CN115896713A - Novel high-bonding-force high-temperature-resistant wear-resistant corrosion-resistant Al 2 O 3 /SiO 2 Composite coating and preparation method thereof - Google Patents
Novel high-bonding-force high-temperature-resistant wear-resistant corrosion-resistant Al 2 O 3 /SiO 2 Composite coating and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a novel high-bonding-force high-temperature-resistant wear-resistant anticorrosive Al 2 O 3 /SiO 2 The composite coating and the preparation method thereof comprise the following steps: plated with Al coatingMetallic or non-metallic material of (2), al 2 O 3 Ceramic coating and SiO 2 And (4) coating. The invention has the beneficial effects that: the invention selects the special silica sol to seal the honeycomb holes generated after micro-arc oxidation, thereby forming the novel Al 2 O 3 /SiO 2 And (4) composite coating. Compared with the prior art, the coating has high binding force, better corrosion resistance and wear resistance, good thermal stability at the temperature of 25-300 ℃, and good application prospect in the field of surface protection.
Description
Technical Field
The invention relates to the field of coating materials, in particular to novel high-bonding-force high-temperature-resistant wear-resistant anticorrosive Al 2 O 3 /SiO 2 A composite coating and a preparation method thereof.
Background
At present, al 2 O 3 The preparation techniques of the base coating mainly include plasma spraying, sol-gel, metal organic decomposition, etc., but Al prepared by these preparation techniques is currently available 2 O 3 The binding force of the coating is relatively low, so that the effective service time of the coating is short. The micro-arc oxidation technology can enable the surface of the nonferrous metal to generate a ceramic film layer, and the ceramic film layer formed through micro-arc oxidation treatment has the characteristics of high density, large binding force and excellent overall performance. The ceramic film layer formed by micro-arc oxidation has high inner side density, but the outer side is loose and porous, the proportion of the loose layer accounts for more than 60% of the whole coating, and the service life of the ceramic layer can be greatly reduced without carrying out subsequent treatment on the ceramic layer formed by micro-arc oxidation. In the prior art, an epoxy resin material is generally adopted to bond and compound a micro-arc oxidation ceramic layer, but the epoxy resin has poor high-temperature resistance and is easy to crack.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a high-bonding-force high-temperature-resistant and high-temperature-resistant cableNovel Al for corrosion resistance of mill 2 O 3 /SiO 2 Composite coating and preparation method thereof, and Al prepared by method 2 O 3 /SiO 2 The composite coating has high binding force, can be used at high temperature, greatly improves the wear resistance and corrosion resistance of the material, and prolongs the service life of the material.
In a first aspect, a novel Al with high binding force, high temperature resistance, wear resistance and corrosion resistance is provided 2 O 3 /SiO 2 A composite coating comprising: metallic or non-metallic material, al, coated with Al coating 2 O 3 Ceramic coating and SiO 2 And (4) coating.
In a second aspect, a novel Al with high binding force, high temperature resistance, wear resistance and corrosion resistance is provided 2 O 3 /SiO 2 The preparation method of the composite coating comprises the following steps:
Preferably, in step 1, the substrate is a metal material or a non-metal material, and the metal material includes a titanium alloy and stainless steel; the non-metallic material comprises carbon fiber and a high polymer material.
Preferably, in step 1, the vapor deposition method includes a physical vapor deposition method and a chemical deposition method; the physical vapor deposition method comprises the steps of vacuum coating, sputtering coating or ion coating.
Preferably, in step 1, the thickness of the metallic aluminum coating is 10 to 500 μm.
Preferably, in step 2, the Al is 2 O 3 The thickness of the ceramic coating is 10-2000 mu m, and the Al 2 O 3 The micro Vickers hardness of the surface of the ceramic coating is 700-1000HV.
Preferably, in step 3, the silica sol slurry contains 50 to 70 percent of silica sol, 10 to 20 percent of ferric hydroxide sol and alpha-Al 2 O 3 The content of the nano powder is 10-20%, the content of the calcium hydroxide is 3-10%, the content of the silicon carbide is 2-5%, and the content of the thickening agent is 2-5%.
Preferably, in step 3, the coating thickness of the silica sol slurry is controlled to be 20 to 90 μm.
