CN113896528A - Method for preparing high-performance zirconia ceramic material through DLP-3D printing - Google Patents
Method for preparing high-performance zirconia ceramic material through DLP-3D printing Download PDFInfo
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Abstract
A method for preparing a high-performance zirconia ceramic material through DLP-3D printing comprises the steps of preparing zirconia ceramic slurry, carrying out photocuring treatment to obtain a zirconia ceramic blank, carrying out degreasing treatment and segmented sintering treatment, wherein the sintering treatment comprises the steps of heating the degreased zirconia ceramic blank to 1000 ℃ in vacuum, preserving heat for 30-40 min, introducing nitrogen, heating to 1250 ℃, preserving heat for 30min, heating to 1450 ℃, preserving heat for 30min, cooling to 1100 ℃, preserving heat for 30min, and then cooling to 1100 ℃, and preserving heat for 30minAnd (5) cooling along with the furnace. The zirconia ceramic material prepared by the invention has excellent uniformity, microcracks and layering phenomena, excellent density of 90.2-99.6%, few defects such as holes and cracks, 230-260 nm of grain size, 13.9-14.6 GPa of Vickers hardness, and 7.67-9.85 MPa.m.fracture toughness1/2The bending strength is 449.3 to 462.7 MPa.
Description
Technical Field
The invention relates to the technical field of additive manufacturing, in particular to a method for preparing a high-performance zirconia ceramic material through DLP-3D printing.
Background
The zirconia ceramic material is an inorganic non-metallic material, and is widely applied to the fields of machinery, electronics, semiconductors, biomedicine and the like due to a series of excellent properties such as high hardness, high strength, high wear resistance, biocompatibility and the like, but the properties of the prepared ceramic material cannot meet the requirements due to the limitation of the traditional production and processing technology, so that the application of the zirconia ceramic material is limited.
The 3D printed zirconia ceramic material can be used for forming ceramic blanks with complex shapes and accurate sizes. However, the 3D printing zirconia ceramic material needs to be degreased and sintered at high temperature, so that the ceramic slurry has high requirements and needs to have high solid content and low viscosity; the higher solid content can improve the sintering density, increase the compactness of the ceramic material, and the lower viscosity can prevent the ceramic material from generating cracks and improve the uniformity of the ceramic material, but the problems in preparing zirconia ceramic slurry are that the solid content is increased, the viscosity is reduced, the solid content is also reduced, and the high solid content and the low viscosity are difficult to maintain at the same time. Secondly, the crystal grains are easy to grow abnormally in the sintering process, so that a large number of air holes in the ceramic blank are difficult to be discharged from grain boundaries in the crystal grains, the ceramic material is difficult to reach higher density, the reduction of the sintering temperature is an effective means for controlling the growth of the material crystal grains and improving the material performance, but the sintering temperature is lower, the sintering densification is hindered, the air holes cannot be completely discharged (the sintering temperature is required to reach about 1600 ℃ to reach the air hole height discharge), the prepared zirconia ceramic material has lower density, and more defects such as pores, cracks and the like exist, so that the hardness and the fracture toughness are not high.
Disclosure of Invention
The invention aims to provide a method for preparing a high-performance zirconia ceramic material through DLP-3D printing.
The purpose of the invention is realized by the following technical scheme:
a method for preparing a high-performance zirconia ceramic material through DLP-3D printing is characterized by comprising the following steps: firstly, preparing zirconia ceramic slurry, carrying out photocuring treatment to obtain a zirconia ceramic blank, then carrying out degreasing treatment and staged sintering treatment, wherein the sintering treatment is to heat the degreased zirconia ceramic blank to 1000 ℃ in vacuum, preserving heat for 30-40 min, then introducing nitrogen, heating to 1250 ℃, preserving heat for 30min, heating to 1400 ℃, preserving heat for 30min, cooling to 1100 ℃, preserving heat for 30min, and then cooling along with a furnace.
Further, the vacuum degree under the vacuum condition is 0.5 to 1X 10-3And Pa, introducing nitrogen, and adjusting the pressure to 1000-3000 Pa.
