CN105506686A - Electroplating method for decorative nickel-copper-gold ternary alloy electroplating bath - Google Patents

Electroplating method for decorative nickel-copper-gold ternary alloy electroplating bath Download PDF

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Publication number
CN105506686A
CN105506686A CN201510976522.XA CN201510976522A CN105506686A CN 105506686 A CN105506686 A CN 105506686A CN 201510976522 A CN201510976522 A CN 201510976522A CN 105506686 A CN105506686 A CN 105506686A
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China
Prior art keywords
plating
copper
electroplating
ornamental
liquid
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CN201510976522.XA
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Chinese (zh)
Inventor
冯正元
冯育华
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Suzhou Venus Craft Plating Decoration Co Ltd
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Suzhou Venus Craft Plating Decoration Co Ltd
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Priority to CN201510976522.XA priority Critical patent/CN105506686A/en
Publication of CN105506686A publication Critical patent/CN105506686A/en
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/021Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal alloy layer
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/56Electroplating: Baths therefor from solutions of alloys
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/18Electroplating using modulated, pulsed or reversing current
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34Pretreatment of metallic surfaces to be electroplated
    • C25D5/36Pretreatment of metallic surfaces to be electroplated of iron or steel
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48After-treatment of electroplated surfaces
    • C25D5/50After-treatment of electroplated surfaces by heat-treatment

Abstract

The invention discloses an electroplating method for a decorative nickel-copper-gold ternary alloy electroplating bath, comprising the following steps: 1, preparing the decorative nickel-copper-gold ternary alloy electroplating bath; 2. carrying out pretreatment on a stainless steel workpiece; 3. pre-plating copper; 4. carrying out nickel-copper-gold ternary alloy electroplating by adopting a unidirectional pulse method; and 5. carrying out aftertreatment. According to the invention, an electroplating method for decorative nickel-copper-gold ternary alloy electroplating bath is an environment-friendly and safe cyanide-free alloy electroplating method, the advancement and superiority of cyanide-free alloy electroplating are sufficiently utilized, the copper layer is pre-plated first, and then alloy is further electroplated, thus solving the difficulty of relatively thin cyanide-free electroplating alloy clad layer, recognized by electroplating industry. According to the invention, indexes of binding force, corrosion resistance, wear resistant property, hardness and the like of a clad layer all can meet the application requirement of coinage, and the alloy clad layer obtained according to the invention is uniform and bright and golden yellow in color.

