KR19990055437A - Chromium-free solution to improve the corrosion resistance of galvanized steel sheet - Google Patents
Chromium-free solution to improve the corrosion resistance of galvanized steel sheet Download PDFInfo
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- KR19990055437A KR19990055437A KR1019970075381A KR19970075381A KR19990055437A KR 19990055437 A KR19990055437 A KR 19990055437A KR 1019970075381 A KR1019970075381 A KR 1019970075381A KR 19970075381 A KR19970075381 A KR 19970075381A KR 19990055437 A KR19990055437 A KR 19990055437A
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- 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
- C23C22/34—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 fluorides or complex fluorides
- C23C22/36—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 fluorides or complex fluorides containing also phosphates
- C23C22/361—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 fluorides or complex fluorides containing also phosphates containing titanium, zirconium or hafnium compounds
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Abstract
본 발명은 무크롬 처리용액에 있어서 질화규소분말 100g, 분산제 4%를 사용하여 얻은 질화규소 분산용액 2-10 중량%(wt%), 산 10-25 wt% 및 커플링 에이전트 0.08-0.15wt% 범위인 것을 특징으로 하는 아연계 도금강판의 내식성을 향상시키는 무크롬 처리용액에 관한 것으로서 기존의 크로메이트 처리시의 문제점을 해소할 수 있는 무크롬 처리용액을 제공하는 것을 요지로 한다.The present invention is in the range of 2-10 wt% (wt%) of silicon nitride dispersion solution, 10-25 wt% of acid and 0.08-0.15wt% of coupling agent in a chromium-free solution using silicon nitride powder 100g, dispersant 4%. The present invention relates to a chromium-free treatment solution for improving the corrosion resistance of zinc-based galvanized steel sheet, and to provide a chromium-free treatment solution that can solve the problems of the conventional chromate treatment.
Description
본 발명은 표면처리강판의 일종인 아연도금강판의 무크롬 처리용액에 관한 것으롭, 보다 상세하게는 아연도금강판의 내식성을 향상시킬 수 있는 무크롬 처리용액에 관한 것이다.The present invention relates to a chromium-free solution of a galvanized steel sheet, which is a kind of surface-treated steel sheet, and more particularly, to a chromium-free solution that can improve the corrosion resistance of a galvanized steel sheet.
아연계도금에 의한 내식성은 하지 금속을 충분히 보호하기 위해서 형성된 도금층의 두께에 의해서 좌우되지만, 부식환경에 노출된 아연계 도금강판은 부식이 진행되어 백청을 형성하기 때문에 도금층 위에 후처리를 많이 실시하여 우수한 내식성을 확보한다. 후처리 종류로는 인산염처리, 크로메이트처리, 도장처리등이 적용된다.Corrosion resistance by zinc-based plating depends on the thickness of the plating layer formed to sufficiently protect the underlying metal.However, since zinc-based galvanized steel sheet exposed to the corrosive environment is subjected to corrosion and forms white blue, Secure excellent corrosion resistance. Phosphate treatment, chromate treatment, coating treatment, etc. are applied as a post-treatment type.
