CN109530193A - A kind of preparation method of etching resistant film - Google Patents
A kind of preparation method of etching resistant film Download PDFInfo
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- CN109530193A CN109530193A CN201811229561.3A CN201811229561A CN109530193A CN 109530193 A CN109530193 A CN 109530193A CN 201811229561 A CN201811229561 A CN 201811229561A CN 109530193 A CN109530193 A CN 109530193A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
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Abstract
The invention discloses a kind of preparation methods of etching resistant film, including following synthesis step: (1) mixing boric acid and ethyl orthosilicate organic solution, obtain solution A；(2) solution A and bismuth nitrate are mixed, obtains corrosion resistant intermediate；(3) by intermediate filming, intermediate body thin film is obtained；(4) intermediate film is heat-treated, first heats and cools down afterwards, obtain etching resistant film.The present invention can extend the etching resistant film corrosion resistant time, while have stronger anticorrosion effect.
Description
Technical field
The present invention relates to a kind of preparation methods of inorganic thin film, and in particular to a kind of preparation method of etching resistant film.
Background technique
Silver is a kind of precious metal material that usage history is long, silver-colored use be earliest since making jewellery, currency,
It is widely used in the manufacture of tableware, craftwork and ornament etc..Silver-colored and its alloy is in atmospheric environment in use, due in atmosphere
The pollution gas contained, such as hydrogen sulfide, sulfur dioxide, nitrogen dioxide, hydrogen chloride and ozone can form electricity on the surface of silver
Solution liquid causes atmospheric corrosion, and the surface of silver is made to generate dark-coloured coherent film, is embodied in silver hair and changes color, influences Silver Jewelry
Beautiful and use.
The fastness measure about silver common at present is divided into two classes: one kind is alloying, but up to the present be there is no into
Ripe commercialization silver alloy product emerges；Another kind of is surface treatment.Surface treatment specifically include that chemical passivation, electrolytic passivation,
Electroplate precious metal, coating protective agent etc..Chemical passivation method easily causes Cr6+Pollution；Electrolytic passivation method, which is removed, can generate Cr6+Pollution is outer,
Also need to consider setting equipment relevant to energization and technological problems；Electroplate precious metal complex process, higher cost；Coating protection
The protective layer that agent generates due to the collective effect of illumination, steam and air, can gradually fail, lose in use in degradation
Protective effect.
Document CN104593795A discloses a kind of silverware light retention agent, is to be compounded according to weight fraction by following substance
It forms: sodium hypophosphite or 5~10 parts of sodium phosphite, 1~5 part of cocoanut fatty acid diethanolamide, 1~3 part of deionized water；
1~2 part of polysorbas20,1~3 part of potassium dihydrogen phosphate, 1~3 part of sodium dihydrogen phosphate, 3~5 parts of sodium carbonate, methyl-prop and triazole 1~
3 parts, 1~3 part of 2- sulfydryl diazosulfide, 1~2 part and 0.5~1 part of odium stearate of lauryl sodium sulfate.This brightener behaviour
Facilitate, silver-colored part surface discolouration phenomenon can be effectively prevent within the scope of certain time, there is certain protective value.But this
The protective layer that brightener is formed can gradually fail under the collective effect of illumination, steam and air, lose protective effect.
Document CN106282984A discloses a kind of anti-silver tarnish drug, be compounded according to weight fraction by following substance and
At: use carbon atom number for 4.2-5.4 parts of the alkyl hydrosulfide of 12-18,0.51-0.64 parts of N- sulphathiazole thioglycolic acid, benzene
And 1.5-1.8 parts of triazole, 0.2-0.4 parts of morpholine, 3.6-4.2 parts of wetting agent, 0.36-0.51 parts of ultraviolet absorbing agent and second two
48-57 parts of alcohol, it is coated on silver-colored part surface.The anti-silver tarnish agent of such ingredient can form good protecting film in silver surface, one
It can effectively prevent fine silver and silver-plated workpiece or product surface metachromatism in range of fixing time, there is good protective value.
But this anti-silver tarnish dosage form at protective film, degradation with aging row can still occur under the collective effect of illumination, steam and air
To lose the protective effect to silver-colored part.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of preparation methods of etching resistant film, can extend etching resistant film
The corrosion resistant time makes the silver for adhering to etching resistant film have better anticorrosion effect.