Description

A kind of electro-plating method of ornamental ambrose alloy gold ternary alloys plating liquid
Technical field
The present invention relates to field of electroplating, be specifically related to a kind of electro-plating method of the ornamental ambrose alloy gold ternary alloys plating liquid for coinage.
Background technology
Commonly use in coinage field the decorative coating materials that electroplated coinage made by gunmetal, current electricity Du Tong ?tin alloy technology mainly adopt containing cyanogen plating or plate respectively after monometallic and adopt heat-treating methods to form alloy layer, harm environment or technique loaded down with trivial details.Ambrose alloy gold ternary alloy has flavous outward appearance, but also can carry out chemical stain in its surface, to reach special decorative effect, therefore, is widely used in decorative coating.Simultaneously ambrose alloy gold ternary alloy has high-wearing feature and high rigidity, therefore, alternative Tong ?tin binary alloy as the decorative coating materials of coinage.The report that current ambrose alloy gold ternary alloys plating liquid is used for coinage is less.
The performance of electroplate liquid is the important factor affecting coating, pursue a kind of form simple, use the direction that current density is wide, electroplate liquid that is easy care is people's effort always.In electroplating process, often there is coating and basal body binding force is poor, color and luster is wayward, coating bright property by the problem such as impact of bottom bright coating, be difficult to realize commercial application.
Summary of the invention
Goal of the invention: for the deficiencies in the prior art, the invention provides the electro-plating method of a kind of ornamental ambrose alloy for coinage gold ternary alloys plating liquid, make method simple, electroplate the coating that obtains and basal body binding force is good, uniform color is bright, method is reproducible.
Technical scheme: for achieving the above object, the present invention by the following technical solutions:
An electro-plating method for ornamental ambrose alloy gold ternary alloys plating liquid, comprises the following steps:
(1) ornamental ambrose alloy gold ternary alloys plating liquid is prepared, the composition of electroplate liquid comprises following component: single nickel salt 30-60g/L, copper sulfate 20-60g/L, hydrochloro-auric acid 8-15g/L, citric acid 5-15g/L, sodium laurylsulfonate 2-3g/L, sodium sulfate 20-40g/L, N-(3-sulfopropyl) pyridinium inner salt 0.2-0.5g/L, and be 8-10 by ammoniacal liquor adjust ph;
(2) stainless steel work-piece pre-treatment, first alkalescence cleaning at 50-60 DEG C, afterwards at room temperature pickling 1-3min, finally use deionized water and ultrapure water rinsing;
(3) copper pre-plating, preplating one deck layers of copper on the stainless steel work-piece after pre-treatment, the thickness of described layers of copper is 10-50 μm;
(4) ambrose alloy gold ternary alloys plating, the stainless steel work-piece after copper pre-plating is placed in electroplate liquid as negative electrode, and graphite is anode, and the temperature keeping electroplate liquid is 20-50 DEG C, and plating adopts unidirectional pulse method, frequency 200-600Hz, dutycycle 30-80%;
(5) aftertreatment, is placed in washed with de-ionized water by the stainless steel work-piece through plating, then places in High Temperature Furnaces Heating Apparatus and heat-treats, packaging after cooling.
Further, in described step (3), the method for copper pre-plating is the one in electroless plating, sputtering method or vapour deposition method.
Further, in described step (4), unidirectional pulse method is pulse potentiostatic method or pulse current method.
Further, the voltage of described pulse potentiostatic method is 10-20V.
Further, the electric current of described pulse current method is 6-15A.
Further, in described step (5), heat treated condition is under reducing atmosphere, and 550-600 DEG C of heating 50-70min, reducing atmosphere uses H 2or H 2-Ar.
Beneficial effect: compared with prior art, the present invention adopt the electro-plating method of ornamental ambrose alloy gold ternary alloys plating liquid be Environmental Safety without cyanogen alloy electroplating method, make full use of the advance without cyanogen alloy plating and superiority, first preplating layers of copper, and then further plating alloy, solve a plating difficult point that generally acknowledged cyanideless electro-plating alloy layer is thinner at present, the index such as bonding force, corrosion resisting property, wear resisting property, hardness of the coating that the present invention obtains all meets coinage application requiring, the alloy layer that the present invention simultaneously obtains is evenly bright, and color is golden yellow.
Embodiment
Below in conjunction with specific embodiment, the present invention is further described, and the description of specific embodiment is only example in essence, instead of intend to limit content disclosed by the invention and application thereof or use.
