KR101159259B1 - Electroless black sulfurie trivalent chromium plating solution and method plating - Google Patents

Electroless black sulfurie trivalent chromium plating solution and method plating Download PDF

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KR101159259B1
KR101159259B1 KR1020120031719A KR20120031719A KR101159259B1 KR 101159259 B1 KR101159259 B1 KR 101159259B1 KR 1020120031719 A KR1020120031719 A KR 1020120031719A KR 20120031719 A KR20120031719 A KR 20120031719A KR 101159259 B1 KR101159259 B1 KR 101159259B1
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plating
dissolution
completely
chromium sulfate
plating solution
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Korean (ko)
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박영진
여운택
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신양에너지 주식회사
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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
    • 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
    • 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
    • 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
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1655—Process features
    • C23C18/1664—Process features with additional means during the plating process
    • C23C18/1669—Agitation, e.g. air introduction
    • 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
    • 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
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1675—Process conditions
    • C23C18/168—Control of temperature, e.g. temperature of bath, substrate

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

PURPOSE: An electroless black sulfuric trivalent chromium plating solution and a plating method thereof are provided to obtain a plated layer without pinholes by uniform deposition on a work piece. CONSTITUTION: An electroless black sulfuric trivalent chromium plating solution is prepared as follows. Chromium sulfate is dissolved completely in distilled water of 1L and zinc acetate and potassium acetate are dissolved in order. Complexing agents, polyalkylene oxide and NTA, are dissolved completely. A reducing agent, potassium boron hydridb, is dissolved completely. A buffer agent, boric acid, is dissolved completely. A stabilizer, thiourea, is dissolved completely. A pH mediatior, potassium hydroxide, is dissolved completely.

Description

무전해 블랙3가 황산크롬 도금액 및 도금방법{Electroless black Sulfurie Trivalent Chromium plating solution and method plating}Electroless black Sulfurie Trivalent Chromium plating solution and method plating

본 발명은 무전해 방식의 흑색도금(black plating)을 위한 블랙3가 황산크롬 도금액 및 도금방법에 관한 것으로, 피도금체의 형상과 재질에 관계없는 균일한 두께의 전착이 이루어지는 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a black trivalent chromium sulfate plating solution and plating method for electroless black plating, and to electrodeposition having a uniform thickness irrespective of the shape and material of the plated body.

일반적으로 흑색도금(Black plating) 하면 M.L-Black, 흑진주, 흑니켈, 흑크롬 등이 있으며, 그 중에서도 ML-Black은 코발트(Co)가 포함되는 문제점이 있고, 흑진주나 흑니켈은 신뢰성은 맞출 수 있으나 가벼운 스크래치(scratch)가 빨리 생기고 내마모성, 내열성이 떨어지는 것이었다.In general, when black plating, there are ML-Black, black pearl, black nickel, and black chromium. Among them, ML-Black has a problem in that cobalt (Co) is included, and black pearl or black nickel can meet reliability. However, light scratches occurred quickly, and wear resistance and heat resistance were poor.

그리고, 직류(D.C)전원을 사용하는 전기블랙 3가 황산크롬 도금액(맥더미드사의 Twilite, 원스트사의 Inncocenco-Black)을 사용하고 있으나, 상기 제품의 사용하는 경우에는 도금 작업을 하지 않아도 도금액이 자연 소모되는 문제, 충분한 전해가 이루어 지지 않으면 검은 얼룩이 발생하는 문제, 고전류 부위에 미도금과 도금이 타는 현상 발생하는 문제, 고전류와 저전류의 도금 두께 편차가 많은 문제, 도금액의 관리가 복잡하고 난이한 문제가 있게 된다.In addition, although an electric black trivalent chromium sulfate plating solution using a direct current (DC) power source (Twilite from McDermid, Inncocenco-Black from Wonst) is used, the plating solution is natural even when the product is not used. Problems of consumption, problems of black stains if not sufficiently electrolytically generated, problems of unplating and plating on high current areas, problems of high plating thickness variations of high currents and low currents, and complicated plating solution management There is a problem.

