CN109267128B - A kind of silver plate Darkening process agent and plating silver chemical Darkening process method - Google Patents
A kind of silver plate Darkening process agent and plating silver chemical Darkening process method Download PDFInfo
- Publication number
- CN109267128B CN109267128B CN201811228512.8A CN201811228512A CN109267128B CN 109267128 B CN109267128 B CN 109267128B CN 201811228512 A CN201811228512 A CN 201811228512A CN 109267128 B CN109267128 B CN 109267128B
- Authority
- CN
- China
- Prior art keywords
- silver
- darkening process
- agent
- plating
- melanism
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/02—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using non-aqueous solutions
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
-
- 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
- C25D3/46—Electroplating: Baths therefor from solutions of silver
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
A kind of silver plate Darkening process agent and plating silver chemical Darkening process method, for the tiny plating piece of electrochemistry melanism should not be utilized, such as silver-plated button, accessory etc., it can be handled with rapid, high volume using the chemistry melanism method, silver coating appearance that treated and performance are all significantly improved, and blackening layer firm stable, there is good binding force with substrate, it does not fade by mechanisms such as wipings, plating piece chemical property is stablized, corrosion resistance greatly enhances, and the plating piece surface of processing is uniform, color is pitch-black, smooth.The advantages that beauty is brought to ornaments etc..
Description
Technical field
The present invention relates to plating and field of surface engineering technique, in particular to a kind of silver plate Darkening process agent and plating patina
Learn Darkening process method.
Background technique
Silver plating process is widely used.It is applied not only to decoration plating, the process industries such as electrical, instrument and meter and illumination also have extensively
Using.Compared to more other common metals, such as copper, tin, zinc and nickel etc., silver-colored electrode potential is higher, so stability is more preferable.
But silvering is easy to change colour, such as can make silver tarnish micro sulfur-containing compound in air.So in order to improve plating
The discoloration-resisting of layer, is typically passed through plating posttreatment.
There are many tarnish reasons of silvering, mainly in natural environment or industrial environment, pernicious gas such as H2S、SO2、
CO2、Cl2Deng, can make silver layer surface occur corrosive chameleon.In high temperature and moist environment, discoloration is become apparent.In addition to environment because
Plain outer, structure, impurity content, thickness of coating itself etc. are also the major reason for influencing anti-discoloration.Prevent coating color
Method mainly has chemical passivation, is generally handled using dichromate solution, forms silver oxide and chromic acid Ag films on surface；Electrification
Passivation is learned, i.e., is immersed silver-plated part in dichromate solution, electrochemical passivation is carried out in cathode, coating surface is made to generate one layer
Passivating film；Apply protective agent post-processing etc..Wherein silver-plated blackening craft is one of effective aftertreatment technology of silver layer passivation.
For most of silver and silver plated item, the metachromatism to black can all be occurred by storing surface for a long time.Decoration at present
There is the demand of the pseudo-classic silver of silver-plated melanism in plating silver products.Using natural melanism not only overlong time, but also surface is not
Uniformly, quality is uncontrollable.There is better corrosion stability after silver-plated melanism, and require even black, tone is beautiful and generous, Er Qiefu
Modern industry and ornaments are closed to black coating dicoration and functional requirement.
Silvering melanism includes chemical melanism and electrochemistry melanism.Electrochemistry melanism is conducive to prepare the plating silvery of big part
Product, but the electrochemistry melanism such as small plating piece, such as silver-plated copper button, decoration hanger is difficult to widely apply.
It is main black agent that previous chemical blackening craft uses ammonium polysulfide mostly, and Zhu Haigang, Zhu Jianlin are in " plating and painting
Decorations ", it 2010, volume 29,7 phases: 12-13 pages, has been reported that in " research of electrosilvering blackening craft " text.Although polysulfide can be with
There is provided element sulphur, but the substance itself and do not have other beneficial functions.In addition, there are melanism temperature height, melanism for this method
The problems such as time is long.
Summary of the invention
In order to make up for the deficiencies of the prior art, the purpose of the present invention is to provide a kind of silver plate Darkening process agent and silver-plated
Chemical Darkening process method, black agent of the invention can not only provide sufficient element sulphur, but also have defencive function, and point
It dissipates uniformly, ensure that blackening layer is uniform in range at a reasonable time, pitch-black light, melanism colour stable, binding force is good, enhancing
Corrosion stability.
