CN110241404A - A kind of oxidation barrier film and preparation method - Google Patents
A kind of oxidation barrier film and preparation method Download PDFInfo
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- CN110241404A CN110241404A CN201910587177.9A CN201910587177A CN110241404A CN 110241404 A CN110241404 A CN 110241404A CN 201910587177 A CN201910587177 A CN 201910587177A CN 110241404 A CN110241404 A CN 110241404A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1229—Composition of the substrate
- C23C18/1241—Metallic substrates
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1291—Process of deposition of the inorganic material by heating of the substrate
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- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
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- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The invention belongs to a kind of oxidation-resistant material, it is specifically related to a kind of oxidation barrier film and preparation method, the component including following parts by weight, 45-60 parts of silica, 5-10 parts of boron oxide, 5-15 parts of zinc oxide, 20-30 parts of potassium oxide, the film is nanoscale, fine and close transparent, uniformly continuous, and it is anti-oxidant, the problem of high temperature resistant, good weatherability, effective solution carrier material easy oxidation discoloration.
Description
Technical field
The invention belongs to a kind of oxidation-resistant material, it is specifically related to a kind of oxidation barrier film and preparation method.
Background technique
Fine silver is a kind of silvery white non-ferrous metal of beauty, deep by people with charming metallic luster and collection ornamental value
Favor, therefore have the laudatory title of the metal of woman, be widely used as jewellery, ornament, silverware, tableware, congratulate gift, medal and discipline
Read coin.Tradition decorations mainly have 3 kinds of trades mark: fine silver, 958 silver medals and 925 silver medals with silver, wherein 958 silver medals and 925 silver medals are using copper as alloy
The bianry alloy that element is constituted.Regardless of the silver of the trade mark, all there are problems that being easy discoloration, in air atmosphere, one section
Jewelry surface loses white gloss and turns yellow, blackening after time, has seriously affected the appreciation effect of ornaments.
In order to improve silver oxidation resistance discoloration, more research has been carried out both at home and abroad for many years.According to prior art way
Diameter can be divided into two classes: surface modification and Alloying Treatment.It includes surface coating and electroplating processing that surface is modified again, but table
Face film there is weatherabilities poor, the short defect of service life, and be electroplated and belong to high pollution industry, it is faced with increasingly serious ring
Packing pressure.Alloying Treatment there is no matured product to interview so far.
Silver-colored anti-discolouring technology progress, Yang Changjiang etc., plating and covering with paint, the 6th phase of volume 28 describe silver-colored fastness
Various modes, such as Alloying Treatment, surface treatment.In surface treatment, there are 10 kinds of modes, 1 using plating or ion sputtering
Technology is in other metals of silver surface plating, for example plates noble metal (at high cost) or Ta, Nb, Ti and Al coat of metal, but by
Rich in coating, anti-tarnishing ability is limited.2 chemical passivations, such as chromating.3 electrochemical passivations, the passivation of 4 galvanic couples, 5 depositions
Oxidation film, on the surface Ag, by sputtering technique or in aqueous solution in the electrophoretic deposition periodic table of elements 3-5 period metal
Al, Be, Zr, Mg, Nb, Ti and obtain sull, 6 organic adsorption passivation layers, 7 resinous coats, 8 self-assembled films, 9 plasmas
Body polymerization, 10 compound organic discoloration inhibitors.The process of surface treatment of silver will be considered to require as follows: keeping silver and its alloy
Original appearance, surface treatment process are nontoxic, and process stabilizing；Technique has good operability；Thickness of coating is wanted
It is thin；It repairs and removal coating is simple；Coating is durable, and the ability including bearing abrasion is strong；Processing cost is low etc..
On May 6th, 2015, Chinese patent application publication number CN104593795 A disclosed a kind of silverware light retention agent,
It is to be compounded according to weight fraction by following substance: sodium hypophosphite or 5-10 parts of sodium phosphite, coco-nut oil fatty acid diethyl
1-5 parts of alkylolamides, 1-3 parts of deionized water；1-2 parts of polysorbas20,1-3 parts of potassium dihydrogen phosphate, 1-3 parts of sodium dihydrogen phosphate, sodium carbonate
3-5 parts, methyl-prop and 1-3 parts of triazole, 1-3 parts of 2- sulfydryl diazosulfide, 1-2 parts of lauryl sodium sulfate and odium stearate
0.5-1 parts.This brightener is easy to operate, and silver-colored part surface discolouration phenomenon can be effectively prevent within the scope of certain time, has one
Fixed protective value.But the protective layer that this brightener is formed gradually fails under the collective effect of illumination, steam and air, loses
Deprotection effect.
