CN111777408A - 3D printing high-strength ZTA ceramic substrate material and preparation process - Google Patents
3D printing high-strength ZTA ceramic substrate material and preparation process Download PDFInfo
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Abstract
The invention belongs to the technical field of ceramics, and particularly relates to a 3D printing high-strength ZTA ceramic substrate material and a preparation process thereof. The 3D printing high-strength ZTA ceramic substrate material comprises the following components in parts by weight: 100 parts of ZTA powder, 4-35 parts of zirconia powder, 40-60 parts of light-cured resin, 0.05-1.0 part of photoinitiator, 10-20 parts of dispersant, 0.5-5.0 parts of sintering aid and 0.1-3 parts of supporting material; the particle size of the ZTA powder is 100nm-5000nm, and the particle size of the zirconia powder is 100nm-1000 nm; the corresponding preparation process comprises the steps of ceramic matrix powder mixing, resin mixed liquid preparation, ZTA ceramic slurry premixing, ZTA ceramic slurry preparation, ZTA ceramic slurry printing and ZTA ceramic blank sintering. The ceramic material prepared by the components has uniform structure and high strength; the operation is simple, and the ZTA ceramic after printing has high compactness and is not easy to crack.
Description
Technical Field
The invention belongs to the technical field of ceramics, and particularly relates to a 3D printing high-strength ZTA ceramic substrate material and a preparation process thereof.
Background
3D printing is a rapid prototyping technology, which is a technology for constructing an object by using a digital model file as a base and using adhesive materials such as powdered metal or plastic and the like and by a layer-by-layer printing mode. And after the section of the layer of the part is generated, moving the workbench downwards by one layer thickness, curing the next layer of the part, and repeating the steps until the printing is finished.
In the traditional preparation process, the material configuration and forming method of ZTA ceramic has important influence on the prepared ZTA ceramic substrate material, the microstructure uniformity of the material is poor, the material is easy to crack in the printing process, and the strength is low.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: aiming at the defects, the invention provides a 3D printing high-strength ZTA ceramic substrate material and a preparation process, wherein the ceramic material prepared by adopting the component has uniform structure and high strength; the operation is simple, and the ZTA ceramic after printing has high compactness and is not easy to crack.
The technical scheme adopted by the invention for solving the technical problems is as follows: the 3D printing high-strength ZTA ceramic substrate material comprises the following components in parts by weight: 100 parts of ZTA powder, 4-35 parts of zirconia powder, 40-60 parts of light-cured resin, 0.05-1.0 part of photoinitiator, 10-20 parts of dispersant, 0.5-5.0 parts of sintering aid and 0.1-3 parts of supporting material;
the particle size of the ZTA powder is 100nm-5000nm, and the particle size of the zirconia powder is 100nm-1000 nm. The ZTA powder and the zirconia powder are used as base materials of the ceramic substrate, the nanoscale ZTA powder and the zirconia powder are selected to be small in printing layer thickness during printing, the powder is uniformly dispersed, the forming precision is high, and the formed ceramic blank is high in density and strength; introducing a certain amount of light-cured resin to ensure the fluidity of ZTA ceramic slurry; the introduction of the sintering aid can effectively improve the powder performance, improve the printability and meet the requirement of rapid forming; the added supporting material can increase the hardness of a blank during printing, and can strengthen the structure and the performance after standing and heating treatment, so that the strength of a printed ceramic substrate is improved, the ceramic has high compactness and is not easy to crack.
Further, the light-cured resin is one or more of epoxy resin, epoxy acrylate and epoxy polyurethane;
the dispersing agent is one or more of polyethylacryloyl, trimethylolpropane triacrylate and hexanediol diacrylate;
the photoinitiator is one or more of dimethylolpropionic acid, trioctylphosphine oxide and diphenylphosphine oxide;
the sintering aid is a composite aid consisting of polyvinyl alcohol and one or more of cuprous oxide, magnesium oxide, lead oxide, titanium oxide and iron oxide;
the support material is one or more of hydroxyapatite and zirconate resin.
