High-precision nitride ceramic material and 3D printing method thereof

Abstract

The invention relates to the technical field of 3D printing, in particular to a high-precision nitride ceramic material and a 3D printing method thereof.The high-precision nitride ceramic material is prepared from, by weight, 60-100 parts of ceramic powder, 0.1-10 parts of a sintering aid, 0.1-10 parts of a coloring agent, 15-30 parts of photosensitive resin, 0.1-2 parts of a dispersing agent, 0.1-10 parts of a plasticizer and 0.1-2 parts of a photoinitiator. According to the high-precision nitride ceramic material, the coloring agent is added, absorption and scattering of a printing blank are regulated and controlled in the printing process, then the printing precision is improved, and finally the high-precision ceramic material is obtained through sintering.

Description

Technical Field

[0001] The present invention relates to the technical field of 3D printing, and in particular to a high-precision nitride ceramic material and a 3D printing method thereof. Background Art

[0002] Stereolithography is widely used in ceramic additive manufacturing due to its high precision, good surface quality and ability to print high-performance ceramic parts. However, due to the scattering between the light source and the ceramic powder in the stereolithography technology, the molding accuracy of ceramic parts is greatly reduced, limiting the wide application of ceramic parts in fine fields. Summary of the invention

[0003] In order to overcome the shortcomings and deficiencies in the prior art, an object of the present invention is to provide a high-precision nitride ceramic material and a 3D printing method thereof.

[0004] The purpose of the present invention is achieved through the following technical scheme: a high-precision nitride ceramic material, comprising the following raw materials in parts by weight: 60-100 parts of ceramic powder, 0.1-10 parts of sintering aid, 0.1-10 parts of colorant, 15-30 parts of photosensitive resin, 0.1-2 parts of dispersant, 0.1-10 parts of plasticizer, and 0.1-2 parts of photoinitiator.

[0005] Preferably, the ceramic powder is at least one of silicon nitride and aluminum nitride, and the particle size of the ceramic powder is 0.1-5 microns.

[0006] Preferably, the sintering aid is at least one of magnesium silicon nitride, magnesium oxide, aluminum oxide and yttrium oxide, and the particle size of the sintering aid is 0.1-1 micron.

[0007] Preferably, the colorant is at least one of iron oxide, copper oxide, erbium oxide, holmium oxide, neodymium oxide, praseodymium oxide, samarium oxide, cerium oxide and terbium oxide, and the particle size of the colorant is 0.1-10 microns.

[0008] Preferably, the photosensitive resin is at least one of ethoxy pentaerythritol tetraacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, o-phenylphenoxyethyl acrylate and 2-phenoxyethyl acrylate.

[0009] Preferably, the plasticizer is at least one of dioctyl phthalate, dibutyl phthalate, tributyl citrate, trioctyl citrate and polyethylene glycol.

[0010] The photoinitiator is at least one of 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio)phenyl]-1-propanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphonic acid ethyl ester, 2-dimethylamino-2-benzyl-1-[4-(4-morpholinyl)phenyl]-1-butanone, and 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone.

[0011] The dispersant is at least one of γ-methacryloxypropyltrimethoxysilane, aluminate coupling agent, γ-aminopropyltriethoxysilane, ester-based quaternary ammonium salt and polyethylene glycol octylphenyl ether.

[0012] A 3D printing method for high-precision nitride ceramic materials comprises the following steps:

[0013] (1) First, ceramic powder and sintering aid are added with an appropriate amount of anhydrous ethanol and silicon nitride grinding balls, and ball milled at a speed of 300-400 rpm for 3-6 hours; after ball milling, the dried ceramic powder is dried by a rotary evaporator and passed through a 50-150 mesh sieve;

[0014] (2) Subsequently, the photosensitive resin and the plasticizer are uniformly mixed by ultrasonication to prepare a photocurable resin; a ceramic slurry with a solid content of 75-85 wt % is prepared by high-speed ball milling with the photocurable resin, colorant, dispersant, photoinitiator and ceramic powder as raw materials, the ball milling speed is 1000-2000 rpm, and the ball milling time is 3-7 min;

[0015] (3) adding the prepared ceramic slurry into a light-curing 3D printer and importing the model information of the ceramic device; selecting appropriate printing parameters to obtain a green body of the ceramic device;

[0016] (4) The above-mentioned ceramic device green body is subjected to degreasing and sintering treatment to obtain a high-precision nitride ceramic material.