인산염처리는 도장처리의 전단계로서 주로 도장 밀착성 확보를 위해 많이 실시하는 반면에 내식성을 얻기 위해서는 크로메이트 및 도장처리를 많이 실시한다. 그러나 도장처리는 내식성을 얻기에는 타당하나 도장밀착성을 확보하기 위해서는 도장하기 전에 필히 인산염처리를 실시하는 번거로움이 있으며 또한 아연도금물질에 대한 도장계 선정에 어려움이 있어서 크로메이트 처리를 많이 실시하고 있다. 1세기 이상 사용한 크로메이트 처리기술은 뛰어난 방청성으로 인해 강판의 화성처리 및 도료용 피그먼트(pigment)로 사용되어 왔으며 크로메이트처리의 용도는 일차방청용, 인산염처리후 실링제(sealing) 및 도장하지용으로 분류할 수 있다. 먼처 일차 방청용을 살펴보면, 그 목표는 내식성 확보에 있고 염수 분무시간 24-72시간을 통상적으로 요구하고 있는 반면에, 인산염처리 후 Cr 실링(sealing)의 목적은 도장후 내식성이며 칼라도장 하지용인 경우에는 도장후 내식성 확보 뿐만 아니라 내 스크래치(scratch)성을 얻기 위해 처리를 한다.Phosphate treatment is a preliminary step of the coating treatment, and is mainly performed to secure coating adhesion, whereas chromate and coating treatment are often performed to obtain corrosion resistance. However, the coating treatment is reasonable to obtain corrosion resistance, but in order to secure the coating adhesion, there is a need to perform phosphate treatment before coating, and it is difficult to select a coating system for zinc-plated materials. The chromate treatment technology used for more than a century has been used for chemical conversion and coating of steel plate due to its excellent rust resistance.The chromate treatment is used for primary rust prevention, sealing and sealing after phosphate treatment. Can be classified. Looking at the primary rust protection first, the goal is to ensure corrosion resistance and usually requires 24-72 hours of salt spraying, whereas the purpose of Cr sealing after phosphate treatment is corrosion resistance after painting and color coating After coating, it is treated not only to secure corrosion resistance but also to obtain scratch resistance.
그러나 위와 같이 내식성을 보완하기 위하여 쉽게 처리하는 크로메이트처리는 1-2g 의 크롬산으로도 후두암을 유발하고 치사가능성도 있는 매우 유독물질일 뿐 아니라 폐수처리등의 환경문제를 유발시킬 수 있어 각국에서는 이에 대한 규제가 엄격하다. 예를들면, 미국의 경우 크로메이트 처리 작업장에서는 대기중의 Cr기준이 1mg/m3 day 이하이고, 유럽에서도 향후 6년내에 Cr6+사용규제 예정이며 미공군의 경우 1989년도 기준으로 크로메이트 용액 톤당 $220 의 폐수처리 비용을 부담하는 비경제적인 요인이 되기도 한다.However, chromate treatment, which is easily processed to compensate for corrosion resistance, can cause laryngeal cancer and mortality even with 1-2g of chromic acid, and can cause environmental problems such as wastewater treatment. Regulation is strict. For example, in the U.S., chromate treatment workplaces have less than 1 mg / m3 of Cr in the atmosphere, and in Europe, the use of Cr 6+ will be regulated within the next six years, while the U.S. Air Force will use $ 220 / ton of chromate solution in 1989. It is also an uneconomical factor in the cost of wastewater treatment.
상기와 같은 문제점을 해결하기 위하여 각국에서도 몰리브데이트(molybdate)계 및 수지계에 대하여 여러 연구결과가 보고되고 있으나 현장 라인에 적용하기에는 여러 한계가 있다. 몰리브데이트는 크로메이트 대체물질로 가장 유력하나 반응성 처리시간이 길고 크로메이트 처리 대비 동등 이상의 내식성을 확보하는 것이 과제로 남아 있다. 몰리브데이트 피막형성에 관한 기초 실험의 성격으로 전기아연도금 강판에 Na2MoO42H2O 30g/l 용액으로 음분극 과전압을 인가하여 몰리브데이트 피막을 형성하는 방법에 관하여 보고(D.R. Gabe, Surface and Coating Technology, 35, 79, 1988)하였으나 반응시간이 5-10 분이 소요되고 내식성도 열위한 문제점이 있다. 그 후 G.D. Wilcox는 아연도금강판에 Na2MoO42H2O 용액을 음분극 시키면서 형성된 피막을 ESCA로 분석하여 피막내의 Mo는 인가한 전압특성에 따라 Mo(Ⅳ) 와 Mo(Ⅴ) 의 혼재 혹은 Mo(Ⅴ) 단독으로 구성되어 있다고 분석하였으나 Cr 피막형성반응과 유사한 (Cr+6-------→ Cr+3) 반응이 Mo계에서도 형성되는 것으로 판단되지만 기술적 한계를 내포하고 있다. (Corrosion science 28, 6, p577, 1988). 