CN112391594A - Platinum channel with zirconia protective coating and preparation method thereof - Google Patents

Platinum channel with zirconia protective coating and preparation method thereof Download PDF

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CN112391594A
CN112391594A CN202011059689.7A CN202011059689A CN112391594A CN 112391594 A CN112391594 A CN 112391594A CN 202011059689 A CN202011059689 A CN 202011059689A CN 112391594 A CN112391594 A CN 112391594A
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plating layer
coating
zro
platinum
platinum channel
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CN112391594B (en
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冯院祥
张伟
姚清伟
林业伟
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Kornerstone Materials Technology Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08Oxides
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03BMANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/18Stirring devices; Homogenisation
    • C03B5/183Stirring devices; Homogenisation using thermal means, e.g. for creating convection currents
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03BMANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B7/00Distributors for the molten glass; Means for taking-off charges of molten glass; Producing the gob, e.g. controlling the gob shape, weight or delivery tact
    • C03B7/02Forehearths, i.e. feeder channels
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02Pretreatment of the material to be coated
    • C23C14/024Deposition of sublayers, e.g. to promote adhesion of the coating
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34Sputtering
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34Sputtering
    • C23C14/3407Cathode assembly for sputtering apparatus, e.g. Target
    • C23C14/3414Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58After-treatment
    • C23C14/584Non-reactive treatment

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Abstract

The invention provides a platinum channel with a zirconia protective coating, wherein the thickness of the zirconia protective coating is 150-350 mu m, and the zirconia protective coating comprises a pre-coating and an anti-oxidation coating; the pre-plating layer comprises the following components in percentage by weight: ZrO (ZrO)2:75wt%‑79wt%;Al2O3:8wt%‑20wt%;SiO28 wt% -15 wt%; 0.05 wt% -0.5 wt% of RxO; and (ZrO)2+Al2O3)wt%=88.0‑95.6wt%,0.8≤Al2O3wt%/SiO2The weight percent is less than or equal to 1.2; the oxidation-resistant plating layer comprises the following components in percentage by weight: ZrO (ZrO)2:88wt%‑90wt%;Al2O3:4.5wt%‑6.5wt%;SiO24.5 wt% -7.5 wt%; RxO 0.05-0.5 wt% (ZrO)2+Al2O3)wt%=92.0‑95.6wt%,0.8≤Al2O3wt%/SiO2The weight percent is less than or equal to 1.2; ZrO in the oxidation resistant plating layer2And Al2O3Is greater than the total ZrO content in the precoating2And Al2O3(ii) total content of (a); and R is an alkali metal or alkaline earth metal element. The invention is composed of double-layer structure and special components, can effectively avoid platinum poisoning, improves the high temperature resistance strength of the platinum channel, has strong oxidation resistance and reducibility, does not react with the atmosphere of the platinum channel, can be tightly attached to the platinum channel, and does not crack or fall off.

Description

Platinum channel with zirconia protective coating and preparation method thereof
Technical Field
The invention relates to the field, in particular to a platinum channel with a zirconia protective coating and a preparation method thereof.