The technical solution that the present invention uses is: a kind of silver plate Darkening process agent, and the Darkening process agent includes
Main black agent, auxiliary black agent and surfactant, the main black agent are straight chained alkyl mercapto alcohol (HS- (CH2)n-1-CH3),
Wherein n=10,11,12,13,14,15,16；The auxiliary black agent isWherein X is-CH3,-
COOH or-NH2One of.
The surfactant logical, OP emulsifier, alkyl phenol polyoxyethylene ether one or more for Qula.One kind is adopted
With the plating silver chemical Darkening process method of silver plate Darkening process agent, comprising the following steps:
(1) electrosilvering processing is carried out to the substrate that is electroplated of needs, obtain it is silver-plated after plating piece；
(2) chemical Darkening process is carried out to the plating piece after silver-plated, blackened solution includes main black agent, auxiliary black agent, table
Face activating agent, melanism time are 10min~20min, and operating temperature is 30 DEG C~55 DEG C.
(3) it is aged 2 hours or more, that is, completes described silver-plated under the silver plate after Darkening process indoors atmospheric environment
Chemical Darkening process.
Main black agent is straight chained alkyl mercapto alcohol (HS- in blackened solution in described step (2) blackening treatment process
(CH2)n-1-CH3, n=10,11,12,13,14,15,16), content 0.1molL-1~1.0molL-1。
Auxiliary black agent is in blackened solution in described step (2) blackening treatment processWherein
X is-CH3,-COOH or-NH2One of, content 0.01molL-1~0.1molL-1。
Surfactant is that Qula is logical, OP emulsifier, alkyl in blackened solution in described step (2) blackening treatment process
The one or more of phenol polyethenoxy ether, content are respectively 0.02g/L~0.5g/L.
The solvent of blackened solution is second alcohol and water in described step (2) blackening treatment process, the content of water is 0~
10%.
The beneficial effects of the present invention are: the present invention provides a kind of silver plate Darkening process agent and plating silver chemical Darkening process
Method can be with rapid, high volume land productivity for the tiny plating piece, such as silver-plated button, accessory etc. that should not utilize electrochemistry melanism
It being handled with the chemistry melanism method, silver coating appearance that treated and performance are all significantly improved, and blackening layer firm stable,
There is good binding force with substrate, do not fade by mechanisms such as wipings, plating piece chemical property is stablized, and corrosion resistance is big
Big enhancing, the plating piece surface of processing is uniform, color is pitch-black, smooth.The advantages that beauty is brought to ornaments etc..
Detailed description of the invention
Fig. 1 is 1 blackening effect schematic diagram of the embodiment of the present invention.
Fig. 2 is 2 blackening effect schematic diagram of the embodiment of the present invention.
Fig. 3 is 3 blackening effect schematic diagram of the embodiment of the present invention.
Fig. 4 is 4 blackening effect schematic diagram of the embodiment of the present invention.
Specific embodiment
It in order to illustrate more clearly of the content of present invention, is described as follows with specific embodiment, specific embodiment does not limit this hair
Bright context.
First to base material carry out electrosilvering, obtain it is silver-plated after plating piece；Then to it is described it is silver-plated after plating piece carry out
Chemical Darkening process, the process of specific Darkening process such as following embodiment, blackening effect as shown in attached drawing 1-4, the present invention for
The tiny plating piece, such as silver-plated button, accessory etc. of electrochemistry melanism should not be utilized, it can be black using the chemistry with rapid, high volume
The processing of change method, silver coating appearance that treated and performance are all significantly improved, and blackening layer firm stable, are had with substrate
Good binding force does not fade by mechanisms such as wipings, and plating piece chemical property is stablized, and corrosion resistance greatly enhances, and locates
The plating piece surface of reason is uniform, color is pitch-black, smooth.The advantages that beauty is brought to ornaments etc..
Embodiment 1
Main black agent is straight chain dodecyl mercapto alcohol (HS- (CH2)11-CH3), content 0.6molL-1.Auxiliary black agent be
To methylbenzene phenyl-sulfhydrate (also known as 4- thiocresol or 4- sulfydryl toluene), content 0.02molL-1.Surfactant is OP emulsifier
Content is respectively 0.1g/L.Solvent is the water of 95% ethyl alcohol and 5%.Melanism time 15min, 40 DEG C of blackening liquid temperature.After melanism
Sample is aged 24 hours.
Embodiment 2
Main black agent is straight chain myristyl mercapto alcohol (HS- (CH2)13-CH3), content 0.8molL-1.Auxiliary black agent be
4- mercaptobenzoic acid, content 0.05molL-1.Surfactant is that Qula leads to 0.01g/L and OP emulsifier 0.1g/L.Solvent is
98% ethyl alcohol and 2% water.Melanism time 20min, blackening liquid temperature 50 C.Sample is aged 48 hours after melanism.