본 발명은 무전해 방식의 흑색도금(black plating)을 위한 블랙3가 황산크롬 도금액을 제공하여 상기 문제를 해결하는 한편 피도금체의 형상에 관계없이 균일한 두께로의 도금이 가능하며, 피도금체의 재질에 관계없이 도금이 이루어지는 한편 도금을 하지 않을 때 도금액 변화가 없고 도금액 관리가 용이하도록 하는 것이다.The present invention solves the above problems by providing a black trivalent chromium sulfate plating solution for electroless black plating, and plating with a uniform thickness is possible regardless of the shape of the plated body. Regardless of the material of the sieve, plating is performed while plating solution is not changed when plating is not performed, and plating solution management is easy.

본 발명은 증류수 1L에 대하여 황산크롬 320g을 완전히 용해한 후 푸로피온산 10.2g, 징크아스테이트(Zinc Acetate):

Figure 112012024874923-pat00001
8.5g, 포타시움아스테이트(Potassium Acetate):
Figure 112012024874923-pat00002
3.0g순으로 용해하며; 다음으로 착화제인 폴리 알킬렌옥사이드 7.5g과 니트리로토리초산 2.0g을 완전히 용해하고; 다음으로 환원제인 수소화 붕소칼륨36g 용해하며; 다음으로 완충제인 붕산 8.5g와 안정제인 티오요소
Figure 112012024874923-pat00003
을 용해하며; 다음으로 P.H조정제로 수산화칼륨 15g을 완전히 용해하여 이루어지는 것으로, 본 발명은 용해 순서를 맞추어 용해를 하여야 한다.The present invention completely dissolves 320 g of chromium sulfate in 1 L of distilled water, and then 10.2 g of propionic acid and zinc acetate (Zinc Acetate):
Figure 112012024874923-pat00001
8.5 g Potasium Acetate:
Figure 112012024874923-pat00002
Dissolve in 3.0 g order; Next, completely dissolving 7.5 g of polyalkylene oxide and 2.0 g of nitrilotoacetic acid as complexing agents; Next, 36 g of potassium borohydride which is a reducing agent is dissolved; Next, 8.5 g of boric acid as a buffer and thiourea as a stabilizer
Figure 112012024874923-pat00003
Dissolves; Next, it is made by completely dissolving 15 g of potassium hydroxide with a pH adjuster. The present invention should dissolve in order of dissolution.

또한 본 발명은 상기 도금액을 이용한 도금 작업에서 도금액의 층별 온도가 다르지 않도록 공기 교반이 이루어지게 하되 교반에 사용되는 공기는 피도금물과 접촉되지 않도록 하고, 도금은 도금액의 온도를 70~78℃로 유지시킨 상태에서 P.H : 6.0~6.5를 유지하도록 하며, 도금이 이루어지는 도금액은 도금 과정에서 연속적인 여과가 이루어지도록 함으로써 도금이 이루어지게 된다.In addition, the present invention in the plating operation using the plating solution to the air stirring so that the temperature of each layer of the plating solution is not different, but the air used for stirring is not in contact with the plated material, the plating is the temperature of the plating solution to 70 ~ 78 ℃ PH: 6.0 ~ 6.5 in the maintained state to maintain the plating, the plating is made by plating is performed by the continuous filtration in the plating process.

본 발명의 무전해 블랙3가 황산크롬 도금액을 이용한 도금에서는 피도금체의 형상에 관계없이 각 부위에 균일한 두께로 전착이 이루어지는 한편 핀홀(Pin hole)이 발생되지 않고 원하는 두께로 도금을 할 수 있으며, 피도금체가 금속 또는 비금속에 관계없이 도금을 할 수 있고, 도금을 하지 않아도 도금액의 변화가 없는 한편 도금액의 관리가 용이한 이점이 있는 것이다.In the plating using the electroless black trivalent chromium sulfate plating solution of the present invention, electrodeposition is performed at a uniform thickness on each site regardless of the shape of the plated body, and plating can be performed at a desired thickness without generating pin holes. In addition, the metal to be plated can be plated irrespective of metals or non-metals, and there is no change in plating solution even without plating, and the plating solution can be easily managed.

