KR100436913B1 - Chromate treatment solution and method for manufacturing chromate treated steel - Google Patents
Chromate treatment solution and method for manufacturing chromate treated steel Download PDFInfo
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- KR100436913B1 KR100436913B1 KR10-1999-0049547A KR19990049547A KR100436913B1 KR 100436913 B1 KR100436913 B1 KR 100436913B1 KR 19990049547 A KR19990049547 A KR 19990049547A KR 100436913 B1 KR100436913 B1 KR 100436913B1
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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
- C23C22/32—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 pulverulent metals
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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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
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Abstract
본 발명은 내식성 및 내연료성이 우수한 자동차 연료탱크용 강판의 크로메이트 처리용액에 관한 것으로, 크로메이트 처리용액은 5~10g/ℓ농도의 크롬과, 5~8g/ℓ농도의 98% 황산과, 10~15g/ℓ농도의 70% 질산을 함유하는 주성분용액 및 5g/ℓ농도의 코발트 금속분말을 함유하는 보조성분용액이 혼합되어 있는 것을 특징으로 하므로, 연료탱크용 강판의 내식성 및 내연료성을 향상시킨다.The present invention relates to a chromate treatment solution of a steel plate for automobile fuel tanks excellent in corrosion resistance and fuel resistance, the chromate treatment solution is chromium 5 ~ 10g / ℓ, 98% sulfuric acid at 5 ~ 8g / ℓ, 10 The main component solution containing 70% nitric acid at a concentration of ˜15 g / l and the auxiliary component solution containing cobalt metal powder at a concentration of 5 g / l are mixed, thereby improving corrosion resistance and fuel resistance of the steel plate for fuel tank. Let's do it.
Description
본 발명은 자동차 연료탱크용 강판의 크로메이트 처리용액 및 크로메이트 처리강판의 제조방법에 관한 것이고, 특히 연료탱크용 강판의 내식성 및 내연료성을 향상시키기 위한 크로메이트 처리용액 및 크로메이트 처리강판의 제조방법에 관한 것이다.The present invention relates to a method for producing a chromate treated solution and chromate treated steel sheet of a steel sheet for automobile fuel tank, and more particularly to a method for producing a chromate treated solution and chromate treated steel sheet for improving the corrosion resistance and fuel resistance of the steel sheet for fuel tank will be.
일반적으로, 자동차의 주요 부품 중 하나인 연료탱크에 사용되는 재료는 우수한 내식성과 내연료성 뿐만 아니라 가공성 및 용접성 등의 여러가지 물성이 요구된다.In general, materials used in fuel tanks, which are one of the main parts of automobiles, require not only excellent corrosion resistance and fuel resistance but also various physical properties such as workability and weldability.
이러한 연료탱크용 소재로서, 종래 실시예에 따르면, 납과 주석의 합금이 피복되어 있는 턴 금속(terne metal)은 내식성 강판으로서 널리 사용되고 있다.As such a fuel tank material, according to a conventional embodiment, a turn metal coated with an alloy of lead and tin is widely used as a corrosion resistant steel sheet.
한편, 도금피막 상에 크롬산염 피막을 형성시켜 내식성을 개선하고, 표면에 광택을 제공하는 크로메이트 처리(chromate treatment) 방법은 반응방식, 도포방식및 전해방식의 3가지로 크게 구별된다.On the other hand, the chromate treatment method of forming a chromate film on the plating film to improve the corrosion resistance and provide gloss on the surface is largely classified into three types: reaction method, coating method and electrolytic method.
상기 도포방식에 따르면, 크로메이트 피막이 가장 우수한 내식성을 확보할 수 있으나, 건조 강판 온도가 200℃ 이상으로 유지되므로, 크로메이트 피막 내에서 Cr6+이 Cr3+로 천이하여 내식성이 열화되는 단점이 있다.According to the coating method, the chromate coating can secure the most excellent corrosion resistance, but since the dry steel sheet temperature is maintained at 200 ℃ or more, there is a disadvantage that Cr 6+ transitions to Cr 3+ in the chromate coating to deteriorate the corrosion resistance.