Embodiment 3
Main black agent is straight chain cetyl mercapto alcohol (HS- (CH2)15-CH3), content 0.5molL-1.Auxiliary black agent be
4- mercaptoaniline, content 0.08molL-1.Surfactant is the OP emulsifier of 0.1g/L and the alkyl phenol polyoxy second of 0.1g/L
Alkene ether.Solvent is the water of 98% ethyl alcohol and 2%.Melanism time 10min, 35 DEG C of blackening liquid temperature.Sample ageing 24 is small after melanism
When.
Embodiment 4
Main black agent is straight chain undecyl mercapto alcohol (HS- (CH2)10-CH3), content 1.0molL-1.Auxiliary black agent be
To methylbenzene phenyl-sulfhydrate (also known as 4- thiocresol or 4- sulfydryl toluene), content 0.01molL-1.Surfactant is 0.4g/L's
The logical alkyl phenol polyoxyethylene ether with 0.1g/L of Qula.Solvent is ethyl alcohol.Melanism time 12min, 55 DEG C of blackening liquid temperature.Melanism
Sample is aged 6 hours afterwards.
Every technical staff's notice: of the invention although the present invention is described according to above-mentioned specific embodiment
Invention thought be not limited in the invention, any repacking with inventive concept will all be included in this patent protection of the patent right
In range.
The above is only a preferred embodiment of the present invention, protection scope of the present invention is not limited merely to above-mentioned implementation
Example, all technical solutions belonged under thinking of the present invention all belong to the scope of protection of the present invention.It should be pointed out that for the art
Those of ordinary skill for, several improvements and modifications without departing from the principles of the present invention, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (7)
1. a kind of silver plate Darkening process agent, which is characterized in that the Darkening process agent includes main black agent, auxiliary black agent
And surfactant, the main black agent are straight chained alkyl mercapto alcohol HS- (CH2)n-1-CH3, wherein n=10,11,12,13,14,
15,16；The auxiliary black agent isWherein X is-CH3,-COOH or-NH2One of.
2. a kind of silver plate Darkening process agent according to claim 1, which is characterized in that the surfactant is song
Draw logical, OP emulsifier, alkyl phenol polyoxyethylene ether one or more.
3. a kind of plating silver chemical Darkening process method using silver plate Darkening process agent described in claim 1, feature exist
In, comprising the following steps:
(1) electrosilvering processing is carried out to the substrate that is electroplated of needs, obtain it is silver-plated after plating piece；
(2) chemical Darkening process carried out to the plating piece after silver-plated, blackened solution includes that main black agent, auxiliary black agent, surface are living
Property agent, the melanism time be 10min~20min, operating temperature be 30 DEG C~55 DEG C；
(3) it is aged 2 hours or more under the silver plate after Darkening process indoors atmospheric environment, that is, completes the plating silver chemical
Darkening process.
4. plating silver chemical Darkening process method according to claim 3, which is characterized in that at described step (2) melanism
Main black agent is straight chained alkyl mercapto alcohol HS- (CH in blackened solution during reason2)n-1-CH3, n=10,11,12,13,14,15,
16, content 0.1molL-1~1.0molL-1。
5. the method for plating silver chemical Darkening process according to claim 4, which is characterized in that described step (2) melanism
Auxiliary black agent is in blackened solution in treatment processWherein X is-CH3,-COOH or-NH2In one
Kind, content 0.01molL-1~0.1molL-1。
6. plating silver chemical Darkening process method according to claim 4, which is characterized in that at described step (2) melanism
Surfactant is that Qula is logical, one or more of OP emulsifier, alkyl phenol polyoxyethylene ether in blackened solution during reason, is contained
Amount is respectively 0.02g/L~0.5g/L.