Further, the ceramic slurry is prepared by adding zirconium oxide powder into an absolute ethyl alcohol solution of Stearic Acid (SA) and Polyethyleneimine (PEI), spray-drying at high temperature and high pressure to obtain modified zirconium oxide powder, adding a premixed solution of polyurethane acrylate (PUA) and 1, 6-hexanediol diacrylate (HDDA) in a mass ratio of 7:3, and then adding a dispersant and a photoinitiator for mixing.
The zirconia powder is prepared from zirconia powder with the particle size of 30-40 nm and gadolinium oxide high powder with the particle size of 70-90 nm according to the mass ratio of 5: 95-15: 85, and the grain size of the zirconia powder is 26-39 nm.
Further, the mass ratio of the SA, the PEI and the absolute ethyl alcohol is 1: 0.5-0.7: 8-9, and the mass ratio of the zirconia powder to the absolute ethyl alcohol solution of the SA and the PEI is 1: 4.5-5.5.
The Digital Light Processing (DLP) 3D printing Process for preparing zirconia ceramic includes such steps as preparing zirconia ceramic slurry in the thickness of 30-70 microns and Light intensity of 283mW/cm2And exposing for 10-30s under an ultraviolet light area source with the wavelength of 405nm, and curing to obtain a zirconia ceramic blank, but the requirement of the technology on zirconia ceramic slurry is high, and the slurry needs to be ensured to have high solid content and lower viscosity.
Because the zirconia ceramic powder used in the invention has smaller grain diameter and is easy to agglomerate and agglomerate, if the slurry has poor uniformity and has the problems of agglomeration, agglomeration and the like, the prepared ceramic green body has low density, the shrinkage is easy to be uneven during sintering, the green body is deformed, and the densification can be realized only by higher temperature, so that the grains grow abnormally.
In the invention, hydroxyl on the surface of zirconia reacts with carboxyl in SA at a certain temperature to generate monomolecular acid, so that the affinity between zirconia powder and resin is enhanced, the internal friction of slurry is reduced, the fluidity of the slurry is increased, in the subsequent high-temperature high-pressure spray drying process, the carboxyl in SA is further activated at high temperature and high pressure and can react with amino in PEI to generate hydrogen bonds, so that coating is formed on the surface of the zirconia, the protonation of amino is promoted by the monomolecular acid, the surface of the powder is positively charged, the steric hindrance effect of the long-chain structure of SA is realized through the electrostatic repulsion, and the zirconia is spheroidized by the high-temperature high-pressure spray drying to reduce the contact area between particles, so that the agglomeration and caking of the powder are synergistically and effectively inhibited, the uniform dispersion of the zirconia powder in the slurry is promoted, and the zirconia powder with two particle sizes is mixed, the powder with larger grain size forms a slurry system of a certain year, and the powder with smaller grain size is filled in the gap of the powder with large grain size to form secondary filling, so that the solid content is increased, the viscosity is not increased, and the foundation is laid for preparing the zirconia ceramic material with high density subsequently.
Further, the dispersant is any one of DISPERBYK-110, DISPERBYK-W969 and DISPERBYK-2020, and the photoinitiator is phenyl bis (2,4, 6-Trimethylbenzoyl) Phosphine Oxide (TPO).
Furthermore, the zirconia ceramic slurry comprises 90-94 wt% of zirconia powder, 1.5-2.5 wt% of dispersant, 0.6-1% of photoinitiator and the balance of premixed liquid.
Further, the degreasing is to heat the cured ceramic blank to 180-200 ℃ from room temperature at the speed of 1-1.5 ℃/min, and keep the temperature for 60 min; heating to 375-385 ℃ at the speed of 1-1.5 ℃/min, and preserving the heat for 120 min; heating to 435-445 ℃ at a speed of 1-1.5 ℃/min, and keeping the temperature for 120 min; heating to 625-630 ℃ at a speed of 1-1.5 ℃/min, and keeping the temperature for 240 min; heating to 1000 ℃ at the speed of 2 ℃/min, preserving heat for 30min, and then carrying out five-stage degreasing treatment by furnace cooling to room temperature.