[0017] Preferably, in step (3), the printing parameters are: laser power is 10-60 mW / cm 2 , the printing layer thickness is 10-100μm, and the exposure time of each layer is 1-30s.

[0018] Preferably, in step (4), degreasing is carried out in two steps: vacuum degreasing and air degreasing. The vacuum degreasing temperature is 400-800°C and the temperature is kept for 1-5 hours. The air degreasing temperature is 400-800°C and the temperature is kept for 1-5 hours.

[0019] Preferably, in step (4), the degreased parts are subjected to gas pressure sintering, the temperature is raised to 1700-1900° C. at a rate of 5-15° C. / min in a nitrogen atmosphere, and the temperature is maintained for 1-6 hours, and the sintering pressure is 1-5 MPa.

[0020] The beneficial effect of the present invention is that the high-precision nitride ceramic material of the present invention adjusts the absorption and scattering of the printed body during the printing process by adding a colorant, thereby improving the printing accuracy, and finally obtaining a high-precision ceramic material through sintering. DETAILED DESCRIPTION

[0021] In order to facilitate the understanding of those skilled in the art, the present invention is further described below in conjunction with embodiments, and the contents mentioned in the implementation modes are not intended to limit the present invention.

[0022] Example 1

[0023] A high-precision nitride ceramic material comprises the following raw materials in parts by weight: 60 parts of ceramic powder, 1 part of sintering aid, 1 part of colorant, 15 parts of photosensitive resin, 0.1 part of dispersant, 1 part of plasticizer, and 0.1 part of photoinitiator.

[0024] The ceramic powder is silicon nitride with a particle size of 0.1 micron.

[0025] The sintering aid is magnesium silicon nitride with a particle size of 0.1 micron.

[0026] The colorant is iron oxide with a particle size of 0.1 micron.

[0027] The photosensitive resin is trimethylolpropane triacrylate.

[0028] The plasticizer is dibutyl phthalate.

[0029] The photoinitiator is 2-hydroxy-2-methyl-1-phenylpropanone.

[0030] The dispersant is γ-methacryloxypropyltrimethoxysilane.

[0031] A 3D printing method for high-precision nitride ceramic materials comprises the following steps:

[0032] (1) First, ceramic powder and sintering aid are added with an appropriate amount of anhydrous ethanol and silicon nitride grinding balls, and ball milled at a speed of 300 rpm for 3 hours; after ball milling, the dried ceramic powder is dried by a rotary evaporator and passed through a 50-mesh sieve;

[0033] (2) Subsequently, the photosensitive resin and the plasticizer are uniformly mixed by ultrasonic mixing to prepare a photocurable resin; a ceramic slurry with a solid content of 75 wt% is prepared by high-speed ball milling using the photocurable resin, colorant, dispersant, photoinitiator and ceramic powder as raw materials, with the ball milling speed of 1000 rpm and the ball milling time of 7 minutes;

[0034] (3) adding the prepared ceramic slurry into a light-curing 3D printer and importing the model information of the ceramic device; selecting appropriate printing parameters to obtain a green body of the ceramic device;

[0035] (4) The above-mentioned ceramic device green body is subjected to degreasing and sintering treatment to obtain a high-precision nitride ceramic material.

[0036] In step (3), the printing parameters are: laser power is 10 mW / cm 2 , the printing layer thickness is 10μm, and the exposure time for each layer is 30s.

[0037] In the step (4), degreasing is carried out in two steps: vacuum degreasing and air degreasing. The vacuum degreasing temperature is 400° C. and the temperature is kept at 400° C. for 5 hours. The air degreasing temperature is 400° C. and the temperature is kept at 5 hours.

