CN114394826B - Manufacturing process of high-performance nano-material ceramic thin-film device - Google Patents
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Abstract
The invention relates to a manufacturing process of a high-performance nano-material ceramic film device, belonging to the technical field of nano-ceramic materials. The manufacturing process comprises the following steps: step one, treating an aluminum alloy base material; and step two, coating the ceramic coating on the surface of the treated aluminum alloy substrate, drying, curing and sintering to obtain the high-performance nano-material ceramic film device. The ceramic coating is prepared by mixing 23-45 parts by weight of silica sol emulsion and 85-100 parts by weight of solution B; the solution B comprises the following raw materials: water, a binder, phenyl trimethoxy siloxane and a functional auxiliary agent; the silica sol emulsion comprises the following raw materials: water, emulsifier, silica sol and auxiliary materials. The bonding strength of the ceramic coating and the base material is improved by introducing the binder and the auxiliary material, the brittle fracture of the ceramic coating during sintering is avoided by introducing the functional auxiliary agent, and the oxidation resistance, the high temperature resistance and the wear resistance of the ceramic film obtained by sintering are enhanced.
Description
Technical Field
The invention belongs to the technical field of nano ceramic materials, and particularly relates to a manufacturing process of a high-performance nano ceramic film device.
Background
The ceramic film is a ceramic material which is made by a special process technology and has the thickness of less than a few micrometers and can still maintain the excellent performance of the ceramic. Among them, ceramic films are commonly used for surface treatment of various parts to prolong the life of the parts, such as fasteners in the mechanical field, aluminum parts in semiconductor devices, and the like.
The preparation method of the ceramic film mainly comprises a chemical vapor deposition technology and a physical vapor deposition technology, wherein the chemical vapor deposition technology is to fill reaction gas into a high vacuum chamber, and the gas is adsorbed on the surface of a substrate to react to generate a film substance. The principle is to use chemical reaction between substances. However, the chemical vapor deposition technique must be carried out at high temperature, so that the selection of the substrate material must be a high-flame-point substance, which causes certain limitations in material selection. In contrast, the physical vapor deposition technology is simple, easy to control and widely applicable, such as evaporation coating, sputtering coating, ion coating, electrophoretic deposition, spraying and the like.
The traditional metal and metal ceramic film has good wear resistance, but has the following defects: the toughness of the film is poor, and the film is fragile and easy to crack. Inorganic ceramic films have been rapidly developed due to their excellent controllability, modifiability enhancement. Therefore, the inorganic ceramic film is used for replacing the metal ceramic film, and the problem of poor toughness of the metal ceramic film is solved.
Disclosure of Invention
The present invention is directed to a process for manufacturing high performance nano-material ceramic thin film devices to solve the problems mentioned in the background above.
The purpose of the invention can be realized by the following technical scheme:
the manufacturing process of the high-performance nano-material ceramic thin-film device comprises the following steps:
step one, treating an aluminum alloy base material: cleaning and drying the surface of an aluminum alloy base material, performing sand blasting treatment, removing sand scraps on the surface of the aluminum alloy base material by using high-pressure air, cleaning the surface of the aluminum alloy base material by using deionized water, completely removing the sand scraps on the surface of the base material, and drying to obtain the treated aluminum alloy base material, wherein the sand is corundum sand with 70-80 meshes as particles and the main component of the corundum sand is Al 2 O 3 ；
And step two, coating the ceramic coating on the surface of the treated aluminum alloy substrate, drying, curing and sintering to obtain the high-performance nano-material ceramic thin-film device, wherein the spraying thickness is 20-28 microns.
The aluminum alloy substrate is a template of a ceramic thin-film device, the application field of the ceramic thin-film device is determined by the forming of the aluminum alloy substrate, and the ceramic thin-film device is one of a fastener and an aluminum part in semiconductor equipment.
Further, drying and curing conditions in the second step: the drying temperature is 30-75 ℃, and the drying time is 8-17h.
Further, the conditions of sintering in step two: the sintering temperature is 200-500 ℃, and the sintering time is 2-4h.
Further, the ceramic coating is prepared by the following steps:
x1, uniformly stirring water, an emulsifier and silica sol at room temperature at 300-400r/min, then adding auxiliary materials, and continuously uniformly stirring to obtain silica sol emulsion;
x2, uniformly stirring water, a binder, phenyl trimethoxy siloxane and a functional auxiliary agent at room temperature and at 500-700r/min to obtain a solution B;
and X3, uniformly stirring the silica sol emulsion and the solution B at room temperature and 700-1000r/min to obtain the ceramic coating.
