CN103741118A - Preparation method of colorful silver product - Google Patents
Preparation method of colorful silver product Download PDFInfo
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- CN103741118A CN103741118A CN201310725297.3A CN201310725297A CN103741118A CN 103741118 A CN103741118 A CN 103741118A CN 201310725297 A CN201310725297 A CN 201310725297A CN 103741118 A CN103741118 A CN 103741118A
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- silverware
- presoma
- cleaning
- oxide film
- zinc
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Abstract
The invention provides a preparation method of a colorful silver product. The preparation method is characterized in that in a vacuum cavity, a self-limiting type chemical vapor deposition method is utilized for alternatively depositing a high-refraction-index zinc oxide film layer and a low-refraction-index aluminium oxide film layer on the silver product, the thicknesses of all the film layers are reasonably adjusted and controlled, so that optical interference occur and further a colorful protective coating is formed. The preparation method provided by the invention has the advantages that not only the appearance of the silver product is enriched, the additional value is increased, but also the protective performance of the silver product is excellent.
Description
Technical field
The invention belongs to noble metal anti-corrosion protection technical field; relate to specifically a kind of preparation method of the colored surface protection coating for silverware; can not only prevent the corrosion of silverware, can also make silverware outward appearance present colored metalluster, color is difficult for fading for a long time.
Background technology
Silverware has good reserve value and use value as silver-colored chapter, Silver Jewelry etc.In recent years, along with the raising of socioeconomic development and living standards of the people, the market requirement of silverware is more and more stronger.But, losing gradually after the beautiful gloss of silver can react with the dusty gas in environment, value can be had a greatly reduced quality accordingly.Meanwhile, various industrial pollution and room air pollution have become one of focal issue of people's concern, and such objective environment is all totally unfavorable to the collection of silverware and use.
The surface protection technique of silverware more and more receives publicity.Cause the reason of silverware variable color more, but the ion all ascribing in essence in silver atoms and air or in liquid form colored compound.Surfacecti proteon is can completely cut off the transparent rete of air molecule and fluid molecule at silverware surface-coated one deck, and this rete must have optical transmission and the environmental stability of height.Existing silverware guard technology has various defects.For example, the passivation of chromic salt inorganics, although passivation effect is better, the toxicity of chromium is larger, is limited to use; Mercaptan self-assembled monolayer, has certain protective effect to silver, but mercaptan has stronger peculiar smell to limit it, further applies, and has especially limited the application aspect Silver Jewelry and silver coin, chapter; Electrolytic passivation, electrolytic passivation can produce hydrogen evolution phenomenon, forms pore, more easily invades corrosive medium.
Defect for above-mentioned existing silverware resist technology; the technology of the present invention utilizes self-limited type chemical gaseous phase depositing process on silverware surface, to prepare the oxide compound supercoat of multi-layer transparent; the thickness of each rete of Reasonable Regulation And Control; form multilayered interference film, obtain the protective coating of the metalluster of particular color.Because color is that transparent oxide layer by multi-layer stable obtains, the interference color that therefore form can be colour-fast for a long time.This technology has been enriched the outward appearance of silverware, and increasing added value silverware has excellent barrier propterty.
Summary of the invention
Object of the present invention, for the deficiency of current techniques, utilizes self-limited type chemical gaseous phase depositing process, in silverware surface preparation, the oxide compound supercoat preparation method of the multi-layer transparent of the interference of light can occur.Not only there is excellent barrier propterty, can also make the coloured metalluster of silverware tool, enriched the outward appearance of silverware, increase added value.
A kind of preparation method of colored silverware, it is characterized in that, in vacuum chamber, the aluminum oxide rete of the method for utilizing self-limited type chemical vapour deposition alternating deposit high refractive index zinc oxide film and low-refraction on silverware, each thicknesses of layers of Reasonable Regulation And Control, make it that optical interference occur, form colored protective coating.