반면, 반응형 크로메이트 피막은 도포형 크로메이트 피막에 비하여 내식성이 다소 열약하나 건조강판 온도 차이에 의한 내식성 열화는 발생하지 않는다. 이는 반응형 크로메이트 피막 형성기구와 도포형 크로메이트 피막 형성기구의 차이에 기인한다. 즉, 반응형 크로메이트 피막은 피막형성과정에서 소지층과 화학적 결합에 의하여 안정적으로 형성되지만, 도포형 크로메이트 피막은 습윤피막내 잔류수분이 기화증발함으로써 건조피막으로 형성되므로, 건조온도에 따른 피막열화가 발생할 수 있다.On the other hand, the reactive chromate coating is somewhat inferior in corrosion resistance compared to the coated chromate coating, but the corrosion resistance deterioration due to the difference in dry steel temperature does not occur. This is due to the difference between the reactive chromate film forming mechanism and the coated chromate film forming mechanism. That is, the reactive chromate film is stably formed by chemical bonding with the base layer during the film formation process, but the coated chromate film is formed as a dry film by evaporation of residual moisture in the wet film, so that the film degradation due to drying temperature May occur.
즉, 반응형 크로메이트 피막은 피막형성과정에서 피막내 Cr6+/Cr3+비가 안정적으로 형성되어 건조온도에 따른 변화가 없는 반면, 도포형 크로메이트 피막은 잔류수분이 증발하면서 Cr6+/Cr3+비가 변화될 수 있다.In other words, the reactive chromate film has a stable Cr 6+ / Cr 3+ ratio in the film during the film formation process and does not change according to the drying temperature, whereas the coated chromate film has Cr 6+ / Cr 3 as the residual moisture evaporates. + The ratio can be changed.
한편, 최근 세계적으로 지구환경에 영향이 적고 자원의 재활용이 용이한 재료의 필요성이 제기되어 환경에 유해한 납을 사용하지 않는 대체 소재의 개발이 요구되고 있는 실정이다. 즉, 자동차 폐차 처리시 발생되는 분진 중의 납에 대한 규제가 강화되고 있다. 따라서, 기존에 사용중인 턴 강판을 대체할 수 있는 무연화 강판에 대한 필요성에 따라 용융알루미늄 도금강판, 아연수지피복강판 등에 관한 개발기술이 이루어지고 있는 실정이다.On the other hand, in recent years, the need for materials that have a low impact on the global environment and easy recycling of resources has been raised. Therefore, development of alternative materials that do not use lead harmful to the environment is required. In other words, regulations on lead in dust generated during the disposal of automobile scrap cars have been tightened. Therefore, according to the need for a lead-free steel sheet that can replace the existing turn steel sheet, the development technology for the molten aluminum plated steel sheet, zinc resin coated steel sheet and the like is being made.
예를 들어, 대한민국 특허공개공보 제97-703448호 및 일본 특개평9-59783호에는, 특수크로메이트를 사용한 연료탱크용 표면처리강판의 제조방법이 개시되어 있다. 그러나, 상기 특허문헌에 따른 크로메이트 처리방법은 가공 후의 내식성 저하를 막기 위하여, 아연-니켈 합금도금피막의 표면에 미세한 균열을 발생시킴으로써, 공정상의 부하를 유발시키며, 또한 연료 중에 함유된 수분에 의한 크롬용출로 인해 내연료성이 열화되는 문제점을 수반하게 된다.For example, Korean Patent Laid-Open Publication No. 97-703448 and Japanese Patent Laid-Open No. Hei 9-59783 disclose a method for producing a surface treated steel sheet for a fuel tank using a special chromate. However, the chromate treatment method according to the above patent document generates a crack in the surface of the zinc-nickel alloy coating film in order to prevent the corrosion resistance after processing, thereby causing a process load, and also due to chromium due to moisture contained in the fuel It is accompanied by a problem that fuel resistance deteriorates due to elution.
또한, 자동차 연료탱크용 강판은 도포형 크로메이트 피막처리 후 기판의 온도가 200℃ 이상 상승하는 수지피막 처리공정을 필연적으로 거치게 되므로, 수지피막 처리시 기판 온도가 상승함으로써 도포형 크로메이트 피막의 내식성이 열화되는 문제점을 유발한다.In addition, the steel sheet for automotive fuel tanks inevitably undergoes a resin coating treatment process in which the substrate temperature rises by 200 ° C. or higher after the coated chromate coating treatment. Therefore, the corrosion of the coated chromate coating is degraded when the substrate temperature increases during the treatment of the resin coating treatment. Cause problems.
