KR20120097054A - 3 3 Trivalent chromium galvanizing solution for bright dark black color and manufacturing method of the same - Google Patents
3 3 Trivalent chromium galvanizing solution for bright dark black color and manufacturing method of the same Download PDFInfo
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 239000011651 chromium Substances 0.000 title claims abstract description 115
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 114
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 238000005246 galvanizing Methods 0.000 title 1
- 238000007747 plating Methods 0.000 claims abstract description 139
- 150000002500 ions Chemical class 0.000 claims abstract description 66
- 239000000243 solution Substances 0.000 claims abstract description 59
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 41
- 239000008139 complexing agent Substances 0.000 claims abstract description 19
- 239000007800 oxidant agent Substances 0.000 claims abstract description 16
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001845 chromium compounds Chemical class 0.000 claims abstract description 14
- 229910001430 chromium ion Inorganic materials 0.000 claims abstract description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical class [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- -1 alkali metal salt Chemical class 0.000 claims description 2
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 2
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 2
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 2
- 230000000536 complexating effect Effects 0.000 claims description 2
- 230000002999 depolarising effect Effects 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 1
- 239000000654 additive Substances 0.000 abstract description 5
- 230000000996 additive effect Effects 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 230000003213 activating effect Effects 0.000 abstract 1
- 238000013019 agitation Methods 0.000 abstract 1
- 238000005868 electrolysis reaction Methods 0.000 abstract 1
- 150000001455 metallic ions Chemical class 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 31
- 230000008859 change Effects 0.000 description 15
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 4
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 3
- 206010028980 Neoplasm Diseases 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 201000011510 cancer Diseases 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- XVVLAOSRANDVDB-UHFFFAOYSA-N formic acid Chemical compound OC=O.OC=O XVVLAOSRANDVDB-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- 102100036848 C-C motif chemokine 20 Human genes 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 101000713099 Homo sapiens C-C motif chemokine 20 Proteins 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- NIFHFRBCEUSGEE-UHFFFAOYSA-N oxalic acid Chemical compound OC(=O)C(O)=O.OC(=O)C(O)=O NIFHFRBCEUSGEE-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/04—Electroplating: Baths therefor from solutions of chromium
- C25D3/06—Electroplating: Baths therefor from solutions of chromium from solutions of trivalent chromium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/04—Electroplating: Baths therefor from solutions of chromium
- C25D3/08—Deposition of black chromium, e.g. hexavalent chromium, CrVI
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Description
본 발명은 3가크롬도금액 및 이의 제조방법에 관한 것으로, 보다 상세하게는 Fe 이온과 Co 이온을 포함하는 무기색상발현제를 첨가하여 광택 흑색 3가크롬도금층의 형성이 가능하도록 한 3가크롬도금액 및 이의 제조방법에 관한 것이다.The present invention relates to a trivalent chromium plating solution and a method for manufacturing the same. More specifically, trivalent chromium enables the formation of a glossy black trivalent chromium plating layer by adding an inorganic color developer including Fe ions and Co ions. It relates to a plating solution and a method of manufacturing the same.
크롬도금은 각종 도금공정 중에서 가장 일반적이며 공정상 최종 처리에 해당되는 도금공정으로서, 통상 아름다운 광택의 금속 표면을 얻고자 하는 장식도금과 내마모성의 증대를 목적으로 하는 경질도금으로 분류될 수 있다.Chromium plating is a plating process that is the most common among the various plating processes and corresponds to the final treatment, and may be classified into decorative plating for obtaining a beautiful glossy metal surface and hard plating for the purpose of increasing wear resistance.
장식도금의 경우 도금 두께는 2/10,000 ~ 1/1,000mm 로서, 식기, 기타 일회용품에서 황동의 표면 도금에 주로 이용되며, 경질도금은 마모 수명의 요구에 따라 달라지지만 5/1,000 내지 수 분의 1mm 정도로 카메라 렌즈의 나사고정부분, 정밀기계의 끼워맞춤 부분, 주형의 내면, 인쇄용 판면 등에 마모 방지 등을 위해 이용된다.In the case of decorative plating, the plating thickness is 2 / 10,000 ~ 1 / 1,000mm, and it is mainly used for surface plating of brass in tableware and other disposable products, and hard plating is 5 / 1,000 to 1mm for several minutes depending on the wear life. It is used to prevent wear of the screw fixing part of the camera lens, the fitting part of the precision machine, the inner surface of the mold, the printing plate surface and the like.
통상 크롬도금은 6가크롬인 크롬산(CrO3)에 황산(H2SO4)을 혼합한 용액을 사용하여 전기도금을 하는데, 양극에는 크롬 금속을 사용하지 않고 납과 같이 황산에 침식되지 않는 것을 사용하고 용액 중의 크롬 감소분은 크롬산으로 보충하여 전착(電着)을 계속한다.In general, chromium plating is electroplated by using a solution of sulfuric acid (H 2 SO 4 ) mixed with chromic acid (CrO 3 ), which is hexavalent chromium. The anode is not chromium metal and is not eroded by sulfuric acid like lead. The chromium reduction in the solution is supplemented with chromic acid to continue electrodeposition.
또한, 크롬도금에 사용하는 도금액 속의 크롬산 농도에는 고농도와 저농도가 있으며, 액의 온도, 전류의 밀도, 즉 도금 조건에 따라 다양한 형태의 도금을 얻을 수 있다. 이와 같이 6가 크롬 도금은 반사도, 색상, 부식, 내식성이 뛰어날 뿐만 아니라 전류 효율이 높다는 장점이 있다.In addition, there are high concentrations and low concentrations of chromic acid in the plating liquid used for chromium plating, and various types of plating can be obtained depending on the temperature of the liquid and the density of the current. As such, hexavalent chromium plating has an advantage of excellent reflectivity, color, corrosion, corrosion resistance, and high current efficiency.
그러나, 이러한 장점에도 불구하고 6가크롬도금은 공정 중에 인체에 치명적인 크롬산 증기를 발생하고 6가크롬이온이 지하수나 강으로 유입될 경우 치명적인 환경오염을 유발하기 때문에 반드시 3가로 환원시켜 처리해야 하는 난제를 안고 있다.However, despite these advantages, hexavalent chromium plating generates critical chromic acid vapor during the process and causes toxic environmental pollution when hexavalent chromium ions enter groundwater or rivers. Is holding.