The contents of the present invention include that the intermediate is the mixing of ethyl orthosilicate, boric acid and bismuth nitrate in organic solvent
Solution, the weight ratio of the ethyl orthosilicate, boric acid and bismuth nitrate are 10-13:1.5-3:7-10.
Preferably, the weight ratio of the ethyl orthosilicate, boric acid and bismuth nitrate is 11:2:8.
The etching resistant film is vitreum, including silica, diboron trioxide and bismuth oxide, the titanium dioxide
The weight ratio of silicon, diboron trioxide and bismuth oxide is 30-35:10-15:50-55.
Preferably, the weight ratio of the silica, diboron trioxide and bismuth oxide is 30:10:50.
The principle of the application generation vitreum etching resistant film are as follows:
It is heat-treated by silica, diboron trioxide and bismuth oxide melt molding, then in the range of relative low temperature,
Glass phase-separating is two phases, and a phase is pure silicon dioxide, another is mutually diboron trioxide and bismuth oxide.
And there are two types of forms for split-phase, one is generation split-phase is begun to more than liquidus temperature, this split-phase is referred to as steady
Determine split-phase；Another kind is just to start split-phase below liquidus temperature, and this split-phase is called metastable split-phase.
And the system phase-separating section of the application is in inverted S-shaped liquidus curve hereinafter, since this split-phase is to send out at a lower temperature
Raw, if therefore suitably selecting composition and melt is cooling, still available uniform vitreum.
Because silver point is 961 DEG C, and conventional means split-phase required temperature is higher, and some even can melt silver-colored part, because
The invention has deliberately evaded this point, has occurred that split-phase at a lower temperature, in energy when designing this vitreum etching resistant film
While vitreum is made, energy consumption when high-volume manufactures can be also reduced.
And be to occur that system split-phase at a lower temperature, by constantly testing discovery, ingredient groups provided by the invention
At the cooling with specific gravity cooperation melt, uniform vitreum can be made；The non-vitreum that production is matched with this, is all deposited in structure
In flaw, the chemical stability of etching resistant film is influenced.
And during rapid cooling, in system, ingredient is simpler, then when melt is cooled to liquidus temperature, compound
Each component part mutually collide be arranged in certain lattice probability it is bigger, the glass of composition also easier crystallization is reducing glass
The generation that also can be reduced devitrification stone while volume defect keeps the vitreous structure of production more stable, this is also in the application
The relatively simple reason of composition.
The etching resistant film includes following synthesis step:
(1) after evenly mixing by ethyl orthosilicate, dehydrated alcohol and deionized water, the ethyl orthosilicate, dehydrated alcohol
Weight ratio with deionized water is 1-2:3-5:8-12, is stirred at room temperature 50-70 minutes and is hydrolyzed, obtains solution A；
Preferably, the weight ratio of ethyl orthosilicate, dehydrated alcohol and deionized water is 1:4:10.
(2) boric acid is added in solution A, is stirred 15-25 minutes under room temperature, the solution B being transparent；
(3) it is slowly added to the bismuth nitrate solution that mass concentration is 10% in solution B, is stirred 100- under room temperature
140 minutes, the intermediate being transparent；
The weight ratio of the ethyl orthosilicate, boric acid and bismuth nitrate is 10-13:1.5-3:7-10.
Preferably, the weight ratio of ethyl orthosilicate, boric acid and bismuth nitrate is 11:2:8.
(4) object was soaked in intermediate after 20-40 seconds and is taken out, object is placed in ventilation 22-26 hours, object table
Face forms intermediate layer；
(5) intermediate layer is heat-treated, the heat treatment includes from room temperature by temperature with the heating speed of 2-3 DEG C/min
Rate is heated to 200-300 DEG C, 200-300 DEG C holding 50-70 minutes, then by temperature from the 200-300 DEG C of liter with 2-3 DEG C/min
Warm rate is heated to 400-500 DEG C, 400-500 DEG C holding 50-70 minutes, then by temperature from 400-500 DEG C with 2-3 DEG C/min
Rate of temperature fall drop to room temperature, obtain corrosion resistant etching resistant film.