상기된 바와 같은 종래의 문제점을 해결하기 위하여, 본 발명은 자동차 연료탱크용 강판으로서, 수지피막 건조온도 변화에 안정적인 반응형 크로메이트 피막의 내식성 및 내연료성을 향상시키기 위하여 금속코발트를 분산시킨 반응형 크로메이트 피막을 제조하기 위한 용액 및 크로메이트 처리된 강판의 제조방법을 제공하는 데 그 목적이 있다.In order to solve the conventional problems as described above, the present invention is a steel sheet for automotive fuel tank, the reaction type dispersing the metal cobalt in order to improve the corrosion resistance and fuel resistance of the reactive chromate coating stable to the resin film drying temperature change It is an object to provide a solution for producing a chromate coating and a method for producing a chromate treated steel sheet.
본 발명에 따르면, 상기 목적을 달성하기 위하여, 크로메이트 처리용액은 5~10g/ℓ농도의 크롬, 5~8g/ℓ농도의 98% 황산 및 10~15g/ℓ농도의 70% 질산을 함유하는 주성분용액과, 5g/ℓ농도의 코발트 금속분말을 함유하는 보조성분용액이 혼합되어 있는 것을 특징으로 한다.According to the present invention, in order to achieve the above object, the chromate treatment solution contains chromium at a concentration of 5 to 10 g / l, 98% sulfuric acid at a concentration of 5 to 8 g / l, and 70% nitric acid at a concentration of 10 to 15 g / l. A solution and an auxiliary component solution containing a cobalt metal powder at a concentration of 5 g / l are mixed.
본 발명의 다른 실시예에 따르면, 자동차 연료탱크용 크로메이트 처리강판의 제조방법은 5~10g/ℓ농도의 크롬과, 5~8g/ℓ농도의 98% 황산과, 10~15g/ℓ농도의 70% 질산을 함유하는 주성분용액을 준비하는 단계와, 5g/ℓ농도의 코발트 금속분말을 함유하는 보조성분용액을 준비하는 단계와, 상기 주성분용액에 대하여 상기 보조성분용액을 중량비로 10% 내지 20% 정도 혼합하여 혼합용액을 준비하는 단계와, 건조피막 부착량이 50~100㎎/㎡이 되도록 상기 혼합용액에 아연-니켈 합금도금강판을 침지시키는 단계로 이루어진 것을 특징으로 한다.According to another embodiment of the present invention, the method for producing a chromate-treated steel sheet for an automotive fuel tank includes chromium having a concentration of 5 to 10 g / l, 98% sulfuric acid at a concentration of 5 to 8 g / l, and 70 to a concentration of 10 to 15 g / l. Preparing a main component solution containing% nitric acid, preparing a secondary component solution containing a cobalt metal powder of 5 g / ℓ concentration, 10% to 20% by weight of the auxiliary component solution to the main component solution Preparing a mixed solution by mixing to a degree, and immersing the zinc-nickel alloy plated steel sheet in the mixed solution so that the dry film adhesion amount is 50 to 100 mg / m 2.
이하, 본 발명에 대하여 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated.
본 발명은 크롬과, 98% 황산과, 70% 질산을 소정 비율로 함유하는 주성분용액에 코발트 금속분말을 함유하는 보조성분용액을 일정 비율로 혼합함으로써, 우수한 내식성과 내연료성을 가지는 반응형 크로메이트 용액을 제공한다.The present invention is a reactive chromate having excellent corrosion resistance and fuel resistance by mixing chromium, 98% sulfuric acid, and 70% nitric acid in a predetermined ratio with a main component solution containing cobalt metal powder. Provide a solution.