즉 6가크롬은 국제암탐색청(International Agency of Research on the Cancer, LARC)으로부터 암발생 물질로 분류되어 있으며, 향후 6가크롬의 사용금지와 함께 이의 대체 기술이 요구되어 최근에는 전 세계적으로 대체 물질 개발을 위한 연구가 활발히 진행되고 있다.In other words, hexavalent chromium is classified as a cancer-causing substance by the International Agency of Research on the Cancer (LARC), and its replacement technology is required in addition to prohibiting the use of hexavalent chromium in the future. Research for the development of materials is actively underway.
6가 크롬도금을 대체할 수 있는 다양한 시도 중에는 이온질화(ion-nitriding), 용사도금(plasma spraying), 이온도금(ion plating)등이 있으나, 6가크롬도금에 비하여 5~10배의 비용이 추가되는 문제와 대형 제품에는 적용이 어려운 문제점이 있다.Various attempts to replace hexavalent chromium plating include ion-nitriding, plasma spraying, and ion plating, but the cost is 5 to 10 times that of hexavalent chromium plating. There are problems to be added and difficult to apply to large products.
이에 따라 3가 크롬을 이용한 크롬도금이 가장 효과적이고 효율적인 것으로 인정받고 있다.Accordingly, chromium plating using trivalent chromium is recognized as the most effective and efficient.
그러나, 3가크롬도금액에 포함되는 3가크롬이온은 수용액 중에 매우 복잡한 배위 화학적 구조를 가지며, 낮은 반응성으로 인하여 크롬도금층 형성이 어려운 문제점이 있다.However, trivalent chromium ions included in the trivalent chromium plating solution have a very complex coordination chemical structure in the aqueous solution, and there is a problem in that a chromium plating layer is difficult to form due to low reactivity.
이에 따라, 다양한 첨가제를 첨가하여 고광택, 고강도를 가지는 3가크롬도금층의 형성이 가능하도록 한 3가크롬도금액이 개발되고 있다.Accordingly, a trivalent chromium plating solution has been developed which enables the formation of a trivalent chromium plating layer having a high gloss and high strength by adding various additives.
예컨대, 대한민국 등록특허 제0572486호에는 도금활성첨가제에 금속 성분을 선택적으로 포함시켜 밀착성이 향상되도록 한 "3가 크롬도금액 조성물과 그 제조방법"이 개시되어 있다.For example, Korean Patent No. 0572486 discloses a "trivalent chromium plating solution composition and its manufacturing method" to selectively include a metal component in a plating active additive to improve adhesion.
그러나, 상기 발명은 20~40A/dm2의 좁은 전류밀도 범위 내에서 3가 크롬 도금층의 형성이 가능하므로 도금 효율이 저하되는 문제점이 있다.However, the present invention has a problem in that the plating efficiency is lowered since the trivalent chromium plating layer can be formed within a narrow current density range of 20 to 40 A / dm 2 .
또한, 논문 "Renewable Energy 30(2005) 2163"에는 코발트 또는 철을 첨가제로 사용할 수 있는 것으로 기재되어 있으나, 실시예에서는 도금의 불균일을 해소하기 위하여 코발트만을 사용하였다.In addition, although the paper "Renewable Energy 30 (2005) 2163" describes that cobalt or iron may be used as an additive, in the examples, only cobalt was used to eliminate the nonuniformity of plating.
한편, 종래의 흑색 크롬 도금액의 경우 phosphate 또는 hypophosphite 등 인(P) 성분을 포함하고 있고, 산성도(acidity)는 강산성인 0.5 ~ 1 사이로 매우 협소하며, 20~40A/dm2 또는 60~80A/dm2의 좁은 전류밀도 범위 내에서만 흑색 도금이 가능한 문제점이 있다.On the other hand, the conventional black chromium plating solution contains a phosphorus (P) component such as phosphate or hypophosphite, the acidity (acidity) is very narrow between 0.5 to 1 which is strongly acidic, and 20 to 40 A / dm 2 or 60 to 80 A / dm There is a problem that black plating is possible only within a narrow current density range of 2 .
본 발명의 목적은 상기와 같은 문제점을 해결하기 위한 것으로, 저-중전류밀도 범위에서 도금액 반응성을 높여 넓은 광택영역(Coverage)의 도금이 가능하도록 함으로써 경제성이 향상되도록 한 광택 흑색 3가크롬도금층을 위한 3가크롬도금액 및 이의 제조방법을 제공하는 것에 있다.An object of the present invention is to solve the above problems, it is possible to increase the reactivity of the plating solution in the low-medium current density range to enable the plating of a wide gloss (Coverage) of the glossy black trivalent chromium plating layer to improve the economic efficiency To provide a trivalent chromium plating solution and a method for producing the same.
본 발명의 다른 목적은, 인(P) 성분을 포함하지 않으며, Fe 이온과 Co 이온을 포함하는 무기색상발현제를 첨가하여 광택 흑색 3가크롬도금층의 형성이 가능하도록 함으로써 bath 수명 안정화로 부가가치가 향상되도록 한 광택 흑색 3가크롬도금층을 위한 3가크롬도금액 및 이의 제조방법을 제공하는 것에 있다.It is another object of the present invention to add an inorganic color expression agent containing no phosphorus (P) component and to form a glossy black trivalent chromium plating layer by adding an inorganic color developer containing Fe ions and Co ions, thereby adding value to stabilizing bath life. The present invention provides a trivalent chromium plating solution for a glossy black trivalent chromium plating layer and a method for producing the same.