Wherein, 200-300 DEG C be melt coring process, keep 50-70 minutes be to make melt in nucleating course
Enough kinetic energy is accumulated, is prepared for the transformation of next stage；400-500 DEG C be melt crystallization process, keep 50-70 minutes
It is to prepare to make melt accumulate enough kinetic energy in crystallization process for the transformation of vitreum；And during heating, it rises
Warm rate cannot be too fast, because if heating rate is too fast, segment has insufficient time to be moved, certainly will will be higher
Temperature realize glass transition, in this case to make melt successful conversion vitreum, need to improve glass transition temperature, have
Body shows as improving the temperature range of melt crystallization, and in the case where melt crystallization temperature is constant, too fast heating will lead to
Vitreum generates flaw, or even can not convert.
Confirm that as long as cooling rate is sufficiently fast, substantially any substance can form vitreum, including metal also has through research
The amorphous state of its high temperature can be able to maintain；, whereas if being lower than melting range inside holding sufficiently long time, then any glass
Glass forms body and can crystallize.Therefore, the key for forming glass is the cooling rate of melt.
And the cool-down method in the application, different from the method for conventional fast cooling, but in the way of gradually cooling down
Vitreum is formed, this is the result that inventor fully takes into account that composition, specific gravity and vitreum temporary stress obtain.
According to Lawson's revised theory, singly-bound can be divided by the ratio of fusing point as the parameter for measuring glass forming ability, singly-bound
Can it is higher, fusing point is lower, oxide glass more easy to form.The ternary system of the application, formation is former by silicon atom, boron
Son, bismuth atom and oxygen atom pass through the uniform Network former of formation of chemical bond, and composition is fallen near eutectic point, this
The reason of being composition of the present invention and specific gravity vitreum easy to form.
And glass is in cooling procedure, after showing that layer is cooled to room temperature, shows that temperature no longer declines, volume is also no longer
It shrinks, but internal layer temperature is higher than outer layer, it will continue cooling and shrinks, and such outer layer starts the pull by internal layer and generates pressure and answer
Power.As internal layer temperature constantly declines, the tensile stress of outer layer and the compression of internal layer are constantly cancelled out each other, when ectonexine temperature one
When cause, no longer there is stress in glass.Although temporary stress disappears with the disappearance of temperature gradient, its stress value should be controlled strictly
System, if being more than the limit of the tensile strength of glass, glass can be burst.
Influence in view of rate of temperature fall to vitreum temporary stress, therefore the application selects in certain temperature range,
Reduce influence of the temporary stress to vitreous structure by way of gradually cooling down.
Cooling rate in the application is by the way that after determining composition and specific gravity, what repeated experiment obtained can form steady
The range for determining vitreum, in addition to considering influence of the temporary stress to vitreous structure, it is also contemplated that rate of temperature fall is to vitrifying temperature
The influence of degree.Because glass transition is not thermodynamical equilibrium process, during rapid cooling, observing time shortens, pine
The relaxation time also shortens, and too fast corresponding with heating rate, segment also has insufficient time to be moved at this time, can also lead
The raising for causing glass transition temperature, influence glass it is body formed when structure stability, therefore the selection of rate of temperature fall range will also be kept away
Exempt from excessively to improve vitrified temperature.
The invention has the benefit that
(1) selection of rate of temperature fall range enables melt to form vitreum etching resistant film, and is not improving glass excessively
In the case where changing temperature, can reduce temporary stress influences vitreous structure.
(2) selection of composition and specific gravity, make melt it is cooling at a lower temperature remain to obtain uniform vitreum it is resistance to
Corrode film, avoids influence of the conventional high temperature cooling means to attachment object, also reduce energy consumption when mass production.
(3) selection of heating rate, makes segment have time enough to be moved, and avoids the raising of glass transition temperature,
Vitreum etching resistant film is set not generate structure flaw.
(4) vitreum etching resistant film can extend the etching resistant film corrosion resistant time, while have preferably corrosion resistant
Effect.