On January 4th, 2017, Chinese invention patent application publication number CN106282984 A disclosed a kind of anti-silver tarnish drug,
It is to be compounded according to weight fraction by following substance: uses carbon atom number for 4.2-5.4 parts of alkyl hydrosulfide, the N- sulphur of 12-18
0.51-0.64 parts of amine thiazole thioglycolic acid, 1.5-1.8 parts of benzotriazole, 0.2-0.4 parts of morpholine, wetting agent 3.6-4.2
Part, 0.36-0.51 parts of ultraviolet absorbing agent and 48-57 parts of ethylene glycol are coated on silver-colored part surface.The anti-silver tarnish agent of such ingredient
Good protecting film can be formed in silver surface, fine silver and silver-plated workpiece or product table can be effectively prevent within the scope of certain time
Face metachromatism has good protective value.But this anti-silver tarnish agent weatherability is still unsatisfactory, is formed
Degradation with aging behavior still occurs under the collective effect of illumination, steam and air for protective film, loses the protective effect to silver-colored part.
The patent that Chinese Patent Application No. is 201811229556.2 discloses a kind of intermediate for preventing silver tarnish, combination
Object, Anti- tarnishing silver and preparation method, at it by the way of silica, diboron trioxide and bismuth oxide
Reason.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of oxidation barrier film and preparation method, which is nanometer ruler
Degree, fine and close transparent, uniformly continuous, and anti-oxidant, high temperature resistant, good weatherability, effective solution carrier material easy oxidation discoloration
The problem of.
The contents of the present invention include a kind of oxidation barrier film, the component including following parts by weight, silica 45-60
Part, 5-10 parts of boron oxide, 5-15 parts of zinc oxide, 20-30 parts of potassium oxide.
Preferably, the component including following parts by weight, 45 parts of silica, 10 parts of boron oxide, 15 parts of zinc oxide, oxidation
30 parts of potassium.Or the component including following parts by weight, 50 parts of silica, 10 parts of boron oxide, 10 parts of zinc oxide, potassium oxide 30
Part.Or the component including following parts by weight, 60 parts of silica, 5 parts of boron oxide, 15 parts of zinc oxide, 20 parts of potassium oxide.
A kind of preparation method of oxidation barrier film, includes the following steps, ethyl orthosilicate, water and polyethylene glycol are mixed,
Mixed liquor is obtained, alkalinity is adjusted to, trimethylborate, tetrahydroxy conjunction sodium zincate and potassium oxide are added under stirring condition, obtains forerunner
Liquid solution；Carrier material is immersed in precursor solution, plated film, heat treatment obtains oxidation barrier film.
Carrier material of the invention be oxidizable material, such as under the environment such as air or sulfiding gas it is oxidizable
Material, such as metal material, such as silver.Plated film mode of the invention is preferably carried out using lifting plated film instrument.Forerunner of the invention
The uniform sol form solution that liquid solution is made of silicon atom, boron atom, zinc atom, potassium atom, oxygen atom and solvent；It is formed
The net that inorganic nanofilms are made of silicon atom, boron atom, zinc atom, potassium atom, oxygen atom by covalent bond and ionic bond
Shape film.
Preferably, the weight ratio of the ethyl orthosilicate, water and polyethylene glycol is 1:10:2.
Preferably, the pH value of the mixed liquor is 8.5-10, and preferred pH is 9, it is preferred to use ammonium hydroxide adjusts pH.
Preferably, the weight ratio of ethyl orthosilicate and trimethylborate is 1:(0.07-0.14).
Preferably, it is 1:(0.05-0.31 that ethyl orthosilicate and tetrahydroxy, which close the weight ratio of sodium zincate), alternatively, positive silicic acid
The weight ratio of ethyl ester and potassium oxide is 1:(0.09-0.13).
Preferably, the mode of the heat treatment is first to be warming up to 200-250 DEG C with 3-6 DEG C/min, then with 0.5-1.5
DEG C/min is warming up to 600-700 DEG C, then natural cooling.Heat treatment is preferably used and is carried out in atmosphere of inert gases, such as nitrogen
Atmosphere is enclosed.