[0038] In the step (4), the degreased parts are subjected to gas pressure sintering, the temperature is raised to 1700° C. at a rate of 10° C. / min in a nitrogen atmosphere, and the temperature is kept for 6 hours, and the sintering pressure is 5 MPa.

[0039] Example 2

[0040] A high-precision nitride ceramic material comprises the following raw materials in parts by weight: 80 parts of ceramic powder, 3 parts of sintering aid, 3 parts of colorant, 18 parts of photosensitive resin, 0.5 parts of dispersant, 3 parts of plasticizer, and 0.5 parts of photoinitiator.

[0041] The ceramic powder is aluminum nitride with a particle size of 0.5 microns.

[0042] The sintering aid is magnesium oxide with a particle size of 0.3 microns.

[0043] The colorant is copper oxide with a particle size of 1 micron.

[0044] The photosensitive resin is o-phenylphenoxyethyl acrylate.

[0045] The plasticizer is tributyl citrate.

[0046] The photoinitiator is 1-hydroxycyclohexyl phenyl ketone.

[0047] The dispersant is an aluminate coupling agent.

[0048] A 3D printing method for high-precision nitride ceramic materials comprises the following steps:

[0049] (1) First, ceramic powder and sintering aid are added with an appropriate amount of anhydrous ethanol and silicon nitride grinding balls, and ball milled at a speed of 320 rpm for 5 hours; after ball milling, the dried ceramic powder is dried by a rotary evaporator and passed through an 80-mesh sieve;

[0050] (2) Subsequently, the photosensitive resin and the plasticizer are uniformly mixed by ultrasonic mixing to prepare a photocurable resin; a ceramic slurry with a solid content of 78 wt % is prepared by high-speed ball milling using the photocurable resin, colorant, dispersant, photoinitiator and ceramic powder as raw materials, at a ball milling speed of 1200 rpm and a ball milling time of 6 min;

[0051] (3) adding the prepared ceramic slurry into a light-curing 3D printer and importing the model information of the ceramic device; selecting appropriate printing parameters to obtain a green body of the ceramic device;

[0052] (4) The above-mentioned ceramic device green body is subjected to degreasing and sintering treatment to obtain a high-precision nitride ceramic material.

[0053] In step (3), the printing parameters are: laser power is 20 mW / cm 2 , the printing layer thickness is 50μm, and the exposure time for each layer is 8s.

[0054] In the step (4), degreasing is carried out in two steps: vacuum degreasing and air degreasing. The vacuum degreasing temperature is 500° C. and the temperature is kept at 4 h. The air degreasing temperature is 500° C. and the temperature is kept at 4 h.

[0055] In the step (4), the degreased parts are subjected to gas pressure sintering, the temperature is raised to 1750° C. at a rate of 10° C. / min in a nitrogen atmosphere, and the temperature is kept for 5 hours, and the sintering pressure is 0.1 MPa.

[0056] Example 3

[0057] A high-precision nitride ceramic material comprises the following raw materials in parts by weight: 93 parts of ceramic powder, 7 parts of sintering aid, 5 parts of colorant, 22 parts of photosensitive resin, 1 part of dispersant, 5 parts of plasticizer and 1 part of photoinitiator.

[0058] The ceramic powder is silicon nitride with a particle size of 1 micron.

[0059] The sintering aid is composed of magnesium silicon nitride with a particle size of 0.5 microns and yttrium oxide in a weight ratio of 5:2.

[0060] The colorant is erbium oxide with a particle size of 5 microns.

[0061] The photosensitive resin is a mixture of ethoxy pentaerythritol tetraacrylate and 1,6-hexanediol diacrylate in a weight ratio of 3:4.

[0062] The plasticizer is dioctyl phthalate.

[0063] The photoinitiator is 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio)phenyl]-1-propanone.

[0064] The dispersant is γ-aminopropyltriethoxysilane.