Background
In the manufacturing process of high-quality glass such as TFT or cover plate, the production line comprises five main processes of batching, kiln, platinum channel, overflow forming, post-processing packaging and the like, wherein the platinum channel is a main bottleneck for restricting the service life and quality of the glass production line. In the platinum channel process, platinum or platinum-rhodium alloy materials are mainly used to manufacture the platinum channel system, and the manufacturing cost is different due to the size of the yield design. The daily production of glass is about 15 tons of platinum channel system, the cost of platinum or platinum-rhodium alloy is as high as about 1.5 hundred million RMB, and the cost is so high that the service life of the platinum channel in the industry is only about 3.5 years. According to observation of the use condition and analysis of the platinum channel in the glass industry, the main reason that the platinum channel becomes the bottleneck of the service life and quality of the glass production line is as follows: once the platinum channel equipment starts to operate in the whole life cycle of the production line, the stable working state is maintained in the high-temperature environment of 1000-1650 ℃ for a long time within a period of years, and the operation is difficult to stop or pause to judge the cause or causes of the defects. The platinum channel system can generate complex chemical reaction and electrochemical reaction combination when running in a long-term high-temperature environment, and comprises a platinum channel assembly with a heating section, a clarifying section, a liquid level hole, a stirring section, a cooling section, a feeding section and the like, so that a large amount of bubbles and noble metal abnormal defects are generated, and the main reasons comprise the following three points:
1. under a long-term high-temperature environment, platinum or a platinum rhodium alloy of the platinum channel can react with oxygen in the air or oxygen in glass to generate platinum oxide or platinum rhodium oxide, and the generated platinum oxide or platinum rhodium oxide is volatilized and lost, so that the strength and stability of the platinum channel system are directly damaged, and the service life is influenced;
2. the volatilized platinum oxide or platinum rhodium oxide can be attached to the refractory material, the insulating material and the platinum channel cold spot area with free liquid level of the platinum channel system, so that platinum oxide or platinum rhodium oxide refining and recycling parts are increased, and the cost of platinum or rhodium recovery is increased. Meanwhile, platinum oxide or platinum-rhodium alloy oxide volatilized in a free liquid surface cold spot area of a platinum system forms triangular, hexagonal or acicular crystals under specific conditions, and when the environment fluctuates, the crystals fall into glass to form a precious metal foreign matter defect, so that the quality is influenced, and the production cost is increased;
3. in the manufacturing process of a kiln and a platinum channel, the glass liquid in the platinum channel contains higher oxygen concentration due to complex chemical reaction and electrochemical reaction in the glass smelting process, including thermal electrolysis in glass, decomposition of multivalent oxide and decomposition of OH-ion groups and water in glass. The main reasons are: when the partial pressure of hydrogen at the interface between the glass and the platinum assembly in the platinum channel is greater than the partial pressure of hydrogen at the external part (non-glass contact surface) between the platinum assemblies, hydrogen permeates out of the glass through the platinum assembly, and bubbles are formed when the oxygen concentration in the glass reaches the limit of the oxygen dissolved in the glass.
Therefore, there is a need for a dense protective layer material that is resistant to high temperature and oxidation and does not contaminate the glass and a method of making a platinum channel system component for isolating oxygen from platinumOr the platinum-rhodium alloy, improves the oxidation resistance of the platinum channel system and reduces hydrogen permeation, thereby prolonging the service life of the platinum channel system and reducing noble metal foreign matters and bubble defects. However, the zirconia mixed material and the manufacturing method of patent CN107739141B require the arc spraying to have extremely high coating uniformity, and are easy to crack, and are not suitable for large-scale industrial production. Chinese patent application 201811513775.3 discloses a coating for platinum channels, but the coating contains SiO2The amount is large, and the silicon is easy to generate simple substance under the high temperature condition, and can react with the metal foil to form PtSi, so that the platinum poisoning is caused, and the platinum pipe is softened at the temperature of 600-800 ℃ to cause the damage of the platinum pipe.
Disclosure of Invention
Therefore, it is necessary to provide a new dense protective layer material which is resistant to high temperature and oxidation and does not contaminate glass, and a method for manufacturing a platinum channel, which is used to isolate oxygen from platinum or platinum-rhodium alloy, improve the oxidation resistance of the platinum channel system and reduce hydrogen permeation, so as to prolong the service life of the platinum channel system and reduce noble metal foreign matter and bubble defects.
In order to achieve the object of the present invention, a first aspect of the present invention provides that the zirconia protective coating includes a precoat layer and an oxidation-resistant coating layer, the precoat layer being disposed between the platinum channel and the oxidation-resistant coating layer; the pre-plating layer comprises the following components in percentage by weight: ZrO (ZrO)2:75wt%-79wt%;Al2O3:8wt%-20wt%;SiO28 wt% -16 wt%; 0.05 wt% -0.5 wt% of RxO; wherein (ZrO)2+Al2O3)wt%=88.0-95.6wt%,0.8≤Al2O3wt%/SiO2wt%≤1.2;
The oxidation-resistant plating layer comprises the following components in percentage by weight: ZrO (ZrO)2:88wt%-90wt%;Al2O3:4.5wt%-6.5wt%;SiO24.5 wt% -7.5 wt%; 0.05 wt% -0.5 wt% of RxO; wherein (ZrO)2+Al2O3)wt%=92.0-95.6wt%,0.8≤Al2O3wt%/SiO2wt%≤1.2;
ZrO in the oxidation resistant plating layer2And Al2O3Is greater than the total ZrO content in the precoating2And Al2O3(ii) total content of (a);
and R is an alkali metal or alkaline earth metal element.