Further, the mass ratio of the silica sol emulsion to the solution B in the step X3 is 23-45:85-100.
Further, the mass ratio of water, the emulsifier, the silica sol and the auxiliary materials in the silica sol emulsion is 60-95:0.5-1.5:17-23:1.5-4.5.
Further, the mass ratio of water, the binder, the phenyl trimethoxy siloxane and the functional auxiliary agent in the solution B is 80-100:1.5-6.5:5.5-11.5:3.5-8.5.
Further, the auxiliary material is a combination of pigments and fillers in any ratio.
Further, the filler is one or a mixture of several of graphene, silicon whisker, bentonite and metal oxide in any ratio.
Further, the emulsifier is sodium lauryl sulfate.
Further, the binder is hydroxyethyl methyl cellulose and methyl cellulose, and the mass ratio of the hydroxyethyl methyl cellulose to the methyl cellulose is 1-3:1-3, mixing.
Further, the functional auxiliary agent is prepared by the following method:
s1, adding carborane and anhydrous tetrahydrofuran into a three-neck flask, introducing nitrogen to drive away air in the three-neck flask, dropwise adding n-butyllithium hexane solution by using a constant-pressure dropping funnel at 0 ℃ in a nitrogen atmosphere, ensuring that the temperature of a reaction system is kept at 0 +/-1 ℃ in the dropwise adding process, the dropwise adding speed is 1 drop/second, after the dropwise adding is completed, slowly heating to room temperature, continuing to stir for 2 hours, then adding benzyl trimethyl ammonium hydroxide methanol solution, stirring for 30 minutes at-0.07 MPa and 40 ℃, removing residual water and methanol in the system, then dropwise adding 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyl disiloxane anhydrous tetrahydrofuran solution by using the constant-pressure dropping funnel, the dropwise adding speed is 1-2 drops/second, after the dropwise adding is completed, slowly heating for reflux reaction for 12 hours, after the reaction is completed, removing tetrahydrofuran by rotary evaporation, extracting for 3 times by using diethyl ether, then washing for 3-5 times by using deionized water, drying the anhydrous magnesium sulfate by filtration, distilling under reduced pressure to obtain carborane, wherein the ratio of benzyl amino silicon carbonate to 3532-n-trimethyl ammonium hydroxide is 3532-aminopropyl-3532: 2.1-2.3:2.1-2.3:2.1-2.3;
in the reaction, firstly, carborane reacts with n-butyllithium to generate dilithium salt of carborane, and then the dilithium salt reacts with 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane to obtain amino-terminated silacarborane;
s2, mixing hydrogen-containing POSS and anhydrous tetrahydrofuran, adding chloroplatinic acid, slowly dropwise adding an acrylic tetrahydrofuran solution by using a constant-pressure funnel at a dropping speed of 1 drop/second, reacting at 60-90 ℃ for 24 hours, performing rotary evaporation, and performing vacuum drying to constant weight to obtain dicarboxy POSS, wherein the molar ratio of the hydrogen-containing POSS to the acrylic acid is 1.1-1.3:4, the mass of the chloroplatinic acid is 8-15% of that of the allyl alcohol;
in the reaction, hydrogen-containing POSS and acrylic acid are reacted under the action of a chloroplatinic acid catalyst, and carboxyl is introduced into the POSS structure by the addition reaction of double bonds;
s3, adding dicarboxyl POSS and DMF (dimethyl formamide) into a three-neck flask with a condensation reflux pipe and a stirring magneton, dropwise adding thionyl chloride by using a constant-pressure dropping funnel under the stirring state, wherein the dropwise adding speed is 1 drop/second, continuously stirring for 30min after dropping is finished, then heating to 78 ℃, stirring for reacting for 2h to obtain chloracylated POSS, performing chloracylation on carboxyl in the dicarboxyl POSS by using the thionyl chloride, wherein the dosage ratio of the dicarboxyl POSS to the DMF to the thionyl chloride is 0.5mol:30-80mL:1.1-1.3mol; adding amino-terminated silicon carborane, triethylamine and dichloromethane into a condensation reflux pipe and a stirring magneton three-neck flask, dripping dichloromethane solution of chloridized POSS by using a constant-pressure dropping funnel at the temperature of 0-4 ℃ in a stirring state, wherein the dripping speed is 1 drop/second, continuously stirring for 30min after complete dripping, naturally heating to room temperature, heating and refluxing for reaction for 5h by using an oil bath pot, decompressing and rotationally steaming at the temperature of 50 ℃ to remove a solvent, recrystallizing by using acetone to obtain a functional auxiliary agent, and utilizing the reaction of acyl chloride and amino in the chloridized POSS, wherein the dosage ratio of the amino-terminated silicon carborane, the triethylamine, the dichloromethane and the chloridized POSS is 0.1mol:0.1-0.15mol:50-100mL:0.11-0.13mol.