한편, G.B. Nielsen 은 이러한 몰리브데이트 용액계에 인산을 첨가하여 Mo/P의 몰분율을 변화하면서 내식성을 비교한 염수분무시험에서는 기존의 Cr시편에 비하여 내식성이 열위하난 프로히젼 테스트(prohesion test)와 EMC 테스트에서는 기존의 Cr 시편과 동등이상의 내식성을 갖는다고 보고하였다. (Conference Modification of Passive Films, Feb, 1993).In order to solve the above problems, various studies have been reported in molybdate and resin systems in various countries, but there are various limitations in applying them to field lines. Molybdate is the most potent alternative to chromate, but its long-lasting treatment time remains a challenge to ensure corrosion resistance at least equal to that of chromate treatment. As a characteristic of the basic experiment on the formation of molybdate film, a report on the method of forming a molybdate film by applying a negative polarization overvoltage with a solution of Na 2 MoO 4 2H 2 O 30g / l on an electroplated steel sheet (DR Gabe, Surface and Coating Technology, 35, 79, 1988), but the reaction time is 5-10 minutes and corrosion resistance is poor. GD Wilcox then analyzed the film formed by negative polarization of Na 2 MoO 4 2H 2 O solution on the galvanized steel sheet by ESCA, and Mo in the film was mixed with Mo (Ⅳ) and Mo (Ⅴ) according to the applied voltage characteristics. It was analyzed that Mo (Ⅴ) alone, but the reaction (Cr +6 ------- → Cr +3 ) similar to Cr film formation reaction was also formed in Mo system, but it has technical limitations. (Corrosion science 28, 6, p577, 1988). On the other hand, GB Nielsen added the phosphoric acid solution to the molybdate solution system to change the mole fraction of Mo / P, and compared the corrosion resistance in the salt spray test compared to the existing Cr specimens, the prohesion test (prohesion test) EMC tests have reported corrosion resistance equivalent to or greater than conventional Cr specimens. (Conference Modification of Passive Films, Feb, 1993).
한편, 일본파카(주)에서는 10여년 전부터 일차방청용 및 칼라강판용으로 Cr대체 물질계에 대한 연구를 하였으나 표면 외관불량 및 내수 2차 밀착성 불량과 비용이 증가되는 문제점이 있다.On the other hand, Nippon Parka Co., Ltd. has been researching Cr substitute materials for primary antirust and color steel sheets for more than 10 years, but there are problems of poor surface appearance, poor water resistance and poor secondary adhesion.
본 발명은 상기와 같은 문제점을 해결하기 위한 것으로서, Cr 이 없는 질화규소 분산처리용액 및 산을 첨가하여 표면처리강판에 피막 처리할 수 있는 무크롬 처리용액을 사용하여 아연도금강판의 내식성을 향상시킬 수 있는 무크롬처리용액으로서, 질화규소 분산처리용액은 질화규소분말을 대상으로 분산제를 사용하여 분산처리하였으며 상기와 같은 방법으로 처리된 질화규소 분산처리 용액에 TiF6 2-를 첨가하여 내식성을 확보하고 또한 Ti 및 Zr 계 커플링 에이전트(coupling agent)를 소량 첨가하여 피막의 밀착성을 동시에 확보하는 무크롬 처리용액을 제공함에 그 목적이 있다.The present invention is to solve the above problems, it is possible to improve the corrosion resistance of galvanized steel sheet by using a non-chromic solution that can be coated on the surface-treated steel sheet by adding a silicon nitride dispersion treatment solution and acid without Cr. As a chromium-free treatment solution, the silicon nitride dispersion treatment solution was dispersed by using a dispersant for the silicon nitride powder, and TiF 6 2- was added to the silicon nitride dispersion treatment solution treated in the same manner as above to ensure corrosion resistance. It is an object of the present invention to provide a chromium-free treatment solution which simultaneously secures the adhesion of a film by adding a small amount of a Zr-based coupling agent.