Pre-plating layer characteristics: ZrO relative to the formulation of the oxidation-resistant coating2Low content of Al2O3And SiO2The content is high, the bonding degree with a platinum channel system component can be good, and the adhesive force is strong. But the oxidation resistance of the coating is slightly weaker than that of the formula of the oxidation-resistant coating, and the coating can be corroded by the atmosphere of platinum channel glass.
The formula characteristics of the antioxidant plating layer are as follows: ZrO relative to the pre-coating formulation2High content of Al2O3And SiO2The content is lower, the oxidation resistance is stronger than that of the preplating layer formula, the platinum channel glass atmosphere can be directly contacted, and the bonding degree and the adhesive force with the preplating layer material are strong.
Meanwhile, the component proportion of the pre-plating layer and the anti-oxidation plating layer both need to meet the following conditions:
1. pre-plating: (ZrO)2+Al2O3)wt%=88.0-95.6wt%,
And (3) oxidation resistant plating: (ZrO)2+Al2O3)wt%=92.0-95.6%;
Oxidation resistant coatings (ZrO)2+Al2O3) (ZrO) of wt% or more of precoating2+Al2O3) wt% to ensure good adhesion and bonding of the protective coating and the platinum channel system component, and the oxidation-resistant coating is not easily corroded by glass atmosphere.
By adjusting ZrO2And Al2O3The proportion ensures that the thermal expansion coefficients of the pre-plating layer and the oxidation-resistant plating layer are close to those of the platinum channel, and avoids the cracking of the heating plating layer;
②、Al2O3wt%/SiO2the value of wt% is between 0.8 and 1.2;
first, SiO is controlled2In an amount of avoiding SiO2Reduced into simple substance Si which reacts with platinum metal in the platinum channel to cause platinum poisoning,the high temperature resistance strength of the platinum channel is reduced.
Second SiO2、Al2O3And the RxO plays a good role in fluxing and bonding, so that the zirconia coating has good oxidation resistance and compactness, is firmly attached to the surface of the platinum channel system component, is not easy to fall off, has no gap, and achieves the effects of preventing the platinum channel from oxidizing and volatilizing with air and protecting the platinum channel.
Preferably, the thermal expansion coefficient of the preplating layer and the oxidation-resistant plating layer is 8.9 multiplied by 10-6/℃-10.0×10-6/℃。
The thermal expansion coefficients of the various materials were measured by heating to 1000 ℃ at room temperature, giving the following results: ZrO (ZrO)2Coefficient of thermal expansion: 9.6X 10-6/℃-10.2×10-6/℃;Al2O3.SiO2Coefficient of thermal expansion of ceramic: 9.0X 10-6/° c; platinum rhodium alloy (platinum channel system component) coefficient of thermal expansion: 9.8X 10-6/℃-9.9×10-6/° c; coefficient of thermal expansion of pure platinum: 9.1X 10-6V. C. In order to be capable of being closely attached to a platinum channel in a high-temperature working environment without cracking and falling off; the thermal expansion coefficients of the pre-plating layer and the oxidation resistant plating layer are close to that of platinum or platinum-rhodium metal, and are controlled to be 8.9 multiplied by 10-6/℃-10.0×10-6/℃。
In the technical scheme, the high temperature resistance of the predetermined layer and the oxidation resistant coating is stronger than that of platinum or platinum-rhodium alloy, the thermal expansion coefficient is close to that of platinum or platinum-rhodium metal, and the platinum-rhodium alloy has strong oxidation resistance and reducibility, does not react with the atmosphere of a platinum channel, can be tightly attached to the platinum channel, and does not crack or fall off at high temperature.