또한, 상기된 바와 같이 제공된 크로메이트 용액을 사용하여, 아연-니켈 합금도금강판 상에 적절한 부착량을 가지도록 크로메이트 처리함으로써, 우수한 내식성, 내연료성 및 내크롬용출성을 갖는 자동차 연료탱크용 강판을 제조한다.In addition, by using the chromate solution provided as described above, by chromate treatment to have an appropriate adhesion amount on the zinc-nickel alloy plated steel sheet, to produce a steel sheet for automotive fuel tank having excellent corrosion resistance, fuel resistance and chrome elution resistance do.
즉, 본 발명에 따르면, 크롬산화물이 순수에 용해되어 있는 용액에 질산, 규불화수소산 및 황산을 투입하여 주성분용액을 제조하고, 코발트 금속분말을 실란커플링 에이젠트에 적정비로 분산시켜 보조성분용액을 제조한다.That is, according to the present invention, nitric acid, hydrofluoric acid and sulfuric acid are added to a solution in which chromium oxide is dissolved in pure water to prepare a main component solution, and cobalt metal powder is dispersed in a silane coupling agent at an appropriate ratio to form an auxiliary component solution. To prepare.
그리고, 이러한 주성분용액과 보조성분용액을 일정비율로 혼합시켜서 혼합용액을 제조한 후, 상기 혼합용액과 에폭시계 실레인이 수용액 상태로 용해되어 있는 경화제 용액을 적정비로 혼합하여 크로메이트 용액을 제조한다.Then, the main component solution and the auxiliary component solution are mixed at a constant ratio to prepare a mixed solution, and then the mixed solution and the curing agent solution in which the epoxy-based silane is dissolved in an aqueous state are mixed at an appropriate ratio to prepare a chromate solution.
즉, 본 발명의 일실시예에 따르면, 5~10g/ℓ농도의 크롬과, 5~8g/ℓ농도의 98% 황산과, 10~15g/ℓ농도의 70% 질산을 함유하는 주성분용액을 제조하고, 내식성 및 내연료성의 향상을 위하여 코발트 금속분말이 실란커플링 에이전트에 5g/ℓ 분산되어 있는 보조성분용액을 제조한 후, 상기 주성분용액에 대하여 상기 보조성분용액이 중량비 10~20%의 비율로 혼합되어 있는 혼합용액을 준비한다. 그리고, 상기 혼합용액과 에폭시계 실레인이 수용액 상태로 용해되어 있는 경화제 용액을 적정비로 혼합하여 크로메이트 용액을 제조한다.That is, according to one embodiment of the present invention, a main component solution containing chromium at a concentration of 5 to 10 g / l, 98% sulfuric acid at a concentration of 5 to 8g / l, and 70% nitric acid at a concentration of 10 to 15g / l is prepared. In order to improve corrosion resistance and fuel resistance, after preparing a co-component solution in which cobalt metal powder is dispersed in the silane coupling agent 5g / l, the co-component solution is a ratio of 10 to 20% by weight of the main component solution Prepare the mixed solution mixed with. In addition, the mixed solution and the curing agent solution in which the epoxy-based silane is dissolved in an aqueous solution are mixed at an appropriate ratio to prepare a chromate solution.
이와같이 제조된 크로메이트 용액에 아연-니켈 합금 전기도금강판을 침지시킨 후, 상기 강판을 건조시켜 피막 부착량 기준으로 50-100mg/㎡ 정도인 크로메이트 피막을 형성한다. 그리고, 상기 강판에 수지피막을 도포처리한 후, 상기 강판을 약 150∼250℃의 온도로 가열하여 우수한 내식성 및 내연료성을 가지는 자동차 연료 탱크용 크로메이트 처리강판을 제조한다.After immersing a zinc-nickel alloy electroplated steel sheet in the chromate solution thus prepared, the steel sheet is dried to form a chromate coating having a thickness of about 50-100 mg / m 2 based on the coating amount. After the resin coating is applied to the steel sheet, the steel sheet is heated to a temperature of about 150 to 250 ° C. to produce a chromate-treated steel sheet for an automotive fuel tank having excellent corrosion resistance and fuel resistance.
이하 본 발명의 구성에 대하여 자세히 설명하도록 하겠다.Hereinafter will be described in detail with respect to the configuration of the present invention.