도 1은 본 발명의 도금액을 이용하는 도금장치도
도 2는 피도금체에 따는 본 발명의 도금 공정도1 is a plating apparatus using the plating solution of the present invention
2 is a plating process diagram of the present invention according to the plated body

본 발명은 순수(증류수) 1L에 대하여 황산크롬 320g을 완전히 용해시킨 다음 푸로피온산 10.2g과 징크아스테이트(Zinc Acetate):

Figure 112012024874923-pat00004
8.5g 및 포타시움아스테이트(Potassium Acetate):
Figure 112012024874923-pat00005
3.0g을 순서대로 용해하고, 다음으로 착화제인 폴리 알킬렌옥사이드 7.5g과 니트리로토리초산 2.0g을 완전히 용해하며, 다음으로 환원제인 수소화 붕소칼륨36g 용해하고, 다음으로 완충제인 붕산 8.5g을 용해하며, 다음으로 안정제인 티오요소
Figure 112012024874923-pat00006
을 용해하고, 다음으로 P.H조정제인 수산화칼륨 15g을 완전히 용해시킴으로써 도금액을 얻는다.The present invention completely dissolves 320 g of chromium sulfate in 1 L of pure water (distilled water), followed by 10.2 g of propionic acid and zinc acetate (Zinc Acetate):
Figure 112012024874923-pat00004
8.5 g and Potassium Acetate:
Figure 112012024874923-pat00005
3.0 g is dissolved in sequence, next, 7.5 g of polyalkylene oxide and 2.0 g of nitrilotoacetic acid, which are complexing agents, are completely dissolved. Next, 36 g of potassium borohydride, which is a reducing agent, is dissolved, and then 8.5 g of boric acid, which is a buffer, is dissolved. Next, thiourea, a stabilizer,
Figure 112012024874923-pat00006
Is dissolved, and then a plating solution is obtained by completely dissolving 15 g of potassium hydroxide as a pH adjuster.

본 발명의 도금액 제조과정에서 상기의 용해순서를 잘못하면 용해가 곤란하며 불용성 물질이 발생하는 한편 도금액의 자기분해가 이루어지는 원인이 되므로, 용액의 용해순서에 따라 용해를 시킨다.If the above dissolution order is incorrect in the plating solution manufacturing process of the present invention, dissolution is difficult and insoluble matters are generated, which causes self-decomposition of the plating solution. Thus, dissolution is performed according to the dissolution order of the solution.

본 발명의 도금액을 이용하여 무전해 도금을 하는 경우 환원제의 산화반응에 의해 도금액중의 금속 이온이 금속으로 환원 석출되는 원리인 것으로, 도금조에 도금액을 채운 후 70~78℃를 유지하는 한편 P.H는 6.0~6.5을 유지하며 공기교반을 통하여 도금액이 균일한 온도를 유지하도록 하고, 피도금물을 넣어 도금이 이루어지게 하되 도금액의 여과는 지속적으로 이루어지게 한다.In the electroless plating using the plating solution of the present invention, the metal ions in the plating solution are reduced and precipitated by the oxidation reaction of the reducing agent, and the pH is maintained at 70 to 78 ° C after filling the plating solution in the plating bath. Maintain 6.0 ~ 6.5 and maintain uniform temperature through air stirring, and put plating material to make plating, but keep filtration of plating solution continuously.

여기서 도금액의 공기 교반을 할 때 고형 미립자가 없어야 하고 공기가 피도금물에 닿지 않도록 한다.When air agitating the plating solution, there should be no solid particles and air should not touch the plated object.