The invention has the beneficial effects that:
1. the invention selects the special silica sol to seal the honeycomb holes generated after micro-arc oxidation, thereby forming the novel Al 2 O 3 /SiO 2 And (4) composite coating. Compared with the prior art, the coating has high binding force, better corrosion resistance and wear resistance, good thermal stability at the temperature of 25-300 ℃, and good application prospect in the field of surface protection.
2. The novel composite coating provided by the invention is not only suitable for metal materials, but also suitable for non-metal materials such as carbon fibers and the like, has a wide application range, and indirectly solves the limitation that the micro-arc oxidation technology is suitable for non-metal metals.
Drawings
FIG. 1 shows Al prepared in the present application 2 O 3 /SiO 2 The structure of the composite coating is shown schematically;
FIG. 2 shows Al prepared in the present application 2 O 3 A schematic of the micro-topography of the coating;
FIG. 3 shows Al prepared by the present application 2 O 3 The coating has a schematic view of honeycomb-shaped pores.
Detailed Description
The present invention will be further described with reference to the following examples. The following examples are set forth merely to provide an understanding of the invention. It should be noted that modifications can be made to the invention by a person skilled in the art without departing from the principle of the invention, and these modifications and modifications also fall within the scope of the claims of the invention.
Example 1:
the composite coating formed by the silica sol has the advantages of good compactness and strong bonding force with metal, and simultaneously has excellent high-temperature resistance, wear resistance and corrosion resistance 2 O 3 /SiO 2 A composite coating and provides a novel Al with high binding force, high temperature resistance, wear resistance and corrosion resistance 2 O 3 /SiO 2 The preparation method of the composite coating comprises the following steps:
the base material comprises a metal material and a non-metal material, the metal material comprises aluminum alloy, titanium alloy, stainless steel and the like, and the non-metal material comprises carbon fiber, a high polymer material and the like.
The vapor deposition method comprises a physical vapor deposition method and a chemical deposition method, wherein the physical vapor deposition method specifically comprises vacuum coating, sputtering coating, ion coating and the like.
Wherein the Al coating has a thickness of 10-500 μm, such as 100 μm, 300 μm, 500 μm, or other thicknesses within this range.
wherein, al 2 O 3 The thickness of the ceramic coating is Al 2 O 3 The ceramic coating has a thickness of 10 μm to 2000 μm, such as 10 μm, 50 μm, 100 μm, 150 μm, or the like, or other thicknesses within this range;
wherein, al 2 O 3 The micro Vickers hardness of the surface of the ceramic coating is 700-1000HV, such as 700HV, 800HV, 900 μm, 1000HV, etc., or other hardness within this range.
Specifically, al 2 O 3 The preparation method of the ceramic coating comprises the following steps:
a1, grinding the surface of the Al coating by using sand paper to remove surface covering materials, then finely grinding or polishing the surface of the Al coating to flatten the surface of the Al coating, and finally ultrasonically removing oil by using ethanol;
b2, taking Al as a cathode, taking a stainless steel sheet as an anode, placing the stainless steel sheet in the electrolyte in parallel, and performing micro-arc oxidation treatment by using a plasma micro-arc oxidation power supply; the electrolyte comprises the following chemical components in percentage by concentration: 8g/L of sodium silicate, 4mL/L of glycerol and 4g/L of sodium hexametaphosphate; the process parameters of the micro-arc oxidation treatment are as follows: pulse frequency of 50-100Hz, duty ratio of 60% and current density of 6A/dm 2 The voltage is 500-800V, and the reaction time is 15-30min under constant voltage;
c3, after the electrolytic deposition is finished, washing for 3-5min by using ionic water, and air-drying;
wherein SiO is formed 2 The coating thickness is 20-90 μm, such as 20 μm, 50 μm, 90 μm, or other thicknesses within this range of values;
in particular, siO 2 The preparation method of the ceramic coating comprises the following steps:
a1, putting the silica sol and the ferric hydroxide sol into a beaker, stirring by a magnetic stirrer at the rotating speed of 100-300 r/min for 1-3h, and aging for 48 h to obtain mixed sol;
b2, mixing alpha-Al 2 O 3 Adding the nano powder, calcium hydroxide, silicon carbide and a thickening agent into silica sol, and stirring uniformly by using a magnetic stirrer at the rotating speed of 500 revolutions per minute for 1-3 hours to obtain a coating based on the silica sol;
c3, spraying the coating to Al 2 O 3 Sealing the coating, and drying to obtain SiO 2 And (4) coating.
