CN110241404B - Anti-oxidation film and preparation method thereof - Google Patents
Anti-oxidation film and preparation method thereof Download PDFInfo
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- CN110241404B CN110241404B CN201910587177.9A CN201910587177A CN110241404B CN 110241404 B CN110241404 B CN 110241404B CN 201910587177 A CN201910587177 A CN 201910587177A CN 110241404 B CN110241404 B CN 110241404B
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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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Abstract
The invention belongs to an antioxidant material, and particularly relates to an antioxidant film and a preparation method thereof, wherein the antioxidant film comprises the following components, by weight, 45-60 parts of silicon dioxide, 5-10 parts of boron oxide, 5-15 parts of zinc oxide and 20-30 parts of potassium oxide, is nano-sized, compact, transparent, uniform and continuous, is antioxidant, high-temperature resistant and good in weather resistance, and effectively solves the problem that a carrier material is easy to oxidize and discolor.
Description
Technical Field
The invention belongs to an antioxidant material, and particularly relates to an antioxidant film and a preparation method thereof.
Background
Pure silver is a beautiful silvery metal, has attractive metallic luster and collection and appreciation values, is deeply favored by people, has the beauty of metal of women, and is widely used as jewelry, ornaments, silverware, tableware, worship gifts, medals and commemorative coins. Traditional silver ornaments mainly have 3 brands: pure silver, 958 silver and 925 silver, wherein 958 silver and 925 silver are binary alloys composed of copper as an alloying element. No matter which brand of silver is used, the problem of easy color change exists, and the surface of the ornament loses white luster and turns yellow and black after a period of time in the atmospheric atmosphere, so that the ornamental effect of the ornament is seriously influenced.
In order to improve the oxidation and discoloration resistance of silver, more researches are carried out at home and abroad for many years. According to the prior art, the method can be divided into two categories: surface modification and alloying treatment. The surface modification comprises surface coating and electroplating treatment, but the surface coating has the defects of poor weather resistance and short service life, and the electroplating belongs to the high-pollution industry and faces increasingly severe environmental protection pressure. And (4) alloying treatment, no mature product interview is available so far.
The research on the silver anti-tarnishing technology is advanced, Yangtze river, and the like, electroplating and coating, and the 28 th 6 th phase describes various modes of silver anti-tarnishing, such as alloying treatment and surface treatment. In the surface treatment, there are 10 ways, 1 plating other metals on the silver surface by electroplating or ion sputtering technique, such as noble metal plating (high cost), or Ta, Nb, Ti and Al metal plating, but the tarnish resistance is limited due to the plating. 2 chemical passivation, such as chromate passivation. 3 electrochemical passivation, 4 galvanic couple passivation, 5 depositing an oxide film, depositing metal Al, Be, Zr, Mg, Nb and Ti of 3 rd to 5 th periods in the periodic table of elements on the surface of Ag by a sputtering technology or electrophoresis in an aqueous solution to obtain an oxide film, 6 organic adsorption passivation layer, 7 resin coating, 8 self-assembly film, 9 plasma polymerization and 10 composite organic antitarnish agent. The following requirements are considered for the surface treatment process of silver: the original appearance of the silver and the silver alloy is kept, the surface treatment process is non-toxic and harmless, and the process is stable; the process has good operability; the thickness of the plating layer needs to be thin; the repair and the removal of the coating are simple; the coating is durable, including the ability to withstand abrasion; low treatment cost and the like.
Chinese patent application publication No. CN 104593795A of 5/6/2015 discloses a silverware brightness maintaining agent, which is prepared by compounding the following materials in parts by weight: 5-10 parts of sodium hypophosphite or sodium phosphite, 1-5 parts of coconut oil fatty acid diethanolamide and 1-3 parts of deionized water; 201-2 parts of tween, 1-3 parts of monopotassium phosphate, 1-3 parts of sodium dihydrogen phosphate, 3-5 parts of sodium carbonate, 1-3 parts of methyl propyl triazole, 1-3 parts of 2-mercaptobenzothiadiazole, 1-2 parts of sodium dodecyl sulfate and 0.5-1 part of sodium stearate. The brightener is convenient to operate, can effectively prevent the surface of a silver piece from discoloring within a certain time range, and has certain protective performance. However, the protective layer formed by the brightener gradually loses efficacy under the combined action of light, water vapor and air.