본 발명의 무전해 블랙3가 황산크롬 도금은 650℃의 내열성을 갖고, 염수분무테스트에서 84시간이 지나도 이상이 발생하지 않는 내식성을 가지며,

Figure 112012024874923-pat00007
℃의 열전도도를 갖고 HV 380~400의 경도를 갖는 특징이 나타난다.Electroless black trivalent chromium sulfate plating of the present invention has a heat resistance of 650 ℃, corrosion resistance that does not occur even after 84 hours in the salt spray test,
Figure 112012024874923-pat00007
It has a thermal conductivity of ℃ and a hardness of HV 380 ~ 400 appears.

이하 본 발명을 첨부된 실시예 도면에 의거 상세히 설명하기로 한다.Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

본 발명의 무전해 블랙3가 황산크롬 도금액을 조성하기 위하여 필요한 약품 및 농도는 아래와 같은 함량과 중량 및 조건을 갖춰 준비한다.The chemicals and concentrations necessary to form the electroless black trivalent chromium sulfate plating solution of the present invention are prepared with the following contents, weights and conditions.

① 금속염: 금속이온의 공급① metal salt: supply of metal ions

황산크롬

Figure 112012024874923-pat00008
Chromium sulfate
Figure 112012024874923-pat00008

푸로피온산

Figure 112012024874923-pat00009
Propionic acid
Figure 112012024874923-pat00009

징크아스테이트(Zinc Acetate):

Figure 112012024874923-pat00010
Zinc Acetate:
Figure 112012024874923-pat00010

포타시움아스테이트(Potassium Acetate):

Figure 112012024874923-pat00011
Potassium Acetate:
Figure 112012024874923-pat00011

② 환원제: 금속이온의 환원② Reducing agent: reduction of metal ions

수소화 붕소칼륨

Figure 112012024874923-pat00012
Potassium borohydride
Figure 112012024874923-pat00012

③ 착화제: 금속수산화물의 산화방지③ complexing agent: prevention of oxidation of metal hydroxide

폴리알킬렌옥사이드

Figure 112012024874923-pat00013
Polyalkylene oxide
Figure 112012024874923-pat00013

니트리로토리초산

Figure 112012024874923-pat00014
Nitrilotoriacetic acid
Figure 112012024874923-pat00014

④ 완충제: 도금반응의 진행으로써 P.H변동을 방지④ Buffer: Prevent P.H fluctuation by progress of plating reaction

붕산

Figure 112012024874923-pat00015
Boric acid
Figure 112012024874923-pat00015

⑤ 안정제: 액중의 미립장에 흡착되어 자연분해방지⑤ Stabilizer: It is adsorbed by fine particles in liquid to prevent natural decomposition

티오요소

Figure 112012024874923-pat00016
Thiourea
Figure 112012024874923-pat00016

⑥ P.H조정제 : 도금액의 P.H조정⑥ P.H adjustment system: P.H adjustment of plating solution

수산화칼륨

Figure 112012024874923-pat00017
Potassium hydroxide
Figure 112012024874923-pat00017

위와 같이 준비된 약품은 아래에 제시된 순서에 따라 용해가 이루어져야만 도금액의 조성이 완료되는 것으로, 그 과정은 다음과 같다.The above-prepared chemicals must be dissolved in the order given below to complete the composition of the plating solution, and the process is as follows.

먼저 쉽게 구할 수 있는 증류수 1L에 대하여 황산크롬 320g을 완전히 용해시키고, 다음으로 푸로피온산 10.2g과 징크아스테이트(Zinc Acetate):