The introduced light-cured resin can increase the solid content of the prepared ceramic slurry, reduce the use of a solvent, shorten the printing time, prevent more solvent from remaining in the ceramic blank and prevent internal holes from being formed in the drying process; the introduced sintering aid is non-single powder, and a composite aid consisting of polyvinyl alcohol and other substances is adopted, so that the phenomenon that the viscosity of ceramic slurry is too high is avoided, the slurry can be coated on a workpiece by a scraper, and the thickness and the uniformity of each layer are ensured. The hydroxyapatite or zirconate tree adopted as the internal supporting material accords with bone growth factors as a forming raw material, has a good support structure, can increase the hardness of a blank, and improves the strength of a 3D printing high ZTA ceramic substrate.
Furthermore, the polyvinyl alcohol accounts for 20-50% of the total weight of the composite auxiliary agent. The use amount of the polyvinyl alcohol is controlled, so that the problems of high porosity and poor bonding strength of a blank caused by too small use amount of the polyvinyl alcohol can be solved when the ZTA ceramic slurry is printed and sprayed, the bonding strength is improved, the excessive yield of the ceramic blank before and after sintering caused by too high content of the polyvinyl alcohol can be avoided, and the structure and the performance of the ceramic blank are improved.
Further, the dispersing agent is polyethylacryloyl, trimethylolpropane triacrylate and hexanediol diacrylate according to a mass ratio of 1: (0.4-1.2): (0.6-0.8) mixing; the photoinitiator is dimethylolpropionic acid, trioctylphosphine oxide and diphenyl phosphine oxide in a mass ratio of (0.5-1): (0.1-0.5): 1 are mixed. The dispersing agent and the photoinitiator with the contents of the components are adopted, the dispersion uniformity of the zirconium oxide and ZTA powder in the resin can be improved by adopting the composite dispersing agent, and the prepared ceramic matrix material has good fluidity and viscosity, and is favorable for ensuring the density and performance uniformity of printing forming and sintering.
A preparation process of a 3D printing high-strength ZTA ceramic substrate material comprises the following steps:
s1, mixing ceramic matrix powder: putting ZTA powder and zirconia powder into a ball mill for ball milling to obtain zirconia/ZTA mixed powder;
s2, preparing a resin mixed solution: placing the light-cured resin in another stirrer, adding the photoinitiator and the dispersant into the light-cured resin, and mixing and stirring for 10-15 minutes to obtain a resin mixed solution;
s3, premixing ZTA ceramic slurry: adding the zirconium oxide/ZTA mixed powder obtained in the operation of S1 into the resin mixed solution prepared in the operation of S2 in batches, and stirring until the mixed powder is completely dispersed to obtain ZTA ceramic slurry premixed solution;
s4, preparing ZTA ceramic slurry: sequentially adding the sintering aid and the support material into the ZTA ceramic slurry premix obtained in the S3 operation, continuously stirring the premix until the sintering aid and the support material are uniformly mixed, standing for 1-2 minutes, and stirring and mixing again for 2-5 minutes to obtain ZTA ceramic slurry;
s5, ZTA ceramic paste printing: pouring the ZTA ceramic slurry prepared in the step S4 into a material groove of a 3D printer, printing to obtain ZTA ceramic substrates, and printing layer by layer to obtain ZTA green bodies;
s6, sintering the ZTA ceramic blank: and sintering the ZTA blank obtained in the operation of S5 to obtain the ZTA ceramic device. According to the preparation method of the 3D printing high-strength ZTA ceramic substrate material, the mixing and feeding sequence of different raw materials is limited, the mixed ZTA ceramic slurry is ensured to have the characteristics of low viscosity and high solid content, the prepared ZTA ceramic device is high in precision, high in density and high in strength, and the problems of cracking and non-uniform density in the ZTA ceramic forming process are effectively solved; the printing process is smooth and the operation is simple.
Further, in the operation S4, the sintering aid is prepared by adding one or more of cuprous oxide, magnesium oxide, lead oxide, titanium oxide, and iron oxide to the polyvinyl alcohol, stirring and mixing, wherein one or more of cuprous oxide, magnesium oxide, lead oxide, titanium oxide, and iron oxide is dispersed in the polyvinyl alcohol.