The temperature rise rate and the heat preservation time of the degreasing process are controlled in stages, so that the resin material is orderly and controllably completely removed, the temperature difference between the inside and the outside of the blank is small, the inside and the outside temperature gradients are avoided, severe deformation is avoided, and the defects of cracks, layering and the like are avoided in the degreasing stage.
Most specifically, the method for preparing the high-performance zirconia ceramic material through DLP-3D printing is characterized by comprising the following steps:
(1) preparation of zirconia ceramic slurry
Mixing zirconium oxide powder 1 with yttrium-stabilized grain size of 26-39 nm and grain size of 30-40 nm and zirconium oxide powder 2 with grain size of 70-90 nm according to the ratio of 5: mixing the raw materials in a mass ratio of 95-15: 85 to form zirconium oxide powder; adding SA and PEI into absolute ethyl alcohol, carrying out water bath to 60 ℃, adding zirconium oxide powder while stirring, and then carrying out spray drying to obtain composite modified zirconium oxide powder, wherein the spray drying is carried out under 10-12 MPa, the air inlet temperature is 220-230 ℃, the air outlet temperature is 60-80 ℃, the fan rotation frequency is 40-50 Hz, and the peristaltic pump rotation speed is 60-70 mL/h; the mass ratio of the SA to the PEI to the absolute ethyl alcohol is 1: 0.5-0.7: 8-9, and the mass ratio of the zirconia powder to the ethanol solution of the SA to the PEI is 1: 4.5-5;
mixing polyurethane acrylate (PUA) and 1, 6-hexanediol diacrylate (HDDA) according to a mass ratio of 7:3 to form a premixed liquid, adding composite modified zirconia powder into the premixed liquid while stirring for multiple times, then sequentially adding a dispersing agent and a phenyl bis (2,4, 6-Trimethylbenzoyl) Phosphine Oxide (TPO) photoinitiator to form a mixture and zirconia grinding balls, wherein the ball-milling rotation speed is 300-350 prm, the ball-milling time is 4-5 h to obtain zirconia ceramic slurry, the percentage content of each component is 90-94 wt% of the zirconia powder, the dispersing agent is 1.5-2.5%, the photoinitiator is 0.6-1%, and the balance is the premixed liquid, and the dispersing agent is any one of DISPERBYK-110, DISPERBYK-W969 and DISPERBYK-2020;
(2) light curing treatment
The zirconia ceramic slurry is coated according to the layer thickness of 30-70um under the condition that the light intensity is 283mW/cm2Exposing for 10-30s under an ultraviolet light area source with the wavelength of 405nm, and curing to obtain a zirconia ceramic blank;
(3) five-stage degreasing treatment
Heating the cured ceramic blank to 180-200 ℃ at the speed of 1-1.5 ℃/min from room temperature in an atmospheric pressure environment, and keeping the temperature for 60 min; heating to 375-385 ℃ at the speed of 1-1.5 ℃/min, and preserving the heat for 120 min; heating to 435-445 ℃ at a speed of 1-1.5 ℃/min, and keeping the temperature for 120 min; heating to 625-630 ℃ at a speed of 1-1.5 ℃/min, and keeping the temperature for 240 min; heating to 1000 ℃ at the speed of 2 ℃/min, preserving heat for 30min, and then cooling to room temperature along with the furnace;
(4) staged sintering
The zirconium oxide ceramic blank after degreasing treatment is subjected to vacuum degree of 0.5-1 multiplied by 10-3Raising the temperature to 1000 ℃ under Pa, preserving heat for 30-40 min, introducing nitrogen, adjusting the pressure to 1000-3000 Pa, raising the temperature to 1250 ℃, preserving heat for 30-40 min, raising the temperature to 1450 ℃, preserving heat for 30-40 min, reducing the temperature to 1100 ℃, preserving heat for 30-40 min, and cooling along with the furnace.