[0065] A 3D printing method for high-precision nitride ceramic materials comprises the following steps:

[0066] (1) First, ceramic powder and sintering aid are added with an appropriate amount of anhydrous ethanol and silicon nitride grinding balls, and ball milled at 350 rpm for 4 h; after ball milling, the dried ceramic powder is dried by a rotary evaporator and passed through a 100-mesh sieve;

[0067] (2) Subsequently, the photosensitive resin and the plasticizer are uniformly mixed by ultrasonic mixing to prepare a photocurable resin; a ceramic slurry with a solid content of 75 wt % is prepared by high-speed ball milling using the photocurable resin, colorant, dispersant, photoinitiator and ceramic powder as raw materials, at a ball milling speed of 1500 rpm and a ball milling time of 5 min;

[0068] (3) adding the prepared ceramic slurry into a light-curing 3D printer and importing the model information of the ceramic device; selecting appropriate printing parameters to obtain a green body of the ceramic device;

[0069] (4) The above-mentioned ceramic device green body is subjected to degreasing and sintering treatment to obtain a high-precision nitride ceramic material.

[0070] In step (3), the printing parameters are: laser power is 60 mW / cm 2 , the printing layer thickness is 20μm, and the exposure time for each layer is 8s.

[0071] In the step (4), degreasing is carried out in two steps: vacuum degreasing and air degreasing. The vacuum degreasing temperature is 600° C. and the temperature is kept for 3 hours. The air degreasing temperature is 600° C. and the temperature is kept for 3 hours.

[0072] In the step (4), the degreased parts are subjected to gas pressure sintering, the temperature is raised to 1800° C. at a rate of 10° C. / min in a nitrogen atmosphere, and the temperature is maintained for 4 hours, and the sintering pressure is 3 MPa.

[0073] Example 4

[0074] A high-precision nitride ceramic material comprises the following raw materials in parts by weight: 95 parts of ceramic powder, 5 parts of sintering aid, 7 parts of colorant, 25 parts of photosensitive resin, 1.5 parts of dispersant, 7 parts of plasticizer and 1.5 parts of photoinitiator.

[0075] The ceramic powder is aluminum nitride with a particle size of 3 microns.

[0076] The sintering aid is yttrium oxide with a particle size of 0.8 microns.

[0077] The colorant is holmium oxide with a particle size of 8 microns.

[0078] The photosensitive resin is a mixture of ethoxy pentaerythritol tetraacrylate and 1,6-hexanediol diacrylate in a weight ratio of 3:4.

[0079] The plasticizer is dioctyl phthalate.

[0080] The photoinitiator is 2,4,6-trimethylbenzoyl-diphenylphosphine oxide.

[0081] The dispersant is an ester-based quaternary ammonium salt.

[0082] A 3D printing method for high-precision nitride ceramic materials comprises the following steps:

[0083] (1) First, ceramic powder and sintering aid are added with an appropriate amount of anhydrous ethanol and silicon nitride grinding balls, and ball milled at 350 rpm for 4 h; after ball milling, the dried ceramic powder is dried by a rotary evaporator and passed through a 100-mesh sieve;

[0084] (2) Subsequently, the photosensitive resin and the plasticizer are uniformly mixed by ultrasonic mixing to prepare a photocurable resin; a ceramic slurry with a solid content of 80 wt% is prepared by high-speed ball milling using the photocurable resin, colorant, dispersant, photoinitiator and ceramic powder as raw materials, at a ball milling speed of 1500 rpm and a ball milling time of 5 min;

[0085] (3) adding the prepared ceramic slurry into a light-curing 3D printer and importing the model information of the ceramic device; selecting appropriate printing parameters to obtain a green body of the ceramic device;

[0086] (4) The above-mentioned ceramic device green body is subjected to degreasing and sintering treatment to obtain a high-precision nitride ceramic material.

[0087] In step (3), the printing parameters are: laser power is 30 mW / cm 2 , the printing layer thickness is 20μm, and the exposure time for each layer is 3s.

[0088] In the step (4), degreasing is carried out in two steps: vacuum degreasing and air degreasing. The vacuum degreasing temperature is 600° C. and the temperature is kept for 3 hours. The air degreasing temperature is 600° C. and the temperature is kept for 3 hours.