주성분용액 제조를 위하여, 순수에 10∼20g/ℓ정도의 크롬산화물을 용해시키면, 크롬산화물는 용해되어 크롬이온, 즉 Cr6+를 생성하여, 용액내 전체 크롬농도는 5~10g/ℓ로 된다. 이때, 상기 주성분용액내 전체 크롬농도가 5g/ℓ 미만으로 유지되면 크로메이트 부착량이 저감하고, 10g/ℓ를 초과한 경우에는 추후에 보조성분으로 투입되는 실란커플링 에이전트와 침적반응을 일으키게 되어 바람직하지 못하게 된다.For the preparation of the main component solution, when 10-20 g / l of chromium oxide is dissolved in pure water, the chromium oxide is dissolved to form chromium ions, namely Cr 6+, and the total chromium concentration in the solution is 5-10 g / l. At this time, if the total chromium concentration in the main component solution is maintained below 5g / ℓ, the amount of chromate adhesion is reduced, if it exceeds 10g / ℓ it is preferable to cause a deposition reaction with the silane coupling agent that is added as a secondary component later I can't.
한편, 98% 황산을 5~8g/ℓ정도로 용해시키면, 황산에 함유된 설페이트음이온이 크로메이트 피막형성을 촉진하는 역할을 하므로, 크로메이트 피막 부착량을 증가시키게 된다. 그러나, 98% 황산이 5g/ℓ 미만으로 용해되어 있으면 피막형성 촉진에 영향을 미치지 못하게 되고, 8g/ℓ를 초과하여 투입되면 오히려 피막형성 반응을 저해하게 된다.On the other hand, when the 98% sulfuric acid is dissolved at about 5 ~ 8g / ℓ, sulfate anion contained in sulfuric acid plays a role in promoting the formation of chromate film, thereby increasing the amount of chromate coating. However, if 98% sulfuric acid is dissolved at less than 5g / L does not affect the promotion of the film formation, if more than 8g / L injected rather than inhibits the film formation reaction.
그리고, 크롬산화물와 98% 황산이 용해된 용액의 산도(pH) 조정, 즉 크로메이트 용액의 산도를 1.0 내지 1.2 정도로 유지하기 위하여, 70% 질산이 10~15g/ℓ정도 투입되는 것이 바람직하다. 이때, 70% 질산이 15g/ℓ를 초과하여 투입되어 용액의 산도가 너무 높으면 피복대상 금속강판에 대한 용액의 에칭력, 즉 부식력이 증대되므로 크로메이트 용액 내에 금속이온 농도가 증가하게 되지만, 70% 질산이 10g/ℓ미만으로 투입되어 용액의 산도가 너무 낮으면 피막반응 속도가 상대적으로 낮아지는 단점이 있다.In addition, in order to adjust the acidity (pH) of the solution in which chromium oxide and 98% sulfuric acid is dissolved, that is, to maintain the acidity of the chromate solution at about 1.0 to 1.2, it is preferable that 70% nitric acid is added at about 10 to 15 g / l. At this time, if 70% nitric acid is added in excess of 15 g / ℓ and the acidity of the solution is too high, the etching force, that is, the corrosion force of the solution to the metal sheet to be coated increases, so that the metal ion concentration in the chromate solution increases, but 70% If the acidity of the solution is too low because nitric acid is less than 10g / ℓ has a disadvantage that the film reaction rate is relatively low.
그리고, 코발트 금속분말을 실란커플링 에이전트에 5g/ℓ정도로 희석하여 보조성분을 제조한다. 이때, 실란커플링 에이전트에 대한 코발트 금속분말의 포화농도가 5g/ℓ이므로, 코발트 금속분말이 5g/ℓ를 초과하여 투입되면 코발트분말의 침전이 발생되어 바람직하지 못하게 된다.Then, the cobalt metal powder is diluted to about 5 g / l in the silane coupling agent to prepare an auxiliary component. At this time, since the saturation concentration of the cobalt metal powder to the silane coupling agent is 5g / ℓ, if the cobalt metal powder is added in excess of 5g / ℓ, precipitation of the cobalt powder is generated undesirably.
