KR101227059B1 - Plating solution and method for zirconium alloy plating and titanium alloy plating - Google Patents
Plating solution and method for zirconium alloy plating and titanium alloy plating Download PDFInfo
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- KR101227059B1 KR101227059B1 KR1020120088709A KR20120088709A KR101227059B1 KR 101227059 B1 KR101227059 B1 KR 101227059B1 KR 1020120088709 A KR1020120088709 A KR 1020120088709A KR 20120088709 A KR20120088709 A KR 20120088709A KR 101227059 B1 KR101227059 B1 KR 101227059B1
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- C25D3/00—Electroplating: Baths therefor
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- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
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- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/52—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating using reducing agents for coating with metallic material not provided for in a single one of groups C23C18/32 - C23C18/50
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- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50
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Abstract
Description
본 기술은 지르코늄 합금 도금 및 티타늄 합금 도금액 및 도금 방법에 관한 것이다.
This technology relates to a zirconium alloy plating and a titanium alloy plating solution and a plating method.
이 기술의 발명자는 2011년 2월 티타늄 이온 수용액을 발명하면서, 이 티타늄 이온 수용액을 이용한 합금 도금이 가능하다는 것을 알고 대한민국 특허 출원번호 10-2011-0074492호의 특허를 발명하였으며, 이외에 대한민국 특허 출원번호 10-2011-0016960호, 대한민국 특허 출원번호 10-2011-0074496호를 통하여 지르코늄 합금 도금 및 티타늄의 합금 도금을 실시 하였다.The inventor of the present invention invented a titanium ion aqueous solution in February 2011 and discovered a patent of Korean Patent Application No. 10-2011-0074492 in recognition of the fact that alloy plating using the aqueous solution of titanium ion is possible. In addition, Korean Patent Application No. 10 -2011-0016960, Korean Patent Application No. 10-2011-0074496, and zirconium alloy plating and titanium alloy plating were carried out.
그러나, 티타늄의 경우 대한민국 특허 출원번호 10-2011-0074492호의 내용과 같이, 전기도금시 저전류 부위에 피복이 되지 않는 문제가 심하게 발생하였고, 이러한 문제를 제거하기 위하여, pH를 상승시키면, Ti의 공석비가 낮아져서 원하는 내식성등의 물성을 얻을 수 없었다.However, in the case of titanium, as described in Korean Patent Application No. 10-2011-0074492, when the electroplating is performed, the problem of not covering the low current portion occurs severely, and in order to eliminate such a problem, The vacancy ratio was lowered and the desired properties such as corrosion resistance could not be obtained.
또한 pH를 더욱 낮추어 Ti의 공석비를 향상시키려고 하면, 도금 범위가 너무 좁아 산업상 이용하기가 불가능할 정도로 도금 범위가 부족하였으며, 표면이 거칠었다. 뿐만 아니라, 도금액은 티타늄 이온의 강한 전기저항 때문에 쉽게 검은 색으로 분해되는 현상이 발생하여 도금액 관리가 어렵다는 단점이 있었다.Further, if the pH is further lowered to improve the vacancy ratio of Ti, the plating range is too narrow, the plating range is insufficient to be industrially applicable, and the surface is rough. In addition, the plating solution is easily decomposed into black due to strong electrical resistance of the titanium ion, which makes it difficult to manage the plating solution.
한편, 대한민국 특허 출원번호 10-2011-0074496호에 의한 지르코늄 합금 전기도금액 조성물 관련된 특허를 통해 지르코늄 합금 도금을 실시할 경우에도 해당 특허에 첨부된 사진에서처럼, 표면 외관이 상품성을 가지지 못할 만큼 심하게 거칠고, 구름낀 현상을 제거하기 어려웠다.On the other hand, when a zirconium alloy plating is performed through a patent related to a zirconium alloy electroplating composition according to Korean Patent Application No. 10-2011-0074496, as shown in the photograph attached to the patent, the surface appearance is so rough , It was difficult to remove the cloudy phenomenon.
이러한 문제는 지르코늄과 티타늄이 다른 도금 가능한 금속에 비하여 낮은 전기전도도를 가지는 금속의 고유 특성과 관계가 있다.This problem is related to the intrinsic properties of metals with low electrical conductivity compared to other platable metals such as zirconium and titanium.
[표 1]에서 보듯 지르코늄과 티타늄의 경우 평상시에 도금금속으로 사용되는 금속에 비하여 현저히 낮은 전기전도도를 보이는 금속으로서, 전해도금에서 가장 많은 전기적 환원력을 요구하는 크롬보다도 전기전도도가 3배 이상 낮은 금속들이다. As shown in Table 1, zirconium and titanium show significantly lower electrical conductivity than metals used as plating metals in ordinary cases. They are metals that have electric conductivity three times lower than that of chromium, which requires the most electricity reduction power in electrolytic plating. admit.
이러한 이유로 도금시에 많은 부하와 저항을 발생시켜 도금액을 분해시키고, 높은 에너지를 요구하였으며, 이렇게 어렵게 도금된 제품도 외관이 상품성을 가지기 어려울 정도로 표면이 거칠었다.For this reason, a large amount of load and resistance were generated during plating to decompose the plating solution, requiring a high energy, and the surface of the plated product was so rough that the appearance did not have commercial merit.
뿐만 아니라 티타늄의 경우, 금속으로 환원되자마자 물(H2O)에서 산소를 빼앗아 O2피막이 발생하는 문제로 수용액 상에서의 도금을 더욱 어렵게 만든다. 다만, 지르코늄의 경우 전통적인 무전해 도금 방식에 의한 합금 도금층을 얻을 수 있었지만, 전기도금 방식에 의하여서는 역시 티타늄만큼 낮은 전기 전도도로 인하여 같은 문제가 발생하였다.In addition, in the case of titanium, the O 2 coating is formed by taking oxygen from water (H 2 O) as soon as it is reduced to metal, which makes plating in the aqueous solution more difficult. However, in the case of zirconium, an alloy plating layer by a conventional electroless plating method could be obtained, but the same problems were also caused by the electroconductivity as low as titanium by the electroplating method.
또한, 착화제로 사용한 DL-Tartaric acid이 티타늄과 지르코늄의 착화제 역할을 하긴 하였지만 충분하지 아니하였고, 공석되는 다른 금속이 같이 연결되지 않는 단독적인 착화제이며, 전도 보조제 역할을 수행하지도 못하여 피복력 향상에 도움이 되지 못하였다.