In the reaction, firstly, thionyl chloride is utilized to chloridize dicarboxy POSS, and then acyl chloride in the chloridized POSS and amino in the amino-terminated silaborane are utilized to carry out polymerization reaction to obtain the functional auxiliary agent, so that the functional auxiliary agent contains the silaborane and the POSS structure.
The invention has the beneficial effects that:
the ceramic coating is coated on the surface of a treated aluminum alloy substrate, and is dried, cured and sintered to obtain a high-performance nano-material ceramic thin-film device, the high-performance nano-material ceramic thin-film device takes the aluminum alloy substrate as a template and can be applied to fasteners and semiconductor equipment, the ceramic coating is prepared by mixing water, an emulsifier, silica sol, an auxiliary material, a binder, phenyltrimethoxy siloxane and a functional auxiliary agent, the bonding strength of the ceramic coating and the substrate is improved by introducing the binder and the auxiliary material, and the cracking of the ceramic coating in the sintering process is reduced by filling the auxiliary material; the high-temperature resistance and the wear resistance of the ceramic film obtained by sintering are enhanced by introducing the functional auxiliary agent, and finally the high-temperature resistance and the wear resistance of a corresponding device are enhanced; the functional auxiliary agent is a polymer containing carborane and POSS structures, the brittle fracture of the ceramic coating during sintering is avoided by utilizing the high-temperature stability and the elastic property of carborane, and the POSS structure is introduced into a carborane chain, so that on one hand, a silicon-oxygen bond of the POSS structure is utilized to promote the formation of hydrogen bonds between the functional auxiliary agent and silica sol and phenyltrimethoxy siloxane, and the compatibility of the functional auxiliary agent and silica sol and phenyltrimethoxy siloxane is enhanced, on the other hand, the nano-structure characteristic of the POSS structure is utilized, the functional auxiliary agent exists in a nano structure in the subsequent sintering process, the sintering by-product is less generated, the obtained ceramic coating is more compact, and the hardness and the wear resistance of the ceramic film are improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
preparation of hydrogen-containing POSS:
a1, uniformly stirring 100mL of isopropanol, 0.12mol of phenyltrimethoxysilane, 2mg of deionized water and 0.1mol of flaky sodium hydroxide, heating a reaction system to 73 ℃ by using an oil bath pot, carrying out reflux reaction for 5 hours under the nitrogen atmosphere, then stirring for reaction for 48 hours at normal temperature, removing the isopropanol from the obtained mixed solution through rotary evaporation, and carrying out vacuum drying for 18 hours at 60 ℃ to obtain octaphenyl polysilsesquioxane sodium salt;
a2, adding 0.1mol of octaphenyl polysilsesquioxane sodium salt into a three-neck flask, adding 150mL of anhydrous tetrahydrofuran under the protection of nitrogen, stirring uniformly, adding 0.21mol of triethylamine, reacting for 1h at 0 ℃ in an ice bath, slowly dropwise adding 70mL of tetrahydrofuran solution containing 0.25mol of methyl dichlorosilane by using a constant-pressure funnel at the dropping speed of 2 drops/second, reacting for 6h, then raising the temperature to room temperature, reacting for 12h, filtering after the reaction is finished, spin-drying the filtrate, separating by using a column (the volume ratio of dichloromethane to petroleum ether is 1:2), and vacuum-drying to constant weight to obtain the hydrogen-containing POSS.