Preferably, the RxO is Na2O、K2O、Li2O or mixtures thereof.
Preferably, the thickness of the zirconia protective coating is 150-350 μm, the thickness of the pre-coating is 15-50 μm, and the thickness of the oxidation-resistant coating is 100-320 μm.
The thickness ensures that the platinum channel system component is isolated from air, plays a role in preventing oxidation and volatilization, and simultaneously reduces hydrogen permeation in the platinum channel component and bubble generation; and the plating layer and the platinum channel component can be firmly attached and combined, and can not fall off in the heating and production processes.
Preferably, the thickness of the zirconia protective coating is 200-300 μm, the thickness of the pre-coating is 20-30 μm, and the thickness of the oxidation-resistant coating is 180-280 μm.
In order to achieve the object of the present invention, the second aspect of the present invention provides a method for preparing a platinum channel with a zirconia protective coating according to the first aspect of the present invention, comprising the steps of:
pre-plating layer batching: weighing and mixing the components according to the components and the content of the pre-plating layer to obtain a pre-plating layer mixture with the uniformity of more than 98%, and preparing a pre-plating layer target material by using the pre-plating layer mixture;
compounding the antioxidant plating layer: weighing and mixing the components according to the components and the content of the antioxidant coating to obtain an antioxidant coating mixture with the uniformity of more than 98%, and preparing a coating target material by using the antioxidant coating mixture;
radio frequency sputtering: sequentially carrying out radio frequency sputtering on the platinum channel by using a pre-plating layer target material and an anti-oxidation plating layer target material; obtaining the platinum channel with the zirconia protective coating.
The mixture can be processed into round or square ceramic target materials by adopting an electric melting casting process and a preparation process. Radio frequency sputtering: sequentially carrying out radio frequency sputtering on the platinum channel by using a pre-plating layer target material and an anti-oxidation plating layer target material; obtaining the platinum channel with the zirconia protective coating.
Compared with the common thermal spraying process, the radio frequency sputtering has the advantages of strong bonding force between the plating layer and the substrate, more stable adhesion force than the common thermal spraying, compact and uniform electroplated layer and the like. The sputtering particles are hardly influenced by gravity, the positions of the target and the substrate can be freely arranged according to the shape of the platinum system component, the nucleation density at the initial stage of film formation is high, and the automatic continuous production can be realized for a long time. The target can be made into various shapes, and is matched with the special design of a machine table to perform better control and most effective sputtering. Radio frequency sputtering, suitable for ceramic insulating target material.
After the sputtering is finished, a compact zirconium oxide protective layer without gaps is formed between the platinum channel and the air contact surface, so that the platinum channel system component and the air are isolated, the platinum channel system component is prevented from being oxidized, volatilized and crystallized, and the defect of metal foreign matters in the platinum channel is reduced. Meanwhile, hydrogen permeation in the platinum channel system component is reduced, and bubble generation is reduced.
Preferably, the particle size of each component of the pre-plating layer target material and the anti-oxidation plating layer target material is 55-150 μm. Preferably, the particle size of each component of the pre-plating layer target material and the anti-oxidation plating layer target material is 75-120 μm. Preferably, the frequency used for the radio frequency sputtering is: 12-15MHz, working vacuum: 0.9X 10-2-1.2×10-2Pa, power density: 1-20W/cm2. And (3) putting the platinum channel component and the zirconia ceramic target material into a sputtering chamber of sputtering equipment specially designed according to the platinum channel component, and bombarding the zirconia ceramic target material by ions generated by high-frequency power discharge to form a sputtering coating process.
Preferably, the power density is 6-15W/cm2
Preferably, the coating rate of the radio frequency sputtering is 60-250 nm/min.
Preferably, the coating rate of the radio frequency sputtering is 120-180 nm/min.
Preferably, the platinum channel is plasma cleaned before the rf sputtering.