Specific embodiment
Embodiment 1
(1) it is sequentially added into 121.36g ethyl orthosilicate, 486g dehydrated alcohol and 1214g deionized water, is uniformly mixed
Afterwards, it is stirred at room temperature 60 minutes and is hydrolyzed, obtain ethyl orthosilicate organic solution；
(2) 17.76g boric acid is added in ethyl orthosilicate organic solution, is stirred 20 minutes under room temperature, obtained in saturating
The solution A of bright shape；
(3) it is slowly added to the bismuth nitrate solution of 775g mass concentration 10% in solution A, is stirred under room temperature
120 minutes, the intermediate being transparent；
(4) silver-colored part was soaked in intermediate after 30 seconds and is taken out, silver-colored part is placed in ventilation 24 hours, silver-colored part surface is formed
Intermediate layer；
(5) intermediate layer is heat-treated, the heat treatment includes from room temperature by temperature with the heating speed of 2.5 DEG C/min
Rate is heated to 250 DEG C, is kept for 60 minutes at 250 DEG C, then temperature is heated to 500 from 250 DEG C of heating rates with 2.5 DEG C/min
DEG C, it is kept for 60 minutes, then temperature is dropped into room temperature from 500 DEG C of rate of temperature fall with 3 DEG C/min, is obtained corrosion resistant at 500 DEG C
Etching resistant film, the weight ratio of silica, diboron trioxide and bismuth oxide is 35:10:50 in the etching resistant film.
Embodiment 2
(1) it is sequentially added into 121.5g ethyl orthosilicate, 486g dehydrated alcohol and 1215g deionized water, after evenly mixing,
It is stirred at room temperature 50 minutes and is hydrolyzed, obtain ethyl orthosilicate organic solution；
(2) 26.6g boric acid is added in ethyl orthosilicate organic solution, stirs 15 minutes under room temperature, is in
The solution A of transparence；
(3) it is slowly added to the bismuth nitrate solution of 775g mass concentration 10% in solution A, is stirred under room temperature
100 minutes, the intermediate being transparent；
(4) silver-colored part was soaked in intermediate after 20 seconds and is taken out, silver-colored part is placed in ventilation 22 hours, silver-colored part surface is formed
Intermediate layer；
(5) intermediate layer is heat-treated, the heat treatment includes from room temperature by temperature with the heating rate of 3 DEG C/min
300 DEG C are heated to, is kept for 50 minutes at 300 DEG C, then temperature is heated to 500 DEG C from 300 DEG C of heating rates with 3 DEG C/min,
It is kept for 50 minutes, then temperature is dropped into room temperature from 500 DEG C of rate of temperature fall with 2.5 DEG C/min, is obtained corrosion resistant resistance at 500 DEG C
Corrode film, the weight ratio of silica, diboron trioxide and bismuth oxide is 35:15:50 in the etching resistant film.
Embodiment 3
(1) it is sequentially added into 121.36g ethyl orthosilicate, 486g dehydrated alcohol and 1214g deionized water, is uniformly mixed
Afterwards, it is stirred at room temperature 70 minutes and is hydrolyzed, obtain ethyl orthosilicate organic solution；
(2) 17.76g boric acid is added in ethyl orthosilicate organic solution, is stirred 25 minutes under room temperature, obtained in saturating
The solution A of bright shape；
(3) it is slowly added to the bismuth nitrate solution of 852g mass concentration 10% in solution A, is stirred under room temperature
140 minutes, the intermediate being transparent；
(4) silver-colored part was soaked in intermediate after 40 seconds and is taken out, silver-colored part is placed in ventilation 26 hours, silver-colored part surface is formed
Intermediate layer；
(5) intermediate layer is heat-treated, the heat treatment includes from room temperature by temperature with the heating speed of 2.2 DEG C/min
Rate is heated to 250 DEG C, is kept for 70 minutes at 250 DEG C, then temperature is heated to 480 from 250 DEG C of heating rates with 2.2 DEG C/min
DEG C, it is kept for 70 minutes, then temperature is dropped into room temperature from 480 DEG C of rate of temperature fall with 2.8 DEG C/min, is obtained corrosion-resistant at 480 DEG C
Etching resistant film, the weight ratio of silica, diboron trioxide and bismuth oxide is 35:10 in the etching resistant film:
55。
Blank group
The experimental procedure of blank group is consistent with embodiment 3, but only includes step (4) and step (5), and by intermediate
Replace with the distilled water of equal quality.