Example 2:
the functional auxiliary agent is prepared by the following method:
s1, adding 1mol of carborane and 100mL of anhydrous tetrahydrofuran into a three-neck flask, introducing nitrogen to drive away air in the three-neck flask, dropwise adding 2.1mol of n-butyl lithium hexane solution by using a constant-pressure dropping funnel at 0 ℃, ensuring that the temperature of a reaction system is kept at 0 +/-1 ℃ in the dropwise adding process, the dropwise adding speed is 1 drop/second, after the dropwise adding is completed, slowly heating to room temperature, continuously stirring for reaction for 2 hours, then adding 80mL of anhydrous tetrahydrofuran solution containing 2.1mol of benzyl trimethyl ammonium hydroxide, stirring for 30 minutes at-0.07 MPa and 40 ℃, removing residual water and methanol in the system, then dropwise adding 2.1mol of 1, 3-bis (3-aminopropyl) -1,1,3,3-tetramethyl disiloxane by using the constant-pressure dropping funnel, the dropwise adding speed is 1 drop/second, after the dropwise adding is completed, slowly heating for reflux reaction for 12 hours, after the reaction is completed, performing rotary evaporation to remove the tetrahydrofuran, extracting 3 times by using 100mL of diethyl ether, then washing 3 times by using 100mL of deionized water, filtering 10g of distilled water, removing anhydrous magnesium sulfate, and drying to obtain anhydrous silicon dioxide, thereby obtaining anhydrous silicon dioxide and obtaining silicon dioxide;
s2, mixing 0.11mol of hydrogen-containing POSS prepared in the example 1 with 60mL of anhydrous tetrahydrofuran, adding chloroplatinic acid with the mass of 8% of that of the propenol, slowly dropwise adding 60mL of tetrahydrofuran solution containing 0.4mol of acrylic acid by using a constant-pressure funnel at the dropping speed of 1 drop/second, reacting at the temperature of 60 ℃ for 24 hours, performing rotary evaporation, and performing vacuum drying to constant weight to obtain dicarboxy POSS;
s3, adding 0.5mol of dicarboxyl POSS and 30mL of DMF (dimethyl formamide) into a three-neck flask with a condensation reflux pipe and a stirring magneton, dropwise adding 1.1mol of thionyl chloride by using a constant-pressure dropping funnel under the stirring state, wherein the dropwise adding speed is 1 drop/second, continuously stirring for 30min after the dropwise adding is finished, heating to 78 ℃, and stirring for reacting for 2h to obtain the chloracylation POSS; adding 0.1mol of amino silicon carborane, 0.1mol of triethylamine and 50mL of dichloromethane into a condensation reflux pipe and a stirring magneton three-neck flask, dropwise adding 50mL of dichloromethane solution containing 0.11mol of chloric acylation POSS by using a constant pressure dropping funnel under the stirring state and the temperature of 0 ℃, wherein the dropwise adding speed is 1 drop/second, continuously stirring for 30min after the dropwise adding is completed, naturally heating to room temperature, heating and refluxing for reaction for 5h by using an oil bath kettle, removing the solvent by decompression rotary evaporation at the temperature of 50 ℃, and recrystallizing by using 100mL of acetone to obtain the functional auxiliary agent.
Example 3:
the functional auxiliary agent is prepared by the following method:
s1, adding 1mol of carborane and 100mL of anhydrous tetrahydrofuran into a three-neck flask, introducing nitrogen to drive away air in the three-neck flask, dropwise adding 2.3mol of n-butyl lithium hexane solution by using a constant-pressure dropping funnel at 0 ℃ under the nitrogen atmosphere, ensuring that the temperature of a reaction system is kept at 0 +/-1 ℃ in the dropwise adding process, keeping the dropwise adding speed at 1 drop/second, after the dropwise adding is completed, slowly heating to room temperature, continuously stirring for 2 hours, then adding an anhydrous tetrahydrofuran solution containing 2.3mol of benzyltrimethyl ammonium hydroxide methanol solution, stirring for 30 minutes at-0.07 MPa and 40 ℃, removing residual water and methanol in the system, then dropwise adding 90mL of anhydrous tetrahydrofuran solution containing 2.3mol of 1, 3-bis (3-aminopropyl) -1,1,3,3-tetramethyl disiloxane by using a constant-pressure dropping funnel, keeping the dropwise adding speed at 2 drops/second, after the dropwise adding is completed, slowly heating for reflux reaction for 12 hours, after the reaction is completed, performing rotary evaporation to remove the tetrahydrofuran, extracting for 3 times by using diethyl ether, then washing 5 times by using 100mL of deionized water, filtering to remove anhydrous magnesium sulfate, and obtaining anhydrous silicon sulfate, and filtering the anhydrous magnesium sulfate, thus obtaining the anhydrous carborane;