Referring to FIG. 1, the invention provides a novel Al with high binding force, high temperature resistance, wear resistance and corrosion resistance 2 O 3 /SiO 2 And (4) composite coating. The prepared novel Al 2 O 3 /SiO 2 The composite coating comprises an Al coating 1 and Al formed on the surface of the coating 1 by a micro-arc oxidation technology 2 O 3 A honeycomb-shaped film 2,Spraying silica sol to Al 2 O 3 SiO obtained after drying of the coating 2 A coating 3; wherein the Al coating 1 comprises a substrate 11, an Al coating 12 deposited on the surface of the substrate 11 2 O 3 The honeycomb-shaped film 2 is formed on the surface of the Al coating 12, and the Al coating 1 and the Al 2 O 3 Honeycomb film 2, siO 2 The forming process of the coating 3 is as described above.
Example 2:
as shown in figure 1, a novel Al with high binding force, high temperature, wear resistance and corrosion resistance 2 O 3 /SiO 2 Composite coating, its structure from the bottom up includes in proper order: substrate and Al coating 1, al 2 O 3 Coating 2,SiO 2 And (3) coating.
Al 2 O 3 /SiO 2 The preparation steps of the composite coating are as follows:
A. plating an Al film by a vacuum coating technology: putting the membrane material and the cleaned substrate into a bell jar, vacuumizing to below 6Pa (about 10-15 minutes) by a mechanical pump, pushing a low valve and heating a diffusion pump, opening a high valve after 45 minutes and vacuumizing for about 15 minutes until the vacuum degree reaches 6.7x10 -3 Pa. Turning on an electron gun for preheating for 3 minutes, slowly adjusting a filament, preheating the film material to be completely red by using small beam current of about 10mA, and adjusting the working beam current to 80-120 mA. After 1 minute, evaporating the test piece for 30 to 50 minutes, closing the sub-gun, naturally cooling the test piece in the clock for 15 to 20 minutes, and then opening the clock to take out the test piece;
B. micro-arc oxidation: grinding the surface of the Al coating by using sand paper to remove surface covering materials, then finely grinding or polishing the surface of the Al coating to flatten the surface of the Al coating, and finally ultrasonically removing oil by using ethanol; taking Al as a cathode, taking a stainless steel sheet as an anode, placing the stainless steel sheet in the electrolyte in parallel, and performing micro-arc oxidation treatment by using a plasma micro-arc oxidation power supply; the electrolyte comprises the following chemical components in percentage by concentration: 8g/L of sodium silicate, 4mL/L of glycerol and 4g/L of sodium hexametaphosphate; the process parameters of the micro-arc oxidation treatment are as follows: pulse frequency of 50-100Hz, duty ratio of 60% and current density of 6A/dm 2 The voltage is 500-800V, and the reaction time is 15-30min under constant voltage; after the electrolytic deposition is finished, washing for 3-5min by using ionic water, and air-drying;
C. hole sealing treatment: putting the silica sol and the ferric hydroxide sol into a beaker, stirring the silica sol and the ferric hydroxide sol by a magnetic stirrer at the rotating speed of 100-300 r/min for 1-3h, and aging the mixture for 48 h to obtain mixed sol; alpha-Al is added 2 O 3 Adding the nano powder, calcium hydroxide, silicon carbide and a thickening agent into silica sol, and stirring uniformly by a magnetic stirrer at the rotating speed of 500 revolutions per minute for 1-3 hours to obtain a coating based on the silica sol; spraying the coating to Al 2 O 3 Sealing the hole of the coating, and drying to obtain SiO 2 And (4) coating. In the coating based on silica sol, the content of silica sol was 70%, the content of iron hydroxide sol was 10%, and α -Al 2 O 3 The content of the nano powder is 10 percent, the content of the calcium hydroxide is 5 percent, the content of the silicon carbide is 3 percent, and the content of the thickening agent is 2 percent.