본 발명은 구리를 포함하는 금속모재 상에 광택 흑색 3가크롬도금층을 위한 3가크롬도금액에 있어서, 상기 3가크롬도금액은, 3가크롬화합물 0.4 ~ 0.6M과, 상기 3가크롬화합물이 수용액 중에서 고분자화 반응이 억제되도록 하는 착화제 0.8 ~ 1.2M과, 3가크롬이온의 전기전도도를 높이기 위한 전도보조제 0.8 ~ 1.2M과, 수용액의 수소이온지수를 안정화하는 완충제 0.8 ~ 1.2M과, 3가크롬이온이 2가로 산화되는 것을 억제하는 감극제 8 ~ 12g/l과, Fe 이온과 Co 이온을 포함하여 광택 흑색 3가크롬도금층의 명도 및 채도를 조절하는 무기색상발현제 2 ~ 14g/l와, 상기 무기색상발현제에 포함된 금속이온을 산화시키는 산화제와, 수소이온지수(pH)를 조정하는 수소이온지수조정제(KOH)를 포함하여 구성되며, 0.1A/dm2 내지 20A/dm2 전류밀도 범위에서 광택 흑색 3가크롬도금층의 형성이 가능한 것을 특징으로 한다.The present invention is a trivalent chromium plating solution for a glossy black trivalent chromium plating layer on a metal base material containing copper, wherein the trivalent chromium plating solution is 0.4 to 0.6M of a trivalent chromium compound and the trivalent chromium compound. 0.8 to 1.2 M of a complexing agent to inhibit the polymerization reaction in the aqueous solution, 0.8 to 1.2 M of a conduction aid for increasing the electrical conductivity of trivalent chromium ion, and 0.8 to 1.2 M of a buffer to stabilize the hydrogen ion index of the aqueous solution. , 8 to 12 g / l of a polarizing agent that inhibits trivalent chromium ion from oxidizing to divalent, and an inorganic color developer that controls the brightness and saturation of a glossy black trivalent chromium plating layer including Fe ions and Co ions. / l, an oxidizing agent for oxidizing the metal ions included in the inorganic color expression agent, and a hydrogen ion index regulator (KOH) for adjusting the hydrogen ion index (pH), 0.1A / dm 2 It is possible to form a glossy black trivalent chromium plating layer in a current density range of 20 A / dm 2 .
상기 무기색상발현제는, 상기 광택 흑색 3가크롬도금층의 명도 조절을 위한 명도조절제 1 ~ 7g/l와,The inorganic color developer, a brightness regulator for adjusting the brightness of the glossy black trivalent
상기 광택 흑색 3가크롬도금층의 채도 조절을 위한 채도조절제 1 ~ 7g/l를 포함하여 구성됨을 특징으로 한다.Characterized in that it comprises a
상기 3가크롬화합물은 황산크롬염(Cr2(SO4)3) 또는 염화크롬염(CrCl3)임을 특징으로 한다.The trivalent chromium compound is characterized in that the chromium sulfate (Cr 2 (SO 4 ) 3 ) or chromium chloride (CrCl 3 ).
상기 산화제는 ammonium persulfate가 적용됨을 특징으로 한다.The oxidant is characterized in that ammonium persulfate is applied.
상기 착화제는 옥살산(oxalic acid), 포름산(formic acid), 옥살산 암모늄염, 포름산 암모늄염, 알칼리 금속염 중 하나 이상을 포함하여 구성됨을 특징으로 한다.The complexing agent is characterized in that it comprises at least one of oxalic acid (oxalic acid), formic acid (formic acid), ammonium oxalate salt, ammonium formate salt, alkali metal salt.
상기 전도보조제는 KCl, NH4Cl, K2SO4, (NH4)2SO4 중 하나 이상을 포함하여 구성됨을 특징으로 한다.The conduction aid is characterized in that it comprises one or more of KCl, NH 4 Cl, K 2 SO 4 , (NH 4 ) 2 SO 4 .
상기 감극제는 NH4Br, NaBr, NaF 중 어느 하나임을 특징으로 한다.The depolarizing agent is characterized in that any one of NH 4 Br, NaBr, NaF.
상기 완충제는 H3BO3가 적용됨을 특징으로 한다.The buffer is characterized in that H 3 BO 3 is applied.
상기 3가크롬화합물과 착화제의 몰농도 비율은 1:0.5 ~ 1:1.5인 것을 특징으로 한다.The molar concentration ratio of the trivalent chromium compound and the complexing agent is characterized in that 1: 0.5 ~ 1: 1.5.
상기 무기색상발현제는, FeCl2, FeSO4, FeS 중 어느 하나인 철이온염이 채택되는 명도조절제와, CoCl2, Co(CN)2, Co(NO3)2, CoSO4 중 어느 하나인 코발트이온염을 포함하는 채도조절제를 포함하여 구성됨을 특징으로 한다.The inorganic color expression agent, a brightness control agent is adopted any one of FeCl 2 , FeSO 4 , FeS and a cobalt ion salt of any one of
본 발명에 의한 광택 흑색 3가크롬도금층을 이용한 3가크롬도금액의 제조방법은, 용기에 증류수를 넣어 70℃로 가열하는 증류수가열단계와, 가열된 증류수에 착화제 0.8 ~ 1.2M을 첨가하는 착화제첨가단계와, 완충제 0.8 ~ 1.2M 첨가하여 용해하는 완충제용해단계와, 0.8 ~ 1.2M의 전도보조제를 첨가하여 용해하는 전도보조제용해단계와, 0.4 ~ 0.6M의 3가크롬화합물을 첨가하여 교반하는 3가크롬교반단계와, 금속이온을 산화하기 위한 산화제를 5 ~ 15g/l 첨가하는 산화제첨가단계와, Fe 이온과 Co 이온을 포함하는 무기색상발현제 2 ~ 14g/l를 첨가하는 무기색상발현제첨가단계와, 수소이온지수조정제(KOH)를 첨가하여 수소이온지수(pH)를 조정하는 수소이온지수조정단계와, 상기 구성이 혼합된 혼합용액을 12시간 이상 반응시켜 착화하는 착화단계로 이루어지는 것을 특징으로 한다.Method for producing a trivalent chromium plating solution using a glossy black trivalent chromium plating layer according to the present invention, the distilled water heating step to put the distilled water in a container and heated to 70 ℃ and adding a complexing agent 0.8 ~ 1.2M to the heated distilled water Adding a complexing agent, a buffer dissolving step of dissolving by adding 0.8 ~ 1.2M of buffer, a conducting aid dissolving step of dissolving by adding 0.8 ~ 1.2M of conducting aid, and adding 0.4 ~ 0.6M trivalent chromium compound Trivalent chrome stirring step of stirring, oxidant addition step of adding 5 to 15 g / l of an oxidizing agent for oxidizing metal ions, and inorganic addition of 2 to 14 g / l of an inorganic color expression agent containing Fe ions and Co ions A color expression agent addition step, a hydrogen ion index adjustment step of adjusting the hydrogen ion index (pH) by adding a hydrogen ion index adjuster (KOH), and a complexing step of reacting the mixed solution mixed with the above composition for 12 hours or more to ignite it Made up of scoop It shall be.