s2, mixing 13mol of the hydrogen-containing POSS prepared in the example 1 with 50mL of anhydrous tetrahydrofuran, adding chloroplatinic acid with the mass of 15% of that of the allyl alcohol, slowly dropwise adding 80mL of tetrahydrofuran solution containing 0.4mol of acrylic acid by using a constant-pressure funnel at the dropping speed of 1 drop/second, reacting at 90 ℃ for 24 hours, performing rotary evaporation, and performing vacuum drying to constant weight to obtain dicarboxyl POSS;
s3, adding 0.5mol of dicarboxyl POSS and 80mL of DMF (dimethyl formamide) into a three-neck flask with a condensation reflux pipe and a stirring magneton, dropwise adding 1.3mol of thionyl chloride by using a constant-pressure dropping funnel under the stirring state, wherein the dropwise adding speed is 1 drop/second, continuously stirring for 30min after the dropwise adding is finished, heating to 78 ℃, and stirring for reacting for 2h to obtain chloracylated POSS; adding 0.1mol of amino silicon carborane, 0.15mol of triethylamine and 100mL of dichloromethane into a condensation reflux pipe and a stirring magneton three-neck flask, dropwise adding 50mL of dichloromethane solution containing 0.13mol of chloric acylation POSS by using a constant-pressure dropping funnel under the stirring state and at the temperature of 4 ℃, wherein the dropwise adding speed is 1 drop/second, continuously stirring for 30min after the dropwise adding is completed, naturally heating to room temperature, heating and refluxing for reaction for 5h by using an oil bath kettle, removing the solvent by decompression rotary evaporation at the temperature of 50 ℃, and recrystallizing by using 100mL of acetone to obtain the functional auxiliary agent.
Example 4:
the ceramic coating is prepared by the following steps:
x1, uniformly stirring 60g of water, 0.5g of emulsifier and 17g of silica sol at room temperature at 300r/min, then adding 1.5g of auxiliary materials, and continuously uniformly stirring to obtain the silica sol emulsion, wherein the auxiliary materials are pigments and fillers according to a mass ratio of 1:1, wherein the filler is silicon whisker, bentonite and alumina according to a mass ratio of 0.2:1:0.7, and the emulsifier is sodium dodecyl sulfate;
and X2, uniformly stirring 80g of water, 1.5g of binder, 5.5g of phenyl trimethoxy siloxane and 3.5g of functional auxiliary agent prepared in example 2 at room temperature and 500r/min to obtain a solution B, wherein the binder is hydroxyethyl methyl cellulose and methyl cellulose according to the mass ratio of 1:1, mixing;
and X3, stirring 23g of silica sol emulsion and 85g of solution B uniformly at room temperature and 700r/min to obtain the ceramic coating.
Example 5:
the ceramic coating is prepared by the following steps:
x1, stirring 85g of water, 1g of emulsifier and 20g of silica sol uniformly at room temperature at 300r/min, then adding 3g of auxiliary material, and continuously stirring uniformly to obtain the silica sol emulsion, wherein the auxiliary material is a filler, and the filler is graphene, bentonite, alumina and manganese oxide according to a mass ratio of 1:1:1:1, and the emulsifier is sodium dodecyl sulfate.
And X2, uniformly stirring 90g of water, 4g of binder, 8g of phenyl trimethoxy siloxane and 6g of functional auxiliary agent prepared in example 3 at room temperature and 600r/min to obtain a solution B, wherein the binder is hydroxyethyl methyl cellulose and methyl cellulose in a mass ratio of 2:3, mixing;
and X3, uniformly stirring 30g of silica sol emulsion and 90g of solution B at room temperature at 800r/min to obtain the ceramic coating.
Example 6:
the ceramic coating is prepared by the following steps:
x1, uniformly stirring 95g of water, 1.5g of emulsifier and 23g of silica sol at room temperature at 400r/min, then adding 4.5g of auxiliary material, and continuously uniformly stirring to obtain the silica sol emulsion, wherein the auxiliary material is a filler, and the filler is silicon whisker, aluminum oxide, manganese oxide and vanadium oxide according to a mass ratio of 1:1:1:1, and the emulsifier is sodium dodecyl sulfate.