Example 3:
Al 2 O 3 /SiO 2 the preparation steps of the composite coating are as follows:
A. plating an Al film by a sputtering coating technology: adopting magnetron sputtering equipment to deposit a metal Al coating on the surface of the substrate, wherein the thickness of the coating is about 15 mu m, and the basic process parameters are as follows: pumping the vacuum degree of the chamber to 5 multiplied by 10 -3 Introducing Ar gas with the purity of 99.999 percent after Pa, keeping the pressure at 0.6Pa, then turning on a power supply of an Al target (with the purity of 99.99 percent), wherein the power of the target is 500-700W, and the deposition time is 3-5h;
B. micro-arc oxidation: grinding the surface of the Al coating by using sand paper to remove surface covering materials, then finely grinding or polishing the surface of the Al coating to flatten the surface of the Al coating, and finally ultrasonically removing oil by using ethanol; taking Al as a cathode, taking a stainless steel sheet as an anode, placing the stainless steel sheet in the electrolyte in parallel, and performing micro-arc oxidation treatment by using a plasma micro-arc oxidation power supply; the electrolyte comprises the following chemical components in percentage by weight: 8g/L of sodium silicate, 4mL/L of glycerol and 4g/L of sodium hexametaphosphate; the process parameters of the micro-arc oxidation treatment are as follows: pulse frequency of 50-100Hz, duty ratio of 60% and current density of 6A/dm 2 The voltage is 500-800V, and the reaction time is 15-30min under constant voltage; after the electrolytic deposition is finished, washing with ionic water for 3-5min, and air-drying;
C. hole sealing treatment: putting silica sol and ferric hydroxide sol intoStirring the mixture by a magnetic stirrer for 1 to 3 hours at the rotating speed of 100 to 300 revolutions per minute for aging for 48 hours to obtain mixed sol; alpha-Al is reacted with 2 O 3 Adding the nano powder, calcium hydroxide, silicon carbide and a thickening agent into silica sol, and stirring uniformly by a magnetic stirrer at the rotating speed of 500 revolutions per minute for 1-3 hours to obtain a coating based on the silica sol; spraying the coating to Al 2 O 3 Sealing the coating, and drying to obtain SiO 2 And (4) coating. In the coating based on silica sol, the content of silica sol was 70%, the content of iron hydroxide sol was 10%, and α -Al 2 O 3 The content of the nano powder is 10 percent, the content of the calcium hydroxide is 5 percent, the content of the silicon carbide is 3 percent, and the content of the thickening agent is 2 percent.
Example 4:
Al 2 O 3 /SiO 2 the preparation steps of the composite coating are as follows:
A. plating an Al film by a vacuum coating technology: putting the film material and the cleaned substrate into a bell jar, mechanically pumping to a vacuum degree below 6Pa (about 10-15 min), pushing a low valve and heating a diffusion pump, opening a high valve to pump to a high vacuum degree after 45 min, wherein the vacuum degree can reach 6.7x10 after about 15 min -3 Pa. Opening an electron gun for preheating for 3 minutes, slowly adjusting a filament, preheating the film material by using small beam current of about 10mA until the film material turns red completely, and adjusting the working beam current to 80-120 mA. After 1 minute, evaporating the test piece for 30 to 50 minutes, closing the sub-gun, naturally cooling the test piece in the clock for 15 to 20 minutes, and then opening the clock to take out the test piece;
B. micro-arc oxidation: grinding the surface of the Al coating by using sand paper to remove surface covering materials, then finely grinding or polishing the surface of the Al coating to flatten the surface of the Al coating, and finally ultrasonically removing oil by using ethanol; taking Al as a cathode, taking a stainless steel sheet as an anode, placing the stainless steel sheet in the electrolyte in parallel, and performing micro-arc oxidation treatment by using a plasma micro-arc oxidation power supply; the electrolyte comprises the following chemical components in percentage by concentration: 8g/L of sodium silicate, 4mL/L of glycerol and 4g/L of sodium hexametaphosphate; the process parameters of the micro-arc oxidation treatment are as follows: pulse frequency of 50-100Hz, duty cycle of 60%, and current density of 6A/dm 2 The voltage is 500-800V, and the reaction time is 15-30min under constant voltage; after the electrolytic deposition is finished, the ion-exchange membrane is usedRinsing with water for 3-5min, and air drying;
C. hole sealing treatment: putting the silica sol and the ferric hydroxide sol into a beaker, stirring by a magnetic stirrer at the rotating speed of 100-300 r/min for 1-3h, and aging for 48 h to obtain mixed sol; alpha-Al is reacted with 2 O 3 Adding the nano powder, calcium hydroxide, silicon carbide and a thickening agent into silica sol, and stirring uniformly by a magnetic stirrer at the rotating speed of 500 revolutions per minute for 1-3 hours to obtain a coating based on the silica sol; spraying the coating to Al 2 O 3 Sealing the coating, and drying to obtain SiO 2 And (4) coating. In the coating based on silica sol, the content of silica sol is 60%, the content of iron hydroxide sol is 15%, and alpha-Al 2 O 3 The content of the nano powder is 15%, the content of the calcium hydroxide is 5%, the content of the silicon carbide is 3%, and the content of the thickening agent is 2%.