Embodiment 1
Prepare ornamental ambrose alloy gold ternary alloys plating liquid, the composition of electroplate liquid comprises following component: single nickel salt 53g/L, copper sulfate 48g/L, hydrochloro-auric acid 13.6g/L, citric acid 12g/L, sodium laurylsulfonate 2.5g/L, sodium sulfate 35g/L, N-(3-sulfopropyl) pyridinium inner salt 0.5g/L, 3-(3-pyridyl)-vinylformic acid 3.2g/L, and be 9.4 by ammoniacal liquor adjust ph.
Stainless steel work-piece pre-treatment, first alkalescence cleaning at 55 DEG C, afterwards at room temperature pickling 1min, finally use deionized water and ultrapure water rinsing.Stainless steel work-piece after pre-treatment will use sputtering method preplating one deck 10 μm of layers of copper.Stainless steel work-piece after copper pre-plating is placed in above-mentioned electroplate liquid as negative electrode, and graphite is anode, and the temperature keeping electroplate liquid is 25 DEG C, and plating adopts unidirectional pulse electric current, and electric current is 10A, frequency 600Hz, dutycycle 60%, and plating obtains coating after half an hour; Use the electroplate liquid that washed with de-ionized water coating surface is remaining, be then placed on logical H in High Temperature Furnaces Heating Apparatus 2heat-treat at 600 DEG C of heating 50min, packaging after cooling.
Embodiment 2
Prepare ornamental ambrose alloy gold ternary alloys plating liquid, the composition of electroplate liquid comprises following component: single nickel salt 30g/L, copper sulfate 30g/L, hydrochloro-auric acid 8g/L, citric acid 15g/L, sodium laurylsulfonate 3g/L, sodium sulfate 40g/L, N-(3-sulfopropyl) pyridinium inner salt 0.2g/L, 3-(3-pyridyl)-vinylformic acid 4g/L, and be 8.2 by ammoniacal liquor adjust ph.
Stainless steel work-piece pre-treatment, first cleans in the alkaline cleaning fluid of 50 DEG C, afterwards at room temperature pickling 3min, finally use deionized water and ultrapure water rinsing.Stainless steel work-piece after pre-treatment will use vapour deposition method preplating one deck 30 μm of layers of copper.Stainless steel work-piece after copper pre-plating is placed in above-mentioned electroplate liquid as negative electrode, and graphite is anode, and the temperature keeping electroplate liquid is 25 DEG C, and plating adopts unidirectional pulse electric current, and electric current is 8A, frequency 500Hz, dutycycle 40%, and plating obtains coating after half an hour; Use the electroplate liquid that washed with de-ionized water coating surface is remaining, be then placed on logical H in High Temperature Furnaces Heating Apparatus 2+ Ar heat-treats at 550 DEG C of heating 60min, packaging after cooling.
Embodiment 3
Prepare ornamental ambrose alloy gold ternary alloys plating liquid, the composition of electroplate liquid comprises following component: single nickel salt 36g/L, copper sulfate 60g/L, hydrochloro-auric acid 15g/L, citric acid 13.9g/L, sodium laurylsulfonate 3g/L, sodium sulfate 36g/L, N-(3-sulfopropyl) pyridinium inner salt 0.4g/L, 3-(3-pyridyl)-vinylformic acid 2g/L, and be 9.1 by ammoniacal liquor adjust ph.
Stainless steel work-piece pre-treatment, first cleans in the alkaline cleaning fluid of 50 DEG C, afterwards at room temperature pickling 2min, finally use deionized water and ultrapure water rinsing.Stainless steel work-piece after pre-treatment will use vapour deposition method preplating one deck 41 μm of layers of copper.Stainless steel work-piece after copper pre-plating is placed in above-mentioned electroplate liquid as negative electrode, and graphite is anode, and the temperature keeping electroplate liquid is 25 DEG C, and plating adopts unidirectional pulse potentiometry, and voltage is 11V, frequency 200Hz, dutycycle 30%, and plating obtains coating after half an hour; Use the electroplate liquid that washed with de-ionized water coating surface is remaining, be then placed on logical H in High Temperature Furnaces Heating Apparatus 2+ Ar heat-treats at 550 DEG C of heating 60min, packaging after cooling.
The coating that embodiment 1-3 obtains is at metallography microscope Microscopic observation, and surperficial free of pinholes, alloy layer integral surface is smooth, and luminance brightness is even.At 300 DEG C, toast 5min, all occur without foaming arch skin situation, illustrate that this alloy layer bonding force is good.Electroplate liquid is recycling repeatedly and is reusing after placing 1 month, and the coating performance obtained does not decline, and this electroplate liquid good stability is described.
Above embodiment just plays illustrated example effect to technical conceive of the present invention; can not limit the scope of the invention with this; those skilled in the art are not departing from the spirit and scope of technical solution of the present invention; modify and be equal to replacement, all should drop within protection scope of the present invention.