Figure 112012042176669-pat00018
8.5g 및 포타시움아스테이트(Potassium Acetate):
Figure 112012042176669-pat00019
3.0g을 순서대로 용해하며, 완전 용해가 이루어진 후에는 착화제인 폴리 알킬렌옥사이드 7.5g과 니트리로토리초산 2.0g을 완전히 용해하고, 다음으로 환원제인 수소화 붕소칼륨36g 용해하며, 다음으로 완충제인 붕산 8.5g을 용해하고, 다음으로 안정제인 티오요소
Figure 112012042176669-pat00020
을 용해하며, 다음으로 P.H조정제인 수산화칼륨 15g을 완전히 용해시킴으로써 도금액을 얻게 된다.First, completely dissolve 320 g of chromium sulfate in 1 L of readily available distilled water, and then 10.2 g of propionic acid and zinc acetate:
Figure 112012042176669-pat00018
8.5 g and Potassium Acetate:
Figure 112012042176669-pat00019
After dissolving 3.0 g in order, after complete dissolution, 7.5 g of polyalkylene oxide and 2.0 g of nitrilotoacetic acid, which are complexing agents, are completely dissolved. Next, 36 g of potassium borohydride, a reducing agent, is dissolved, followed by boric acid as a buffer. Dissolve 8.5 g and then stabilize the thiourea
Figure 112012042176669-pat00020
Then, the plating solution is obtained by completely dissolving 15 g of potassium hydroxide, a pH adjuster.

본 발명의 도금액은 상기 과정에 따라 얻어지게 되나, 주의해야 할 점은 도금액 제조과정에서 상기의 약품의 용해순서를 잘못할 경우 용해가 곤란한 경우가 발생하는 한편 불용성 물질이 발생하거나 도금액의 자기분해가 이루어지는 원인이 되므로, 반드시 용액의 용해순서에 따라 완전 용해가 이루어지도록 한다.Although the plating solution of the present invention is obtained according to the above process, it should be noted that if the dissolution order of the chemicals in the plating solution manufacturing process is difficult to dissolve, insoluble matters occur or self-decomposition of the plating solution occurs. Since this may cause a complete dissolution, make sure that complete dissolution is performed according to the dissolution order of the solution.

상기 과정에 의해 얻어진 도금액은 도 1에 도시된 도금조(10)에 넣고 피도금물의 표면에 도금이 이루어지도록 한다.The plating liquid obtained by the above process is put in the plating bath 10 shown in FIG. 1 so that plating is performed on the surface of the plated object.

본 발명의 도금조(10)는 하측으로 가열관(11)이 형성되어 보일러(12)로부터 공급되는 증기가 통과하게 함으로써 도금조(10)에 담긴 도금액이 가열될 수 있도록 하고, 도금조(10)에 채워진 도금액은 온도계와 액면계를 이용하여 상태 체크가 이루어질 수 있도록 하며, 도금조(10)의 내부에 설치된 에어배관(15)을 통하여 에어가 배출되면서 교반이 이루어지게 한다.In the plating bath 10 of the present invention, the heating tube 11 is formed at the lower side to allow the steam supplied from the boiler 12 to pass therethrough so that the plating liquid contained in the plating bath 10 can be heated, and the plating bath 10 The plating liquid filled in) allows the state check to be performed using a thermometer and a liquid level meter, and the stirring is performed while the air is discharged through the air pipe 15 installed in the plating bath 10.

그리고, 도금조(10)의 도금액은 필터펌프(16)를 통하여 예비조(17)와 순환되면서 필터에 의한 여과가 지속적으로 이루어지게 한다.In addition, the plating solution of the plating bath 10 is circulated with the preliminary bath 17 through the filter pump 16 to continuously filter the filter.

본 발명은 상기 도금조(10)에 도금액을 채우고, 피도금물을 넣은 후 도금액의 온도와 PH 를 맞추어주게 되면 도금이 이루어지게 되는 것으로, 여기서 도금액의 작업 온도는 70~78℃를 유지하도록 하고, 정확한 온도 조절은 균일한 도금 두께를 얻을 수 있어 품질을 향상시킬 수 있다.The present invention is to fill the plating solution in the plating bath 10, after putting the plating object to match the temperature and the pH of the plating solution is to be made, where the working temperature of the plating solution to maintain 70 ~ 78 ℃ Accurate temperature control can achieve uniform plating thickness and improve quality.