Further, the stirring speed of the stirrer is 200-300 rpm. The proper stirring speed of the stirrer is controlled, the dispersion uniformity in the preparation process of the ceramic slurry is ensured, the microstructure of the printed ceramic substrate material is uniform, and the quality of the prepared device is high.
Furthermore, in the printing of the S5ZTA ceramic slurry, the ZTA ceramic substrate is cured by ultraviolet irradiation, and the wavelength of the ultraviolet light is 350-380 nm.
Furthermore, the S6ZTA ceramic substrate is sintered by microwave vacuum sintering at 1430-1500 deg.C for 0.5-2h, and the sintering vacuum degree in the microwave sintering furnace is 0.2-200 Pa. The ZTA ceramic device is sintered by microwave, has the advantage of high heating speed, can inhibit the growth of a crystal grain structure, and has high ZTA ceramic compactness and difficult cracking.
The invention has the beneficial effects that:
1. the ZTA powder and the zirconia powder are used as base materials of the ceramic substrate, the nanoscale ZTA powder and the zirconia powder are selected to be small in printing layer thickness during printing, the powder is uniformly dispersed, the forming precision is high, and the formed ceramic blank is high in density and strength; introducing a certain amount of light-cured resin to ensure the fluidity of ZTA ceramic slurry; the introduction of the sintering aid can effectively improve the powder performance, improve the printability and meet the requirement of rapid forming; the added supporting material can increase the hardness of a blank during printing, and can strengthen the structure and the performance after standing and heating treatment, so that the strength of a printed ceramic substrate is improved, the ceramic has high compactness and is not easy to crack; the introduced light-cured resin can increase the solid content of the prepared ceramic slurry, reduce the use of a solvent, shorten the printing time, prevent more solvent from remaining in the ceramic blank and prevent internal holes from being formed in the drying process; the introduced sintering aid is non-single powder, and a composite aid consisting of polyvinyl alcohol and other substances is adopted, so that the phenomenon that the viscosity of ceramic slurry is too high is avoided, the slurry can be coated on a workpiece by a scraper, and the thickness and the uniformity of each layer are ensured. The hydroxyapatite or zirconate tree adopted as the internal supporting material accords with bone growth factors as a forming raw material, has a good support structure, can increase the hardness of a blank, and improves the strength of a 3D printing high ZTA ceramic substrate.
2. The use amount of the polyvinyl alcohol is controlled, so that the blank cannot have the problems of high porosity and poor bonding strength caused by too small use amount of the polyvinyl alcohol when the ZTA ceramic slurry is printed and sprayed, the bonding strength is improved, the excessive yield of the ceramic blank before and after sintering caused by too high content of the polyvinyl alcohol is avoided, and the structure and the performance of the ceramic blank are improved; the dispersing agent and the photoinitiator with the contents of the components are adopted, the dispersion uniformity of the zirconium oxide and ZTA powder in the resin can be improved by adopting the composite dispersing agent, and the prepared ceramic matrix material has good fluidity and viscosity, and is favorable for ensuring the density and performance uniformity of printing forming and sintering.
3. According to the preparation method of the 3D printing high-strength ZTA ceramic substrate material, the mixing and feeding sequence of different raw materials is limited, the mixed ZTA ceramic slurry is ensured to have the characteristics of low viscosity and high solid content, the prepared ZTA ceramic device is high in precision, high in density and high in strength, and the problems of cracking and non-uniform density in the ZTA ceramic forming process are effectively solved; the printing process is smooth, and the operation is simple; the proper stirring speed of the stirrer is controlled, the dispersion uniformity in the preparation process of the ceramic slurry is ensured, the microstructure of the printed ceramic substrate material is uniform, and the quality of the prepared device is high; the ZTA ceramic device is sintered by microwave, has the advantage of high heating speed, can inhibit the growth of a crystal grain structure, and has high ZTA ceramic compactness and difficult cracking.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The 3D printing high-strength ZTA ceramic substrate material comprises the following components in parts by weight: 100 parts of ZTA powder, 6 parts of zirconia powder, 40 parts of light-cured resin, 0.1 part of photoinitiator, 10 parts of dispersant, 0.8 part of sintering aid and 0.5 part of support material;
the particle size of the ZTA powder is 200nm-500nm, and the particle size of the zirconia powder is 100nm-1000 nm; the light-cured resin is formed by mixing epoxy resin and epoxy acrylate according to the mass ratio of 1: 1; the dispersing agent is formed by mixing trimethylolpropane triacrylate and hexanediol diacrylate according to the mass ratio of 1: 0.8; the photoinitiator is dimethylolpropionic acid; the sintering aid is a composite aid consisting of polyvinyl alcohol, cuprous oxide, magnesium oxide and lead oxide, and the mass ratio of the cuprous oxide to the magnesium oxide to the lead oxide is 1:2: 1; the polyvinyl alcohol accounts for 40% of the total weight of the composite auxiliary agent; the support material is hydroxyapatite.