The self-limited type chemical vapour deposition of described zinc oxide refers to: vacuum chamber is heated to the temperature range of 100～200 ℃, after vacuum is evacuated to below 20hPa, more than first passing into zinc ethyl presoma pulse 0.1s, guarantee that zinc ethyl is adsorbed on silverware surface in chemical saturated adsorption mode, high pure nitrogen guarantees that unnecessary presoma is pumped more than cleaning 3s; Then more than passing into water presoma 0.1s, assurance water and the before zinc ethyl on the silverware surface of absorption carry out chemical reaction and obtain Zinc oxide film, more than high pure nitrogen cleans 4s, guarantee that unreacted water molecules and by product are eliminated;
The self-limited type chemical vapour deposition of described aluminum oxide refers to: vacuum chamber is heated to the temperature range of 100～200 ℃, after vacuum is evacuated to below 20hPa, more than first passing into trimethyl aluminium presoma pulse 0.1s, guarantee that trimethyl aluminium is adsorbed on silverware surface in chemical saturated adsorption mode, high pure nitrogen guarantees that unnecessary presoma is pumped more than cleaning 3s; Then more than passing into water presoma 0.1s, assurance water and the before trimethyl aluminium on the silverware surface of absorption carry out chemical reaction and obtain pellumina, more than high pure nitrogen cleans 4s, guarantee that unreacted water molecules and by product are eliminated.
Preferably, the silverware that deposit must pass through the ultrasonic cleaning of acetone, dehydrated alcohol and deionized water successively, and vacuum-drying keeps the surface cleaning of silverware.
Preferably, presoma zinc ethyl is passed into the burst length that is at least 0.1s, the cleaning burst length is at least 3s; Pass into water vapor pulse and be at least 0.1s, the cleaning burst length is at least 4s, completes like this deposition of the zinc oxide of a circulation, and the loop number of depositing zinc oxide is depending on the thickness of zinc-oxide film, and 0.2nm/ circulates; Presoma trimethyl aluminium is passed into the burst length that is at least 0.1s, the cleaning burst length is at least 3s; Pass into water vapor pulse and be at least 0.1s, the cleaning burst length is at least 4s, completes like this deposition of the aluminum oxide of a circulation, and the loop number of deposition of aluminium oxide is depending on the thickness of aluminum oxide film, and 0.2nm/ circulates.
Preferably, the pellumina of alternating deposit high refractive index Zinc oxide film and low-refraction, obtains ZnO/Al
2o
3/ ZnO or ZnO/Al
2o
3/ ZnO/Al
2o
3the multilayer film of/ZnO such three layers or five-layer structure; / 4th reference wavelength optical thicknesses that the thickness of every layer of Zinc oxide film is zinc oxide simultaneously, 1/4th reference wavelength optical thicknesses that the thickness of every layer of pellumina is aluminum oxide.
Further preferably, described reference wavelength is from ultraviolet, and visible ray is to any wavelength of near infrared range.
By above-mentioned steps difference making ZnO/Al on silver-colored chapter
2o
3/ ZnO or ZnO/Al
2o
3/ ZnO/Al
2o
3the film of/ZnO such three layers or five-layer structure, preparation temperature is 100～200 ℃.Because the reference wavelength of selecting is different, obtain the colour silver chapter of different colours.
At room temperature carry out the sulphur corrosion test of thioacetyl amine aqueous solution to the silver-colored chapter of colour.First weigh the thioacetamide of 0.035g, be dissolved in 400ml deionized water; The anhydrous sodium acetate that continues weighing 0.033g is dissolved in above-mentioned solution; Finally the colour silver chapter of overlay film being immersed to institute joins in solution.Aluminum oxide film prepared by the Comparison on Corrosion experimental result surface self-limited type chemical vapour deposition mode of 8 hours has a remarkable effect to silverware is anticorrosive.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described.
Embodiment 1:
Selection reference wavelength is 405nm, and four/wavelength optical thickness of corresponding zinc oxide is 48.21nm, and four/wavelength optical thickness of aluminum oxide is 61.93nm.With vacuum pump, reaction chamber is extracted into the rough vacuum below 20hPa and is heated to specific temperature of reaction, then the High Purity Nitrogen cleaning reaction chamber that is 5N by purity.By silver-colored chapter ultrasonic cleaning 10-30 minute in acetone, dehydrated alcohol and high purity deionized water successively respectively, the vertical modes of emplacement of take is placed in the vacuum drying oven 40 minutes that temperature is 100 ℃.Question response cavity temperature reaches 150 ℃ silverware is put into reaction chamber.