The platinum channel assembly is conveyed to a 1000-grade dust-free workshop, field workers wear dust-free room protective clothing, wear rubber gloves and take hairs into the dust-free protective clothing, brand-new dust-free cloth is used for wiping the inner and outer layer surfaces of the platinum channel assembly, surface foreign matters and dust are removed, and the inner and outer layer surfaces of the platinum channel assembly are preliminarily cleaned by 98% of absolute ethyl alcohol. And then putting the platinum channel assembly which is initially cleaned and qualified into plasma cleaning equipment for surface treatment, removing organic matters and other dirt of the platinum channel assembly, and enhancing the surface activity of the platinum channel assembly so as to enhance the adhesion and bonding force of the plating layer and the platinum channel assembly.
Different from the prior art, the technical scheme at least comprises the following beneficial effects: the zirconia protective coating adopted by the invention comprises a precoating layer and an antioxidant coating, wherein the precoating layer can be tightly combined with the platinum channel, and the antioxidant coating can be tightly combined with the precoating layer.
Drawings
FIG. 1 is a temperature rise curve of a platinum channel in a glass production line.
Detailed Description
To explain technical contents, structural features, and objects and effects of the technical solutions in detail, the following detailed description is given with reference to the accompanying drawings in conjunction with the embodiments.
In this embodiment, since the platinum channel module is expensive, a 50 × 50mm platinum piece was used as the platinum module, and the results were verified.
Example 1 preparation of a platinum sheet with a protective coating of zirconia
Pre-plating layer batching: according to ZrO2:79.0wt%;Al2O3:9.8wt%;SiO2:11.1%;Na2O: 0.1 wt%; weighing and mixing the components to obtain a pre-plating layer mixture with the uniformity of more than 98%, and preparing a ceramic pre-plating layer target material by using the pre-plating layer mixture through an electric melting casting process;
compounding the antioxidant plating layer: according to the following steps: ZrO (ZrO)2:90.0wt%;Al2O3:4.5wt%;SiO2:5.4wt%;Na2O: 0.1 wt%; weighing and mixing the components to obtain an antioxidant coating mixture with the uniformity of more than 98%, and preparing a ceramic antioxidant coating target material by using the antioxidant coating mixture through an electric melting casting process;
the thermal expansion coefficient of the precoating is 9.8 multiplied by 10-6/℃;
The thermal expansion coefficient of the oxidation-resistant coating is 9.6 multiplied by 10-6/℃。
The grain diameter of each component of the pre-plating layer target material and the anti-oxidation plating layer target material is 75-120 mu m.
Radio frequency sputtering: cleaning a platinum channel (after plasma is used for cleaning, sequentially using a pre-plating layer target material and an anti-oxidation plating layer target material for radio frequency sputtering to obtain the platinum channel with the zirconia protective plating layer, wherein the frequency of the radio frequency sputtering is 13.56MHz, and the working vacuum degree is 1 multiplied by 10-2Pa, power density: 15 +/-2.5W/cm2. The film plating rate of the radio frequency sputtering is 138 +/-15 nm/min.
The platinum sheet with the zirconia protective coating obtained in the example 1 has the thickness of 205-220 μm, and the zirconia protective coating comprises 23-28 μm pre-coating and 182-192 μm oxidation-resistant coating.
Example 2 preparation of a platinum sheet with a protective coating of zirconia
Pre-plating layer batching: according to ZrO2:77.5wt%;Al2O3:11.2wt%;SiO2:11.2wt%;Na2O: 0.1 percent; weighing and mixing the components to obtain a pre-plating layer mixture with the uniformity of more than 98%, and preparing a ceramic pre-plating layer target material by the pre-plating layer mixture by adopting an electric melting casting process;
compounding the antioxidant plating layer: according to the following steps: ZrO (ZrO)2:89.0%;Al2O3:5.45wt%;SiO2:5.5wt%;Na2O:0.05 percent; weighing and mixing the components to obtain an antioxidant coating mixture with the uniformity of more than 98%, and preparing a ceramic antioxidant coating target material from the antioxidant coating mixture by adopting an electric melting casting process;
the thermal expansion coefficient of the precoating is 9.85 multiplied by 10-6/℃;
The thermal expansion coefficient of the oxidation-resistant plating layer is 9.65 multiplied by 10-6/℃。
The grain diameter of each component of the pre-plating layer target material and the anti-oxidation plating layer target material is 75-120 mu m.