Although DL-Tartaric acid used as a complexing agent was a complexing agent for titanium and zirconium, it was not sufficient. However, it was not sufficient for other complex metals to be bonded together and could not serve as a conductive auxiliary agent. It did not help.
따라서 전통적인 전기도금 방식으로는 피복력이 우수하며, 높은 내식성과 내산성을 가진 지르코늄 합금 도금층 또는 티타늄 합금 도금층을 낮은 pH에서 얻는 것은 어려웠다.
Therefore, it has been difficult to obtain a zirconium alloy plating layer or a titanium alloy plating layer having a high corrosion resistance and acid resistance at a low pH by a conventional electroplating method.
본 발명의 목적은 피복력이 우수한 티타늄 또는 지르코늄 합금 도금방법을 제공하는 것이다.An object of the present invention is to provide a titanium or zirconium alloy plating method excellent in coating ability.
본 발명의 다른 목적은 제공된 도금 방법을 원활하게 사용하기 위한 도금액을 제공하는 것이다.Another object of the present invention is to provide a plating solution for smoothly using the provided plating method.
본 발명의 또 다른 목적은 제공된 도금액을 이용하여 외관이 미려하고, 높은 내구성을 가진 지르코늄 합금 도금층 또는 티타늄 합금 도금층을 가진 도금제품을 제공하는 것이다.
Another object of the present invention is to provide a plated product having a zirconium alloy plating layer or a titanium alloy plating layer having a good appearance and high durability by using the plating solution provided.
본 발명에 의한 티타늄 및 지르코늄 합금 도금액으로 도금된 제품은 높은 내구성과 뛰어난 장식성으로 향후 표면처리 전반을 빠른 속도로 대체해 나갈 것이다.The product plated with the titanium and zirconium alloy plating solution according to the present invention will rapidly replace the entire surface treatment with high durability and excellent decorative property in the future.
특히 6가 크롬 대체기술로써 높은 내구성과 내식성을 가지는 것은 물론, 우수한 피복력을 가지고 있기 때문에 종래의 도금 공정에서 아무런 무리 없이 사용할 수 있을 뿐만 아니라, 높은 욕 안정성으로 경제성 또한 뛰어나다.Especially, it has high durability and corrosion resistance as an alternative to hexavalent chromium, and it has excellent covering power, so it can be used without any trouble in the conventional plating process, and also has excellent economical efficiency with high bath stability.
본 발명의 기술적 사상 또는 보호 범위 내에서 당 분야의 통상의 지식을 가진 자에 의해 본 발명의 변형이나 개량이 가능함이 명백하다. 따라서, 본 발명의 단순한 변형 내지 변경은 모두 본 발명의 영역에 속하는 것으로 본 발명의 구체적인 보호 범위는 첨부된 특허 청구 범위 및 그 동등범위에 의하여 명확해질 것이다.
It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Accordingly, it is intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents.
도 1은 연결형 착화제의 모형도.
도 2는 지르코늄-니켈 순수 전기 도금 사진.
도 3은 지르코늄-니켈 복합 환원 도금 사진.
도 4는 티타늄-니켈 순수 전기 도금 사진.
도 5는 티타늄-니켈 복합 환원 도금 사진.1 is a model diagram of a coupling complex;
2 is a zirconium-nickel pure electroplating photograph.
3 is a zirconium-nickel composite reduction plating photograph.
Figure 4 is a pure titanium electroplating photo.
FIG. 5 is a photograph of a titanium-nickel composite reduction plating. FIG.
상기 목적을 달성하기 위하여 본 발명에서는, 티타늄 및 지르코늄 합금 도금층을 형성하기 위한 복합 환원 도금방법을 제공한다.In order to achieve the above object, the present invention provides a composite reduction plating method for forming a titanium and zirconium alloy plating layer.
또한 복합 환원 도금방법을 선택적으로 사용할 수 있는 도금액을 제공한다.Also provided is a plating solution capable of selectively using a complex reduction plating method.
또한, 본 발명은 복합환원 도금방법을 사용할 수 있는 도금액의 제조방법에 있어서, a) 지르코늄화합물 또는 티타늄 화합물 중 적어도 하나 이상을 제공하는 단계; 및 b) 상기 a)단계의지르코늄 또는 티타늄 화합물을 액상화시키는 단계; c) 상기 b)단계의 액상에 착화제로 구연산 화합물을 투입하는 단계; 상기 d)단계의 용액에 티타늄 또는 지르코늄과 합금화될 주요 금속화합물을 용해하는 단계; e) 상기 d)단계의 액상에 필요에 따라 환원제를 투입하는 단계; f) 상기 e)단계의 액상에 필요에 따라 보조금속이온을 추가적으로 투입하는 단계; g) 상기합금도금액의 pH를 조절하는 단계;를 포함하는 티타늄 및 지르코늄 합금복합환원방식 도금액의 제조방법을 제공한다.The present invention also provides a method for producing a plating solution capable of using a complex reduction plating method, comprising the steps of: a) providing at least one of a zirconium compound or a titanium compound; And b) liquefying the zirconium or titanium compound of step a); c) introducing the citric acid compound as a complexing agent into the liquid phase of step b); Dissolving the main metal compound to be alloyed with titanium or zirconium in the solution of step d); e) adding a reducing agent if necessary to the liquid phase of step d); f) additionally adding auxiliary metal ions to the liquid phase of step e) as required; and g) adjusting the pH of the alloy. The present invention also provides a method for producing a titanium and zirconium alloy composite reduction plating solution.
이하에서는 본원 발명의 구성수단의 작용과 바람직한 실시예를 중심으로 본원발명을 상세하게 설명한다.Hereinafter, the present invention will be described in detail with reference to the operation of the constituent means of the present invention and a preferred embodiment thereof.
도금에 사용할 지르코늄 이온 및 티타늄 이온을 을 첨가하는 방법은 종류가 많고 다양하다. Methods for adding zirconium ions and titanium ions to be used for plating are many and varied.