상기 무기색상발현제첨가단계에서, 상기 산화제는 ammonium persulfate가 적용됨을 특징으로 한다.In the inorganic color expression agent addition step, the oxidizing agent is characterized in that the ammonium persulfate is applied.
상기 무기색상발현제첨가단계에서, 상기 무기색상발현제는, 상기 광택 흑색 3가크롬도금층의 명도 조절을 위해 Fe 이온을 포함하는 명도조절제 1 ~ 7g/l와, 상기 광택 흑색 3가크롬도금층의 채도 조절을 위해 Co 이온을 포함하는 채도조절제 1 ~ 7g/l를 포함하는 것을 특징으로 한다.In the inorganic color expressing agent addition step, the inorganic color expressing agent, the
위에서 상세히 설명한 바와 같이 본 발명에 의한 광택 흑색 3가크롬도금층을 위한 3가크롬도금액에서는, 무기색상발현제로서 Fe 이온과 Co 이온이 포함되며, 저-중전류밀도 범위에서 도금액 반응성을 높여 넓은 광택영역(Coverage)의 도금이 가능하다.As described in detail above, in the trivalent chromium plating solution for the glossy black trivalent chromium plating layer according to the present invention, Fe ions and Co ions are included as the inorganic color developer, and the plating solution reactivity is increased in a low-medium current density range. Plating of gloss area is possible.
따라서, 경제성이 향상되며 bath 수명 안정화로 부가가치가 향상되는 이점이 있다.Therefore, there is an advantage that the economic value is improved and the added value is improved by stabilizing the bath life.
또한, 도금층 형성이 보다 용이하며, 두께가 고른 도금층의 형성이 가능한 이점이 있다.In addition, there is an advantage that the plating layer can be formed more easily, and the plating layer having a uniform thickness can be formed.
뿐만 아니라, 도금층의 형성 속도가 빨라지므로 생산성이 향상되는 이점이 있다.In addition, since the formation speed of the plating layer is increased, productivity is improved.
도 1 은 본 발명에 의한 3가크롬도금액의 조성 및 전해도금 조건을 보인 표.
도 2 는 본 발명에 의한 3가크롬도금액의 제조방법을 나타낸 공정순서도.
도 3 은 본 발명에 의한 3가크롬도금액에서 무기색상발현제의 일 구성인 Fe 이온의 함량 변화에 따른 3가크롬도금층의 외관 변화를 비교한 실험 결과.
도 4 는 본 발명에 의한 3가크롬도금액에서 무기색상발현제의 일 구성인 Co 이온의 함량을 증가시에 3가크롬도금층의 외관 변화를 나타낸 실험 결과.
도 5 는 본 발명에 의한 3가크롬도금액에서 무기색상발현제의 일 구성인 Co 이온의 함량을 3g/l로 고정하고 Fe 이온의 함량을 변화시에 증가시에 3가크롬도금층의 외관 변화를 비교한 실험 결과.
도 6 은 본 발명에 의한 3가크롬도금액에서 무기색상발현제의 일 구성인 Co 이온의 함량을 5g/l로 고정하고 Fe 이온의 함량을 변화시에 증가시에 3가크롬도금층의 외관 변화를 비교한 실험 결과.
도 7 은 본 발명에 의한 3가크롬도금액에서 무기색상발현제의 일 구성인 Co 이온의 함량을 7g/l로 고정하고 Fe 이온의 함량을 변화시에 증가시에 3가크롬도금층의 외관 변화를 비교한 실험 결과.1 is a table showing the composition and electroplating conditions of the trivalent chromium plating solution according to the present invention.
2 is a process flowchart showing a method for producing a trivalent chromium plating solution according to the present invention.
3 is an experimental result comparing the appearance change of the trivalent chromium plating layer according to the change in the content of Fe ions which is one component of the inorganic color expression in the trivalent chromium plating solution according to the present invention.
Figure 4 is an experimental result showing the appearance change of the trivalent chromium plating layer when increasing the content of Co ions which is one component of the inorganic color developer in the trivalent chromium plating solution according to the present invention.
5 is a change in appearance of the trivalent chromium plating layer when the content of Co ions, which is one component of the inorganic color developer, is increased to 3 g / l in the trivalent chromium plating solution according to the present invention, and the content of Fe ions is increased. Experimental results compared.
6 is a change in appearance of the trivalent chromium plating layer when the content of Co ions, which is one component of the inorganic color developer, is increased to 5 g / l in the trivalent chromium plating solution according to the present invention, and the content of Fe ions is increased. Experimental results compared.
7 is a change in appearance of the trivalent chromium plating layer when the content of Co ions, which is one component of the inorganic color developer, is increased to 7 g / l and the content of Fe ions is increased in the trivalent chromium plating solution according to the present invention. Experimental results compared.
이하 상기와 같은 3가크롬도금액의 제조방법을 첨부된 도 1 및 도 2를 참조하여 설명한다.Hereinafter, a method of manufacturing a trivalent chromium plating solution as described above will be described with reference to FIGS. 1 and 2.
도 1에는 본 발명에 의한 3가크롬도금액의 조성 및 전해도금 조건을 보인 표가 도시되어 있고, 도 2 는 본 발명에 의한 3가크롬도금액의 제조방법을 나타낸 공정순서도가 도시되어 있다.1 is a table showing the composition and electroplating conditions of the trivalent chromium plating solution according to the present invention, Figure 2 is a process flow chart showing a method for producing a trivalent chromium plating solution according to the present invention.