Chinese patent application publication No. CN 106282984A, 1/4/2017, discloses a silver-resistant color changing agent which is prepared by compounding the following substances in parts by weight: 4.2-5.4 parts of alkyl mercaptan with 12-18 carbon atoms, 0.51-0.64 part of N-sulfathiazole thioglycolic acid, 1.5-1.8 parts of benzotriazole, 0.2-0.4 part of morpholine, 3.6-4.2 parts of wetting agent, 0.36-0.51 part of ultraviolet absorbent and 48-57 parts of ethylene glycol are coated on the surface of a silver piece. The silver discoloration inhibitor with the components can form a good protective film on the surface of silver, can effectively prevent the surface discoloration phenomenon of pure silver and silver-plated workpieces or products within a certain time range, and has good protective performance. However, the weather resistance of the silver discoloration inhibitor is still unsatisfactory, and the formed protective film still has aging degradation behavior under the combined action of illumination, water vapor and air, so that the protective effect on silver pieces is lost.
Chinese patent application No. 201811229556.2 discloses an intermediate, a composition, a discoloration-preventing silver and a preparation method thereof, which are used for treating silver in the form of silica, boron trioxide and bismuth trioxide.
Disclosure of Invention
The technical problem to be solved by the invention is to provide an antioxidant film and a preparation method thereof, wherein the film is nanoscale, compact, transparent, uniform, continuous, antioxidant, high-temperature resistant and good in weather resistance, and the problem that a carrier material is easy to oxidize and discolor is effectively solved.
The invention relates to an antioxidant film, which comprises the following components, by weight, 45-60 parts of silicon dioxide, 5-10 parts of boron oxide, 5-15 parts of zinc oxide and 20-30 parts of potassium oxide.
Preferably, the composition comprises the following components, by weight, 45 parts of silicon dioxide, 10 parts of boron oxide, 15 parts of zinc oxide and 30 parts of potassium oxide. Or comprises the following components of 50 parts by weight of silicon dioxide, 10 parts by weight of boron oxide, 10 parts by weight of zinc oxide and 30 parts by weight of potassium oxide. Or comprises the following components, by weight, 60 parts of silicon dioxide, 5 parts of boron oxide, 15 parts of zinc oxide and 20 parts of potassium oxide.
A preparation method of an antioxidant film comprises the following steps of mixing ethyl orthosilicate, water and polyethylene glycol to obtain a mixed solution, adjusting the mixed solution to be alkaline, adding trimethyl borate, sodium tetrahydroxy zincate and potassium oxide under the stirring condition to obtain a precursor solution; and (3) immersing the carrier material into the precursor solution, coating a film, and carrying out heat treatment to obtain the antioxidant film.
The carrier material of the present invention is a material that is easily oxidized, such as a material that is easily oxidized in the air or in a sulfur gas environment, for example, a metal material, such as silver, etc. The coating mode of the invention is preferably carried out by a dip coating instrument. The precursor solution is a uniform sol solution consisting of silicon atoms, boron atoms, zinc atoms, potassium atoms, oxygen atoms and a solvent; the formed inorganic nano film is a net film formed by silicon atoms, boron atoms, zinc atoms, potassium atoms and oxygen atoms through covalent bonds and ionic bonds.
Preferably, the weight ratio of the ethyl orthosilicate to the water to the polyethylene glycol is 1:10: 2.
Preferably, the pH of the mixed solution is 8.5 to 10, more preferably 9, and the pH is preferably adjusted with ammonia water.
Preferably, the weight ratio of the ethyl orthosilicate to the trimethyl borate is 1: (0.07-0.14).
Preferably, the weight ratio of the ethyl orthosilicate to the sodium tetrahydroxy zincate is 1 (0.05-0.31), or the weight ratio of the ethyl orthosilicate to the potassium oxide is 1: (0.09-0.13).
Preferably, the heat treatment mode is to heat up to 200-250 ℃ at 3-6 ℃/min, then to 600-700 ℃ at 0.5-1.5 ℃/min, and then to cool naturally. The heat treatment is preferably performed in an inert gas atmosphere, such as a nitrogen atmosphere.
The invention adopts two temperature-rising stages, wherein the speed of each temperature-rising stage is different, the speed is fast first and then the speed is slow, and then the film is naturally cooled.
The method has the beneficial effects that the oxide is adopted to treat the surface of the metal silver to form the isolation film, which is a common method, and the essence is to form the passivation film to isolate the silver from the external environment. The oxidation resistance of the alumina is related to the thickness of the alumina, the greater the thickness, the stronger the oxidation resistance, the greater the thickness, the obviously worse the color, brightness and touch, usually keeping the thickness of 100-150nm, so as to achieve the balance between the appearance and the protective performance (see silver coin discoloration mechanism and discoloration resistance technical research, Zhang Ji steel, penultimate paragraph of 4.3.1).