티타늄의 경우 발명자의 발명에 의하여 확인된 이산화티타늄을 진한 황산에 용해하여 사용할 수도 있고, 사염화티타늄을 티타늄 클로라이드로 만들어 사용할 수도 있으며, 이 이외에 삼염화티타늄, 이염화티타늄등 다양한 티타늄 화합물이 있다.In the case of titanium, titanium dioxide identified by the inventor's invention may be dissolved in concentrated sulfuric acid, or titanium tetrachloride may be used as titanium chloride. In addition, various titanium compounds such as titanium trichloride, titanium dichloride and the like can be used.
또 지르코늄의 경우에도 사염화 지르코늄(ZrCl4), 황산지르코늄 (Zr(SO4)2·4H2O), 지르코늄 옥시 클로라이드 (ZrOCl2 8H2O), 이산화지르코늄 ( ZrO2 ), 아세트산, 지르코늄 염 ( cas no. 7585-20-8 ) 등 약 40여종에 이른다.In the case of zirconium, zirconium tetrachloride (ZrCl 4 ), zirconium sulfate (Zr (SO 4 ) 2 .4H 2 O), zirconium oxychloride (ZrOCl 2 8H 2 O), zirconium dioxide (ZrO 2 ), acetic acid, cas no. 7585-20-8).
따라서 본 발명은 상기 목적을 달성하기 위한 방편으로 손쉽게 지르코늄 또는 티타늄 이온을 얻을 수 있는 황산지르코늄, 옥시염화지르코늄 및 황산티타늄을 출발물질로 하여 설명하지만 여기에 국한되는 것은 아니다.Accordingly, the present invention will be described with reference to zirconium sulfate, zirconium oxychloride, and titanium sulfate which can easily obtain zirconium or titanium ions as a starting material, but the present invention is not limited thereto.
본 발명은 티타늄과 지르코늄 이온이 전기전도도가 나빠서 순수한 전기의 환원력으로는 높은 피복력을 확보할 수 없기 때문에, 환원제를 이용한 화학적 환원과 전기적 환원을 도금시에 모두 사용하여 높은 피복력을 확보하여, 티타늄 및 지르코늄 합금 도금의 문제를 해결한다.Since titanium and zirconium ions have poor electrical conductivity and can not secure a high covering power with a pure electricity reducing power, it is possible to use both a chemical reduction using a reducing agent and an electric reduction at the time of plating to secure a high covering power, Solves the problem of zirconium alloy plating.
지르코늄의 경우 화학적 환원제로 무전해 합금 도금이 가능하지만, 티타늄의 경우에는 수용액속에서 무전해 합금 도금을 하고자 하면, 처음에는 환원반응이 일어나지만, 이후 도금액 내의 물(H2O)에서 산소를 받아들여 산화피막을 쉽게 만들기 때문에 이후 두께도금이 불가능한 단점이 있다. (반응은 지속되지만 도금층이 형성되지는 않는다.)In the case of zirconium, electroless alloy plating is possible as a chemical reducing agent. However, in the case of titanium, if electroless alloy plating is performed in an aqueous solution, reduction reaction occurs at first, then oxygen in water (H 2 O) So that it is impossible to perform thickness plating afterwards. (The reaction is continued, but no plating layer is formed.)
또한 전기도금에 있어서는 전술한 바와 같이 낮은 전기전도도로 인하여, 넓은 피복력을 얻기가 어려웠다. Further, in electroplating, it has been difficult to obtain a wide covering ability due to the low electric conductivity as described above.
넓은 피복력을 얻고자 pH를 상승시킬 경우 낮은 공석비로 인하여, 내식성 또는 내산성이 낮아져 합금 도금의 의미가 줄어드는 단점이 있었다. When the pH is increased to obtain a wide coverage, the corrosion resistance or acid resistance is lowered due to a low vacancy ratio, and the meaning of the alloy plating is reduced.
본 발명은 이러한 문제를 해결하기 위하여, 치환도금이 아닌 환원도금 방식에 사용되는 화학적 환원제를 도금액에 첨가하여 화학적 환원력을 이용하면서, 전기를 인가하는 방식으로 전기의 환원력을 동시에 사용하여 티타늄과 지르코늄이 가지고 있는 부족한 전기전도도를 극복한다.In order to solve the above problems, the present invention provides a method of reducing the amount of titanium and zirconium in a plating solution by using a chemical reducing agent, which is used in a reducing plating method other than displacement plating, Overcome the lack of electrical conductivity that you have.
본 발명에 있어서 환원제는 차아인산이온과 붕소이온 또는 포르말린, 글리옥실산, 히드라진을 사용할 수 있다. 좀 더 구체적으로는 차아인산나트륨, 차아인산칼륨, 차아인산암모늄, 디메틸아민보란(DMAB), 디에틸아민보란(DEAB), 수소화붕소나트륨, 히드라진, 포르말린, 글리옥실산 등을 들 수 있다. In the present invention, as the reducing agent, a hypophosphite ion and a boron ion or formalin, glyoxylic acid, and hydrazine can be used. More specifically, there may be mentioned sodium hypophosphite, potassium hypophosphite, ammonium hypophosphite, dimethylamine borane (DMAB), diethylamine borane (DEAB), sodium borohydride, hydrazine, formalin and glyoxylic acid.
이러한 환원제의 사용과 함께, 0.5A/dm2 내지 10A/dm2의 전기를 인가하여 도금하여, 폭 넓은 피복력을 확보할 수 있다. 0.5A/dm2 미만은 인가하는 전류량이 너무 미약하여 효과가 미미하고, 10A/dm2 초과의 높은 전류까지는 필요로 하지 않는다.With the use of such a reducing agent, plating can be performed by applying electricity of 0.5 A / dm 2 to 10 A / dm 2 to secure wide coverage. When the current is less than 0.5 A / dm 2, the amount of current to be applied is too weak and the effect is insignificant, and a high current exceeding 10 A / dm 2 is not required.
또한, 이러한 환원제와 전기적 환원을 동시에 사용하기에 적합한 착화제로서 종래에 사용하는 DL-Tartaric acid은 전도보조제 역할을 하지도 못하고, 같이 도금하는 금속들과의 연결형 착화제 역할도 하지 못하여 적합하지 아니하다. 즉, DL-tartaric acid는 티타늄 이온이나 지르코늄 이온의 착화제 역할은 하였지만, 같이 공석되는 니켈이나 코발트에 대하여는 착화제 역할을 수행하지 못하였기 때문에 높은 피복력을 얻기가 더더욱 힘들었다. DL-Tartaric acid, which is conventionally used as a complexing agent suitable for simultaneously using the reducing agent and the electric reduction, is not suitable because it does not serve as a conduction auxiliary agent and can not serve as a coupling agent for a metal to be plated together . That is, although DL-tartaric acid was a complexing agent for titanium ions and zirconium ions, it was harder to obtain a high coating power because it did not function as a complexing agent for nickel or cobalt which was co-deposited.