And X2, uniformly stirring 100g of water, 6.5g of binder, 11.5g of phenyl trimethoxy siloxane and 8.5g of functional auxiliary agent prepared in example 2 at room temperature and 700r/min to obtain a solution B, wherein the binder is hydroxyethyl methyl cellulose and methyl cellulose according to the mass ratio of 3:1, mixing;
and X3, uniformly stirring 45g of silica sol emulsion and 100g of solution B at room temperature under 1000r/min to obtain the ceramic coating.
Example 7:
the high-performance nano-material ceramic thin-film device is prepared by the following steps:
step one, treating an aluminum alloy base material: cleaning and drying the surface of an aluminum alloy base material, performing sand blasting treatment, removing sand scraps on the surface of the aluminum alloy base material by using high-pressure air, cleaning the surface of the aluminum alloy base material by using deionized water, completely removing the sand scraps on the surface of the base material, and drying to obtain the treated aluminum alloy base material, wherein the sand is corundum sand with 70 meshes in particle size and mainly comprises Al 2 O 3 ；
And step two, coating the ceramic coating prepared in the embodiment 4 on the surface of the treated aluminum alloy substrate, drying and curing for 17h at 30 ℃, and then sintering for 4h at 200 ℃ to obtain the high-performance nano-material ceramic thin-film device, wherein the spraying thickness is 20 microns.
Example 8:
the high-performance nano-material ceramic thin-film device is prepared by the following steps:
step one, treating an aluminum alloy base material: cleaning and drying the surface of an aluminum alloy base material, performing sand blasting treatment, removing sand scraps on the surface of the aluminum alloy base material by using high-pressure air, cleaning the surface of the aluminum alloy base material by using deionized water, completely removing the sand scraps on the surface of the base material, and drying to obtain the treated aluminum alloy base material, wherein the used sand is corundum with 75 meshes, and the main component of the corundum is Al 2 O 3 ；
And step two, coating the ceramic coating prepared in the embodiment 5 on the surface of the treated aluminum alloy substrate, drying and curing at 55 ℃ for 13h, and then sintering at 400 ℃ for 3h to obtain the high-performance nano-material ceramic thin-film device, wherein the spraying thickness is 28 microns.
Example 9:
the high-performance nano-material ceramic thin-film device is prepared by the following steps:
step one, treating an aluminum alloy base material: cleaning and drying the surface of an aluminum alloy base material, performing sand blasting treatment, removing sand scraps on the surface of the aluminum alloy base material by using high-pressure air, cleaning the surface of the aluminum alloy base material by using deionized water, completely removing the sand scraps on the surface of the base material, and drying to obtain the treated aluminum alloy base material, wherein the sand is corundum sand with 80-mesh particles and the main component of the corundum sand is Al 2 O 3 ；
And step two, coating the ceramic coating prepared in the embodiment 6 on the surface of the treated aluminum alloy substrate, drying and curing at 75 ℃ for 8h, and then sintering at 500 ℃ for 2h to obtain the high-performance nano-material ceramic thin-film device, wherein the spraying thickness is 28 microns.
Comparative example 1:
the functional assistant is amino terminated silaborane prepared in step S1 of example 2.
Comparative example 2:
the functional adjuvant was the hydrogen-containing POSS prepared in example 1.
Comparative example 3:
the ceramic coating is prepared by the following steps: compared with example 2, the functional assistant is prepared in comparative example 1, and the rest is the same.
Comparative example 4:
the ceramic coating is prepared by the following steps: in comparison with example 3, the functional aid was prepared in comparative example 1, and the rest was the same.
Comparative example 5:
the high-performance nano-material ceramic thin-film device is prepared by the following steps: in comparison to example 7, a ceramic coating was prepared as in comparative example 4.
Comparative example 6:
the high-performance nano-material ceramic thin-film device is prepared by the following steps: in comparison to example 8, a ceramic coating was prepared as in comparative example 5.
Example 10:
the ceramic thin film devices obtained in examples 7 to 9 and comparative examples 5 to 6 were subjected to the following performance tests:
and (3) testing the adhesive force: testing according to GB/T5210-2006 standard (cross-cut method);
flexibility test: testing according to GB/T1731-2020 standard;
impact resistance test: testing according to GB/T1732-2020 standard;
and (3) testing hardness: testing according to GB/T6739-2006 standard;
liquid medium resistance test: testing according to GB/T9274-1998 standard;
the above test data are shown in table 1.
TABLE 1
As can be seen from the above data, the adhesion, flexibility, impact resistance and liquid medium resistance of the ceramic thin film devices obtained in examples 7 to 9 are significantly superior to those of the ceramic thin film devices obtained in comparative examples 5 to 6, indicating that the ceramic thin film devices obtained in the present invention have excellent flexibility, impact resistance and liquid medium resistance.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (8)
1. The manufacturing process of the high-performance nano-material ceramic thin-film device is characterized by comprising the following steps of: the method comprises the following steps:
step one, processing an aluminum alloy base material;
coating the ceramic coating on the surface of the treated aluminum alloy substrate, drying, curing and sintering to obtain a high-performance nano-material ceramic thin-film device;
the ceramic coating is prepared by mixing 23-45 parts by weight of silica sol emulsion and 85-100 parts by weight of solution B; the solution B comprises the following raw materials: water, a binder, phenyl trimethoxy siloxane and a functional auxiliary agent;
the functional auxiliary agent is prepared by the following method:
after mixing dicarboxyl POSS and DMF, dropwise adding thionyl chloride under the stirring state, continuously stirring for 30min after dropwise adding, then heating to 78 ℃, and stirring for reacting for 2h to obtain chloridized POSS; and (2) mixing amino-terminated silacarborane, triethylamine and dichloromethane, dropwise adding a dichloromethane solution of chlorinoylated POSS under the stirring state at 0-4 ℃, continuously stirring for 30min after completely dropwise adding, heating to room temperature, carrying out reflux reaction for 5h, carrying out rotary evaporation, and recrystallizing to obtain the functional auxiliary agent.
2. The manufacturing process of the high-performance nano-material ceramic thin-film device according to claim 1, characterized in that: in the second step, the spraying thickness is 20-28 μm, and the drying and curing conditions are as follows: the drying temperature is 30-75 ℃, and the drying time is 8-17h.
3. The manufacturing process of the high-performance nano-material ceramic thin-film device according to claim 1, characterized in that: sintering conditions in the second step: the sintering temperature is 200-500 ℃, and the sintering time is 2-4h.
4. The manufacturing process of the high-performance nano-material ceramic thin film device according to claim 1, wherein: the dosage ratio of the dicarboxyl POSS to the DMF to the thionyl chloride is 0.5mol:30-80mL:1.1-1.3mol; the dosage ratio of the amino-terminated carborane to the triethylamine to the dichloromethane to the chloric acylated POSS is 0.1mol:0.1-0.15mol:50-100mL:0.11-0.13mol.
5. The manufacturing process of the high-performance nano-material ceramic thin-film device according to claim 1, characterized in that: the silica sol emulsion comprises the following raw materials in parts by weight: 60-95 parts of water, 0.5-1.5 parts of emulsifier, 17-23 parts of silica sol and 1.5-4.5 parts of auxiliary material.
6. The manufacturing process of the high-performance nano-material ceramic thin-film device according to claim 1, characterized in that: the solution B comprises the following raw materials in parts by weight: 80-100 parts of water, 1.5-6.5 parts of binder, 5.5-11.5 parts of phenyl trimethoxy siloxane and 3.5-8.5 parts of functional auxiliary agent.
7. The manufacturing process of the high-performance nano-material ceramic thin-film device according to claim 6, wherein: the amino-terminated silaborane is prepared by the following steps:
after carborane and anhydrous tetrahydrofuran are mixed, n-butyl lithium hexane solution is dripped at 0 ℃ in a nitrogen atmosphere, after the dripping is completely finished, the temperature is slowly increased to room temperature, the reaction is continuously stirred for 2 hours, then benzyl trimethyl ammonium hydroxide methanol solution is added, the reaction is stirred for 30 minutes at 40 ℃ under the pressure of minus 0.07MPa, then 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyl disiloxane anhydrous tetrahydrofuran solution is dripped, after the dripping is completely finished, the reflux reaction is carried out for 12 hours, and after the reaction is finished, rotary evaporation, extraction, washing, anhydrous magnesium sulfate drying, filtering and reduced pressure distillation are carried out, so that the amino-terminated carborane is obtained.
8. The manufacturing process of the high-performance nano-material ceramic thin-film device according to claim 7, wherein: the molar ratio of carborane, n-butyl lithium, benzyl trimethyl ammonium hydroxide, 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane is 1:2.1-2.3:2.1-2.3:2.1-2.3.
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