[0089] In the step (4), the degreased parts are subjected to gas pressure sintering, the temperature is raised to 1850° C. at a rate of 10° C. / min in a nitrogen atmosphere, and the temperature is maintained for 4 hours, and the sintering pressure is 0.1 MPa.

[0090] Example 5

[0091] A high-precision nitride ceramic material comprises the following raw materials in parts by weight: 100 parts of ceramic powder, 10 parts of sintering aid, 10 parts of colorant, 30 parts of photosensitive resin, 2 parts of dispersant, 10 parts of plasticizer and 2 parts of photoinitiator.

[0092] The ceramic powder is silicon nitride with a particle size of 5 microns.

[0093] The sintering aid is aluminum oxide with a particle size of 1 micron.

[0094] The colorant is neodymium oxide with a particle size of 10 microns.

[0095] The photosensitive resin is 2-phenoxyethyl acrylate.

[0096] The plasticizer is polyethylene glycol.

[0097] The photoinitiator is ethyl 2,4,6-trimethylbenzoylphenylphosphonate.

[0098] The dispersant is polyethylene glycol octyl phenyl ether.

[0099] A 3D printing method for high-precision nitride ceramic materials comprises the following steps:

[0100] (1) First, ceramic powder and sintering aid are added with an appropriate amount of anhydrous ethanol and silicon nitride grinding balls, and ball milled at a speed of 400 rpm for 6 hours; after ball milling, the dried ceramic powder is dried by a rotary evaporator and passed through a 150-mesh sieve;

[0101] (2) Subsequently, the photosensitive resin and the plasticizer are uniformly mixed by ultrasonic mixing to prepare a photocurable resin; a ceramic slurry with a solid content of 85 wt % is prepared by high-speed ball milling with the photocurable resin, colorant, dispersant, photoinitiator and ceramic powder as raw materials, the ball milling speed is 2000 rpm, and the ball milling time is 3 min;

[0102] (3) adding the prepared ceramic slurry into a light-curing 3D printer and importing the model information of the ceramic device; selecting appropriate printing parameters to obtain a green body of the ceramic device;

[0103] (4) The above-mentioned ceramic device green body is subjected to degreasing and sintering treatment to obtain a high-precision nitride ceramic material.

[0104] In step (3), the printing parameters are: laser power is 40 mW / cm 2, the printing layer thickness is 70μm, and the exposure time for each layer is 15s.

[0105] In the step (4), degreasing is carried out in two steps: vacuum degreasing and air degreasing. The vacuum degreasing temperature is 800° C. and the temperature is kept at 800° C. for 1 hour. The air degreasing temperature is 800° C. and the temperature is kept at 800° C. for 1 hour.

[0106] In the step (4), the degreased parts are subjected to gas pressure sintering, the temperature is raised to 1900° C. at a rate of 10° C. / min in a nitrogen atmosphere, and the temperature is maintained for 1 hour, and the sintering pressure is 1 MPa.

[0107] Comparative Example 1

[0108] The difference between the comparative example and the embodiment 3 is that no colorant is added.

[0109] After testing, the precision of the high-precision nitride ceramic materials obtained in Examples 1-5 of the present invention is improved by more than 50% compared with that in Comparative Example 1. It can be seen that the high-precision nitride ceramic materials of the present invention improve the printing precision by adding colorants to adjust the absorption and scattering of the printed body during the printing process, and finally obtain high-precision ceramic materials through sintering.

[0110] In addition, the performance test results of the high-precision nitride ceramic materials prepared in Examples 1-5 of the present invention are as follows:

[0111] Test items Bending strength(MPa) Hardness(GPa) <![CDATA[Thermal conductivity (W·m -1 ·K -1 )]]> Density(%) Example 1 832 15 38 98.7 Example 2 452 12 165 99.8 Example 3 897 16 45 99.3 Example 4 483 13 173 99.5 Example 5 864 17 42 98.9

[0112] It can be seen from the above table that the high-precision silicon nitride ceramic materials prepared in Examples 1, 3, and 5 of the present invention have high density, high bending strength and hardness; the high-precision aluminum nitride ceramic materials prepared in Examples 2 and 4 of the present invention have high density, high hardness and thermal conductivity.