여기서 연결형 착화제란 티타늄 및 지르코늄과 주요 공석 금속인 니켈 및 코발트가 한가지의 착화제를 사이에 두고 공통으로 사용할 수 있는 착화제를 뜻한다. Herein, the term "coupling agent" refers to a complexing agent that can be commonly used with titanium and zirconium, and nickel and cobalt, which are major vacancy metals, between one complexing agent.
이 외에 금, 백금, 구리, 파라듐, 납, 은을 합금 도금용 주요금속으로 사용하여 도금하는 경우에도, 폭 넓은 피복력을 확보하여 준다.In addition, even when plated with gold, platinum, copper, palladium, lead, or silver as the main metal for alloy plating, wide coverage is ensured.
이러한 합금 도금용 주요 금속 이온의 공급원으로서, 황산니켈, 설파민산니켈, 염화니켈, 초산니켈, 황산코발트, 염화코발트, 황산코발트암모늄, 염화제2금(AuCl3·2H2O), 염화제2금수소산(HAuC14·4H20), 시안화금(AuCN), 시안화제1금칼륨(KAu(CN)2·2H20), 시안화제1금나트륨(NaAu(CN)2), 염화백금산, 염화제2백금, 질산백금암모늄, 황산구리, 염화구리, 시안화구리, 피로인산구리, 황산팔라듐, 염화팔라듐, 질산팔라듐암모늄, 초산납, 붕불화납, 질산납, 염기성탄산납, 질산은, 염화은, 산화은, 황산은, 시안화은, 시안화은칼륨, 시안화은나트륨 등의 금속화합물을 용해하여 사용할 수 있다.As the source of the main metal ions for such alloy plating, there are nickel sulfate, nickel sulfamide, nickel chloride, nickel acetate, cobalt sulfate, cobalt chloride, cobalt ammonium sulfate, ferric chloride (AuCl 3 .2H 2 O) (HAuCl 4 .4H 2 O), cyanide gold (AuCN), cyanating agent 1 potassium potassium (KAu (CN) 2 .2H 2 O), gold sodium cyanide (NaAu (CN) 2 ), chloroplatinic acid, It is also possible to use silver salts such as silver platinum, copper sulfate, copper chloride, copper cyanide, copper pyrophosphate, palladium sulfate, palladium chloride, ammonium palladium nitrate, lead acetate, lead pentafluoride, lead nitrate, basic lead carbonate, silver nitrate, Potassium, sodium cyanide, or the like may be dissolved and used.
본 발명에 있어서 착화제는 구연산 이온 즉, 구연산 화합물 군에서 선택할 수 있으며, 더욱 구체적으로는 구연산, 구연산나트륨, 구연산암모늄을 사용할 수 있다. 이 구연산 이온은 티타늄과 지르코늄이 단일금속으로 도금되지 않는 금속으로 알려져 있기 때문에 공석되는 금속으로 사용되는 주요금속인 니켈 및 코발트와 어떠한 환경에서도 공통의 착화제 역할로 서로를 연결하여 준다. In the present invention, the complexing agent may be selected from a group of citrate ions, that is, a group of citrate compounds. More specifically, citric acid, sodium citrate, and ammonium citrate may be used. This citrate ion is known to be a metal that is not plated with a single metal of titanium and zirconium, and thus serves as a common complexing agent for nickel and cobalt, the main metals used as the metal to be released, in any environment.
예를 들어 Ti-Ni, Ti-Co, Zr-Ni, Zr-Co, Ti-Zr-Ni, Ti-Zr-Co, Ti-Zr-Ni-Co등의 조합에 있어서 완벽한 연결형 착화제 역할을 하여주며, 그 양에 따라 전도 보조제 역할까지 충실히 수행하여 주기 때문에 DL-Tartaric acid를 쓸 때보다 더 폭넓은 피복력을 확보할 수 있으나, 이 경우에도 화학적 환원과 전기적 환원을 동시에 사용한 경우보다 더 넓은 피복력을 갖지는 않는다.Ti-Zr-Co, and Ti-Zr-Ni-Co, for example, Ti-Ni, Ti-Co, Zr-Ni, Zr-Co, Ti-Zr- In addition, DL-Tartaric acid is used as a conductive auxiliary agent in accordance with its amount. However, in this case, it is possible to obtain a larger coverage than the case of using chemical reduction and electrical reduction at the same time It does not.
이 연결형 착화제인 구연산 이온은 , 화학적 환원제를 통한 환원반응과 전기환원에 있어서도 동시에 착화제로서와 전도보보제로서의 역할을 충실하게 수행해낸다. The citric acid ion, which is a linking complexing agent, fulfills its role as a reversing agent as a complexing agent at the same time in the reduction reaction and the electro-reduction through a chemical reducing agent.
뿐만 아니라, 종래에 코발트 및 니켈과 공석이 자유로웠던 각종 금속이온들의 추가적인 투입을 통해 다양한 합금 도금층을 얻을 수 있다. 예를 들면, Au, Pt, Cu, Pd, Pb, Ag와의 공석을 손쉽게 유도할 수 있다. In addition, a variety of alloy plating layers can be obtained through addition of various metal ions conventionally free from cobalt and nickel and vacancies. For example, vacancies with Au, Pt, Cu, Pd, Pb, and Ag can be easily induced.
이러한 금속이온들 예를 들면, Au, Pt, Cu, Pd, Pb, Ag와 Ti 또는 Zr합금 도금에 있어서도 구연산 이온은 DL-Tartaric Acid에 비하여, 폭 넓은 도금 범위를 확보할 수 있으며, 전도 보조제 역할을 담당한다. 또한, 한원제를 투입하여 복합환원 방식의 도금도 가능하다.In the plating of these metal ions, for example, Au, Pt, Cu, Pd, Pb, Ag and Ti or Zr alloy, citric acid ion can secure a wide plating range as compared with DL-Tartaric Acid, . In addition, it is also possible to apply a complex reduction method by applying a single agent.