The present invention uses two temperature rise periods, and the speed of each temperature rise period is had any different, first quick and back slow, then naturally cold
But, using this heat treatment mode, the degree of being completely embedded of oxidation barrier film can be improved to greatest extent, improves the antioxygen of film
Change effect.
The invention has the advantages that being handled using oxide metal silver surface, it is common for forming isolation film
Method, essence are to form passivating film, and silver and external environment are isolated.Common oxide has aluminium oxide, aluminium oxide
Oxidation resistance is related with its thickness, and thickness is bigger, and oxidation resistance is stronger, and thickness is bigger, color, brightness and sense of touch
It can obviously be deteriorated, generally remain it with a thickness of 100-150nm, it is made to reach balance between appearance and protective performance (see silver coin
Discoloration mechanism and fastness technical research, second from the bottom section of Zhang Jigang, 4.3.1).
Nonmetallic and metal hydrolysis precursor is passed through heat by the way of metal and nonmetal oxide proportion by the present invention
The mode of processing obtains nonmetal oxide silica, boron oxide and metal oxide zinc, potassium oxide, makes silicon atom, boron
The reticulated film that atom, zinc atom, potassium atom and oxygen atom are formed by covalent bond and ionic bond, film itself are transparent,
It, can not be by surfacecti proteon film while keeping the performance of color, brightness and the sense of touch of silver itself etc. silver itself
Influence, greatly improve its oxidation resistance.Raw material of the invention is cheap, and potassium oxide is added, keeps system filming performance more preferable,
Film is more evenly continuous；Potassium oxide and zinc oxide is added, so that its oxidation resistance is stronger.The present invention is not by four kinds of oxide sheets
Body is added to the surface of silverware by modes such as splashes, but by way of oxide precursor, make different oxide precursors that
This is compatible, and after forming oxide eventually by heat treatment, four kinds of oxides form connection relationship each other, so that film itself is more
Densification, antioxidant effect are stronger.
The present invention is basic unit with ethyl orthosilicate, hydrolyzes to form silica network structure, trimethylborate, tetrahydroxy
Close sodium zincate and potassium oxide to be inserted into silica network structure, improve filming performance, by the processing of this formula, make its into
Compatible with each other before row heat treatment, whole system is relatively uniform, will not generate precipitating in advance, destroy the uniformity of system, finally
When by heat treatment film forming, film is more uniform continuous.
The present invention utilizes the Sol-gel process and sequencing heat treatment process of ethyl orthosilicate, covers silver surface
The transparent inorganic nanofilms of one layer of densification do not influence the appearance and feel of fine silver, greatly improve anti-oxidant, the anticorrosion of silver
Performance, simultaneously because the characteristic of inoranic membrane itself, solves the problems, such as that weatherability, high temperature resistant etc. can not be ignored, due to its processing
Process safety environmental protection, solves the problems, such as that electroplating technology easily causes environmental pollution, is with a wide range of applications.
Detailed description of the invention
Fig. 1 is the appearance figure of silverware of the present invention.
Fig. 2 is the appearance figure of 1 silverware of comparative example.
Specific embodiment
Embodiment 1
Inorganic nanofilms of the invention, SiO2、B2O3, ZnO and K2The weight ratio of O is 45:10:15:30.
Its specific preparation process the following steps are included:
1) 20gTESO (ethyl orthosilicate), 200g H the preparation of precursor solution: are weighed2O and 40g polyethylene glycol,
In 500ml beaker after mixing, with ammonium hydroxide tune PH=9,12h is stirred under room temperature, is slowly added to 0.97g in whipping process
(CH3O)3B, 0.57g Na2[Zn(OH)4] and 1g K2O obtains vitreosol shape solution, as presoma after the completion of stirring.
2) preparation of anti-oxidant silver: fine silver is immersed in precursor solution, with plated film instrument plated film is lifted, after natural drying,
It is heat-treated by following temperature program:
After being heat-treated both anti-oxidant silver, anti-oxidant silver are placed in the corrosive environments such as atmosphere, sweat, hydrogen sulfide atmosphere not
Can be corroded discoloration, can keep the original gloss of metal for a long time.