Radio frequency sputtering: cleaning platinum channel with plasma, and sequentially performing RF sputtering with pre-plating layer target and oxidation-resistant plating layer target to obtain platinum with zirconium oxide protective plating layerThe frequency of the radio frequency sputtering is as follows: 13.56MHz, working vacuum: 1X 10-2Pa, power density: 15 +/-2.5W/cm2. The film plating rate of the radio frequency sputtering is 138 +/-15 nm/min.
The platinum sheet with the zirconia protective coating obtained in the example 2 has the thickness of 205-220 μm, and the zirconia protective coating comprises 23-28 μm pre-coating and 182-192 μm oxidation-resistant coating.
Example 3 preparation of a platinum sheet with a protective coating of zirconium oxide
Pre-plating layer batching: according to ZrO2:75wt%;Al2O3:13.6wt%;SiO2:11.35wt%;Na2O:0.05 percent; weighing and mixing the components to obtain a pre-plating layer mixture with the uniformity of more than 98%, and preparing a ceramic pre-plating layer target material by using the pre-plating layer mixture through an electric melting casting process;
compounding the antioxidant plating layer: according to the following steps: ZrO (ZrO)2:88.0%;Al2O3:6.5wt%;SiO2:5.4wt%;Na2O: 0.1 percent; weighing and mixing the components to obtain an antioxidant coating mixture with the uniformity of more than 98%, and preparing a ceramic antioxidant coating target material by using the antioxidant coating mixture through an electric melting casting process;
the thermal expansion coefficient of the precoating is 9.9 multiplied by 10-6/℃;
The thermal expansion coefficient of the oxidation-resistant coating is 9.7 multiplied by 10-6/℃。
The grain diameter of each component of the pre-plating layer target material and the anti-oxidation plating layer target material is 75-120 mu m.
Radio frequency sputtering: cleaning a platinum channel (after plasma is used for cleaning, sequentially using a pre-plating layer target material and an anti-oxidation plating layer target material for radio frequency sputtering to obtain the platinum channel with the zirconia protective plating layer, wherein the frequency of the radio frequency sputtering is 13.56MHz, and the working vacuum degree is 1 multiplied by 10-2Pa, power density: 15 +/-2.5W/cm2. The film plating rate of the radio frequency sputtering is 138 +/-15 nm/min.
The platinum sheet with the zirconia protective coating obtained in the example 3 has the thickness of 205-220 μm, and the zirconia protective coating comprises 23-28 μm pre-coating and 182-192 μm oxidation-resistant coating.
And (3) performance testing:
the platinum sheets having a protective coating of zirconia prepared in example 1/2/3 were placed in a glass melting furnace, respectively, and the furnace temperature was simulated according to a temperature rise curve of a platinum channel of a glass production line (as shown in FIG. 1), and the temperature was raised from room temperature to 1400 ℃. + -. 5 ℃ using the glass melting furnace;
in test 1, a platinum sheet with a protective coating of zirconia was placed across the crucible headspace, with no glass frit in the crucible, and was held at 1400 ℃. + -. 5 ℃ for 84 hours. And then, the temperature is reversely reduced to the normal temperature according to the temperature rise curve shown in figure 1, and finally, the platinum sheet with the zirconia protective coating has no appearance cracking and shedding phenomenon.
In test 2, a platinum sheet with a protective coating of zirconia was placed horizontally in the top space of the crucible, and 200g of a glass powder formulation was placed at the bottom of the crucible, and the crucible was maintained at a constant temperature of 1400 ℃. + -. 5 ℃ for 120 hours. Then, the temperature is reversely reduced to the normal temperature according to the temperature rise curve of the figure 1. Finally, a thin layer of glass condensate is attached to the surface of the platinum sheet with the zirconia protective coating, and the appearance detection shows that the platinum sheet does not crack or fall off.