이 연결형 착화제의 사용으로 인하여, 지르코늄 합금 도금 또는 티타늄 합금 도금에 있어서도 0.5A/1dm2 의 미세한 전류만 흘려도 제품의 미세한 부분까지 골고루 넓은 범위를 피복할 수 있게 되며, pH 2.0 미만의 강산 환경하에서 티타늄 및 지르코늄의 공석을 유도할 수 도 있기 때문에 티타늄과 지르코늄의 많은 공석이 이루어지며, 10A/dm2 이하의 많은 양의 전류를 이용하여 폭 넓은 범위에 두께도금도 가능하다.
Due to the use of this coupling type complexing agent, zirconium alloy plating or titanium alloy plating can cover a wide range evenly to a fine portion of the product even if only a minute current of 0.5 A / 1 dm 2 is flowed. Under a strong acid environment of less than pH 2.0 Titanium and zirconium vacancies can be induced, so that many vacancies of titanium and zirconium are formed, and a wide range of thickness plating is possible by using a large amount of current less than 10 A / dm 2 .
[실시예 1] [Example 1]
옥시염화지르코늄 8수화물 100gZirconium oxychloride octahydrate 100 g
염화니켈 20gNickel chloride 20g
구연산 60gCitric acid 60g
붕산 30gBoric acid 30g
전류밀도 : 2.5A/dm2 Current density: 2.5 A / dm 2
양극 : 카본 양극Anode: carbon anode
상기 재료를 순수 600ml에 용해한 후 물을 체워 1리터의 도금액을 제조하였으며, 온도는 85℃, pH 1.5에서 30분에 걸쳐 도금을 실시하였다. 시편은 황동 시편을 세정하여 사용하였다. 실험결과 전면부에는 고르게 피복되었으나, 배면엔 거의 도금이 되지 아니하였다. 결과는 도 2에서 확인할 수 있다. 이후 전류량을 10A/dm2 까지 상승시켰지만 배면에 도금이 거의 올라가지 아니하였다.
The above material was dissolved in 600 ml of pure water, and then water was filled to prepare a 1 liter plating solution. The plating was performed at a temperature of 85 ° C and a pH of 1.5 for 30 minutes. The specimens were cleaned of brass specimens. As a result of the experiment, the front part was covered evenly, but the rear part was hardly plated. The results are shown in Fig. Thereafter, the amount of current was increased to 10 A / dm 2 , but the plating was scarcely raised on the backside.
[실시예 2] [Example 2]
도금용액 : 실시예 1의 용액.Plating solution: The solution of Example 1.
환원제 : 차아인산나트륨 20g/LReducing agent: Sodium hypophosphite 20g / L
전류밀도 : 2.5A/dm2 Current density: 2.5 A / dm 2
양극 : 이리듐 코팅 양극Bipolar: Iridium-coated anode
상기 실시예1의 용액에 차아인산 나트륨을 첨가하고 용해한 후 85℃, pH 1.5에서 30분에 걸쳐 도금을 실시하였다. 도금제품은 앞면과 뒷면이 모두 소지금속이 보이지 않도록 도금되었다. 결과는 도 3에서 확인할 수 있다. 이후 전류량을 0.5A/dm2 까지 낮추어 새로운 시편에 도금을 하였을 때도 배면까지 고르게 도금되었다.Sodium hypophosphite was added to the solution of Example 1 and dissolved, followed by plating at 85 DEG C and pH 1.5 for 30 minutes. Plated products were plated so that both the front and back sides were not visible. The results are shown in Fig. After that, the current was reduced to 0.5 A / dm 2, and even when the new specimen was plated, it was evenly plated to the backside.
실제 도금되기에는 미약한 전류이지만, 지속적으로 환원반응을 유도하는 역할을 하여, 낮은 pH에서도 환원제가 환원 역할을 같이 담당하는 효과를 가져와서 이런 결과가 나오는 것으로 판단되었다.
Although it is a weak current for actual plating, it plays a role of continuously inducing a reduction reaction, and it is judged that such a result is obtained that the reducing agent plays a role of reducing at low pH.
[실시예 3] [Example 3]
황산티탄 (TiOSO4 2H2O) 50g50 g of titanium sulfate (TiOSO 4 2H 2 O)
구연산 60gCitric acid 60g
요소 15gElement 15g
염화니켈 20gNickel chloride 20g
붕산 30gBoric acid 30g
전류밀도 : 2.5A/dm2 Current density: 2.5 A / dm 2
양극 : 이리듐 코팅 양극Bipolar: Iridium-coated anode
pH 3.5 ( 염산 및 암모니아 사용 )pH 3.5 (using hydrochloric acid and ammonia)
온도 90℃의 조건에서 황동시편에 30분에 걸쳐 도금을 실시하였다. 도금은 비교적 고르게 도금되었으나, 배면에는 도금이 거의 되지 아니하였다. 결과는 도 4를 통해 확인할 수 있다.
And the brass specimens were plated for 30 minutes at a temperature of 90 ° C. The plating was relatively uniformly plated, but the backside was hardly plated. The results are shown in FIG.
[실시예 4] [Example 4]
도금용액 : 실시예 3의 용액.Plating solution: solution of Example 3.
첨가제 : 차아인산나트륨 20g/LAdditive: Sodium hypophosphite 20g / L
전류밀도 : 2.5A/dm2 Current density: 2.5 A / dm 2
pH 1.5 ( 염산 및 암모니아 사용 )pH 1.5 (using hydrochloric acid and ammonia)
양극 : 이리듐 코팅 양극Bipolar: Iridium-coated anode
상기 실시예3의 용액에 화학적 환원제인 차아인산 나트륨을 첨가하고 용해한 후 85℃, pH 1.5에서 30분에 걸쳐 도금을 실시하였다. 도금제품은 앞면과 뒷면이 모두 소지금속이 보이지 않도록 도금되었다. 결과는 도 5를 통해 확인할 수 있다.
Sodium hypophosphite, a chemical reductant, was added to the solution of Example 3, and the solution was plated at 85 DEG C and pH 1.5 for 30 minutes. Plated products were plated so that both the front and back sides were not visible. The results are shown in FIG.