그리고, 도금을 위해서는 정기적으로 P.H를 점검하고 30% 수산화칼륨용액으로 표준 P.H범위(6.0~6.3)의 범위를 유지하도록 하고, 에어배관(15)에서 배출되는 에어를 이용하여 도금액의 공기 교반이 이루어지도록 하되 공기가 피도금물과 부딪히지 않도록 하며, 도금액은 도금이 진행되는 동안 연속적이 여과가 이루어지게 함으로써 피도금의 표면에 형성되는 도금피막의 품질을 향상시키도록 한다.In addition, for plating, the pH is periodically checked and the standard PH range (6.0 to 6.3) is maintained with 30% potassium hydroxide solution, and the air is stirred in the plating solution by using the air discharged from the air pipe 15. To prevent the air from colliding with the plated material, the plating solution is to improve the quality of the plated film formed on the surface of the plated by the continuous filtration during the plating process.

이와 같은 무전해 블랙3가 황산크롬도금이 이루어지는 것은 환원제의 산화반응에 의해 도금액 중의 금속 이온이 금속으로 환원되며 석출되는 원리를 이용하게 된다.The electroless black trivalent chromium sulfate plating is used to utilize the principle that the metal ions in the plating solution are reduced to metal by the oxidation reaction of the reducing agent and precipitated.

본원발명에서의 환원제의 산화반응(수소화붕소칼륨

Figure 112012024874923-pat00021
)은 아래와 같다.Oxidation reaction of reducing agent in the present invention (potassium borohydride)
Figure 112012024874923-pat00021
) Is shown below.

Figure 112012024874923-pat00022
Figure 112012024874923-pat00022

Figure 112012024874923-pat00023
Figure 112012024874923-pat00023

Figure 112012024874923-pat00024
Figure 112012024874923-pat00024

Figure 112012024874923-pat00025
Figure 112012024874923-pat00025

이와 같이 환원제의 산화 반응에 의해 전자가 공급되면 전극전위는 비한 값으로 되어 금속 이온이 환원된다.In this way, when electrons are supplied by the oxidation reaction of the reducing agent, the electrode potential becomes indefinite and metal ions are reduced.

그리고, 국부 캐소드(Cathode : 금속 또는 수소가 전기 화학적으로 석출하는 극) 반응에서는 다음과 같은 이온과 물의 환원이 일어난다.In addition, in the local cathode (cathode), the following reduction of ions and water occurs.

Figure 112012024874923-pat00026
Figure 112012024874923-pat00026

Figure 112012024874923-pat00027
Figure 112012024874923-pat00027

① 환원제 :

Figure 112012024874923-pat00028
① reducing agent:
Figure 112012024874923-pat00028

② 피도금체 :

Figure 112012024874923-pat00029
② Plated Body:
Figure 112012024874923-pat00029

③ 도금액의 이온 :

Figure 112012024874923-pat00030
도금③ ion of plating solution:
Figure 112012024874923-pat00030
Plated

이러한 과정을 거쳐 이루어지는 무전해 블랙3가 황산크롬 도금은 피도금물의 형상에 관계없이 각 부위에 균일한 두께로 전착이 이루어지는 효과와, 핀홀(Pin hole)이 없고 임의 두께로 도금 할 수 있는 효과와, 금속면상 뿐 아니라 비 금속면 상에도 도금 할 수 있는 효과와, 도금을 하지 않아도 도금액 변화가 없는 효과와, 도금액 관리가 용이한 효과가 있게 된다.Electroless Black Trivalent Chromium Sulfate plating through this process has the effect of electrodeposition with uniform thickness on each part regardless of the shape of the plated object, and the effect of plating with any thickness without pin hole. And the effect of plating on not only the metal surface but also on the non-metal surface, the effect of not changing the plating liquid without plating, and the effect of the plating liquid management being easy.

그리고, 본 발명의 무전해 블랙3가 황산크롬 도금의 특징은 650℃의 내열성을 갖고, 염수분무테스트 84시간 이상 수행하여도 이상이 없는 내식성을 가지며

Figure 112012024874923-pat00031
℃의 열전도를 갖고, HV 380~400의 경도를 갖는다.In addition, the electroless black trivalent chromium sulfate plating feature of the present invention has a heat resistance of 650 ℃, corrosion resistance without abnormality even if the salt spray test is performed for more than 84 hours.
Figure 112012024874923-pat00031
It has a thermal conductivity of ℃, and has a hardness of HV 380 ~ 400.