A preparation process of a 3D printing high-strength ZTA ceramic substrate material, which is prepared from raw materials such as the 3D printing high-strength ZTA ceramic substrate material, comprises the following steps:
s1, mixing ceramic matrix powder: putting ZTA powder and zirconia powder into a ball mill for ball milling to obtain zirconia/ZTA mixed powder;
s2, preparing a resin mixed solution: placing the light-cured resin in another stirrer, adding the photoinitiator and the dispersant into the light-cured resin together, wherein the stirring speed of the stirrer is 200-300 rpm, preferably 280rpm, and mixing and stirring for 10-15 minutes to obtain a resin mixed solution;
s3, premixing ZTA ceramic slurry: adding the zirconium oxide/ZTA mixed powder obtained in the operation of S1 into the resin mixed solution prepared in the operation of S2 in batches, and stirring until the mixed powder is completely dispersed to obtain ZTA ceramic slurry premixed solution;
s4, preparing ZTA ceramic slurry: sequentially adding the sintering aid and the support material into the ZTA ceramic slurry premix obtained in the S3 operation, continuously stirring the premix until the sintering aid and the support material are uniformly mixed, standing for 1-2 minutes, and stirring and mixing again for 2-5 minutes to obtain ZTA ceramic slurry; wherein the sintering aid is prepared by adding calculated amounts of cuprous oxide, magnesium oxide and lead oxide into polyvinyl alcohol, stirring and mixing, and uniformly dispersing the cuprous oxide, the magnesium oxide and the lead oxide in the polyvinyl alcohol;
s5, ZTA ceramic paste printing: pouring the ZTA ceramic slurry prepared in the step S4 into a trough of a 3D printer, printing to obtain a ZTA ceramic substrate, curing the ZTA ceramic substrate under ultraviolet irradiation, and printing layer by layer to obtain a ZTA green body, wherein the wavelength of the ultraviolet light is 350-380 nm, preferably 355 nm;
s6, sintering the ZTA ceramic blank: sintering the ZTA blank obtained in the operation of S5 by adopting a microwave vacuum sintering method, wherein the sintering temperature is 1430-1500 ℃, the sintering time is 0.5-2h, and the specific sintering time is determined according to the size of a printed ceramic device; the sintering vacuum degree in a microwave sintering furnace is 0.2-200Pa, and the ZTA ceramic device is prepared.
Example 2
The 3D printing high-strength ZTA ceramic substrate material comprises the following components in parts by weight: 100 parts of ZTA powder, 12 parts of zirconia powder, 50 parts of light-cured resin, 0.05-1.0 part of photoinitiator, 12 parts of dispersant, 2.0 parts of sintering aid and 0.5 part of support material;
the particle size of the ZTA powder is 500nm-2000nm, and the particle size of the zirconia powder is 100nm-500 nm; the light-cured resin is formed by mixing epoxy acrylate and epoxy polyurethane according to the mass ratio of 1: 1; the dispersant is polyethylacryloyl; the photoinitiator is dimethylolpropionic acid and trioctylphosphine oxide; the sintering aid is a composite aid consisting of polyvinyl alcohol and titanium oxide; the polyvinyl alcohol accounts for 25% of the total weight of the composite auxiliary agent; the support material is hydroxyapatite.
The method of manufacturing the ZTA ceramic device of this example was the same as that of example 1.