상술된 바와 같이 제조된 주성분용액에 보조성분 용액이 중량비로 10~20% 혼합된 혼합용액에 아연-니켈 합금도금강판을 침지시키면, 아연-니켈 합금도금강판에 반응형 크로메이트 피막이 형성되며, 보조성분용액에 첨가된 코발트는 피막 내에 분산존재하게 된다.When the zinc-nickel alloy plated steel sheet is immersed in the mixed solution in which the auxiliary component solution is mixed by 10 to 20% by weight in the main component solution prepared as described above, a reactive chromate film is formed on the zinc-nickel alloy plated steel sheet. Cobalt added to the solution is dispersed in the coating.
그리고, 상기 피막 내의 코발트는 실란 커플링 에이전트와 결합하여 크로메이트 피막의 가교성을 증대시키므로, 상기 피막의 내식성과 내연료성을 향상시킨다. 또한, 상기 피막에 존재하는 코발트는 전자를 방출하여 4가 혹은 5가의 금속이온으로 천이하며, 이러한 금속이온에 의하여 아연-니켈 합금도금강판의 산화반응 보다 먼저 진행되는 소위 자기수복효과가 발생함으로 크로메이트 피막의 내식성과 내연료성이 증가한다.In addition, cobalt in the coating increases the crosslinkability of the chromate coating by binding to a silane coupling agent, thereby improving corrosion resistance and fuel resistance of the coating. In addition, the cobalt present in the film releases electrons and transitions to tetravalent or pentavalent metal ions, and the metal ions are chromated because the so-called self-healing effect occurs before the oxidation reaction of the zinc-nickel alloy plated steel sheet. The corrosion resistance and fuel resistance of the film increase.
이하 본 발명의 실시예를 중심으로 보다 상세히 설명하다.Hereinafter, the embodiment of the present invention will be described in more detail.
< 실시예 1 ><Example 1>
먼저, 하기 표 1을 참조하면, 비교재1은 코발트 금속성분이 혼합되어 있지 않은 용액이고, 비교재2는 코발트 금속성분만이 혼합되어 있는 용액이고, 비교재3은 실란커플링 에이전트만이 혼합되어 있는 용액이다. 본 발명에 따른 크로메이트 용액과 상기 비교재들의 용액에 아연-니켈 합금이 30 g/㎡ 정도 부착되어 있는 전기도금강판의 시편을 침지시키고, 40℃의 온도에서 10초간 크로메이트 처리한 후, 상기 시편의 내식성, 내연료성을 비교평가 하였다.First, referring to Table 1 below, Comparative Material 1 is a solution in which cobalt metal components are not mixed, Comparative Material 2 is a solution in which only cobalt metal components are mixed, and Comparative Material 3 is mixed with only silane coupling agents. Solution. After immersing a specimen of an electroplated steel sheet having a zinc-nickel alloy of about 30 g / m 2 attached to a solution of the chromate solution and the comparative materials according to the present invention, and after chromate treatment for 10 seconds at a temperature of 40 ℃, Corrosion resistance and fuel resistance were evaluated.
이때, 내식성은 ASTM B-117의 조건으로 5% 백청 발생시 까지의 소요시간으로 평가하였으며, 내연료성은 상기 시편을 컵으로 가공한 후, 가솔린과 3.5% 염수의혼합용액에 3개월간 침적하여 표면의 녹발생 정도를 비교관찰 하였다.At this time, the corrosion resistance was evaluated by the time required until the occurrence of 5% white rust under the conditions of ASTM B-117, and the fuel resistance was processed into a cup, and then immersed in a mixed solution of gasoline and 3.5% saline for 3 months to The degree of rust development was observed.
즉, 본 실험에서는 크로메이트 용액에서 주성분용액의 용액성분비를 고정한 후, 보조성분용액이 혼합되지 않은 용액(비교재1), 코발트 금속성분만 첨가되어 있는 용액(비교재2) 및 실란커플링 에이전트만 첨가되어 있는 용액(비교재3)의 물성을 비교 평가하였다. 비교평가 결과 본 발명에 따른 크로메이트 용액의 내식성과 내연료성이 향상된 것을 알 수 있다.That is, in this experiment, after fixing the solution component ratio of the main component solution in the chromate solution, the solution in which the auxiliary component solution was not mixed (Comparative Material 1), the solution containing only the cobalt metal component (Comparative Material 2) and the silane coupling agent were added. The physical properties of the prepared solution (Comparative Material 3) were evaluated. Comparative evaluation results show that the corrosion resistance and fuel resistance of the chromate solution according to the present invention is improved.