[실시예 5] [Example 5]
황산티탄 (TiOSO4 2H2O) 50g50 g of titanium sulfate (TiOSO 4 2H 2 O)
황산지르코늄 (Zr(SO4)2 4H2O) 30gZirconium sulfate (Zr (SO 4 ) 2 4H 2 O) 30 g
구연산 80gCitric acid 80g
요소 15gElement 15g
염화니켈 20gNickel chloride 20g
붕산 30gBoric acid 30g
첨가제 : 차아인산나트륨 20g/LAdditive: Sodium hypophosphite 20g / L
전류밀도 : 2.5A/dm2 Current density: 2.5 A / dm 2
pH 1.5 ( 염산 및 암모니아 사용 )pH 1.5 (using hydrochloric acid and ammonia)
양극 : 이리듐 코팅 양극Bipolar: Iridium-coated anode
상기의 조성으로 1리터를 건욕하여 Ti-Zr-Ni도금을 85℃의 온도에서 1시간 동안 실시하였으며, 도금두께는 약 10.0㎛이 측정되었다.
One liter of the above composition was subjected to a bath of Ti-Zr-Ni plating at a temperature of 85 캜 for 1 hour, and a plating thickness of about 10.0 탆 was measured.
[실시예 6] [Example 6]
황산티탄 (TiOSO4 2H2O) 50g50 g of titanium sulfate (TiOSO 4 2H 2 O)
황산지르코늄 (Zr(SO4)2 4H2O) 30gZirconium sulfate (Zr (SO 4 ) 2 4H 2 O) 30 g
구연산 80gCitric acid 80g
요소 15gElement 15g
황산코발트 20gCobalt sulfate 20g
염화암모늄 50gAmmonium chloride 50 g
붕산 30gBoric acid 30g
첨가제 : 차아인산나트륨 20g/LAdditive: Sodium hypophosphite 20g / L
전류밀도 : 2.5A/dm2 Current density: 2.5 A / dm 2
pH 1.5 ( 염산 및 암모니아 사용 )pH 1.5 (using hydrochloric acid and ammonia)
양극 : 이리듐 코팅 양극Bipolar: Iridium-coated anode
상기의 조성으로 1리터를 건욕하여 Ti-Zr-Co도금을 85℃의 온도에서 1시간 동안 실시하였으며, 도금두께는 약 8.0㎛이 측정되었다.One liter of the above composition was subjected to a bath of Ti-Zr-Co plating at a temperature of 85 캜 for 1 hour, and a plating thickness of about 8.0 탆 was measured.
본 발명에 있어서 전도 보조제를 쓸 수 있다. 전도보조제는 환원제의 투입 여부와 상관없이 사용할 수 있으며, 나트륨화합물, 칼륨화합물, 암모늄화합물들을 쓸 수 있다.In the present invention, a conductive auxiliary agent can be used. The conductive auxiliary can be used regardless of whether or not a reducing agent is added, and sodium compounds, potassium compounds, and ammonium compounds can be used.
좀 더 자세하게는 황산나트륨, 황산칼륨, 황산암모늄, 염화나트륨, 염화칼륨, 염화암모늄, 질산나트륨, 질산칼륨, 질산 암모늄 등을 사용할 수 있으나, 나트륨 또는 칼륨에 비하여 암모늄 화합물들이 더 바람직하다.More specifically, ammonium compounds are more preferable than sodium or potassium, although sodium sulfate, potassium sulfate, ammonium sulfate, sodium chloride, potassium chloride, ammonium chloride, sodium nitrate, potassium nitrate, ammonium nitrate and the like can be used.
따라서, 황산암모늄, 염화암모늄, 질산암모늄을 사용하는 것이 바람직하며, 이 중 질산암모늄은 위험물질이므로 사용을 자제하는 것이 더욱 바람직하다.
Therefore, it is preferable to use ammonium sulfate, ammonium chloride or ammonium nitrate, among which ammonium nitrate is a dangerous substance, so it is more preferable to refrain from using it.
[실시예 7] [Example 7]
황산티탄 (TiOSO4 2H2O) 50g50 g of titanium sulfate (TiOSO 4 2H 2 O)
황산지르코늄 (Zr(SO4)2 4H2O) 30gZirconium sulfate (Zr (SO 4 ) 2 4H 2 O) 30 g
구연산 100gCitric acid 100g
요소 15gElement 15g
황산코발트 20gCobalt sulfate 20g
염화니켈 20gNickel chloride 20g
염화암모늄 50gAmmonium chloride 50 g
붕산 30gBoric acid 30g
첨가제 : 차아인산나트륨 20g/LAdditive: Sodium hypophosphite 20g / L
전류밀도 : 2.5A/dm2 Current density: 2.5 A / dm 2
pH 1.5 ( 염산 및 암모니아 사용 )pH 1.5 (using hydrochloric acid and ammonia)
양극 : 이리듐 코팅 양극Bipolar: Iridium-coated anode
상기의 조성으로 1리터를 건욕하여 Ti-Zr-Co-Ni도금을 85℃의 온도에서 1시간 동안 실시하였으며, 도금두께는 약 8.0㎛이 측정되었다.
One liter of the above composition was subjected to a bath of Ti-Zr-Co-Ni plating at a temperature of 85 캜 for 1 hour, and a plating thickness of about 8.0 탆 was measured.
[실시예 8][Example 8]
여기서, 상기 [표 2]에서의 pH는 도금 실시예에서 사용된 도금액의 pH임.
Here, the pH in Table 2 is the pH of the plating solution used in the plating example.
도금된 각 제품은 일반적인 염수분무로 내식성을 테스트 하는 것이 의미를 가지기 어려울 만큼 초 고내식성을 발휘한다. 특히 pH가 2.0 미만인 경우 두께도금을 한 경우에는 질산 원액에서도 표면이 거의 침식되지 않는다. Each of the plated products is very resistant to corrosion with a common salt spray that makes it difficult to test for corrosion resistance. Particularly, when the pH is less than 2.0, even when the thickness is plated, the surface is hardly eroded even in the nitric acid stock solution.
이러한 낮은 pH에서 도금을 행할 수 있도록 하여주는 것이 화학적 환원제와 전기적 환원방법을 동시에 사용하기에 가능한 것이며, 이 과정에서 연결형 착화제인 구연산 이온이 착화제로서 뿐만 아니라 전도 보조제로서도 큰 역할을 담당한다.It is possible to use a chemical reducing agent and an electric reduction method at the same time to allow plating at such a low pH. In this process, citric acid ion as a coupling complexing agent plays a large role not only as a complexing agent but also as a conductive auxiliary agent.