[0113] The above embodiments are preferred implementation schemes of the present invention. In addition, the present invention may also be implemented in other ways. Any obvious replacement without departing from the concept of the present invention is within the protection scope of the present invention.

Claims

1. A high-precision nitride ceramic material, characterized in that: The invention comprises the following raw materials in parts by weight: 60-100 parts of ceramic powder, 0.1-10 parts of sintering aid, 0.1-10 parts of colorant, 15-30 parts of photosensitive resin, 0.1-2 parts of dispersant, 0.1-10 parts of plasticizer and 0.1-2 parts of photoinitiator.

2. A high-precision nitride ceramic material according to claim 1, characterized in that: The ceramic powder is at least one of silicon nitride and aluminum nitride, and the particle size of the ceramic powder is 0.1-5 microns.

3. The high-precision nitride ceramic material according to claim 1, characterized in that: The sintering aid is at least one of magnesium silicon nitride, magnesium oxide, aluminum oxide and yttrium oxide, and the particle size of the sintering aid is 0.1-1 micron.

4. The high-precision nitride ceramic material according to claim 1, characterized in that: The colorant is at least one of iron oxide, copper oxide, erbium oxide, holmium oxide, neodymium oxide, praseodymium oxide, samarium oxide, cerium oxide and terbium oxide, and the particle size of the colorant is 0.1-10 microns.

5. The high-precision nitride ceramic material according to claim 1, characterized in that: The photosensitive resin is at least one of ethoxy pentaerythritol tetraacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, o-phenylphenoxyethyl acrylate and 2-phenoxyethyl acrylate.

6. The high-precision nitride ceramic material according to claim 1, characterized in that: The plasticizer is at least one of dioctyl phthalate, dibutyl phthalate, tributyl citrate, trioctyl citrate and polyethylene glycol.

7. A 3D printing method for high-precision nitride ceramic materials according to any one of claims 1 to 6, characterized in that: The steps include: (1) First, ceramic powder and sintering aid are added with an appropriate amount of anhydrous ethanol and silicon nitride grinding balls, and ball milled at a speed of 300-400 rpm for 3-6 hours; after ball milling, the dried ceramic powder is dried by a rotary evaporator and passed through a 50-150 mesh sieve; (2) Subsequently, the photosensitive resin and the plasticizer are uniformly mixed by ultrasonication to prepare a photocurable resin; a ceramic slurry with a solid content of 75-85 wt % is prepared by high-speed ball milling with the photocurable resin, colorant, dispersant, photoinitiator and ceramic powder as raw materials, the ball milling speed is 1000-2000 rpm, and the ball milling time is 3-7 min; (3) adding the prepared ceramic slurry into a light-curing 3D printer and importing the model information of the ceramic device; selecting appropriate printing parameters to obtain a green body of the ceramic device; (4) The above-mentioned ceramic device green body is subjected to degreasing and sintering treatment to obtain a high-precision nitride ceramic material.

8. A 3D printing method for high-precision nitride ceramic materials according to claim 7, characterized in that: In step (3), the printing parameters are: laser power is 10-60mW / cm 2 , the printing layer thickness is 10-100μm, and the exposure time of each layer is 1-30s.

9. The 3D printing method of high-precision nitride ceramic material according to claim 7, characterized in that: In the step (4), degreasing is carried out in two steps: vacuum degreasing and air degreasing. The vacuum degreasing temperature is 400-800°C and the temperature is kept for 1-5 hours. The air degreasing temperature is 400-800°C and the temperature is kept for 1-5 hours.

10. The 3D printing method of high-precision nitride ceramic material according to claim 7, characterized in that: In the step (4), the degreased parts are subjected to gas pressure sintering, the temperature is raised to 1700-1900° C. at a rate of 5-15° C. / min in a nitrogen atmosphere, and the temperature is kept for 1-6 hours. The sintering pressure is 0.1-5 MPa.