(1) presoma zinc ethyl is passed into reaction chamber, burst length 0.1s, the burst length of cleaning presoma is 3s; Then pass into the water vapor pulse of 0.1s, then wash unnecessary water vapor with the 4s burst length.So far complete the deposition of the zinc-oxide film of a circulation, the about 0.2nm of thickness.Carry out obtaining after 241 such circulations the zinc-oxide film of 48.2nm.
(2) presoma trimethyl aluminium passes into reaction chamber, burst length 0.1s, and the burst length of cleaning presoma is 3s; Then pass into the water vapor pulse of 0.1s, then wash unnecessary water vapor with the 4s burst length.So far complete the deposition of the aluminum oxide film of a circulation, the about 0.1nm of thickness.Carry out obtaining after 619 such circulations the aluminum oxide film of 61.9nm.
(3) repeat aforementioned (1) technical process, the zinc-oxide film of deposition 48.2nm.
So far on silver-colored chapter, deposited ZnO(48.2nm)/Al
2o
3(61.9nm)/ZnO(48.2) deposition of trilamellar membrane structure.This silver-colored chapter presents golden gloss under indoor incandescent lamps.The sulphur corrosion nondiscoloration in 8 hours in the aqueous solution of the anhydrous sodium acetate that comprises the thioacetamide of 0.035g, 0.033g and 400ml deionized water of silver chapter; And the corrosion of overlay film silver chapter similarity condition does not present chocolate for 8 hours.Contrast and experiment surface self-limited type chemical vapour deposition mode three layers of oxide coating that prepare, that present gold have remarkable anti-sulphur corrosion effect.
Embodiment 2:
Selection reference wavelength is 550nm, and four/wavelength optical thickness of corresponding zinc oxide is 65.48nm, and four/wavelength optical thickness of aluminum oxide is 84.41nm.With vacuum pump, reaction chamber is extracted into the rough vacuum below 20hPa and is heated to specific temperature of reaction, then the High Purity Nitrogen cleaning reaction chamber that is 5N by purity.By silver-colored chapter ultrasonic cleaning 10-30 minute in acetone, dehydrated alcohol and high purity deionized water successively respectively, the vertical modes of emplacement of take is placed in the vacuum drying oven 40 minutes that temperature is 100 ℃.Question response cavity temperature reaches 150 ℃ silverware is put into reaction chamber.
(1) presoma zinc ethyl is passed into reaction chamber, burst length 0.1s, the burst length of cleaning presoma is 3s; Then pass into the water vapor pulse of 0.1s, then wash unnecessary water vapor with the 4s burst length.So far complete the deposition of the zinc-oxide film of a circulation, the about 0.2nm of thickness.Carry out obtaining after 328 such circulations the zinc-oxide film of 65.6nm.
(2) presoma trimethyl aluminium passes into reaction chamber, burst length 0.1s, and the burst length of cleaning presoma is 3s; Then pass into the water vapor pulse of 0.1s, then wash unnecessary water vapor with the 4s burst length.So far complete the deposition of the aluminum oxide film of a circulation, the about 0.1nm of thickness.Carry out obtaining after 844 such circulations the aluminum oxide film of 84.4nm.
(3) repeat aforementioned (1) technical process, the zinc-oxide film of deposition 65.6nm.
So far on silver-colored chapter, deposited ZnO(65.6nm)/Al
2o
3(84.4nm)/ZnO(65.6) deposition of trilamellar membrane structure.This silver-colored chapter presents blue gloss under indoor incandescent lamps.The sulphur corrosion nondiscoloration in 8 hours in the aqueous solution of the anhydrous sodium acetate that comprises the thioacetamide of 0.035g, 0.033g and 400ml deionized water of silver chapter; And the corrosion of overlay film silver chapter similarity condition does not present chocolate for 8 hours.Contrast and experiment surface self-limited type chemical vapour deposition mode three layers of oxide coating that prepare, that present blueness have remarkable anti-sulphur corrosion effect.