본 발명에 따른 3가크롬도금액은 구리를 포함하는 금속모재에 광택을 가지는 흑색(bright dark black color) 3가크롬도금층을 형성하기 위한 것으로, 본 발명의 실시예에서 3가크롬화합물은 Cr2(SO4)3, 착화제로 포름산(HCOOH)과 옥살산(oxalic acid) 중 어느 하나, 전도보조제로 NH4Cl, 완충제로는 H3BO3, 감극제로는 NH4Br, 산화제는 5~15g/l의 ammonium persulfate가 적용되었다.The trivalent chromium plating solution according to the present invention is to form a bright dark black color trivalent chromium plating layer on a metal base material containing copper, and in the embodiment of the present invention, the trivalent chromium compound is Cr 2. (SO 4 ) 3 , any one of formic acid (HCOOH) and oxalic acid as complexing agent, NH 4 Cl as conduction aid, H 3 BO 3 as buffer, NH 4 Br as stimulant, 5 ~ 15g / l ammonium persulfate was applied.
그리고, 상기 3가크롬도금액에는 무기색상발현제가 더 포함된다. 상기 무기색상발현제는 Fe 이온과 Co 이온을 포함하여 3가크롬도금층의 명도와 채도를 결정할 수 있도록 하는 구성이다.In addition, the trivalent chromium plating solution further includes an inorganic color developer. The inorganic color developer includes Fe ions and Co ions to determine brightness and saturation of the trivalent chromium plated layer.
즉, 상기 무기색상발현제는 3가크롬도금층의 명도를 조절하기 위한 명도조절제와, 채도를 조절하기 위한 채도조절제를 포함하여 구성되며, 상기 명도조절제에는 Fe 이온이 포함되고, 채도조절제에는 Co 이온이 포함된다.That is, the inorganic color expression agent comprises a brightness control agent for adjusting the brightness of the trivalent chromium plating layer, and a saturation control agent for adjusting the saturation, the brightness control agent includes Fe ions, the chromaticity control agent Co ions This includes.
보다 구체적으로는, 상기 무기색상발현제는 FeCl2, FeSO4, FeS 중 어느 하나인 철이온염이 채택되는 명도조절제와, CoCl2, Co(CN)2, Co(NO3)2, CoSO4 중 어느 하나인 코발트이온염을 포함하는 채도조절제를 포함하여 구성된다.More specifically, the inorganic color expression agent is FeCl 2 , FeSO 4 , one of the lightness adjusting agent is adopted iron Fe salt of FeS, CoCl2, Co (CN) 2, Co (NO3) 2, CoSO4 And a saturation modifier comprising a cobalt ion salt.
본 발명의 실시예에서 상기 무기색상발현제는 1~7g/l의 FeCl2와 1~7g/l의 CoCl2 가 포함된다.In an embodiment of the present invention, the inorganic color developer includes 1 to 7 g / l FeCl 2 and 1 to 7 g / l CoCl 2 .
이하 상기와 같이 구성되는 3가크롬도금액을 제조하는 방법을 첨부된 도 2를 참조하여 설명한다.Hereinafter, a method of manufacturing a trivalent chromium plating solution configured as described above will be described with reference to FIG. 2.
먼저, 용기에 증류수 400ml를 넣어 70℃로 가열하는 증류수가열단계(S100)를 실시한다. 이후 가열된 증류수에 착화제(포름산)을 46g 첨가한 후 40 내지 50℃까지 냉각시킨다(착화제첨가단계:S200)First, the distilled water heating step (S100) to put 400ml of distilled water in a container and heated to 70 ℃. Thereafter, 46 g of a complexing agent (formic acid) is added to the heated distilled water, and then cooled to 40 to 50 ° C. (complexing agent addition step: S200).
이때 상기 3가크롬화합물과 착화제의 몰농도 비율은 1:0.5 ~ 1:1.5인 것이 바람직하다.At this time, the molar concentration ratio of the trivalent chromium compound and the complexing agent is preferably 1: 0.5 to 1: 1.5.
그런 다음 완충제(H3BO3)를 60g 첨가한 후 70℃로 가열하여 완전히 용해시킨다.(완충제용해단계(S300))Then, 60 g of the buffer (H 3 BO 3 ) is added, followed by heating to 70 ° C. to dissolve completely. (Buffer dissolving step (S300))
상기 완충제가 용해되면 전도보조제(NH4Cl) 53.5g, 및 KCl 74,5g 을 첨가한 후 용해시킨다(전도보조제용해단계:S400).When the buffer is dissolved, 53.5 g of a conduction aid (NH 4 Cl), and 74,5 g of KCl are added and then dissolved (conduction aid dissolution step: S400).
상기 전도보조제가 용해된 용기에 3가크롬화합물을 첨가하여 16 내지 24시간 동안 교반하는 3가크롬교반단계(S500)를 실시하게 된다.The trivalent chromium compound is added to the vessel in which the conductive support agent is dissolved, and the trivalent chrome stirring step (S500) of stirring for 16 to 24 hours is performed.
이후 금속이온을 산화하기 위한 산화제를 5 ~ 15g/l 첨가하는 산화제첨가단계(S600)를 실시하게 된다.Thereafter, an oxidizer addition step (S600) of adding 5 to 15 g / l of an oxidant for oxidizing metal ions is performed.
상기 산화제는 ammonium persulfate가 채택되었다.The oxidant was ammonium persulfate.
이후 본 발명의 요부 구성인 무기색상발현제를 첨가하는 무기색상발현제첨가단계(S700)가 실시된다.Thereafter, an inorganic color expressing agent adding step (S700) of adding an inorganic color expressing agent which is a main component of the present invention is performed.
상기 무기색상발현제의 구성인 명도조절제는 1~7 g/l의 FeCl2, 채도조절제는 1~7 g/l의 CoCl2가 적용되었다.Brightness control agent of the inorganic
이후 수소이온지수조정제에 의해 수소이온지수(pH)가 조정된다(수소이온지수조정단계:S800).Then, the hydrogen ion index (pH) is adjusted by the hydrogen ion index adjuster (hydrogen ion index adjustment step: S800).
마지막으로 상기한 구성들을 12시간 이상 반응시켜 착화하는 착화단계(S900)를 실시하여 3가크롬도금액의 제조를 완료하게 된다.Finally, the ignition step (S900) is performed by reacting the above components for 12 hours or more to complete the preparation of the trivalent chromium plating solution.
상기와 같은 과정에 따라 제조된 3가크롬도금액의 수소이온지수(pH)는 2~4 범위가 바람직하다.The hydrogen ion index (pH) of the trivalent chromium plating solution prepared according to the above process is preferably in the range of 2-4.