If the control is improper in the sintering process, the temperature conduction generates gradient in the ceramic blank, the sintering shrinkage of the surface layer and the center of the blank is inconsistent, the densification is uneven, and the blank deforms, at the moment, if the defects such as holes, microcracks and the like exist in the blank, the defects are increased and become fracture sources, so that the cracking occurs, high-energy atoms cause substance migration, the grain boundary diffusion is formed, the abnormal growth of grains easily occurs, and the performance reduction such as hardness, fracture toughness and the like is caused.
In the sintering process, firstly, sintering is carried out at 1000 ℃ under the condition of lower vacuum degree, so that closed air holes are formed in a ceramic blank, then, the pressure is adjusted, so that pressure difference is formed inside and outside the closed air holes, the temperature is sequentially increased to 1250 ℃ and 1400 ℃, and segmented short-time heat preservation sintering is carried out, so that the closed air holes are uniformly and slowly shrunk, wherein the zirconia powder with larger grain size mainly generates densification in the initial sintering stage, no grain growth exists, the zirconia powder with smaller grain size has grain growth in the initial sintering stage, and the grain growth and densification synchronously occur. The growth of the air holes is controlled by the growth of crystal grains and the densification, the former synchronously grows the air holes and the crystal grains, the interaction of the driving force of the movement of the crystal grain interface and the traction force applied to the air holes by the interface is adjusted in the later sintering process, so that the crystal grain boundary can move with the air holes to diffuse, and the latter shrinks the air holes to cooperate to form high densification to the ceramic body. In the final cooling and heat preservation process, the surface of the ceramic material generates crystal form transformation from a tetragonal form to a monoclinic form, and volume expansion is generated, so that residual compressive stress is formed on the surface of the ceramic material, and the toughness of the material is enhanced.
The invention has the following technical effects:
the zirconia ceramic material prepared by the invention has excellent uniformity, no microcrack and delamination, excellent compactness up to 90.2-99.6%, few defects such as holes and cracks, 230-260 nm of grain size, 13.9-14.6 GPa of Vickers hardness, and 7.67-9.85 MPa.m.toughness of fracture1/2The bending strength is 449.3 to 462.7 MPa.
Drawings
FIG. 1: the zirconia ceramic slurry prepared by the invention has the characteristics.
FIG. 2: the surface topography of the zirconia ceramic slurry prepared by the invention after photocuring.
FIG. 3: the surface topography of the sintered zirconia ceramic material is shown.
Detailed Description
The present invention is described in detail below by way of examples, it should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and those skilled in the art can make some insubstantial modifications and adaptations of the present invention based on the above-mentioned disclosure.
Example 1
A method for preparing a high-performance zirconia ceramic material through DLP-3D printing is characterized by comprising the following steps:
(1) preparation of zirconia ceramic slurry
Mixing zirconium oxide powder 1 with yttrium-stabilized grain size of 26-39 nm and particle size of 30nm and zirconium oxide powder 2 with particle size of 70nm according to the ratio of 5: 95 to form zirconia powder; adding SA and PEI into absolute ethyl alcohol, carrying out water bath to 60 ℃, adding zirconium oxide powder while stirring, and then carrying out spray drying to obtain composite modified zirconium oxide powder, wherein the spray drying is carried out under 10MPa, the air inlet temperature is 230 ℃, the air outlet temperature is 60 ℃, the fan rotation frequency is 50Hz, and the peristaltic pump rotation speed is 70 mL/h; the mass ratio of the SA to the PEI to the absolute ethyl alcohol is 1:0.5:8, and the mass ratio of the zirconia powder to the ethanol solution of the SA to the PEI is 1: 4.5;