Example 3
The 3D printing high-strength ZTA ceramic substrate material comprises the following components in parts by weight: 100 parts of ZTA powder, 30 parts of zirconia powder, 60 parts of light-cured resin, 1.0 part of photoinitiator, 20 parts of dispersant, 4.5 parts of sintering aid and 2.5 parts of support material; the particle size of the ZTA powder is 100nm-5000nm, and the particle size of the zirconia powder is 100nm-1000 nm; the light-cured resin is epoxy polyurethane; the dispersing agent is composed of polyethylacryloyl, trimethylolpropane triacrylate and hexanediol diacrylate according to the mass ratio of 1: 0.5: 0.6 mixing; the photoinitiator is diphenyl phosphine oxide; the photoinitiator is dimethylolpropionic acid, trioctylphosphine oxide and diphenylphosphine oxide in a mass ratio of 0.5: 0.2: 1, mixing; the sintering aid is a composite aid consisting of polyvinyl alcohol and magnesium oxide and iron oxide in a mass ratio of 2: 1; the polyvinyl alcohol accounts for 25% of the total weight of the composite auxiliary agent; the support material is hydroxyapatite.
The method of manufacturing the ZTA ceramic device of this example was the same as that of example 1.
Example 4
The 3D printing high-strength ZTA ceramic substrate material comprises the following components in parts by weight: 100 parts of ZTA powder, 30 parts of zirconia powder, 45 parts of light-cured resin, 0.8 part of photoinitiator, 20 parts of dispersant, 2.5 parts of sintering aid and 1.6 parts of supporting material; the particle size of the ZTA powder is 800nm-2000nm, and the particle size of the zirconia powder is 400nm-800 nm; the light-cured resin is formed by mixing epoxy resin, epoxy acrylate and epoxy polyurethane according to the mass ratio of 2:1: 3; the dispersing agent is composed of polyethylacryloyl, trimethylolpropane triacrylate and hexanediol diacrylate according to the mass ratio of 1: 1.2: 0.6 mixing; the photoinitiator is dimethylolpropionic acid, trioctylphosphine oxide and diphenylphosphine oxide in a mass ratio of 0.8: 0.4: 1, mixing; the sintering aid is a composite aid consisting of polyvinyl alcohol and cuprous oxide and lead oxide in a mass ratio of 2: 1; the polyvinyl alcohol accounts for 45 percent of the total weight of the composite auxiliary agent; the support material is formed by mixing hydroxyapatite and zirconate resin according to the mass ratio of 3: 1.
The method of manufacturing the ZTA ceramic device of this example was the same as that of example 1.
In examples 1-4, the sum of the volume of the resin, ZTA, and zirconia powder was kept constant, and the zirconia was uniformly distributed in the alumina matrix by electron microscope observation.
The density, Vickers hardness, flexural strength and fracture toughness of the ZTA ceramic device in example 1 reach 5.62g/cm320.84GPa, 650MPa and 6.2 MPa.m1/2。
The density, Vickers hardness, bending strength and fracture toughness of the ZTA ceramic device in example 2 reach 5.52g/cm320.21GPa, 640MPa and 6.3 MPa.m1/2。
The density, Vickers hardness, flexural strength and fracture toughness of the ZTA ceramic device in example 3 reach 5.74g/cm321.53GPa, 670MPa and 6.3 MPa.m1/2。
In example 4, the density, Vickers hardness, bending strength and fracture toughness of the ZTA ceramic device reach 5.86g/cm322.08GPa, 720MPa and 6.8 MPa.m1/2。
Therefore, the ceramic material prepared by adopting the components has uniform structure and high strength; the operation is simple, and the ZTA ceramic after printing has high compactness and is not easy to crack.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (9)
- The 3D printed high-strength ZTA ceramic substrate material is characterized by comprising the following components in parts by weight: 100 parts of ZTA powder, 4-35 parts of zirconia powder, 40-60 parts of light-cured resin, 0.05-1.0 part of photoinitiator, 10-20 parts of dispersant, 0.5-5.0 parts of sintering aid and 0.1-3 parts of supporting material;the particle size of the ZTA powder is 100nm-5000nm, and the particle size of the zirconia powder is 100nm-1000 nm.