Embodiment 3:
Selection reference wavelength is 650nm, and four/wavelength optical thickness of corresponding zinc oxide is 77.38nm, and four/wavelength optical thickness of aluminum oxide is 100.12nm.With vacuum pump, reaction chamber is extracted into the rough vacuum below 20hPa and is heated to specific temperature of reaction, then the High Purity Nitrogen cleaning reaction chamber that is 5N by purity.By silver-colored chapter ultrasonic cleaning 10-30 minute in acetone, dehydrated alcohol and high purity deionized water successively respectively, the vertical modes of emplacement of take is placed in the vacuum drying oven 40 minutes that temperature is 100 ℃.Question response cavity temperature reaches 150 ℃ silverware is put into reaction chamber.
(1) presoma zinc ethyl is passed into reaction chamber, burst length 0.1s, the burst length of cleaning presoma is 3s; Then pass into the water vapor pulse of 0.1s, then wash unnecessary water vapor with the 4s burst length.So far complete the deposition of the zinc-oxide film of a circulation, the about 0.2nm of thickness.Carry out obtaining after 387 such circulations the zinc-oxide film of 77.4nm.
(2) presoma trimethyl aluminium passes into reaction chamber, burst length 0.1s, and the burst length of cleaning presoma is 3s; Then pass into the water vapor pulse of 0.1s, then wash unnecessary water vapor with the 4s burst length.So far complete the deposition of the aluminum oxide film of a circulation, the about 0.1nm of thickness.Carry out obtaining after 1001 such circulations the aluminum oxide film of 100.1nm.
(3) repeat aforementioned (1) technical process, the zinc-oxide film of deposition 77.4nm.
So far on silver-colored chapter, deposited ZnO(77.4nm)/Al
2o
3(100.1nm)/ZnO(77.4) deposition of trilamellar membrane structure.This silver-colored chapter presents green gloss under indoor incandescent lamps.The sulphur corrosion nondiscoloration in 8 hours in the aqueous solution of the anhydrous sodium acetate that comprises the thioacetamide of 0.035g, 0.033g and 400ml deionized water of silver chapter; And the corrosion of overlay film silver chapter similarity condition does not present chocolate for 8 hours.Contrast and experiment surface self-limited type chemical vapour deposition mode three layers of oxide coating that prepare, that present green have remarkable anti-sulphur corrosion effect.
By embodiment 1 to embodiment 3, can be found out use self-limited type chemical vapour deposition at silver-colored Zhang Shangneng, to prepare the multilayer film that make silver coin present multicolour, and this multilayer film to have excellent anti-sulphur corrosion ability to silver-colored chapter.
Claims (5)
1. the preparation method of a colored silverware, it is characterized in that, in vacuum chamber, the aluminum oxide rete of the method for utilizing self-limited type chemical vapour deposition alternating deposit high refractive index zinc oxide film and low-refraction on silverware, each thicknesses of layers of Reasonable Regulation And Control, make it that optical interference occur, form colored protective coating;
The self-limited type chemical vapour deposition of described zinc oxide refers to: vacuum chamber is heated to the temperature range of 100～200 ℃, after vacuum is evacuated to below 20hPa, more than first passing into zinc ethyl presoma pulse 0.1s, guarantee that zinc ethyl is adsorbed on silverware surface in chemical saturated adsorption mode, high pure nitrogen guarantees that unnecessary presoma is pumped more than cleaning 3s; Then more than passing into water presoma 0.1s, assurance water and the before zinc ethyl on the silverware surface of absorption carry out chemical reaction and obtain Zinc oxide film, more than high pure nitrogen cleans 4s, guarantee that unreacted water molecules and by product are eliminated;
The self-limited type chemical vapour deposition of described aluminum oxide refers to: vacuum chamber is heated to the temperature range of 100～200 ℃, after vacuum is evacuated to below 20hPa, more than first passing into trimethyl aluminium presoma pulse 0.1s, guarantee that trimethyl aluminium is adsorbed on silverware surface in chemical saturated adsorption mode, high pure nitrogen guarantees that unnecessary presoma is pumped more than cleaning 3s; Then more than passing into water presoma 0.1s, assurance water and the before trimethyl aluminium on the silverware surface of absorption carry out chemical reaction and obtain pellumina, more than high pure nitrogen cleans 4s, guarantee that unreacted water molecules and by product are eliminated.