상술한 실시 예는 본 발명의 바람직한 실시 예에 대해 기재한 것이지만, 본 발명은 이에 한정되지 않고 본 발명의 기술적인 사상에서 벗어나지 않는 범위 내에서 다양한 형태로 변경 실시할 수 있음은 본 발명의 기술분야에 종사하는 통상의 기술자들에게 있어서 명백한 것이다.While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, As will be appreciated by those of ordinary skill in the art.
Claims (29)
Electroplating solution for titanium alloy plating using citric acid compound as complexing agent.
The electroplating solution for plating a titanium alloy according to claim 1, wherein the titanium is used as a starting material of a citric acid compound, wherein titanium citrate is used as a starting material.
b) 상기 a)단계의 티타늄화합물을 물에 녹여 액상화시키는 단계;
c) 상기 b)단계의 액상에 착화제로 구연산 화합물을 투입하는 단계;
d) 상기 c)단계의 액상화된 용액에 티타늄과 합금화될 니켈, 코발트, 금, 백금, 구리, 팔라듐, 납, 은, 지르코늄 금속 및 이들 금속의 금속화합물 중 적어도 하나 이상의 물질을 용해하는 단계;
g) 상기 d)단계의 액상에서 pH를 1.0 ~ 12.0으로 조절하는 단계;를 포함하는 구연산 화합물을 착화제로 사용하는 티타늄 합금 도금을 위한 전기 도금액의 제조방법.
a) providing a titanium compound; And
b) liquefying the titanium compound of step a) in water;
c) introducing the citric acid compound as a complexing agent into the liquid phase of step b);
d) dissolving at least one of nickel, cobalt, gold, platinum, copper, palladium, lead, silver, zirconium metal and metal compounds of these metals to be alloyed with titanium in the liquefied solution of step c);
g) adjusting the pH in the liquid phase of step d) to 1.0 to 12.0, and using the citric acid compound as a complexing agent.
코발트 화합물은 황산코발트, 염화코발트, 황산코발트암모늄 중 어느 하나의 군 또는 2 이상의 군을 혼합하여 형성하며,
금 화합물은 염화제2금(AuCl3·2H2O), 염화제2금수소산(HAuC14·4H20), 시안화금(AuCN), 시안화제1금칼륨(KAu(CN)2·2H20), 시안화제1금나트륨(NaAu(CN)2) 중 어느 하나의 군 또는 2 이상의 군을 혼합하여 형성하고,
백금 화합물은 염화백금산, 염화제2백금, 질산백금암모늄 중 어느 하나의 군 또는 2 이상의 군을 혼합하여 형성된 것을 특징으로 하며,
구리화합물은 황산구리, 염화구리, 시안화구리, 피로인산구리 중 어느 하나의 군 또는 2 이상의 군을 혼합하여 형성된 것을 특징으로 하며, 팔라듐 화합물은 황산팔라듐, 염화팔라듐, 질산팔라듐암모늄 중 어느 하나의 군 또는 2 이상의 군을 혼합하여 형성하고,
납 화합물은 초산납, 붕불화납, 질산납, 염기성탄산납 중 어느 하나의 군 또는 2 이상의 군을 혼합하여 형성하며,
은화합물은 질산은, 염화은, 산화은, 황산은, 시안화은, 시안화은칼륨, 시안화은나트륨 중 어느 하나의 군 또는 2 이상의 군을 혼합하여 형성하며, 지르코늄 화합물은 황산지르코늄, 옥시염화지르코늄, 디염화지르코늄, 플루오린화 지르코늄, 지르코늄 질산염, 아세트산 지르코늄 염, 지르코늄 옥탄산염, 탄산 칼륨 지르코늄 염 중 어느 하나의 군 또는 2 이상의 군을 혼합하여 형성하는 것을 특징으로 하는 구연산 화합물을 착화제로 사용하는 티타늄 합금 도금을 위한 전기 도금액의 제조방법.
4. The method according to claim 3, wherein the nickel compound in step d) is formed by mixing any one of nickel sulfate, nickel sulfide nickel, nickel chloride and nickel acetate,
The cobalt compound is formed by mixing any one of cobalt sulfate, cobalt chloride, ammonium cobalt sulfate, or two or more groups,
Gold compound is ferric chloride gold (AuCl 3 · 2H 2 O) , the second gold acid chloride (HAuC1 4 · 4H 2 0) , cyanide, gold (AuCN), cyan agent 1 potassium gold (KAu (CN) 2 · 2H 2 0) and gold sodium cyanide (NaAu (CN) 2 ) or a mixture of two or more groups,
The platinum compound is characterized in that it is formed by mixing any one of the group consisting of chloroplatinic acid, platinous chloride and ammonium platinum nitrate, or a mixture of two or more groups.
The copper compound is characterized in that it is formed by mixing any one group or two or more of copper sulfate, copper chloride, copper cyanide and copper pyrophosphate, and the palladium compound is any one of palladium sulfate, palladium chloride and palladium ammonium nitrate Two or more groups are mixed and formed,
The lead compound is formed by mixing any one of the group consisting of acetic acid lead, lead borofluoride, lead nitrate, and basic lead carbonate,
The silver compound is formed by mixing any one of the group consisting of silver nitrate, silver chloride, silver oxide, silver sulfate, silver cyanide, potassium silver cadmium and silver silver cadmium or a mixture of two or more of the groups. The zirconium compound may be selected from zirconium sulfate, zirconium oxychloride, zirconium dichloride, The electroplating solution for electroplating of a titanium alloy using a citric acid compound as a complexing agent is formed by mixing at least one group selected from zirconium, zirconium nitrate, zirconium acetate, zirconium octanoate and potassium carbonate zirconium salt. Gt;
The method according to claim 3, wherein the citric acid compound used as a complexing agent in step c) is a citric acid compound which is used in combination with any one of citric acid, sodium citrate and ammonium citrate or two or more groups. A method for manufacturing an electroplating solution for titanium alloy plating.
The method according to claim 3, further comprising the step of adding e) a reducing agent between steps d) and g), wherein the citric acid compound is used as a complexing agent.