Comparative example 1
The experimental procedure of comparative example 1 is consistent with embodiment 3, but the additional amount of boric acid is changed to 50g in step (2).
Comparative example 2
The experimental procedure of comparative example 2 is consistent with embodiment 3, but changes the additional amount of bismuth nitrate solution in step (3)
For 1500g.
Comparative example 3
The experimental procedure of comparative example 3 is consistent with embodiment 3, but will heat up in step (5) speed adjust be 6 DEG C/
min。
Comparative example 4
The experimental procedure of comparative example 4 is consistent with embodiment 3, but in step (5) by rate of temperature fall be adjusted to 6 DEG C/
min。
For the anti-corrosion effects for examining etching resistant film, following experiment is now done.
Neutral salt spray test, test procedure are carried out to the silver-colored part for being attached with etching resistant film are as follows:
(1) silver-colored part is placed in salt fog cabinet, makes its main exposed surface with a vertical 15-30 ° of angle, difference is implemented
The silver-colored part of example production enables salt fog free settling on all silver-colored parts, and the saline solution on silver-colored part surface is not dropped in any other
On silver-colored part.In addition, not constituting any spatial masking effect between silver-colored part, it is not in contact with each other and keeps being electrically insulated to each other, silver-colored part and branch
Frame also remains electrically isolated from, and does not generate any gap in structure.
(2) testing liquid of atomization is sprayed into when testing, mist is equably deposited in silver-colored part surface under Gravitative Loads.It is described
Testing liquid is the sodium chloride salt aqueous solution of mass concentration 5%, and solution pH value is the neutral range of 6-7, and test temperature is 35 ± 1
DEG C, the rate of settling of salt fog is in 1-2ml/80cm2.h between.
(3) by the way of continuously spraying using 24 hours, when experiment, is 120 hours a length of.After 24 hours spraying, in 80cm2
Horizontal area on per hour averagely collect 1-2ml salt water, wherein the mass concentration of sodium chloride be 5 ± 1% ranges.
Acetic acid salt spray test, test procedure are carried out to the silver-colored part for being attached with etching resistant film are as follows:
(1) silver-colored part is placed in salt fog cabinet, makes its main exposed surface with a vertical 15-30 ° of angle, difference is implemented
The silver-colored part of example production enables salt fog free settling on all silver-colored parts, and the saline solution on silver-colored part surface is not dropped in any other
On silver-colored part.In addition, not constituting any spatial masking effect between silver-colored part, it is not in contact with each other and keeps being electrically insulated to each other, silver-colored part and branch
Frame also remains electrically isolated from, and does not generate any gap in structure.
(2) testing liquid of atomization is sprayed into when testing, mist is equably deposited in silver-colored part surface under Gravitative Loads.Test
Solution is to add glacial acetic acid in the sodium chloride solution of mass concentration 5%, and pH value is adjusted to 3.1-3.3, total solid in solution
Content is no more than 200ppm, and test temperature is controlled at 35 ± 1 DEG C, and the rate of settling of acetic acid salt fog is between 1-2ml/80cm2.h.
(3) by the way of continuously spraying using 24 hours, when test, is 60 hours a length of.After 24 hours spraying, 80cm2's
1-2ml salt water is averagely collected on horizontal area per hour, wherein the mass concentration of sodium chloride is 5 ± 1% ranges.
Mantoquita is carried out to the silver-colored part for being attached with etching resistant film and accelerates acetic acid salt spray test, test procedure are as follows:
(1) silver-colored part is placed in salt fog cabinet, makes its main exposed surface with a vertical 15-30 ° of angle, difference is implemented
The silver-colored part of example production enables salt fog free settling on all silver-colored parts, and the saline solution on silver-colored part surface is not dropped in any other
On silver-colored part.In addition, not constituting any spatial masking effect between silver-colored part, it is not in contact with each other and keeps being electrically insulated to each other, silver-colored part and branch
Frame also remains electrically isolated from, and does not generate any gap in structure.
(2) testing liquid of atomization is sprayed into when testing, mist is equably deposited in silver-colored part surface under Gravitative Loads.Test
Solution is to add glacial acetic acid in the sodium chloride solution of mass concentration 5%, and pH value is adjusted to 3.1-3.3, total solid in solution
Content is no more than 200ppm, adds a small amount of copper chloride, strong to induce corrosion, and test temperature is 50 DEG C, the sedimentation of acetic acid salt fog
Rate is between 1-2ml/80cm2.h.