mixing polyurethane acrylate (PUA) and 1, 6-hexanediol diacrylate (HDDA) according to a mass ratio of 7:3 to form a premixed liquid, adding composite modified zirconia powder into the premixed liquid for multiple times while stirring, then sequentially adding a DISPERBYK-W969 dispersant and a phenylbis (2,4, 6-Trimethylbenzoyl) Phosphine Oxide (TPO) photoinitiator to form a mixture and zirconia grinding balls, wherein the ball-milling rotation speed is 300prm, the ball-milling time is 5 hours, and the zirconia ceramic slurry is obtained, wherein the percentage content of each component is 94wt% of zirconia powder, 1.5% of dispersant, 1% of photoinitiator and the balance of the premixed liquid;
(2) light curing treatment
The zirconia ceramic slurry is coated according to the thickness of 30um under the condition that the light intensity is 283mW/cm2Exposing for 10s under an ultraviolet light surface light source with the wavelength of 405nm, and curing to obtain a zirconia ceramic blank;
(3) five-stage degreasing treatment
Heating the cured ceramic blank to 180 ℃ from room temperature at the speed of 1 ℃/min under the atmospheric pressure environment, and preserving the heat for 60 min; heating to 375 ℃ at the speed of 1 ℃/min, and keeping the temperature for 120 min; heating to 435 deg.C at 1 deg.C/min, and maintaining for 120 min; heating to 625 deg.C at 1 deg.C/min, and maintaining for 240 min; heating to 1000 ℃ at the speed of 2 ℃/min, preserving heat for 30min, and then cooling to room temperature along with the furnace;
(4) staged sintering
Degreasing the zirconium oxide ceramic blank at the vacuum degree of 1 × 10-3Heating to 1000 deg.C under Pa, maintaining the temperature for 30min, introducing nitrogen, and adjusting pressure toRaising the temperature to 1250 ℃ under 1000Pa, preserving heat for 30min, raising the temperature to 1450 ℃, preserving heat for 30min, reducing the temperature to 1100 ℃, preserving heat for 30min, and then cooling along with the furnace.
The zirconia ceramic slurry prepared in this example has a solid content of 94wt%, a viscosity of 1.39 Pa · s (the viscosity difference detected by different viscosity detectors is large, in the present invention, a rotational rheometer AR 1500ex, TA Instruments, US is used for detecting the viscosity), and the viscosity decreases with the increase of the shear rate, the prepared zirconia ceramic material has an excellent density of up to 99.6%, and has few defects such as holes and cracks, the grain size of the material is 230-260 nm, the vickers hardness is 13.9GPa, and the fracture toughness is 9.85MPa · m1/2The bending strength was 449.3 MPa.
Example 2
A method for preparing a high-performance zirconia ceramic material through DLP-3D printing is characterized by comprising the following steps:
(1) preparation of zirconia ceramic slurry
Mixing zirconia powder 1 with yttrium stable grain size of 26-39 nm and grain size of 40nm and zirconia powder 2 with grain size of 90nm according to the mass ratio of 15:85 to form zirconia powder; adding SA and PEI into absolute ethyl alcohol, carrying out water bath to 60 ℃, adding zirconium oxide powder while stirring, and then carrying out spray drying to obtain composite modified zirconium oxide powder, wherein the spray drying is carried out under 12MPa, the air inlet temperature is 220 ℃, the air outlet temperature is 80 ℃, the rotating frequency of a fan is 40Hz, and the rotating speed of a peristaltic pump is 60 mL/h; the mass ratio of SA, PEI and absolute ethyl alcohol is 1: 0.7:9, and the mass ratio of the zirconia powder to the ethanol solution of SA and PEI is 1: 5;
mixing polyurethane acrylate (PUA) and 1, 6-hexanediol diacrylate (HDDA) according to a mass ratio of 7:3 to form a premixed liquid, adding composite modified zirconia powder into the premixed liquid for multiple times while stirring, then sequentially adding a DISPERBYK-110 dispersant and a phenyl bis (2,4, 6-Trimethylbenzoyl) Phosphine Oxide (TPO) photoinitiator to form a mixture and zirconia grinding balls, wherein the grinding speed is 350prm, the grinding time is 4 hours to obtain zirconia ceramic slurry, the percentage content of each component is 90wt% of zirconia powder, the percentage content of the dispersant is 2.5%, the percentage content of the photoinitiator is 1%, and the balance is the premixed liquid;