이하 상기와 같은 과정에 따라 제조된 3가크롬도금액에서 무기색상발현제의 첨가량의 변화에 따른 3가크롬도금층의 색상 및 광택 변화를 실험하였다.Hereinafter, the change in color and gloss of the trivalent chromium plating layer according to the change in the amount of the inorganic color developer was added in the trivalent chromium plating solution prepared according to the above procedure.
보다 구체적으로는, 상기한 본 발명의 제조방법에 따라 제조된 3가크롬도금액에 구리 시편을 담지한 후 음극을 연결하게 된다. 그리고, 상기 도금조에는 양극을 인가하여 전류를 흘리게 된다.More specifically, the negative electrode is connected after supporting the copper specimen in the trivalent chromium plating solution prepared according to the manufacturing method of the present invention described above. In addition, an anode is applied to the plating bath to flow a current.
이때, 상기 도금조에서 양극과 연결되는 부위는 graphite 및 불용성양극이 사용됨이 바람직하다. 보다 상세하게는, 상기 불용성 양극은 Ir,Ta, Pt 중 하나 이상을 포함하는 복합체가 적용된다.In this case, it is preferable that graphite and an insoluble anode are used as a portion connected to the anode in the plating bath. More specifically, the insoluble anode is a composite containing at least one of Ir, Ta, Pt is applied.
그리고, 상기 전류인가시에 유효전류 인가범위는 0.1 내지 20A/dm2 범위 내에서 실시하였으며, 착화제로서 옥살산(oxalic acid)이 적용되었다. 상기 착화제는 포름산(formic acid)이 채택되어도 무방하다.In addition, when the current is applied, the effective current application range was performed within the range of 0.1 to 20 A / dm 2 , and oxalic acid was applied as the complexing agent. The complexing agent may be adopted formic acid (formic acid).
도 3과 같이, 상기 첨가제로서 옥살산(oxalic acid)이 적용되고, 전도보조제로서 SO4염+Cl염과 Cl염을 각각 적용하였으며, 전류밀도는 0.1A/dm2에서 20A/dm2로 변화시켰을 때 도금층의 명도 및 채도 변화를 살펴보았다.As shown in FIG. 3, oxalic acid was applied as the additive, and SO 4 salt + Cl salt and Cl salt were used as conduction aids, respectively, and the current density was changed from 0.1 A / dm 2 to 20 A / dm 2 . When the brightness and saturation of the plating layer was examined.
먼저, 도 3 은 본 발명에 의한 3가크롬도금액에서 무기색상발현제의 일 구성인 Fe 이온의 함량 변화에 따른 3가크롬도금층의 외관 변화를 비교한 실험 결과로서, 도 1과 같이 구성된 3가크롬도금액을 도금조 내부에 준비한 다음 다수 시편을 동일한 크기로 잘라 준비하게 된다. 이때 상기 명도조절제인 Co이온은 1g/l로 고정하고 Fe 이온은 1g/l 또는 3g/l로 서로 다르게 적용하였다.First, FIG. 3 is an experimental result comparing the appearance change of the trivalent chromium plating layer according to the change of the content of Fe ions, which is one component of the inorganic color expression agent, in the trivalent chromium plating solution according to the present invention. After preparing the chromium plating solution in the plating bath, a plurality of specimens are cut to the same size and prepared. At this time, Co ions, which are brightness regulators, were fixed at 1 g / l and Fe ions were applied differently at 1 g / l or 3 g / l.
그 결과, Co이온의 농도가 1g/l 로 낮을 때에는 광택 흑색의 색상이 저전류 밀도 범위에서 일부 생성이 되긴 하나, 중/고전류 밀도의 대부분 영역에서는 광택을 가지는 옅은 흑색의 3가크롬도금층이 형성되었다.As a result, when the concentration of Co ions is as low as 1 g / l, a part of the gloss black color is generated in the low current density range, but a light black trivalent chromium plating layer is formed in most regions of the medium / high current density. It became.
또한 도 3의 결과와 같이 Fe 이온의 함량에 따라 흑색의 명도가 달라지는 것을 확인하였다.In addition, it was confirmed that the brightness of black is changed according to the content of Fe ions as shown in FIG.
따라서, Fe 이온은 명도조절제로서 사용되고 있음을 알 수 있다.Therefore, it can be seen that Fe ions are used as the brightness control agent.
도 4는 본 발명에 의한 3가크롬도금액에서 무기색상발현제의 일 구성인 Co 이온의 함량을 증가시에 3가크롬도금층의 외관 변화를 나타낸 실험 결과로서, Fe 이온과 Co 이온의 함량을 2g/l로 동일하게 고정하였다.Figure 4 is an experimental result showing the appearance change of the trivalent chromium plating layer when increasing the content of Co ions which is one component of the inorganic color developer in the trivalent chromium plating solution according to the present invention, the content of Fe ions and Co ions The same was fixed at 2 g / l.
그 결과, Co 이온 함량이 조금 더 증가함에 따라 광택 흑색 색상이 저전류 밀도 범위에서 중전류 밀도 범위까지 확산되었다.As a result, the glossy black color diffused from the low current density range to the medium current density range as the Co ion content increased slightly.
따라서, Co 이온은 3가크롬도금액에 있어서 채도조절제로 사용됨을 알 수 있다.Therefore, it can be seen that Co ion is used as a saturation regulator in the trivalent chromium plating solution.
도 5는 본 발명에 의한 3가크롬도금액에서 무기색상발현제의 일 구성인 Co 이온의 함량을 3g/l로 고정하고 Fe 이온의 함량을 변화시에 증가시에 3가크롬도금층의 외관 변화를 비교한 실험 결과로서, Co 이온의 함량은 3g/l로 동일하게 고정하고, Fe 이온의 함량은 1g/l, 3g/l로 서로 상이하게 첨가하였다.5 is a change in appearance of the trivalent chromium plating layer when the content of Co ions, which is one component of the inorganic color developer, is increased to 3 g / l in the trivalent chromium plating solution according to the present invention, and the content of Fe ions is increased. As a result of the comparison, the content of Co ions was fixed to 3g / l equally, and the content of Fe ions was added differently to 1g / l and 3g / l.