- 2. The 3D printed high strength ZTA ceramic substrate material according to claim 1, wherein: the light-cured resin is one or more of epoxy resin, epoxy acrylate and epoxy polyurethane;the dispersing agent is one or more of polyethylacryloyl, trimethylolpropane triacrylate and hexanediol diacrylate;the photoinitiator is one or more of dimethylolpropionic acid, trioctylphosphine oxide and diphenylphosphine oxide;the sintering aid is a composite aid consisting of polyvinyl alcohol and one or more of cuprous oxide, magnesium oxide, lead oxide, titanium oxide and iron oxide;the support material is one or more of hydroxyapatite and zirconate resin.
- 3. The 3D printed high strength ZTA ceramic substrate material according to claim 2, wherein: the polyvinyl alcohol accounts for 20-50% of the total weight of the composite auxiliary agent.
- 4. The 3D printed high strength ZTA ceramic substrate material according to claim 2, wherein: the dispersing agent is composed of polyethylacryloyl, trimethylolpropane triacrylate and hexanediol diacrylate according to the mass ratio of 1: (0.4-1.2): (0.6-0.8) mixing;the photoinitiator is dimethylolpropionic acid, trioctylphosphine oxide and diphenyl phosphine oxide in a mass ratio of (0.5-1): (0.1-0.5): 1 are mixed.
- A process for preparing a 3D printed high strength ZTA ceramic substrate material, wherein the raw material is as defined in any one of claims 1-4, comprising the steps of:s1, mixing ceramic matrix powder: putting ZTA powder and zirconia powder into a ball mill for ball milling to obtain zirconia/ZTA mixed powder;s2, preparing a resin mixed solution: placing the light-cured resin in another stirrer, adding the photoinitiator and the dispersant into the light-cured resin, and mixing and stirring for 10-15 minutes to obtain a resin mixed solution;s3, premixing ZTA ceramic slurry: adding the zirconium oxide/ZTA mixed powder obtained in the operation of S1 into the resin mixed solution prepared in the operation of S2 in batches, and stirring until the mixed powder is completely dispersed to obtain ZTA ceramic slurry premixed solution;s4, preparing ZTA ceramic slurry: sequentially adding the sintering aid and the support material into the ZTA ceramic slurry premix obtained in the S3 operation, continuously stirring the premix until the sintering aid and the support material are uniformly mixed, standing for 1-2 minutes, and stirring and mixing again for 2-5 minutes to obtain ZTA ceramic slurry;s5, ZTA ceramic paste printing: pouring the ZTA ceramic slurry prepared in the step S4 into a material groove of a 3D printer, printing to obtain ZTA ceramic substrates, and printing layer by layer to obtain ZTA green bodies;s6, sintering the ZTA ceramic blank: and sintering the ZTA blank obtained in the operation of S5 to obtain the ZTA ceramic device.
- 6. The process for preparing a 3D printed high-strength ZTA ceramic substrate material according to claim 5, wherein: in the operation of S4, the sintering aid is prepared by adding one or more of cuprous oxide, magnesium oxide, lead oxide, titanium oxide, and iron oxide to polyvinyl alcohol, stirring and mixing, and dispersing one or more of cuprous oxide, magnesium oxide, lead oxide, titanium oxide, and iron oxide in polyvinyl alcohol.
- 7. The process for preparing a 3D printed high-strength ZTA ceramic substrate material according to claim 5, wherein: the stirring speed of the stirrer is 200-300 rpm.
- 8. The process for preparing a 3D printed high-strength ZTA ceramic substrate material according to claim 5, wherein: in the printing of the S5ZTA ceramic slurry, the ZTA ceramic substrate is cured by ultraviolet irradiation, and the wavelength of the ultraviolet light is 350-380 nm.
- 9. The process for preparing a 3D printed high-strength ZTA ceramic substrate material according to claim 5, wherein: the S6ZTA ceramic substrate is sintered by microwave vacuum sintering at 1430-1500 deg.C for 0.5-2h, and in a microwave sintering furnace at 0.2-200 Pa.
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