이러한 목적을 달성하기 위한 본 발명은 무크롬 처리용액에 있어서 질화규소분말 100g, 분산제 4%를 사용하여 얻은 질화규소 분산용액 2-10 중량%(wt%), 산 10-25 wt% 및 커플링 에이전트 0.08-0.15wt% 범위인 것을 특징으로 하는 아연계 도금강판의 내식성을 향상시키는 무크롬 처리용액을 제공하는 것을 특징으로 한다.In order to achieve the above object, the present invention provides a silicon nitride dispersion solution 2-10% by weight (wt%), acid 10-25 wt% and a coupling agent 0.08 in a chromium-free solution using 100 g of silicon nitride powder and 4% of a dispersant. It is characterized by providing a chromium-free treatment solution to improve the corrosion resistance of the zinc-based galvanized steel sheet characterized in that the range of -0.15wt%.
이하, 본 발명을 상세히 설명하기로 한다.Hereinafter, the present invention will be described in detail.
본 발명은 무크롬 처리용액에 있어서 질화규소분말 100g, 분산제 4%를 사용하여 얻은 질화규소 분산용액 2-10 중량%(wt%), 산 10-25 wt% 및 커플링 에이전트 0.08-0.15wt% 범위인 것을 특징으로 하는 아연계 도금강판의 내식성을 향상시키는 무크롬 처리용액에 관한 것이며 처리방법은 롤코팅 화성처리방법이 더욱 바람직하다.The present invention is in the range of 2-10 wt% (wt%) of silicon nitride dispersion solution, 10-25 wt% of acid and 0.08-0.15wt% of coupling agent in a chromium-free solution using silicon nitride powder 100g, dispersant 4% It relates to a chromium-free treatment solution for improving the corrosion resistance of the zinc-based galvanized steel sheet, the treatment method is more preferably a roll coating chemical treatment method.
본 발명에서는 질화규소 분산용액 2-10 중량%(wt%), 산인 H2TiF610-25 wt% 및 커플링 에이전트 0.08-0.15wt% 로 제한하였는데 그 이유는 다음과 같다.In the present invention, the silicon nitride dispersion solution 2-10 wt% (wt%), the acid H 2 TiF 6 10-25 wt% and the coupling agent was limited to 0.08-0.15wt% for the following reasons.
먼저, 질화규소 분산용액이 2wt% 이하일 경우에는 내식성 향상에 기여하는 질화규소가 충분치 않아 우수한 내식성을 확보할 수 없으며 10wt% 이상일 경우에는 내식성은 확보되지만 처리된 강판의 표면외관이 불량해지고 피막밀착성이 열화될 우려가 크기 때문에 상기 질화규소 분산용액 농도를 2-10wt% 로 제한함이 바람직하다.First, when the silicon nitride dispersion solution is 2wt% or less, silicon nitride, which contributes to the improvement of corrosion resistance, is not sufficient to secure excellent corrosion resistance. If it is 10wt% or more, corrosion resistance is secured, but the surface appearance of the treated steel sheet is poor and the film adhesion is deteriorated. Since the concern is large, it is preferable to limit the silicon nitride dispersion solution to 2-10wt%.