The invention adopts a mode of proportioning the metal and the nonmetal oxide, and obtains the nonmetal oxide silicon oxide, the boron oxide, the metal oxide zinc oxide and the potassium oxide from the hydrolysis precursor of the nonmetal and the metal by a heat treatment mode, so that a silicon atom, a boron atom, a zinc atom, a potassium atom and an oxygen atom form a net-shaped film through covalent bonds and ionic bonds, the film is transparent, the silver performance such as color, brightness, touch and the like can be kept, the influence of a surface protection film can be avoided, and the oxidation resistance of the silver can be greatly improved. The raw materials of the invention are cheap, and the potassium oxide is added, so that the film forming performance of the system is better, and the film is more uniform and continuous; the potassium oxide and the zinc oxide are added, so that the oxidation resistance of the composite material is stronger. According to the invention, the four oxides are not added to the surface of the silverware by means of sputtering and the like, but different oxide precursors are compatible with each other by means of the oxide precursors, and after the oxides are formed by heat treatment, the four oxides form a connection relationship with each other, so that the film is more compact and has stronger oxidation resistance.
The invention takes ethyl orthosilicate as a basic unit, the ethyl orthosilicate is hydrolyzed to form a silica network structure, trimethyl borate, tetrahydroxy sodium zincate and potassium oxide are inserted into the silica network structure to improve the film forming performance, the trimethyl borate, the tetrahydroxy sodium zincate and the potassium oxide are compatible with each other before heat treatment through the treatment of the formula, the whole system is relatively uniform, precipitation cannot be generated in advance, the uniformity of the system is damaged, and finally, when a film is formed through heat treatment, the film is more uniform and continuous.
The invention utilizes the sol-gel gelation process and the programmed heat treatment process of the ethyl orthosilicate to cover a layer of compact and transparent inorganic nano film on the surface of the silver, does not affect the appearance and the hand feeling of pure silver, greatly improves the oxidation resistance and the corrosion resistance of the silver, solves the problem of non-neglect of weather resistance, high temperature resistance and the like due to the characteristics of the inorganic film, solves the problem of environmental pollution easily caused by an electroplating process due to the safe and environment-friendly processing process, and has wide application prospect.
Drawings
FIG. 1 is a surface appearance view of a silverware according to the invention.
Fig. 2 is a surface appearance view of a silverware of comparative example 1.
Detailed Description
Example 1
The inorganic nano-film, SiO, of the present invention2、B2O3ZnO and K2The weight ratio of O is 45: 10: 15: 30.
the specific preparation process comprises the following steps:
1) preparing a precursor solution: weighing 20g of TESO (ethyl orthosilicate) and 200g H2O and 40g of polyethylene glycol are uniformly mixed in a 500ml beaker, the PH value is adjusted to 9 by ammonia water, the mixture is stirred for 12 hours at normal temperature, and 0.97g of (CH) is slowly added in the stirring process3O)3B，0.57g Na2[Zn(OH)4]And 1g K2And O, stirring to obtain a transparent sol solution, namely the precursor.
2) Preparing antioxidant silver: immersing pure silver into the precursor solution, coating with a dip coating instrument, naturally drying, and carrying out heat treatment according to the following temperature-rising program:
after the heat treatment, the oxidation resistant silver is obtained, and the oxidation resistant silver can not be corroded and discolored when placed in corrosive environments such as atmosphere, sweat, hydrogen sulfide atmosphere and the like, and can keep the original luster of the metal for a long time.
Example 2
The inorganic nano-film, SiO, of the present invention2、B2O3ZnO and K2The weight ratio of O is 50: 10: 10: 30.
the specific preparation process comprises the following steps:
1) preparing a precursor solution: weighing 100g of TESO and 1000g H2O and 200g of polyethylene glycol are uniformly mixed in a 2500ml beaker, the pH value is adjusted to 9 by ammonia water, the mixture is stirred for 12 hours at normal temperature, and 4.5g of (CH) is slowly added in the stirring process3O)3B，1.74g Na2[Zn(OH)4]And 5g K2And O, stirring to obtain a transparent sol solution, namely the precursor.
2) Preparing antioxidant silver: immersing pure silver into the precursor solution, coating with a dip coating instrument, naturally drying, and carrying out heat treatment according to the following temperature-rising program:
after the heat treatment, the oxidation resistant silver is obtained, and the oxidation resistant silver can not be corroded and discolored when placed in corrosive environments such as atmosphere, sweat, hydrogen sulfide atmosphere and the like, and can keep the original luster of the metal for a long time.