From the above tests and tests it can be shown that: the high temperature resistance of the preset layer and the oxidation resistant plating layer is stronger than that of platinum or platinum-rhodium alloy, the thermal expansion coefficient is close to that of platinum or platinum-rhodium metal, and the preset layer and the oxidation resistant plating layer have strong oxidation resistance and reducibility, do not react with the atmosphere of a platinum channel, can be tightly attached to the platinum channel, and do not crack or fall off.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or terminal that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or terminal. Without further limitation, an element defined by the phrases "comprising … …" or "comprising … …" does not exclude the presence of additional elements in a process, method, article, or terminal that comprises the element. Further, herein, "greater than," "less than," "more than," and the like are understood to exclude the present numbers; the terms "above", "below", "within" and the like are to be understood as including the number.
It should be noted that, although the above embodiments have been described herein, the invention is not limited thereto. Therefore, based on the innovative concepts of the present invention, the technical solutions of the present invention can be directly or indirectly applied to other related technical fields by making changes and modifications to the embodiments described herein, or by using equivalent structures or equivalent processes performed in the content of the present specification and the attached drawings, which are included in the scope of the present invention.

Claims (10)

1. A platinum channel with a zirconia protective coating is characterized in that the zirconia protective coating comprises a precoating and an antioxidant coating, and the precoating is arranged between the platinum channel and the antioxidant coating; the pre-plating layer comprises the following components in percentage by weight: ZrO (ZrO)2:75wt%-79wt%;Al2O3:8wt%-20wt%;SiO28 wt% -16 wt%; 0.05 wt% -0.5 wt% of RxO; wherein (ZrO)2+Al2O3)wt%=88.0-95.6wt%,0.8≤Al2O3wt%/SiO2 wt%≤1.2;
The oxidation-resistant plating layer comprises the following components in percentage by weight: ZrO (ZrO)2:88wt%-90wt%;Al2O3:4.5wt%-6.5wt%;SiO24.5 wt% -7.5 wt%; 0.05 wt% -0.5 wt% of RxO; wherein (ZrO)2+Al2O3)wt%=92.0-95.6wt%,0.8≤Al2O3 wt%/SiO2 wt%≤1.2;
The antibodyZrO in oxide coatings2And Al2O3Is not less than the total content of ZrO in the precoating2And Al2O3(ii) total content of (a);
and R is an alkali metal or alkaline earth metal element.
2. The platinum channel of claim 1, wherein said pre-plating and said oxidation resistant plating each have a coefficient of thermal expansion of 8.9 x 10-6/℃-10.0×10-6/℃。
3. The platinum channel of claim 1, wherein said RxO is Na2O、K2O、Li2O or mixtures thereof.
4. The platinum channel as claimed in claim 1, wherein the thickness of the zirconia protective coating is 150-350 μm, the thickness of the pre-coating is 15-50 μm, and the thickness of the oxidation-resistant coating is 100-320 μm.
5. The platinum channel as claimed in claim 4, wherein the thickness of the zirconia protective coating is 200-300 μm, the thickness of the pre-coating is 20-30 μm, and the thickness of the oxidation-resistant coating is 180-280 μm.
6. A method for preparing a platinum channel with a zirconia protective coating according to any one of claims 1 to 5, comprising the steps of:
pre-plating layer batching: weighing and mixing the components according to the components and the content of the pre-plating layer to obtain a pre-plating layer mixture with the uniformity of more than 98%, and preparing a pre-plating layer target material by using the pre-plating layer mixture;
compounding the antioxidant plating layer: weighing and mixing the components according to the components and the content of the antioxidant coating to obtain an antioxidant coating mixture with the uniformity of more than 98%, and preparing an antioxidant coating target material by using the antioxidant coating mixture;
radio frequency sputtering: sequentially carrying out radio frequency sputtering on the platinum channel by using a pre-plating layer target material and an anti-oxidation plating layer target material; obtaining the platinum channel with the zirconia protective coating.
7. The method according to claim 6, wherein the pre-plated target material and the anti-oxidation plated target material have a particle size of 55-150 μm.
8. The method of claim 6, wherein the RF sputtering is performed at a frequency of: 12-15MHz, working vacuum: 0.9X 10-2-1.2×10-2Pa, power density: 1-20W/cm2
9. The method according to claim 6, wherein the coating rate of the RF sputtering is 60-250 nm/min.
10. The method of claim 6, wherein the platinum channel is plasma cleaned prior to RF sputtering.
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