8. The method according to claim 7, wherein the reducing agent in step e) is selected from the group consisting of polyphosphoric acid, sodium hypophosphite, potassium hypophosphite, ammonium hypophosphite, dimethylamine borane (DMAB), diethylamine borane (DEAB), sodium borohydride, hydrazine, Formalin, or a mixture of two or more of the above-mentioned citric acid compounds as a complexing agent. The method for producing an electroplating solution for plating a titanium alloy according to claim 1,
The electroplating solution for plating a titanium alloy according to claim 8, wherein the reducing agent is added when plating is performed by a complex reduction method which is a metal reduction using both electrical reduction and chemical reduction. Gt;
4. The method according to claim 3, further comprising the step of adding f) a metal ion to be alloyed between steps d) and g), wherein the step of f) further comprises the step of f) A method for producing an electroplating solution.
11. The method according to claim 10, wherein the metal ion to be further alloyed in step f) is one selected from the group consisting of Au, Pt, Cu, Pd, Pb, Ag and Zr, Wherein the plating solution is used as a complexing agent.
A plating product in which at least one layer of the plating layer plated with the plating solution of claim 1 is plated.
Electroplating solution for zirconium alloy plating using citric acid compound as complexing agent.
The electroplating solution for zirconium alloy plating according to claim 16, wherein the zirconium is used as a starting material, zirconium sulfate or zirconium oxychloride as a starting material.
b) 상기 a)단계의 지르코늄화합물을 물에 녹여 액상화시키는 단계;
c) 상기 b)단계의 액상에 착화제로 구연산 화합물을 투입하는 단계;
d) 상기c)단계의 액상화된 용액에 지르코늄과 합금화될 니켈, 코발트, 금, 백금, 구리, 팔라듐, 납, 은 금속 및 이들 금속의 금속화합물 중 적어도 하나 이상의 물질을 용해하는 단계;
g) 상기 d)단계의 액상에서 pH를 1.0 ~ 12.0으로 조절하는 단계;를 포함하는 구연산 화합물을 착화제로 사용하는 지르코늄 합금 도금을 위한 전기 도금액의 제조방법.
a) providing a zirconium compound; And
b) liquefying the zirconium compound of step a) in water;
c) introducing the citric acid compound as a complexing agent into the liquid phase of step b);
d) dissolving at least one of nickel, cobalt, gold, platinum, copper, palladium, lead, silver metal and metal compounds of these metals to be alloyed with zirconium in the liquefied solution of step c);
g) adjusting the pH in the liquid phase of step d) to 1.0 to 12.0, wherein the citric acid compound is used as a complexing agent for the electroplating solution for zirconium alloy plating.
19. The method according to claim 18, wherein the nickel compound in step d) is formed by mixing any one of nickel sulfate, nickel sulfide nickel, nickel chloride and nickel acetate or two or more groups, and the cobalt compound is cobalt sulfate, cobalt chloride, Wherein the gold compound is at least one selected from the group consisting of gold chloride (AuCl 3 .2H 2 O), ferric chloride (HAuCl 4 .4H 2 O), cyanide gold (AuCN), cyanating agent 1 gold potassium (KAu (CN) 2 .2H 2 O), and gold sodium cyanide (NaAu (CN) 2 ) Wherein the copper compound is formed by mixing any one of the group consisting of chloroplatinic acid, platinous chloride and ammonium nitrate, or a mixture of two or more groups. The copper compound may be any one group selected from among copper sulfate, copper chloride, copper cyanide and copper pyrophosphate Characterized in that it is formed by mixing two or more groups, Wherein the lead compound is formed by mixing any one of the group consisting of palladium sulfate, palladium chloride and ammonium palladium nitrate or a combination of two or more groups, and the lead compound is formed by mixing any one of the group consisting of acetic acid lead, boron fluoride, lead nitrate, Wherein the silver compound is formed by mixing any one of the group consisting of silver nitrate, silver chloride, silver oxide, silver sulfate, silver cyanide, potassium silver cyanide and silver cyanide, or a mixture of two or more groups. Gt; < RTI ID = 0.0 > 11. < / RTI >
19. The method according to claim 18, wherein the citric acid compound to be used as a complexing agent in step c) is a citric acid compound which is a mixture of any one of citric acid, sodium citrate and ammonium citrate, A method for manufacturing an electroplating solution for plating a zirconium alloy.
The electroplating solution as claimed in claim 18, further comprising e) adding a reducing agent between steps d) and g) as a complexing agent.
22. The method according to claim 21, wherein the reducing agent in step e) is selected from the group consisting of polyphosphoric acid, sodium hypophosphite, potassium hypophosphite, ammonium hypophosphite, dimethylamine borane (DMAB), diethylamine borane (DEAB), sodium borohydride, hydrazine, Formalin, or a mixture of two or more of the above-mentioned citric acid compounds as a complexing agent. The method for producing an electroplating solution for plating a zirconium alloy according to claim 1,
The electric charge for zirconium alloy plating as a complexing agent according to claim 22, wherein the reducing agent is added when plating is performed by a complex reduction system (metal reduction system using both electrical reduction and chemical reduction) A method for producing a plating solution.
19. The method according to claim 18, further comprising the step of adding f) between the step d) and the step g), further comprising the step of f) adding the metal ion to be alloyed to the zirconium alloy plating A method for producing an electroplating solution.
The method according to claim 24, wherein the metal ion to be further alloyed in step f) is one selected from the group consisting of Au, Pt, Cu, Pd, Pb, Ag and Ti, As a complexing agent, for the plating of zirconium alloy.
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| JP2001355094A (en) * | 2000-06-13 | 2001-12-25 | Citizen Watch Co Ltd | Base material having ornamental coating film and its manufacturing method |
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| US3074860A (en) * | 1959-01-16 | 1963-01-22 | Satoh Shinzoh | Electrolytic process for the production of metallic titanium from aqueous solution of titanium compounds |
| KR101165219B1 (en) * | 2012-04-30 | 2012-07-16 | 이을규 | Reducing ni-zr alloy electroless plating bath and plating products |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20150096132A (en) * | 2014-02-14 | 2015-08-24 | 영남대학교 산학협력단 | A Nickel-Teflon Composite Coating Method |
| KR20160018612A (en) * | 2014-05-23 | 2016-02-17 | 윤종오 | method for wet electroplating |
| KR102024419B1 (en) * | 2014-05-23 | 2019-09-23 | 윤종오 | method for wet electroplating |
| KR101661629B1 (en) * | 2016-03-11 | 2016-09-30 | 주식회사 베프스 | Plationg solution of Amorphous PZT and plating method of the same |
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| WO2013172673A1 (en) | 2013-11-21 |
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