Example 3
The inorganic nano-film, SiO, of the present invention2、B2O3ZnO and K2The weight ratio of O is 60: 5: 15: 20.
the specific preparation process comprises the following steps:
1) preparing a precursor solution: weighing 200g of TESO, 2000g H2O and 400g of polyethylene glycol are uniformly mixed in a 5000ml beaker, the PH value is adjusted to 9 by ammonia water, the mixture is stirred for 12 hours at normal temperature, and 3.7g of (CH) is slowly added in the stirring process3O)3B，4.2g Na2[Zn(OH)4]And 4.9g K2And O, stirring to obtain a transparent sol solution, namely the precursor.
2) Preparing antioxidant silver: immersing pure silver into the precursor solution, coating with a dip coating instrument, naturally drying, and carrying out heat treatment according to the following temperature-rising program:
after the heat treatment, the oxidation resistant silver is obtained, and the oxidation resistant silver can not be corroded and discolored when placed in corrosive environments such as atmosphere, sweat, hydrogen sulfide atmosphere and the like, and can keep the original luster of the metal for a long time.
Comparative example 1
The protocol of example 1 of the applicant's prior patent application (CN201811229556.2) was adopted.
Experimental example 1
Hydrogen sulfide atmosphere corrosion: preparing 10% sodium sulfide solution, placing the solution into a transparent sealed box, placing the solution in comparative example 1 and the solution in the example into the sealed box at the room temperature of 35 ℃, and observing the discoloration condition every half hour.
Corrosion of sodium sulfide solution: a10% sodium sulfide solution was prepared, and the comparative example and the example were completely immersed in the sodium sulfide solution at the same time, taken out after 1 minute, left in the air, and repeated 1 time every 1 hour.
TABLE 1 antioxidant Properties of various compounds
| Corrosion in hydrogen sulfide atmosphere | Corrosion by sodium sulfide solution | |
| Comparative example 1 | After 12 hours, a little yellow spots appeared | Partial yellowing after 4 hours |
| Example 1 | No discoloration after 12 hours | After 6 hours, very few corners appeared yellow spots |
| Example 2 | No discoloration after 12 hours | After 6 hours, very few corners appeared yellow spots |
| Example 3 | No discoloration after 12 hours | After 6 hours, very few corners appearedYellow dot |
As can be seen from the data in Table 1, the antioxidant properties of the present invention are better than those of comparative example 1.
As can be seen from a comparison of fig. 1 and 2, the film of fig. 1 is more uniform and continuous, and the silverware of the invention better retains the luster and brightness of the pure silver itself.
Claims (8)
1. An antioxidant film is characterized by comprising the following components, by weight, 45-60 parts of silicon dioxide, 5-10 parts of boron oxide, 5-15 parts of zinc oxide and 20-30 parts of potassium oxide; the preparation method of the antioxidant film comprises the following steps of mixing ethyl orthosilicate, water and polyethylene glycol to obtain a mixed solution, adjusting the mixed solution to be alkaline, and adding trimethyl borate, sodium tetrahydroxy zincate and potassium oxide under the stirring condition to obtain a precursor solution; and (3) immersing the carrier material into the precursor solution, coating a film, and carrying out heat treatment to obtain the antioxidant film.
2. The oxidation-resistant film according to claim 1, which comprises 45 parts by weight of silicon dioxide, 10 parts by weight of boron oxide, 15 parts by weight of zinc oxide and 30 parts by weight of potassium oxide.
3. The oxidation-resistant film according to claim 1, which comprises 50 parts by weight of silica, 10 parts by weight of boron oxide, 10 parts by weight of zinc oxide and 30 parts by weight of potassium oxide.
4. The oxidation-resistant film according to claim 1, which comprises 60 parts by weight of silica, 5 parts by weight of boron oxide, 15 parts by weight of zinc oxide and 20 parts by weight of potassium oxide.
5. The oxidation resistant film of claim 1 wherein the pH of said mixture is 8.5 to 10.
6. The oxidation-resistant film according to claim 1 or 5, wherein the weight ratio of ethyl orthosilicate to trimethyl borate is 1: (0.07-0.14).
7. The antioxidant film as claimed in claim 1 or 5, wherein the weight ratio of ethyl orthosilicate to sodium tetrahydroxy zincate is 1 (0.05-0.31), or the weight ratio of ethyl orthosilicate to potassium oxide is 1: (0.09-0.13).
8. The oxidation-resistant film as set forth in claim 1 or 5, wherein the heat treatment is carried out by heating to 200-250 ℃ at 3-6 ℃/min, heating to 600-700 ℃ at 0.5-1.5 ℃/min, and naturally cooling.
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Citations (8)
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| 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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