Embodiment 2
Inorganic nanofilms of the invention, SiO2、B2O3, ZnO and K2The weight ratio of O is 50:10:10:30.
Its specific preparation process the following steps are included:
1) 100gTESO, 1000g H the preparation of precursor solution: are weighed2O and 200g polyethylene glycol, in 2500ml beaker
In after mixing, with ammonium hydroxide tune PH=9, stir 12h under room temperature, 4.5g (CH be slowly added in whipping process3O)3B, 1.74g
Na2[Zn(OH)4] and 5g K2O obtains vitreosol shape solution, as presoma after the completion of stirring.
2) preparation of anti-oxidant silver: fine silver is immersed in precursor solution, with plated film instrument plated film is lifted, after natural drying,
It is heat-treated by following temperature program:
After being heat-treated both anti-oxidant silver, anti-oxidant silver are placed in the corrosive environments such as atmosphere, sweat, hydrogen sulfide atmosphere not
Can be corroded discoloration, can keep the original gloss of metal for a long time.
Embodiment 3
Inorganic nanofilms of the invention, SiO2、B2O3, ZnO and K2The weight ratio of O is 60:5:15:20.
Its specific preparation process the following steps are included:
1) 200gTESO, 2000g H the preparation of precursor solution: are weighed2O and 400g polyethylene glycol, in 5000ml beaker
In after mixing, with ammonium hydroxide tune PH=9, stir 12h under room temperature, 3.7g (CH be slowly added in whipping process3O)3B, 4.2g
Na2[Zn(OH)4] and 4.9g K2O obtains vitreosol shape solution, as presoma after the completion of stirring.
2) preparation of anti-oxidant silver: fine silver is immersed in precursor solution, with plated film instrument plated film is lifted, after natural drying,
It is heat-treated by following temperature program:
After being heat-treated both anti-oxidant silver, anti-oxidant silver are placed in the corrosive environments such as atmosphere, sweat, hydrogen sulfide atmosphere not
Can be corroded discoloration, can keep the original gloss of metal for a long time.
Comparative example 1
Using the scheme in the embodiment 1 of the previous patent application of the applicant (CN201811229556.2).
Experimental example 1
Hydrogen sulfide atmosphere corrosion: 10% sodium sulfide solution is configured, is put into transparent sealing case, 35 DEG C of room temperature, will be compared
Example 1 and embodiment are put into seal box simultaneously, observe its discoloration every half an hour.
Sodium sulfide solution corrosion: configuring 10% sodium sulfide solution, and comparative example and embodiment are completely immersed in vulcanization simultaneously
It in sodium solution, takes out, is placed in air after 1 minute, be repeated 1 times every 1 hour.
The antioxygenic property table of the different compounds of table 1
| Hydrogen sulfide atmosphere corrosion | Sodium sulfide solution corrosion | |
| Comparative example 1 | There is a little place yellow point occur after 12 hours | Partial region turns yellow after 4 hours |
| Embodiment 1 | Still without discoloration after 12 hours | After 6 hours, there is yellow point in few edge |
| Embodiment 2 | Still without discoloration after 12 hours | After 6 hours, there is yellow point in few edge |
| Embodiment 3 | Still without discoloration after 12 hours | After 6 hours, there is yellow point in few edge |
By the data of table 1 it is found that the present invention is relative to comparative example 1, antioxygenic property is more preferable.
By the comparison of Fig. 1 and Fig. 2 it is found that the film of Fig. 1 is more uniform continuous, silverware of the invention is preferably remained
The color and brightness of fine silver itself.
Claims (9)
1. a kind of oxidation barrier film, characterized in that the component including following parts by weight, 45-60 parts of silica, boron oxide 5-
10 parts, 5-15 parts of zinc oxide, 20-30 parts of potassium oxide.
2. oxidation barrier film as described in claim 1, characterized in that the component including following parts by weight, silica 45
Part, 10 parts of boron oxide, 15 parts of zinc oxide, 30 parts of potassium oxide.
3. oxidation barrier film as described in claim 1, characterized in that the component including following parts by weight, silica 50
Part, 10 parts of boron oxide, 10 parts of zinc oxide, 30 parts of potassium oxide.
4. oxidation barrier film as described in claim 1, characterized in that the component including following parts by weight, silica 60
Part, 5 parts of boron oxide, 15 parts of zinc oxide, 20 parts of potassium oxide.