7. plating silver chemical Darkening process method according to claim 4, which is characterized in that at described step (2) melanism
The solvent of blackened solution is second alcohol and water during reason, and the content of water is 0~10%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811228512.8A CN109267128B (en) | 2018-10-22 | 2018-10-22 | A kind of silver plate Darkening process agent and plating silver chemical Darkening process method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811228512.8A CN109267128B (en) | 2018-10-22 | 2018-10-22 | A kind of silver plate Darkening process agent and plating silver chemical Darkening process method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109267128A CN109267128A (en) | 2019-01-25 |
| CN109267128B true CN109267128B (en) | 2019-07-26 |
Family
ID=65194130
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811228512.8A Active CN109267128B (en) | 2018-10-22 | 2018-10-22 | A kind of silver plate Darkening process agent and plating silver chemical Darkening process method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109267128B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005047570A2 (en) * | 2003-11-14 | 2005-05-26 | F.Lli Calegaro Di Luigi Di Francesco Calegaro S.P.A. | Surface finishing method for silver and its alloys |
| CN104254642A (en) * | 2012-05-09 | 2014-12-31 | 奥野制药工业株式会社 | Blackening treatment solution for black cr-co alloy plating film |
| KR101691988B1 (en) * | 2016-06-07 | 2017-01-02 | 노성태 | A method for making hologram design on metal plating layer and plated material with hologram design on the surface |
| CN107761146A (en) * | 2017-10-27 | 2018-03-06 | 嘉兴学院 | A kind of method of silver-plated Darkening process |
-
2018
- 2018-10-22 CN CN201811228512.8A patent/CN109267128B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005047570A2 (en) * | 2003-11-14 | 2005-05-26 | F.Lli Calegaro Di Luigi Di Francesco Calegaro S.P.A. | Surface finishing method for silver and its alloys |
| CN104254642A (en) * | 2012-05-09 | 2014-12-31 | 奥野制药工业株式会社 | Blackening treatment solution for black cr-co alloy plating film |
| KR101691988B1 (en) * | 2016-06-07 | 2017-01-02 | 노성태 | A method for making hologram design on metal plating layer and plated material with hologram design on the surface |
| CN107761146A (en) * | 2017-10-27 | 2018-03-06 | 嘉兴学院 | A kind of method of silver-plated Darkening process |
Non-Patent Citations (1)
| Title |
|---|
| 电镀银黑化工艺研究;朱海刚 等;《电镀与涂饰》;20100731;第29卷(第7期);第12-13页 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109267128A (en) | 2019-01-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3067443B1 (en) | Nickel and/or chromium plated member and method for manufacturing the same | |
| TW200510060A (en) | Metallic nano-particle and method for producing same, liquid dispersion of metallic nano-particle and method for producing same, metal thin line, metal film and method for producing same | |
| CN102808203B (en) | Gold-plating process using gold potassium citrate | |
| CN103361701B (en) | A kind of rose aluminium section bar and electrolysis coloring processes thereof | |
| CN110369712B (en) | Preparation method of silver-coated copper powder | |
| US1988012A (en) | Metal deposites in oxide coatings | |
| CN109183096B (en) | Surface electroplating liquid for alloy and electroplating process | |
| Brown et al. | The development of chemical conversion coatings on aluminium | |
| CN1772950A (en) | No-palladium activating recipe for chemical nickel plating on plastic surface and its technological process | |
| CN109267128B (en) | A kind of silver plate Darkening process agent and plating silver chemical Darkening process method | |
| CN106048672B (en) | It is a kind of neutral without cyanogen Brush Plating silver plating liquid and its preparation process and application method | |
| Sato et al. | Substrate (Ni)-catalyzed electroless gold deposition from a noncyanide bath containing thiosulfate and sulfite: II. Deposit characteristics and substrate effects | |
| CN103526218B (en) | A kind of titanium alloy anodic oxidation activation moves back the ageing method of the two-in-one solution of film | |
| CN111519219A (en) | Silver electroplating liquid composite additive and preparation method and application thereof | |
| CN102766871A (en) | Silver-plated antitarnish protectant composition | |
| CN107761146B (en) | A kind of method of silver-plated Darkening process | |
| CN206927957U (en) | A kind of multicolour aluminum alloy casing | |
| Zhang et al. | Effects of high current density on the characteristics of zinc films electroplated in ethaline electrolyte | |
| CN111101179A (en) | Electrodeposition treatment method of copper foil and composite copper foil material | |
| Ding et al. | Process and theoretical research on electroplating Cu–Sn alloys of low Sn | |
| GB810818A (en) | Improvements in or relating to processes for electrolytically coating metals with a platinum layer | |
| Yefan et al. | Process of electroless silver coated Al-Mg alloy powder | |
| CN212025442U (en) | Organic vacuum deposition system with upward deposition surface of substrate base plate | |
| CN112831779A (en) | Method for preparing passivation solution for zinc plating and cadmium plating | |
| CN106521580A (en) | Tetravalent tin Sn-Co-Zn ternary alloy chromium-substituting electroplating liquid and electroplating method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |