CN109081698B - Method for preparing non-oxide ceramic through photocuring 3D printing - Google Patents

Method for preparing non-oxide ceramic through photocuring 3D printing Download PDF

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CN109081698B
CN109081698B CN201810813422.9A CN201810813422A CN109081698B CN 109081698 B CN109081698 B CN 109081698B CN 201810813422 A CN201810813422 A CN 201810813422A CN 109081698 B CN109081698 B CN 109081698B
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oxide
powder
photocuring
ceramic
oxide ceramic
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CN109081698A (en
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陈志伟
吴利翔
牛文彬
林锐霖
郭伟明
程艳玲
林华泰
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Guangdong University of Technology
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Abstract

The invention belongs to the technical field of ceramics, and discloses a method for preparing non-oxide ceramics by photocuring 3D printing. The method comprises the following specific steps: s1, uniformly paving non-oxide powder serving as a raw material into a powder layer; s2, introducing oxygen to exhaust gas in the furnace, heating the powder layer to 800-1400 ℃ in an oxidizing atmosphere to oxidize, and preserving heat to obtain powder particles A; s3, mixing the monomer, the oligomer, the photoinitiator, the photosensitizer, the sensitizer and the defoaming agent to obtain a premixed solution, mixing the powder particles A with the premixed solution to prepare ceramic slurry, and then carrying out photocuring molding to obtain a mixed material B; and S4, carrying out glue removal on the molded mixed material B, removing a resin part, and then sintering to obtain the non-oxide ceramic. The method is simple and convenient, and can oxidize large-batch silicon carbide powder. The compact oxide layer formed on the surface can improve the forming effect, can also improve the utilization rate of illumination, and is beneficial to the forming of photocuring.

Description

Method for preparing non-oxide ceramic through photocuring 3D printing
Technical Field
The invention belongs to the technical field of ceramics, and particularly relates to a method for preparing non-oxide ceramics by photocuring 3D printing.
Background
The non-oxide ceramic not only has excellent normal-temperature mechanical properties such as high bending strength, good corrosion resistance, high abrasion resistance and low friction coefficient, but also has good high-temperature mechanical properties (strength, creep resistance and the like). Wherein SiC and Si3N4、TiB2Etc. as non-oxide ceramic material with excellent performance in petroleum, chemical and micro industryThe method has wide application in the industrial fields of electronics, automobiles, aerospace, aviation, paper making, laser, mining, atomic energy and the like. Today, the additive manufacturing of non-oxide ceramics is also undoubtedly becoming hot. On the other hand, although non-oxide ceramics have superior properties compared to oxide ceramics, disadvantages are also evident, such as difficulty in sintering and difficulty in achieving additive manufacturing by photocuring techniques, etc. In particular, the technology still has defects in the aspect of photocuring and molding, and the defects are related to the physical properties of non-oxides.
The sintering problem of the non-oxide ceramics can be solved by equipment and a process method at present, but the problem of photocuring forming still has not been solved well. When the non-oxide ceramic powder is subjected to photocuring forming, the refractive index value of the non-oxide ceramic powder seriously influences the curing forming of the non-oxide, the larger the difference value between the refractive index of the non-oxide ceramic powder and the refractive index of the photosensitive resin is, the harder the non-oxide ceramic powder is to be formed, and the larger the refractive index difference value between the non-oxide ceramic powder and the photosensitive resin is, the larger the refractive index of the non-oxide ceramic powder is generally, and the larger the refractive index of the non-oxide ceramic powder is. Based on the above background and current situation, there is an urgent need for a new method to solve the problems of non-oxide photo-curing molding. The invention changes the surface composition of non-oxide powder to generate a layer of oxide film on the surface, thereby changing the physical property of the particle surface and overcoming the problems of difficult sintering, difficult printing and the like.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, the invention aims to provide a method for preparing non-oxide ceramics by photocuring 3D printing, which is used for oxidizing the surface of non-oxide powder, can oxidize silicon carbide powder in large batches, and is simple and convenient in oxidation method.
The purpose of the invention is realized by the following technical scheme:
a method for preparing non-oxide ceramic by photocuring 3D printing comprises the following specific steps:
s1, uniformly paving non-oxide powder serving as a raw material into a powder layer;
s2, introducing oxygen to exhaust gas in the furnace, heating the powder layer to 800-1400 ℃ in an oxidizing atmosphere to oxidize, and preserving heat to obtain non-oxide powder particles A with surfaces coated by oxides;
s3, mixing the monomer, the oligomer, the photoinitiator, the photosensitizer, the sensitizer and the defoaming agent to obtain a premixed solution, mixing the powder particles A with the premixed solution to prepare ceramic slurry, and then carrying out photocuring molding to obtain a mixed material B;
and S4, carrying out glue removal on the molded mixed material B, removing a resin part, and then sintering to obtain the non-oxide ceramic.
Preferably, the non-oxide powder in step S1 is Si3N4、SiC、AlN、TiB2Or ZrB2More than one of them.
Preferably, the particle size of the non-oxide powder in step S1 is 20nm to 10 μm, and the purity of the non-oxide powder is 98 to 100%.
Preferably, the thickness of the powder layer in step S1 is 0.1-100 mm.
Preferably, in the step S2, the temperature rising rate is 5-20 ℃/min, and the heat preservation time is 1-20 h.
Preferably, in the step S3, the powder particles a account for 20-60% of the mass of the ceramic slurry.
Preferably, the monomer in step S3 is one or more of hexanediol diacrylate, alkoxy acrylate, urethane diacrylate, urethane acrylate, urethane hexaacrylate, pentaerythritol acrylate, or tripropylene glycol diacrylate; the oligomer is more than one of acrylate, acrylamide or silane acrylate; the photoinitiator is more than one of (2,4, 6-trimethylbenzoyl) diphenyl phosphine oxide, phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, 2,4, 6-trimethylbenzoyl ethyl phosphate, bis (2, 6-difluoro-3-pyrrolyl phenyl ferrocene), 2-isopropyl thioxanthone, 4-phenylbenzophenone or 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinyl benzyl phenyl) butanone; the photosensitizer is more than one of m-tetrahydroxyphenyl chlorin, protoporphyrin tin, benzoporphyrin derivative monoacid, tolylene blue, phthalocyanine or N-asparaginyl chlorin; the sensitizer is more than one of aliphatic tertiary amine, ethanolamine tertiary amine, tertiary amine benzoate or acryloxy tertiary amine; the defoaming agent is more than one of basf-8034A, basf-NXZ or Pico-555.
Preferably, the mass ratio of the monomer to the oligomer to the photoinitiator to the photosensitizer to the sensitizer to the defoaming agent is (10-90): (10-90): (0.1-5): (0.1-5): (0.1-5): (0.1-5).
Preferably, the temperature of the binder removal in the step S4 is 450-500 ℃, the sintering temperature is 1700-2100 ℃, and the sintering time is 1-10 h.
The non-oxide ceramic prepared by the method.
The equipment of the invention can be used for small heat treatment furnaces such as common muffle furnaces, box furnaces, tube furnaces and the like. In addition, when the non-oxide powder is oxidized, the uniformity and the thickness of an oxide film can be ensured by controlling the oxidation time and the temperature. The refractive index of the oxide is smaller than that of the non-oxide, so that the difference between the refractive index of the oxide and that of the photosensitive resin can be reduced, the difference between the refractive indexes of the ceramic surface and that of the photosensitive resin can be reduced by forming the oxide layer on the surface of the non-oxide powder, the forming effect is improved, the color of the generated oxide is lighter than that of the non-oxide, the absorption of light is weaker, the utilization rate of illumination is improved in the photocuring process, and the photocuring forming is facilitated.
Compared with the prior art, the invention has the following beneficial effects:
1. the pre-oxidation of the non-oxide can be realized by a small heat treatment furnace such as a muffle furnace, a box furnace, a tube furnace and the like, the uniformity and the thickness of an oxide film can be ensured by controlling the oxidation time and the temperature, and the preparation of compact non-oxide ceramics with complex shapes can be realized;
2. the invention forms a compact oxide layer on the surface of the non-oxide, can improve the refractive index of the surface of the non-oxide ceramic, reduce the difference of the refractive indexes of the surface of the ceramic and the photosensitive resin and improve the forming effect;
3. the color of the oxide generated by the invention is lighter than that of the non-oxide, the absorption to light is weaker, the utilization rate of illumination can be improved in the photocuring process, and the photocuring forming is also facilitated.
Detailed Description
The following examples are presented to further illustrate the present invention and should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
1. Uniformly spreading SiC powder with the particle size of 100nm and the purity of 99 percent into a powder layer with the thickness of 5m m by taking the SiC powder with the uniform particle size as a raw material, and putting the powder layer into a heat treatment furnace for preparing oxidation; introducing oxygen to exhaust gas in the furnace, raising the temperature to 900 ℃ at the heating rate of 20 ℃/min, preserving the temperature for 5 hours, and continuously introducing oxygen in the oxidation process. Finally obtaining the surface coating SiO2Coated non-oxide powder particles a 1;
2. the preparation method comprises the following steps of (1) mixing a monomer hexanediol diacrylate, an oligomer acrylate, a photoinitiator (2,4, 6-trimethylbenzoyl) diphenyl phosphine oxide, a photosensitizer benzoporphyrin derivative monoacid, a sensitizer aliphatic tertiary amine and an antifoaming agent basf-8034A in a mass ratio of 20: 78: 0.5: 0.5: 0.5: 0.5 to obtain a premix B1,
3. mixing the oxidized powder particles A1 with sintering aid (Al)2O3-Y2O3) Then mixing the mixture with 40% of the premixed liquid B1 to prepare ceramic slurry C1, and then carrying out photocuring molding to prepare a mixed material D1;
4. and (3) carrying out glue removal at 450 ℃ on the molded mixed material D1, removing a resin part, and then carrying out heat preservation at 1900 ℃ for 2h for sintering to obtain the compact SiC ceramic, wherein the density of the compact SiC ceramic is higher than 95%.
The SiC ceramic has a hardness of 20GPa, a bending strength of 1000MPa and a fracture toughness of 10MPam1/2。
Example 2
1. Si with uniform particle size3N4Powder as raw material, Si3N4Uniformly spreading the powder with particle diameter of 1 μm and purity of 99% to obtain a powder layer with thickness of 10mm, heating to 900 deg.C at a temperature rise rate of 30 deg.C/min, maintaining for 8 hr for oxidation, and introducing oxygen continuously during oxidation to obtain SiO coated surface2Coated non-oxide powder particles a 2;
2. the preparation method comprises the following steps of (1) mixing a monomer hexanediol diacrylate, an oligomer acrylate, a photoinitiator (2,4, 6-trimethylbenzoyl) diphenyl phosphine oxide, a photosensitizer benzoporphyrin derivative monoacid, a sensitizer aliphatic tertiary amine and an antifoaming agent basf-8034A in a mass ratio of 20: 78: 0.5: 0.5: 0.5: 0.5, obtaining a premix B1;
3. preparing ceramic slurry C2 with the ceramic content accounting for 50% by adopting the method of the embodiment 1, and carrying out photocuring molding on the ceramic slurry to obtain a mixed material D2;
4. carrying out 500 ℃ glue removal on the molded mixed material D2, removing the resin part, then carrying out 1800 ℃ heat preservation for 2h sintering to obtain compact Si3N4The compactness of the ceramic is higher than 95%.
Si as above3N4The hardness of the ceramic is 18GPa, the bending strength is 1200MPa, and the fracture toughness is 12MPam1/2。
Example 3
1. AlN powder with uniform particle size is used as a raw material, the AlN powder has the particle size of 5 mu m and the purity of 99 percent, the AlN powder is uniformly paved into a powder layer with the thickness of 10mm, the temperature is raised to 800 ℃ at the heating rate of 10 ℃/min, the temperature is kept for 8 hours for oxidation, and SiO coated on the surface of the powder layer is obtained2Coated non-oxide powder particles a 3;
2. continuously introducing oxygen in the oxidation process, preparing ceramic slurry C3 with the ceramic content accounting for 60% by adopting the method in the embodiment 1, and carrying out photocuring molding on the ceramic slurry to obtain a mixed material D3;
3. and (3) carrying out 500 ℃ glue removal on the molded mixed material, removing a resin part, and then carrying out 1700 ℃ heat preservation for 2h for sintering to obtain compact AlN ceramic, wherein the density of the AlN ceramic is higher than 95%.
The obtained AlN ceramic has the hardness of 16GPa, the bending strength of 1000MPa and the fracture toughness of 8MPam1/2。
Example 4
1. TiB with uniform particle size2Powder as raw material, TiB2The powder with particle diameter of 1 μm and purity of 99% is uniformly spread into a powder layer with thickness of 10mm, heated to 900 deg.C at a heating rate of 10 deg.C/min, and maintained for 8h for oxidation to obtain SiO coated surface2Coated non-oxide powder particles a 4;
2. continuously introducing oxygen in the oxidation process, preparing ceramic slurry C4 with the ceramic content accounting for 40% by adopting the method in the embodiment 1, and carrying out photocuring molding on the ceramic slurry to obtain a mixed material D4;
3. removing glue at 500 ℃ from the formed mixed material D4, removing the resin part, and then carrying out heat preservation at 2000 ℃ for 2h for sintering to obtain compact TiB2The compactness of the ceramic is higher than 95%.
The resulting TiB2The hardness of the ceramic is 30GPa, the bending strength is 1000MPa, and the fracture toughness is 10MPam1/2。
Example 5
1. ZrB with uniform particle size2Powder as raw material ZrB2The powder has particle diameter of 5 μm and purity of 99%, and is uniformly spread into a powder layer with thickness of 10mm, heated to 1000 deg.C at a heating rate of 10 deg.C/min, and maintained for 8 hr for oxidation to obtain SiO coated surface2Coated non-oxide powder particles a 5;
2. continuously introducing oxygen in the oxidation process, preparing ceramic slurry C5 with the ceramic content of 45% by adopting the method in the embodiment 1, and carrying out photocuring molding on the ceramic slurry to obtain a mixed material D4;
3. carrying out 500 ℃ binder removal on the molded mixed material D4, removing resin parts, then carrying out 2100 ℃ heat preservation for 2h, and sintering to obtain compact ZrB2The compactness of the ceramic is higher than 95%.
ZrB2The hardness of the ceramic is 35GPa, the bending strength is 1200MPa, and the fracture toughness is 8MPam1/2。
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations and simplifications are intended to be included in the scope of the present invention.

Claims (4)

1. A method for preparing non-oxide ceramic through photocuring 3D printing is characterized by comprising the following specific steps:
s1, using non-oxide powder Si3N4、SiC、AlN、TiB2Or ZrB2More than one of them is used as raw material, and uniformly spread into powder layer;
s2, introducing oxygen to exhaust gas in the furnace, heating the powder layer to 800-1400 ℃ in an oxidizing atmosphere to oxidize, and preserving heat to obtain non-oxide powder particles A with oxide coated on the surface; the heating rate is 5-20 ℃/min, and the heat preservation time is 1-20 h;
s3, mixing the components in a mass ratio of 20: 78: 0.5: 0.5: 0.5: 0.5 of monomer, oligomer, photoinitiator, photosensitizer, sensitizer and defoamer are mixed to obtain premixed liquid, the powder particles A are mixed with the premixed liquid to prepare ceramic slurry, and then photocuring molding is carried out to obtain mixed material B; the monomer is hexanediol diacrylate, the oligomer is acrylate, the photoinitiator is (2,4, 6-trimethylbenzoyl) diphenyl phosphine oxide, the photosensitizer is benzoporphyrin derivative monoacid, the sensitizer is aliphatic tertiary amine, and the defoaming agent is basf-8034A; the powder particles A account for 20-60% of the mass of the ceramic slurry;
s4, removing glue from the molded mixed material B at 450-500 ℃, removing a resin part, and sintering at 1700-2100 ℃ for 1-10 hours to obtain non-oxide ceramic; the density of the non-oxide ceramic is higher than 95%.
2. The method for preparing non-oxide ceramic through photocuring 3D printing according to claim 1, wherein the particle size of the non-oxide powder in step S1 is 20nm to 10 μm, and the purity of the non-oxide powder is 98 to 100%.
3. The method for preparing non-oxide ceramic through photocuring 3D printing according to claim 1, wherein the thickness of the powder layer in the step S1 is 0.1-100 mm.
4. A non-oxide ceramic prepared according to the method of any one of claims 1-3.
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