2. the preparation method of colored silverware according to claim 1, is characterized in that, the silverware that deposit must pass through the ultrasonic cleaning of acetone, dehydrated alcohol and deionized water successively, and vacuum-drying keeps the surface cleaning of silverware.
3. the preparation method of a kind of colored silverware according to claim 1, is characterized in that, presoma zinc ethyl is passed into the burst length that is at least 0.1s, and the cleaning burst length is at least 3s; Pass into water vapor pulse and be at least 0.1s, the cleaning burst length is at least 4s, completes like this deposition of the zinc oxide of a circulation, and the loop number of depositing zinc oxide is depending on the thickness of zinc-oxide film, and 0.2nm/ circulates; Presoma trimethyl aluminium is passed into the burst length that is at least 0.1s, the cleaning burst length is at least 3s; Pass into water vapor pulse and be at least 0.1s, the cleaning burst length is at least 4s, completes like this deposition of the aluminum oxide of a circulation, and the loop number of deposition of aluminium oxide is depending on the thickness of aluminum oxide film, and 0.2nm/ circulates.
4. the preparation method of colored silverware according to claim 1, is characterized in that, the pellumina of alternating deposit high refractive index Zinc oxide film and low-refraction, obtains ZnO/Al
2o
3/ ZnO or ZnO/Al
2o
3/ ZnO/Al
2o
3the multilayer film of/ZnO such three layers or five-layer structure; / 4th reference wavelength optical thicknesses that the thickness of every layer of Zinc oxide film is zinc oxide simultaneously, 1/4th reference wavelength optical thicknesses that the thickness of every layer of pellumina is aluminum oxide.
5. the preparation method of colored silverware according to claim 4, is characterized in that, described reference wavelength is from ultraviolet, and visible ray is to any wavelength of near infrared range.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108867025A (en) * | 2018-06-01 | 2018-11-23 | 大连理工大学 | A kind of colored carbon fiber material based on one-dimensional photonic crystal and its preparation method |
| CN109750273A (en) * | 2019-01-25 | 2019-05-14 | 中国地质大学（北京） | A method for improving the stability of silver jewelry by coating based on atomic layer deposition |
| CN117904597A (en) * | 2024-01-17 | 2024-04-19 | 哈尔滨工业大学 | A super-hydrophobic self-cleaning transparent ultra-thin coating and its preparation method and application |
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Patent Citations (3)
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| JP2007039713A (en) * | 2005-08-01 | 2007-02-15 | Toray Ind Inc | Method and apparatus for manufacturing substrate having oxide film |
| CN101962492A (en) * | 2009-07-24 | 2011-02-02 | 林文广 | Novel multi-layer coating angularly heterochrome interference color pearlescent pigment |
| CN101974734A (en) * | 2010-11-30 | 2011-02-16 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing substrate material with multilayer composite protective film |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108867025A (en) * | 2018-06-01 | 2018-11-23 | 大连理工大学 | A kind of colored carbon fiber material based on one-dimensional photonic crystal and its preparation method |
| CN109750273A (en) * | 2019-01-25 | 2019-05-14 | 中国地质大学（北京） | A method for improving the stability of silver jewelry by coating based on atomic layer deposition |
| CN117904597A (en) * | 2024-01-17 | 2024-04-19 | 哈尔滨工业大学 | A super-hydrophobic self-cleaning transparent ultra-thin coating and its preparation method and application |
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| CN103741118B (en) | 2016-06-15 |
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