본 발명은 피대상물의 종류에 관계없이 도금이 이루어지는 것으로, 피대상물에 따라 도2의 공정도에 도시된 바와 같이 도금 공정에 약간의 차이를 보이게 되나, 블랙3가 황산크롬의 무전해 도금이 이루어지기 전의 전처리 과정이 상이할 뿐, 블랙 도금 과정은 동일하다.According to the present invention, the plating is performed regardless of the type of the object, and as shown in the process diagram of FIG. 2, there is a slight difference in the plating process, but the electroless plating of the black trivalent chromium sulfate is performed. Only the pretreatment process is different, and the black plating process is the same.

10 : 도금조 11 : 가열관
12 : 보일러 15 : 에어배관
16 : 필터펌프 17 : 예비조10 plating bath 11: heating tube
12: boiler 15: air piping
16: filter pump 17: preliminary tank

Claims (2)

증류수 1L에 황산크롬
Figure 112012042176669-pat00032
을 완전히 용해시킨 후 푸로피온산
Figure 112012042176669-pat00033
과 징크아스테이트(Zinc Acetate):
Figure 112012042176669-pat00034
및 포타시움아스테이트(Potassium Acetate):
Figure 112012042176669-pat00035
을 순서대로 완전 용해하고,
상기 황산크롬과 푸로피온산 및 징크아스테이트와 포타시움아스테이트의 금속염 용해가 완료되면 착화제인 폴리알킬렌옥사이드
Figure 112012042176669-pat00036
와 니트리로토리초산
Figure 112012042176669-pat00037
을 완전히 용해하고,
상기 착화제의 용해가 완료되면 환원제인 수소화 붕소칼륨
Figure 112012042176669-pat00038
을 완전 용해하며,
상기 환원제의 용해가 완료되면 완충제인 붕산
Figure 112012042176669-pat00039
을 완전 용해하고,
상기 완충제의 용해가 완료되면 안정제인 티오요소
Figure 112012042176669-pat00040
를 완전 용해하며,
상기 안정제의 용해가 완료되면 P.H조정제인 수산화칼륨
Figure 112012042176669-pat00041
을 완전 용해하여 얻어지는 무전해 블랙3가 황산크롬 도금액.Chromium sulfate in 1 liter of distilled water
Figure 112012042176669-pat00032
Complete dissolution of the propionic acid
Figure 112012042176669-pat00033
And zinc acetate:
Figure 112012042176669-pat00034
And Potassium Acetate:
Figure 112012042176669-pat00035
Completely dissolve in order,
When the metal salt dissolution of the chromium sulfate, the propionic acid, the zinc asate and the potassium asate is completed, the polyalkylene oxide as a complexing agent
Figure 112012042176669-pat00036
And nitrilotriacetic acid
Figure 112012042176669-pat00037
Dissolve completely,
When dissolution of the complexing agent is completed, potassium borohydride as a reducing agent
Figure 112012042176669-pat00038
Dissolve completely
When dissolution of the reducing agent is completed, boric acid as a buffer
Figure 112012042176669-pat00039
Dissolve completely,
When dissolution of the buffer is complete, thiourea, a stabilizer
Figure 112012042176669-pat00040
Dissolve completely,
When dissolution of the stabilizer is completed, potassium hydroxide which is a pH regulator
Figure 112012042176669-pat00041
An electroless black trivalent chromium sulfate plating solution obtained by completely dissolving. 증류수 1L에 황산크롬
Figure 112012042176669-pat00042
을 완전히 용해시킨 후 푸로피온산
Figure 112012042176669-pat00043
과 징크아스테이트(Zinc Acetate):
Figure 112012042176669-pat00044
및 포타시움아스테이트(Potassium Acetate):
Figure 112012042176669-pat00045
을 순서대로 완전 용해하고, 상기 황산크롬과 푸로피온산 및 징크아스테이트와 포타시움아스테이트의 금속염 용해가 완료되면 착화제인 폴리알킬렌옥사이드
Figure 112012042176669-pat00046
와 니트리로토리초산
Figure 112012042176669-pat00047
을 완전히 용해하고, 상기 착화제의 용해가 완료되면 환원제인 수소화 붕소칼륨
Figure 112012042176669-pat00048
을 완전 용해하며, 상기 환원제의 용해가 완료되면 완충제인 붕산
Figure 112012042176669-pat00049
을 완전 용해하고, 상기 완충제의 용해가 완료되면 안정제인 티오요소