한편 H2TiF6의 경우 10-25 wt% 범위로 한정을 하였으며 그 이유는 다음과 같다. 즉 10 wt% 이하이면 아연도금강판과의 충분한 반응이 발생하지 못하여 균일한 피막이 형성되지 않아서 표면외관 및 내식성이 불량해진다. 그러나 25wt% 이상일 경우에는 강판과의 반응이 너무 지나쳐서 아연도금강판의 아연이 많이 녹아 나와서, 즉 과에칭이 발생되어 적청발생이 용이해지는 문제점이 있으므로 강판과의 반응성 및 내식성의 상관관계를 고려하여 H2TiF6농도를 10-25wt% 로 제한하는 것이 바람직하다.Meanwhile, in the case of H 2 TiF 6 it was limited to the range of 10-25 wt%, for the following reasons. That is, if it is 10 wt% or less, sufficient reaction with the galvanized steel sheet does not occur, and a uniform coating is not formed, resulting in poor surface appearance and corrosion resistance. However, if it is 25wt% or more, the reaction with the steel sheet is so excessive that the zinc of the galvanized steel sheet melts a lot, that is, there is a problem in that red etching occurs easily due to overetching, so considering the correlation between the reactivity and the corrosion resistance with the steel sheet H It is desirable to limit the 2 TiF 6 concentration to 10-25 wt%.
피막의 밀착성을 향상시키기 위하여 Zr 또는 Ti 계 커플링 에이전트를 0.08-0.15wt%로 제한하였는 데 0.08wt 이하이면 충분한 피막밀착성을 확보할 수 없는 반면에 0.15wt% 이상이면 용액의 안정성에 문제가 발생하므로 상기와 같은 범위로 제한하는 것이 바람직하다.In order to improve the adhesion of the film, Zr or Ti-based coupling agent was limited to 0.08-0.15wt%. If it is 0.08wt or less, sufficient film adhesion cannot be secured, whereas if it is 0.15wt% or more, the stability of the solution will occur. Therefore, it is preferable to limit the above range.
이하, 실시예를 통하여 본 발명을 구체적으로 설명한다.Hereinafter, the present invention will be described in detail through examples.
(실시예)(Example)
본 발명에서 사용된 실리콘 화합물은 질화규소 분말로서 분산제를 이용하여 분산처리를 실시함으로서 분산처리된 질화규소 용액을 준비하였으며 비교하기 위해 실리콘 화합물인 분산처리된 실리카(Silica)를 같이 병행 처리하였다. 분산 처리된 실리콘 화합물에 물과 산을 첨가하여 무크롬 용액을 준비하여 사용된 산은 TiF6 2-이다. 또한 처리 피막의 밀착성을 향상시키기 위하여 상기와 같이 준비된 무크롬용액에 Ti 및 Zr 계 커플링 에이전트를 소량 첨가하여 각 피막의 특성을 조사하였으며 바 코터(bar coater) # 3 으로 표면처리강판인 EG 및 GI 소재에 무크롬 용액을 코팅하여 MT 70℃ 범위에서 5초간 건조시켜 무크롬 피막을 형성시켰다. 무크롬 피막의 물성은 내식성, 표면외관, 부착량 및 SEM 피막분석을 평가하였다. 이 때, 내식성을 평가하기 위하여 염수분무 시험장치(JIS E2731)를 이용하여 5% NaCl, 35℃, 분산압 1Kg/m2의 분사압력으로 분사한 후 5% 백청 발생시간을 측정하였다. 또한 색차계를 사용하여 백색도 등 표면색상을 측정하였으며 광택계를 사용하여 광택도를 측정하여 처리된 시편의 표면외관을 평가하였다. 한편, 무크롬 피막 부착량을 측정하기 위하여 무크롬 용액으로 처리된 시편 50φ의 피막을 제거시킨 용액의 Si, Ti를 분석하여 부착량을 측정하여 부착량을 구하였다. 이 때 Cr-free 피막을 제거하는데 사용된 용액은 HCl이다.The silicon compound used in the present invention was prepared by dispersing the silicon nitride solution by dispersing with a dispersant as silicon nitride powder, and was treated in parallel with the silica treated as a silicon compound. Used to prepare the chromium-free solution by the addition of water and acid to the silicon compound dispersion treatment acid it is TiF 6 2-. In addition, in order to improve the adhesion of the treated film, a small amount of Ti and Zr coupling agents were added to the chromium-free solution prepared as described above, and the characteristics of each film were investigated. The EG and the surface-treated steel sheet were coated with a bar coater # 3. A chromium-free solution was coated on the GI material and dried for 5 seconds in the MT 70 ° C to form a chromium-free film. The physical properties of the chromium-free film were evaluated for corrosion resistance, surface appearance, adhesion amount, and SEM film analysis. At this time, in order to evaluate the corrosion resistance by using a salt spray test apparatus (JIS E2731) 5% NaCl, 35 ℃, the dispersion pressure was measured after the injection pressure of 1Kg / m 2 5% white blue development time was measured. In addition, the surface color such as whiteness was measured using a color difference meter, and the surface appearance of the treated specimen was evaluated by measuring the glossiness using a glossmeter. On the other hand, in order to measure the amount of chromium-free coating, the amount of adhesion was determined by analyzing the amount of adhesion by analyzing the Si and Ti of the solution from which the coating of 50 φ of the specimen treated with the chromium-free solution was removed. At this time, the solution used to remove the Cr-free film is HCl.