< 실시예 2 ><Example 2>
주성분용액과 보조성분용액의 혼합비율 변화에 따른 크로메이트 피막의 내식성과 내연료성을 하기 표 2에 기재하였다. 즉, 보조성분용액을 혼합하지 않은 용액을 비교재1로 기재하였으며, 보조성분용액의 혼합 중량비 함량 변화에 따른 결과를 발명예로 기재하였다.The corrosion resistance and fuel resistance of the chromate film according to the mixing ratio of the main component solution and the auxiliary component solution are shown in Table 2 below. That is, the solution without mixing the auxiliary component solution was described as Comparative Material 1, and the result according to the change in the mixed weight ratio content of the auxiliary component solution was described as the invention example.
크로메이트 피막 중량은 무게 감량법에 의해 측정하였다. 발명예2를 참조하면, 보조성분용액의 혼합 중량비가 5%일 경우 내식성 및 내연료성의 향상 효과를 기대할 수 없다는 것을 알 수 있고, 발명예2와 3를 참조하면, 보조성분용액의 혼합 중량비가 10%∼20%일 경우 내식성 및 내연료성이 가장 우수한 것을 알 수 있다.The chromate coating weight was measured by the weight loss method. Referring to Inventive Example 2, it can be seen that when the mixing weight ratio of the auxiliary component solution is 5%, the improvement effect of corrosion resistance and fuel resistance cannot be expected. Referring to the invention examples 2 and 3, the mixing weight ratio of the auxiliary component solution is In the case of 10% to 20%, it can be seen that corrosion resistance and fuel resistance are the best.
한편, 발명예4를 참조하면, 보조성분용액의 혼합 중량비가 25%를 넘어갈 경우, 내식성 및 내연료성이 다소 열악해진다는 것을 알 수 있는 데, 이는 보조성분용액의 중량비 증가에 따른 주성분용액의 혼합비율 감소로 크로메이트 피막의 부착량이 오히려 감소하기 때문인 것으로 판단된다.On the other hand, referring to Inventive Example 4, when the mixing weight ratio of the auxiliary component solution exceeds 25%, it can be seen that the corrosion resistance and fuel resistance is somewhat poor, which is due to the increase in the weight ratio of the auxiliary component solution It is considered that the amount of adhesion of the chromate coating is rather reduced due to the decrease in the mixing ratio.
따라서, 본 발명에 따르면, 코발트를 함유한 크로메이트 용액에 아연-니켈 합금도금 강판을 침지하여 크로메이트 처리할 경우, 보조성분용액에 첨가된 코발트가 크로메이트층 내에 분산되므로, 기존 강판대비 내식성과 내연료성이 우수한 연료 탱크용 소재를 만들 수 있다.Therefore, according to the present invention, when the zinc-nickel alloy plated steel sheet is immersed in a chromate solution containing cobalt and chromated, the cobalt added to the auxiliary component solution is dispersed in the chromate layer, which is more corrosion resistant and fuel resistant than the conventional steel sheet. This excellent fuel tank material can be made.
이상, 상기 내용은 본 발명의 바람직한 실시예를 단지 예시한 것으로, 본 발명이 속하는 분야의 당업자는 첨부된 청구범위에 기재된 본 발명의 사상 및 요지로부터 벗어남이 없이 본 발명에 대한 수정 및 변경을 가할 수 있다.The foregoing merely illustrates preferred embodiments of the invention, and those skilled in the art to which the invention pertains may make modifications and changes to the invention without departing from the spirit and gist of the invention as set forth in the appended claims. Can be.
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| KR19990067737A (en) * | 1998-01-07 | 1999-08-25 | 사또미 유따까 | Surface treatment process for hot-dip zinciferous plated steel sheet |
| KR20010002691A (en) * | 1999-06-16 | 2001-01-15 | 홍영철 | Method for coating a cromate on galvanized wire |
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| KR19990067737A (en) * | 1998-01-07 | 1999-08-25 | 사또미 유따까 | Surface treatment process for hot-dip zinciferous plated steel sheet |
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