 ° C and 80% relative humidity, and then measured the whiteness to evaluate the difference in whiteness from the original. As the difference in whiteness before and after the evaluation of blackening resistance increases, blackening may progress more severely. In general, when the difference in whiteness is less than 2, it may be determined that the blackening resistance is excellent. The chromate coating amount was measured by weight loss method.
상기 표 1에서 보여지는 바와 같이 T-Cr2.0 및 FA 4.0조건의 크로메이트 처리 용액에 처리온도 40℃, 침지시간 40 초의 조건으로 처리한 결과 크로메이트 피막 부착량은 37∼40mg/m2 으로 측정되었고 내흑변성은 5로 측정되어 흑변이 상당히 진행되었음을 알수 있다.(비교예 1) 반면 상기 크로메이트 용액에 3메칠5피로졸린이 크로메이트 피막에 흡착되어 흑변의 원인이 되는 용존산소의 활성화 에너지를 증가시켜 ZnO의 생성을 억제하였기 때문인 것으로 판단된다.As shown in Table 1, the chromate coating was measured at 37 to 40 mg / m2 and treated with chromate treatment solution under T-Cr2.0 and FA 4.0 conditions at a treatment temperature of 40 ° C. and a soaking time of 40 seconds. The stiffness was measured to be 5, indicating that the black stools proceeded considerably. (Comparative Example 1) On the other hand, 3 methyl 5 pyrazoline was adsorbed to the chromate film in the chromate solution to increase the activation energy of dissolved oxygen causing black stools, thereby producing ZnO. It seems to be because it suppressed.
발명예 2와 발명예 3에서 보여지듯이 3메칠5피로졸린이 2∼10g/L 투입되었을 때 내흑변성1로 측정되어 가장 바람직한 농도 범위인 것으로 나타났다.As shown in Inventive Example 2 and Inventive Example 3, when 3 to 5 g of pyrozoline was added 2-10 g / L, it was measured as blackening resistance 1, and it appeared to be the most preferable concentration range.
본 발명에 의하여 크로메이트 용액에 3메칠5피로졸린을 첨가한 용액으로 크로메이트처리할 경우 내흑변성이 현저히 개선되는 전기아연도금 크로메이트 피막제조가 가능한 우수한 효과가 있다.According to the present invention, when chromate is treated with a solution in which 3 methyl 5 pyrazoline is added to the chromate solution, it is possible to produce an electro zinc plated chromate coating in which blackening resistance is remarkably improved.
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| KR1019970072725A KR100345885B1 (en) | 1997-12-23 | 1997-12-23 | Chromate method of electrogalvanized steel sheet for improving blackening resistance |
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