Claims (6)

1. an electro-plating method for ornamental ambrose alloy gold ternary alloys plating liquid, is characterized in that, comprise the following steps:
(1) ornamental ambrose alloy gold ternary alloys plating liquid is prepared, the composition of electroplate liquid comprises following component: single nickel salt 30-60g/L, copper sulfate 20-60g/L, hydrochloro-auric acid 8-15g/L, citric acid 5-15g/L, sodium laurylsulfonate 2-3g/L, sodium sulfate 20-40g/L, N-(3-sulfopropyl) pyridinium inner salt 0.2-0.5g/L, and be 8-10 by ammoniacal liquor adjust ph;
(2) stainless steel work-piece pre-treatment, first alkalescence cleaning at 50-60 DEG C, afterwards at room temperature pickling 1-3min, finally use deionized water and ultrapure water rinsing;
(3) copper pre-plating, preplating one deck layers of copper on the stainless steel work-piece after pre-treatment, the thickness of described layers of copper is 10-50 μm;
(4) ambrose alloy gold ternary alloys plating, the stainless steel work-piece after copper pre-plating is placed in electroplate liquid as negative electrode, and graphite is anode, and the temperature keeping electroplate liquid is 20-50 DEG C, and plating adopts unidirectional pulse method, frequency 200-600Hz, dutycycle 30-80%;
(5) aftertreatment, is placed in washed with de-ionized water by the stainless steel work-piece through plating, then places in High Temperature Furnaces Heating Apparatus and heat-treats, packaging after cooling.
2. the electro-plating method of ornamental ambrose alloy gold ternary alloys plating liquid according to claim 1, it is characterized in that, in described step (3), the method for copper pre-plating is the one in electroless plating, sputtering method or vapour deposition method.
3. the electro-plating method of ornamental ambrose alloy gold ternary alloys plating liquid according to claim 1, it is characterized in that, in described step (4), unidirectional pulse method is pulse potentiostatic method or pulse current method.
4. the electro-plating method of ornamental ambrose alloy gold ternary alloys plating liquid according to claim 3, it is characterized in that, the voltage of described pulse potentiostatic method is 10-20V.
5. the electro-plating method of ornamental ambrose alloy gold ternary alloys plating liquid according to claim 3, it is characterized in that, the electric current of described pulse current method is 6-15A.
6. the electro-plating method of ornamental ambrose alloy gold ternary alloys plating liquid according to claim 1, it is characterized in that, in described step (5), heat treated condition is under reducing atmosphere, 550-600 DEG C of heating 50-70min.
CN201510976522.XA 2015-12-23 2015-12-23 Electroplating method for decorative nickel-copper-gold ternary alloy electroplating bath Pending CN105506686A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110699721A (en) * 2019-11-20 2020-01-17 长春黄金研究院有限公司 Cyanide-free gold-copper alloy electroplating solution and application thereof

Citations (6)

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Publication number Priority date Publication date Assignee Title
JPS5428236A (en) * 1977-08-04 1979-03-02 Seiko Epson Corp Hard gold alloy plating method
JPS5620191A (en) * 1979-07-24 1981-02-25 Nippon Dento Kogyo Kk Preparation of hard gold alloy coat
CN101289756A (en) * 2007-04-19 2008-10-22 恩索恩公司 Electrolyte and method for electrolytic deposition of gold-copper alloys
CN102899694A (en) * 2012-03-27 2013-01-30 南京造币有限公司 Copper-nickel alloy-plated coin product and preparation method thereof
CN104178784A (en) * 2014-08-15 2014-12-03 中国海洋大学 Preparation method of metal surface copper-nickel alloy
CN104321470A (en) * 2012-04-19 2015-01-28 迪普索尔化学株式会社 Copper-nickel alloy electroplating bath and plating method

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5428236A (en) * 1977-08-04 1979-03-02 Seiko Epson Corp Hard gold alloy plating method
JPS5620191A (en) * 1979-07-24 1981-02-25 Nippon Dento Kogyo Kk Preparation of hard gold alloy coat
CN101289756A (en) * 2007-04-19 2008-10-22 恩索恩公司 Electrolyte and method for electrolytic deposition of gold-copper alloys
CN102899694A (en) * 2012-03-27 2013-01-30 南京造币有限公司 Copper-nickel alloy-plated coin product and preparation method thereof
CN104321470A (en) * 2012-04-19 2015-01-28 迪普索尔化学株式会社 Copper-nickel alloy electroplating bath and plating method
CN104178784A (en) * 2014-08-15 2014-12-03 中国海洋大学 Preparation method of metal surface copper-nickel alloy

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Title
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110699721A (en) * 2019-11-20 2020-01-17 长春黄金研究院有限公司 Cyanide-free gold-copper alloy electroplating solution and application thereof

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Application publication date: 20160420