Claims (8)
1. Novel high-bonding-force high-temperature-resistant wear-resistant corrosion-resistant Al 2 O 3 /SiO 2 A composite coating, comprising: metallic or non-metallic material coated with Al coating, al 2 O 3 Ceramic coating and SiO 2 And (4) coating.
2. The high-binding-force, high-temperature-resistant, wear-resistant and corrosion-resistant novel Al as claimed in claim 1 2 O 3 /SiO 2 The preparation method of the composite coating is characterized by comprising the following steps:
step 1, preparing a metal aluminum coating on the surface of a clean matrix by a vapor deposition method;
step 2, processing the metallic aluminum coating obtained in the step 1 by a micro-arc oxidation technology to generate Al 2 O 3 A ceramic coating;
step 3, using silica sol slurry to the Al obtained in the step 2 through dip coating-curing process 2 O 3 Sealing the ceramic coating to form Al 2 O 3 /SiO 2 And (4) composite coating.
3. The high binding force high temperature resistant according to claim 2Novel wear-resistant and corrosion-resistant Al 2 O 3 /SiO 2 The preparation method of the composite coating is characterized in that in the step 1, the substrate is made of a metal material or a non-metal material, and the metal material comprises titanium alloy and stainless steel; the non-metallic material comprises carbon fiber and a high polymer material.
4. The high-bonding-force, high-temperature-resistant, wear-resistant and corrosion-resistant novel Al as claimed in claim 2 2 O 3 /SiO 2 The preparation method of the composite coating is characterized in that in the step 1, the vapor deposition method comprises a physical vapor deposition method and a chemical deposition method; the physical vapor deposition method includes vacuum coating, sputtering coating or ion coating.
5. The high-bonding-force, high-temperature-resistant, wear-resistant and corrosion-resistant novel Al as claimed in claim 2 2 O 3 /SiO 2 The preparation method of the composite coating is characterized in that in the step 1, the thickness of the metal aluminum coating is 10-500 mu m.
6. The high-bonding-force, high-temperature-resistant, wear-resistant and corrosion-resistant novel Al as claimed in claim 2 2 O 3 /SiO 2 The preparation method of the composite coating is characterized in that in the step 2, the Al is 2 O 3 The thickness of the ceramic coating is 10-2000 mu m, and the Al 2 O 3 The micro Vickers hardness of the surface of the ceramic coating is 700-1000HV.
7. The high-bonding-force, high-temperature-resistant, wear-resistant and corrosion-resistant novel Al as claimed in claim 2 2 O 3 /SiO 2 The preparation method of the composite coating is characterized in that in the step 3, the content of the silica sol in the silica sol slurry is 50-70%, the content of the ferric hydroxide sol is 10-20%, and the alpha-Al 2 O 3 The content of the nano powder is 10-20%, the content of the calcium hydroxide is 3-10%, the content of the silicon carbide is 2-5%, and the content of the thickening agent is 2-5%.
8. The method of claim 2High-binding-force high-temperature-resistant wear-resistant corrosion-resistant novel Al 2 O 3 /SiO 2 The preparation method of the composite coating is characterized in that in the step 3, the coating thickness of the silica sol slurry is controlled to be 20-90 mu m.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117586696A (en) * | 2024-01-18 | 2024-02-23 | 宁波卓翔科技有限公司 | Ceramic organic-inorganic composite high-temperature anticorrosive paint |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117586696A (en) * | 2024-01-18 | 2024-02-23 | 宁波卓翔科技有限公司 | Ceramic organic-inorganic composite high-temperature anticorrosive paint |
| CN117586696B (en) * | 2024-01-18 | 2024-04-26 | 宁波卓翔科技有限公司 | Ceramic organic-inorganic composite high-temperature anticorrosive paint |
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