주사전사현미경(SEM)을 이용하여 배율 2000 및 5000 배에서 무크롬 피막 결정형상을 관찰하여 피막처리성을 평가하였다. 또한, 무크롬 용액을 장기 보존(20이상)할 경우 용액이 엉기거나 또는 침전 발생되는등 용액의 안정성도 평가하였다.Using the scanning electron microscope (SEM), the chromium-free film crystal shape was observed at magnifications of 2000 and 5000 times to evaluate the film treatability. In addition, when the chromium-free solution was stored for a long time (20 or more), the stability of the solution was also evaluated, such as lumping or precipitation.
상기 표 1에서와 같이 무크롬용액이 본 발명의 범위를 만족하는 발명예(1-3, 6-8, 11-13)의 경우에는 내식성, 표면외관, 피막부착량, 피막밀착성 및 용액안정성의 특성이 모두 우수하게 나타났으며, 반면에 무크롬 용액이 본발명의 범위를 만족하지 못하는 비교예(4,5,8,9,10,14,15)의 경우에는 상기 피막 및 용액 특성들을 동시에 모두 만족하지 못함을 알 수 있다.In the case of the invention examples (1-3, 6-8, 11-13) in which the chromium-free solution satisfies the scope of the present invention as shown in Table 1 above, the characteristics of corrosion resistance, surface appearance, coating weight, film adhesion and solution stability All of them were excellent, whereas in the case of Comparative Example (4,5,8,9,10,14,15), where the chromium-free solution did not satisfy the scope of the present invention, both the film and the solution properties were simultaneously It can be seen that they are not satisfied.
본 발명에 의한 Cr 이 없는 질화규소 분산처리용액 및 산을 첨가하여 표면처리강판에 피막 처리할 수 있는 무크롬 처리용액을 사용하여 아연도금강판의 내식성을 향상시킬 수 있는 효과가 있다.By using a Cr-free silicon nitride dispersion treatment solution and an acid according to the present invention and using a chromium-free treatment solution which can be coated on the surface-treated steel sheet, there is an effect of improving the corrosion resistance of the galvanized steel sheet.
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| KR1019970075381A KR100345883B1 (en) | 1997-12-27 | 1997-12-27 | Free chrome treating solution for improving the corrosing resistance of the galvanized steel iron |
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| KR1019970075381A KR100345883B1 (en) | 1997-12-27 | 1997-12-27 | Free chrome treating solution for improving the corrosing resistance of the galvanized steel iron |
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| KR100437634B1 (en) * | 1999-12-14 | 2004-06-26 | 주식회사 포스코 | Resin for non-Cr passivation steel sheet |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100437634B1 (en) * | 1999-12-14 | 2004-06-26 | 주식회사 포스코 | Resin for non-Cr passivation steel sheet |
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