Figure 112012042176669-pat00050
를 완전 용해하며, 상기 안정제의 용해가 완료되면 P.H조정제인 수산화칼륨
Figure 112012042176669-pat00051
을 완전 용해하여 얻어지는 무전해 블랙3가 황산크롬 도금액은 도금조(10)에 넣고,
상기 도금조(10)에 설치된 가열관(11)으로 증기를 공급하여 도금액의 온도가 70~78℃를 유지하는 한편 P.H는 6.0~6.5가 유지되게 하며,
도금조(10)에 설치된 에어배관(15)을 통하여 에어교반이 이루어져 도금액의 층별 온도차이를 없애주되 에어는 피도금물과 접촉되지 않게 하고,
상기 도금조(10)의 도금액은 지속적인 여과가 이루어지게 하면서 피도금물에 무전해 도금이 이루어지게 하는 것을 특징으로 하는 무전해 블랙3가 황산크롬 도금방법.Chromium sulfate in 1 liter of distilled water
Figure 112012042176669-pat00042
Complete dissolution of the propionic acid
Figure 112012042176669-pat00043
And zinc acetate:
Figure 112012042176669-pat00044
And Potassium Acetate:
Figure 112012042176669-pat00045
In order to completely dissolve the polysulfate, polyalkylene oxide as a complexing agent when the dissolution of the metal salt of chromium sulfate, propionic acid and zinc asate and potashium state is completed
Figure 112012042176669-pat00046
And nitrilotriacetic acid
Figure 112012042176669-pat00047
Completely dissolved, and upon completion of dissolution of the complexing agent, potassium borohydride as a reducing agent
Figure 112012042176669-pat00048
Completely dissolved, and when the dissolution of the reducing agent is completed, a boric acid buffer
Figure 112012042176669-pat00049
Dissolve completely, and when the dissolution of the buffer is complete,
Figure 112012042176669-pat00050
Completely dissolved, and when the dissolution of the stabilizer is completed, potassium hydroxide
Figure 112012042176669-pat00051
The electroless black trivalent chromium sulfate plating solution obtained by completely dissolving the solution was placed in the plating bath 10.
By supplying steam to the heating tube 11 installed in the plating bath 10 to maintain the temperature of the plating liquid 70 ~ 78 ℃ while maintaining the pH of 6.0 ~ 6.5,
Air stirring is performed through the air pipe 15 installed in the plating bath 10 to eliminate the temperature difference of each layer of the plating liquid, but the air does not come into contact with the plated material,
The plating solution of the plating bath 10 is electroless black trivalent chromium sulfate plating method characterized in that the electroless plating is performed on the plated material while the continuous filtration is made.
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Publication number Priority date Publication date Assignee Title
KR101348208B1 (en) 2013-06-11 2014-01-06 배민수 Electroless plating tank for heat exchange

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110033656A (en) * 2009-09-25 2011-03-31 한양화학(공) Aquous composition for forming trivalent chromium coating and method of forming black trivalent chromium coating using same

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110033656A (en) * 2009-09-25 2011-03-31 한양화학(공) Aquous composition for forming trivalent chromium coating and method of forming black trivalent chromium coating using same

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101348208B1 (en) 2013-06-11 2014-01-06 배민수 Electroless plating tank for heat exchange

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