(3) by the way of continuously spraying using 24 hours, when test, is 24 hours a length of.After 24 hours spraying, 80cm2's
1-2ml salt water is averagely collected on horizontal area per hour, wherein the mass concentration of sodium chloride is 5 ± 1% ranges.
Table 1 detects influence of the different factors to vitreum etching resistant film corrosion resistance
Our experiments show that the silver-colored part performance of glassivation body etching resistant film is good, silver-colored part is not made to be corroded.And because with
The improper and improper preparation of suitable parameters etching resistant film is measured, because there is flaw in vitreous structure, though also there is certain anti-corruption
Corrosion, but with the increase of the extension of etching time and corrosion strength, it can make self structure impaired in corrosion process, silver can be made
Part is by a degree of corrosion.This experiment proves that, for a long time and in the case where deep-etching, the vitreum of the application preparation
Etching resistant film has good corrosion resistant performance.
Claims (10)
1. a kind of preparation method of etching resistant film, which comprises the following steps:
(1) boric acid and ethyl orthosilicate organic solution are mixed, obtains solution A；
(2) solution A and bismuth nitrate are mixed, obtains corrosion resistant intermediate；
(3) by intermediate filming, intermediate body thin film is obtained；
(4) intermediate film is heat-treated, the heat treatment includes that intermediate body thin film is first gradually heated to 200-300
DEG C, constant temperature for a period of time after, then be gradually heated to 400-500 DEG C, constant temperature for a period of time after, then be gradually cooled to room temperature, obtain
Etching resistant film.
2. the preparation method of etching resistant film as described in claim 1, which is characterized in that the rate of temperature fall when cooling is
2-3℃/min。
3. the preparation method of etching resistant film as claimed in claim 1 or 2, which is characterized in that the heating speed when heating
Rate is 2-3 DEG C/min.
4. the preparation method of etching resistant film as described in claim 1, which is characterized in that the ethyl orthosilicate organic solution
Including ethyl orthosilicate, second alcohol and water, the ethyl orthosilicate, second alcohol and water weight ratio be 1-2:3-5:8-12.
5. the preparation method of etching resistant film as claimed in claim 1 or 2, which is characterized in that the ethyl orthosilicate, ethyl alcohol
Weight ratio with water is 1:4:10.
6. the preparation method of etching resistant film as described in claim 1, which is characterized in that the ethyl orthosilicate, boric acid and
The weight ratio of bismuth nitrate is 10-13:1.5-3:7-10.
7. the preparation method of etching resistant film as claimed in claim 1 or 2, which is characterized in that the ethyl orthosilicate, boric acid
Weight ratio with bismuth nitrate is 11:2:8.
8. the preparation method of etching resistant film as claimed in claim 1 or 2, which is characterized in that the filming includes by object
Taking-up after part is soaked in corrosion resistant intermediate, object surface form intermediate body thin film.
9. the preparation method of etching resistant film as claimed in claim 1 or 2, which is characterized in that the soaking time is 20-60
Second.
10. the preparation method of etching resistant film as claimed in claim 1 or 2, which is characterized in that the constant temperature time is 50-
70 minutes.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110158064A (en) * | 2019-07-02 | 2019-08-23 | 郴州市金贵银业股份有限公司 | A kind of anti-oxidant silver-colored and preparation method |
| CN110241404A (en) * | 2019-07-02 | 2019-09-17 | 郴州市金贵银业股份有限公司 | A kind of oxidation barrier film and preparation method |
| CN110578134A (en) * | 2019-08-22 | 2019-12-17 | 湖南省佳川冶金科技有限公司 | Amorphous film capable of preventing silver discoloration and preparation method and application thereof |
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| CN110241404B (en) * | 2019-07-02 | 2021-06-25 | 郴州市金贵银业股份有限公司 | Anti-oxidation film and preparation method thereof |
| CN110578134A (en) * | 2019-08-22 | 2019-12-17 | 湖南省佳川冶金科技有限公司 | Amorphous film capable of preventing silver discoloration and preparation method and application thereof |
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