5. a kind of preparation method of oxidation barrier film according to any one of claims 1-4, characterized in that including walking as follows
Suddenly, ethyl orthosilicate, water and polyethylene glycol are mixed, obtains mixed liquor, be adjusted to alkalinity, boric acid front three is added under stirring condition
Ester, tetrahydroxy close sodium zincate and potassium oxide, obtain precursor solution；Carrier material is immersed in precursor solution, plated film, at heat
Reason, obtains oxidation barrier film.
6. the preparation method of oxidation barrier film as claimed in claim 5, characterized in that the pH value of the mixed liquor is 8.5-
10。
7. such as the preparation method of oxidation barrier film described in claim 5 or 6, characterized in that ethyl orthosilicate and boric acid front three
The weight ratio of ester is 1:(0.07-0.14).
8. such as the preparation method of oxidation barrier film described in claim 5 or 6, characterized in that ethyl orthosilicate and tetrahydroxy close
The weight ratio of sodium zincate is 1:(0.05-0.31), alternatively, the weight ratio of ethyl orthosilicate and potassium oxide is 1:(0.09-0.13).
9. such as the preparation method of oxidation barrier film described in claim 5 or 6, characterized in that the mode of the heat treatment is first
It is warming up to 200-250 DEG C with 3-6 DEG C/min, is then warming up to 600-700 DEG C with 0.5-1.5 DEG C/min, then natural cooling.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4704009B2 (en) * | 2004-11-01 | 2011-06-15 | 株式会社資生堂 | Method for suppressing discoloration of silver product surface and product by this method |
| JP2011208176A (en) * | 2010-03-29 | 2011-10-20 | Oriental Mekki Kk | Discoloration preventive film for silver-plated film, and method for forming the same |
| CN101463462B (en) * | 2007-12-20 | 2011-11-02 | （沈阳）中国印钞造币总公司沈阳造币技术研究所 | Invisible fastness anti-tarnishing layer for silver coin surface and preparation method |
| CN102268709A (en) * | 2011-07-06 | 2011-12-07 | 浙江大学 | Loading method and application of metal surface corrosion inhibitor |
| CN102758200A (en) * | 2012-07-16 | 2012-10-31 | 南京大学 | Preparing method for sol-gel silica film |
| CN106756977A (en) * | 2016-12-20 | 2017-05-31 | 南京九致信息科技有限公司 | Thermoelectricity metallic film and preparation method thereof |
| CN107227451A (en) * | 2017-06-26 | 2017-10-03 | 广东振华科技股份有限公司 | The vacuum coating method and noble metal coated article of a kind of noble metal oxygen-proof film |
| CN109530193A (en) * | 2018-10-22 | 2019-03-29 | 郴州市金贵银业股份有限公司 | A kind of preparation method of etching resistant film |
-
2019
- 2019-07-02 CN CN201910587177.9A patent/CN110241404B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4704009B2 (en) * | 2004-11-01 | 2011-06-15 | 株式会社資生堂 | Method for suppressing discoloration of silver product surface and product by this method |
| CN101463462B (en) * | 2007-12-20 | 2011-11-02 | （沈阳）中国印钞造币总公司沈阳造币技术研究所 | Invisible fastness anti-tarnishing layer for silver coin surface and preparation method |
| JP2011208176A (en) * | 2010-03-29 | 2011-10-20 | Oriental Mekki Kk | Discoloration preventive film for silver-plated film, and method for forming the same |
| CN102268709A (en) * | 2011-07-06 | 2011-12-07 | 浙江大学 | Loading method and application of metal surface corrosion inhibitor |
| CN102758200A (en) * | 2012-07-16 | 2012-10-31 | 南京大学 | Preparing method for sol-gel silica film |
| CN106756977A (en) * | 2016-12-20 | 2017-05-31 | 南京九致信息科技有限公司 | Thermoelectricity metallic film and preparation method thereof |
| CN107227451A (en) * | 2017-06-26 | 2017-10-03 | 广东振华科技股份有限公司 | The vacuum coating method and noble metal coated article of a kind of noble metal oxygen-proof film |
| CN109530193A (en) * | 2018-10-22 | 2019-03-29 | 郴州市金贵银业股份有限公司 | A kind of preparation method of etching resistant film |
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| CN110241404B (en) | 2021-06-25 |
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