그 결과, Co 이온의 함량을 3g/l로 높였을 때, 광택 흑색 색상이 고전류 밀도까지 확산되는 경향을 보였으며, Fe 이온의 함량이 증가하는 경우 0.15~16 A/dm2의 넓은 전류 밀도 범위에서 균일한 광택 흑색을 갖는 3가크롬도금층이 형성되었다.As a result, when the Co ion content was increased to 3g / l, the gloss black color tended to diffuse up to the high current density, and when the Fe ion content was increased, a wide current density range of 0.15 to 16 A / dm 2 was obtained. In, a trivalent chromium plated layer having a uniform glossy black was formed.
따라서, Co 이온 3g/l과, Fe 이온 3g/l을 포함하는 3가크롬도금액이 가장 바람직한 실시 예인 것을 알 수 있다.Therefore, it can be seen that the trivalent chromium plating solution containing 3 g / l of Co ions and 3 g / l of Fe ions is the most preferred embodiment.
도 6은 본 발명에 의한 3가크롬도금액에서 무기색상발현제의 일 구성인 Co 이온의 함량을 5g/l로 고정하고 Fe 이온의 함량을 변화시에 증가시에 3가크롬도금층의 외관 변화를 비교한 실험 결과로서, Co 이온의 농도를 5g/l로 높이게 되면 광택 흑색 색상이 급격히 감소되어 전류 밀도 전영역이 광택이 있는 옅은 흑색으로 변하는 것을 확인하였다.6 is a change in the appearance of the trivalent chromium plating layer when the content of Co ions, which is one component of the inorganic color developer, is increased to 5 g / l in the trivalent chromium plating solution according to the present invention and increased when the content of Fe ions is changed. As a result of the comparison, when the concentration of Co ion was increased to 5g / l, it was confirmed that the gloss black color was sharply reduced and the entire current density area was changed to the gloss pale black.
도 7은 본 발명에 의한 3가크롬도금액에서 무기색상발현제의 일 구성인 Co 이온의 함량을 7g/l로 고정하고 Fe 이온의 함량을 변화시에 증가시에 3가크롬도금층의 외관 변화를 비교한 실험 결과로서, Co 이온의 함량을 7g/l로 고정하고 Fe 이온 함량을 각각 5g/l, 7g/l로 서로 상이하게 적용하였다.7 is a change in appearance of the trivalent chromium plating layer when the content of Co ions, which is one component of the inorganic color developer, is fixed to 7 g / l in the trivalent chromium plating solution according to the present invention and increases when the content of Fe ions is changed. As a result of the comparison, the Co ion content was fixed at 7 g / l and the Fe ion content was applied differently at 5 g / l and 7 g / l, respectively.
그 결과, Co 이온의 함량이 7g/l로 높게 첨가된 상태에서는 Fe 이온 함량이 증가하더라도 앞선 실험의 농도 변화에 따른 추세를 벗어나 dark black color가 고전류 밀도 영역에서 출현하였다.As a result, in the state in which the Co ion content was added as high as 7g / l, even if the Fe ion content increased, the dark black color appeared in the high current density region beyond the trend of the concentration change of the previous experiment.
상기와 같은 실험 결과에 따라 Fe 이온과 Co 이온은 흑색을 발현하는 매체로서 작용함을 알 수 있으며, 두 이온의 비에 의해 color의 명도 및 채도 변화가 결정됨을 알 수 있다.According to the experimental results as described above, it can be seen that Fe ions and Co ions act as a medium for expressing black color, and the brightness and saturation changes of color are determined by the ratio of the two ions.
이러한 본 발명의 범위는 상기에서 예시한 실시예에 한정하지 않고, 상기와 같은 기술범위 안에서 당업계의 통상의 기술자에게 있어서는 본 발명을 기초로 하는 다른 많은 변형이 가능할 것이다.The scope of the present invention is not limited to the above-described embodiments, and many other modifications based on the present invention will be possible to those skilled in the art within the scope of the present invention.
S100. 증류수가열단계 S200. 착화제첨가단계
S300. 완충제용해단계 S400. 전도보조제용해단계
S500. 3가크롬교반단계 S600. 산화제첨가단계
S700. 무기색상발현제첨가단계 S800. 수소이온지수조정단계
S900. 착화단계S100. Distilled water heating step S200. Complexing agent addition step
S300. Buffer dissolution step S400. Conduction Aid Dissolving Step
S500. Trivalent chrome stirring step S600. Oxidizer Addition Step
S700. Inorganic color expression addition step S800. Hydrogen ion index adjustment stage
S900. Ignition stage
Claims (13)
상기 3가크롬도금액은,
3가크롬화합물 0.4 ~ 0.6M과,
상기 3가크롬화합물이 수용액 중에서 고분자화 반응이 억제되도록 하는 착화제 0.8 ~ 1.2M과,
3가크롬이온의 전기전도도를 높이기 위한 전도보조제 0.8 ~ 1.2M과,
수용액의 수소이온지수를 안정화하는 완충제 0.8 ~ 1.2M과,
3가크롬이온이 2가로 산화되는 것을 억제하는 감극제 8 ~ 12g/l과,
Fe 이온과 Co 이온을 포함하여 광택 흑색 3가크롬도금층의 명도 및 채도를 조절하는 무기색상발현제 2 ~ 14g/l와,
상기 무기색상발현제에 포함된 금속이온을 산화시키는 산화제와,
수소이온지수(pH)를 조정하는 수소이온지수조정제(KOH)를 포함하여 구성되며,
0.1A/dm2 내지 20A/dm2 전류밀도 범위에서 광택 흑색 3가크롬도금층의 형성이 가능한 것을 특징으로 하는 광택 흑색 3가크롬도금층을 위한 3가크롬도금액.In a trivalent chromium plating solution for a glossy black trivalent chromium plating layer on a metal base material containing copper,
The trivalent chromium plating solution,
Trivalent chromium compound 0.4 ~ 0.6M,
0.8 to 1.2 M of a complexing agent to inhibit the polymerization reaction of the trivalent chromium compound in an aqueous solution;
0.8 ~ 1.2M conduction aid to increase the electrical conductivity of trivalent chromium ion,
0.8 ~ 1.2M buffer to stabilize the hydrogen ion index of the aqueous solution,
8-12 g / l of a polarizing agent which suppresses trivalent chromium ion from oxidizing to divalent,
Inorganic color developer 2 ~ 14g / l to control the brightness and saturation of the glossy black trivalent chromium plating layer including Fe ions and Co ions,
An oxidizing agent for oxidizing the metal ions included in the inorganic color developer;
It includes a hydrogen ion index adjuster (KOH) to adjust the hydrogen ion index (pH),
0.1 A / dm 2 Trivalent chromium plating solution for a glossy black trivalent chromium plating layer, characterized in that the formation of a glossy black trivalent chromium plating layer in the current density range of 20A / dm 2 .
상기 광택 흑색 3가크롬도금층의 명도 조절을 위한 명도조절제 1 ~ 7g/l와,
상기 광택 흑색 3가크롬도금층의 채도 조절을 위한 채도조절제 1 ~ 7g/l를 포함하여 구성됨을 특징으로 하는 광택 흑색 3가크롬도금층을 위한 3가크롬도금액.The method of claim 1, wherein the inorganic color expression agent,
Brightness control agent 1 ~ 7g / l for adjusting the brightness of the glossy black trivalent chromium plating layer,
Trivalent chromium plating solution for a glossy black trivalent chromium plating layer, characterized in that it comprises a saturation regulator 1 ~ 7g / l for controlling the saturation of the glossy black trivalent chromium plating layer.
FeCl2, FeSO4, FeS 중 어느 하나인 철이온염이 채택되는 명도조절제와,
CoCl2, Co(CN)2, Co(NO3)2, CoSO4 중 어느 하나인 코발트이온염을 포함하는 채도조절제를 포함하여 구성됨을 특징으로 하는 광택 흑색 3가크롬도금층을 이용한 3가크롬도금액.The method of claim 1, wherein the inorganic color expression agent,
Brightness control agent is adopted any one of FeCl 2 , FeSO 4 , FeS ions,
A trivalent chromium plating solution using a glossy black trivalent chromium plating layer, comprising a saturation regulator comprising a cobalt ion salt of CoCl 2, Co (CN) 2, Co (NO 3) 2, or CoSO 4.
가열된 증류수에 착화제 0.8 ~ 1.2M을 첨가하는 착화제첨가단계와,
완충제 0.8 ~ 1.2M 첨가하여 용해하는 완충제용해단계와,
0.8 ~ 1.2M의 전도보조제를 첨가하여 용해하는 전도보조제용해단계와,
0.4 ~ 0.6M의 3가크롬화합물을 첨가하여 교반하는 3가크롬교반단계와,
금속이온을 산화하기 위한 산화제를 5 ~ 15g/l 첨가하는 산화제첨가단계와,
Fe 이온과 Co 이온을 포함하는 무기색상발현제 2 ~ 14g/l를 첨가하는 무기색상발현제첨가단계와,
수소이온지수조정제(KOH)를 첨가하여 수소이온지수(pH)를 조정하는 수소이온지수조정단계와,
상기 구성이 혼합된 혼합용액을 12시간 이상 반응시켜 착화하는 착화단계로 이루어지는 것을 특징으로 하는 광택 흑색 3가크롬도금층을 위한 3가크롬도금액의 제조방법.Distilled water heating step of putting distilled water in a container and heating to 70 ℃,
Adding a complexing agent to the heated distilled water by adding a complexing agent 0.8 to 1.2M,
A buffer dissolving step of dissolving by adding 0.8 to 1.2 M of buffer,
A conduction aid dissolving step of dissolving by adding 0.8 ~ 1.2M conduction aid,
A trivalent chrome stirring step of adding and stirring 0.4 to 0.6M trivalent chromium compound,
An oxidizer addition step of adding 5 to 15 g / l of an oxidizing agent for oxidizing metal ions,
Adding an inorganic color expressing agent containing 2 to 14 g / l of an inorganic color expressing agent containing Fe ions and Co ions,
A hydrogen ion index adjustment step of adjusting a hydrogen ion index (pH) by adding a hydrogen ion index regulator (KOH),
Method for producing a trivalent chromium plating solution for a glossy black trivalent chromium plating layer, characterized in that the composition is composed of a complexing step of reacting the mixed solution mixed for 12 hours or more.
상기 산화제는 ammonium persulfate가 적용됨을 특징으로 하는 광택 흑색 3가크롬도금층을 위한 3가크롬도금액의 제조방법.The method of claim 11, wherein in the inorganic color expression adding step,
The oxidizing agent is a method for producing a trivalent chromium plating solution for a glossy black trivalent chromium plating layer, characterized in that ammonium persulfate is applied.
상기 무기색상발현제는,
상기 광택 흑색 3가크롬도금층의 명도 조절을 위해 Fe 이온을 포함하는 명도조절제 1 ~ 7g/l와,
상기 광택 흑색 3가크롬도금층의 채도 조절을 위해 Co 이온을 포함하는 채도조절제 1 ~ 7g/l를 포함하는 것을 특징으로 하는 광택 흑색 3가크롬도금층을 위한 3가크롬도금액의 제조방법.The method of claim 11 or 12, wherein in the inorganic color expression adding step,
The inorganic color developer,
Brightness control agent 1 ~ 7g / l containing Fe ions to control the brightness of the glossy black trivalent chromium plating layer,
Method for producing a trivalent chromium plating solution for a glossy black trivalent chromium plating layer, characterized in that it comprises a saturation regulator 1 ~ 7g / l containing Co ions for controlling the saturation of the glossy black trivalent chromium plating layer.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200121618A (en) * | 2019-04-16 | 2020-10-26 | 박종규 | Cr-P Alloy Plating Solution Compositions and Plating Methods Using Thereof |
| CN114875459A (en) * | 2022-05-10 | 2022-08-09 | 成立航空股份有限公司 | Trivalent chromium plating solution and black chromium plating layer |
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| US4359345A (en) | 1981-04-16 | 1982-11-16 | Occidental Chemical Corporation | Trivalent chromium passivate solution and process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200121618A (en) * | 2019-04-16 | 2020-10-26 | 박종규 | Cr-P Alloy Plating Solution Compositions and Plating Methods Using Thereof |
| CN114875459A (en) * | 2022-05-10 | 2022-08-09 | 成立航空股份有限公司 | Trivalent chromium plating solution and black chromium plating layer |
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