(2) light curing treatment
The zirconia ceramic slurry is coated according to the thickness of 70um under the condition that the light intensity is 283mW/cm2Exposing for 30s under an ultraviolet light surface light source with the wavelength of 405nm, and curing to obtain a zirconia ceramic blank;
(3) five-stage degreasing treatment
Heating the cured ceramic blank to 200 ℃ at the speed of 1.5 ℃/min from room temperature in an atmospheric pressure environment, and keeping the temperature for 60 min; heating to 385 ℃ at the speed of 1.5 ℃/min, and keeping the temperature for 120 min; heating to 445 deg.C at 1.5 deg.C/min, and maintaining for 120 min; heating to 630 ℃ at a speed of 1.5 ℃/min, and keeping the temperature for 240 min; heating to 1000 ℃ at the speed of 2 ℃/min, preserving heat for 30min, and then cooling to room temperature along with the furnace;
(4) staged sintering
The degreased zirconia ceramic body is processed in a vacuum degree of 0.5 multiplied by 10-3Heating to 1000 ℃ under Pa, preserving heat for 40min, introducing nitrogen, adjusting the pressure to 3000Pa, heating to 1250 ℃, preserving heat for 40min, heating to 1450 ℃, preserving heat for 40min, cooling to 1100 ℃, preserving heat for 40min, and cooling along with the furnace.
The zirconia ceramic slurry prepared in this example had a solid content of 90wt% and a solids content of 30S-1The viscosity under the shearing rate is 1.03 Pa.s, the viscosity is reduced along with the increase of the shearing rate, the prepared zirconia ceramic material has excellent compactness up to 90.2 percent, few defects such as holes, cracks and the like, the grain size of the material is 230-260 nm, the Vickers hardness is 13.9GPa, and the fracture toughness is 7.67 MPa.m1/2The flexural strength was 455.4 MPa.
Example 3
A method for preparing a high-performance zirconia ceramic material through DLP-3D printing is characterized by comprising the following steps:
(1) preparation of zirconia ceramic slurry
Mixing zirconium oxide powder 1 with yttrium stable grain size of 26-39 nm and particle size of 35nm and zirconium oxide powder 2 with particle size of 80nm according to a mass ratio of 10:90 to form zirconium oxide powder; adding SA and PEI into absolute ethyl alcohol, carrying out water bath to 60 ℃, adding zirconium oxide powder while stirring, and then carrying out spray drying to obtain composite modified zirconium oxide powder, wherein the spray drying is carried out under 12MPa, the air inlet temperature is 225 ℃, the air outlet temperature is 70 ℃, the rotating frequency of a fan is 45Hz, and the rotating speed of a peristaltic pump is 65 mL/h; the mass ratio of SA, PEI and absolute ethyl alcohol is 1: 0.6:8.5, and the mass ratio of the zirconia powder to the ethanol solution of SA and PEI is 1: 4.5;
mixing polyurethane acrylate (PUA) and 1, 6-hexanediol diacrylate (HDDA) according to a mass ratio of 7:3 to form a premixed liquid, adding composite modified zirconia powder into the premixed liquid for multiple times while stirring, then sequentially adding DISPERBYK-2020 dispersant and phenyl bis (2,4, 6-Trimethylbenzoyl) Phosphine Oxide (TPO) photoinitiator to form a mixture and zirconia grinding balls, wherein the grinding speed is 300-350 prm, the grinding time is 4-5 h, and the zirconia ceramic slurry is obtained, wherein the percentage content of each component is 91wt% of zirconia powder, the percentage content of dispersant is 2%, the percentage content of photoinitiator is 0.8%, and the balance is the premixed liquid;
(2) light curing treatment
The zirconia ceramic slurry is coated according to the thickness of 50um under the condition that the light intensity is 283mW/cm2Exposing for 20s under an ultraviolet light surface light source with the wavelength of 405nm, and curing to obtain a zirconia ceramic blank;
(3) five-stage degreasing treatment
Heating the cured ceramic blank to 190 ℃ from room temperature at the speed of 1 ℃/min under the atmospheric pressure environment, and preserving the heat for 60 min; heating to 380 ℃ at the speed of 1.5 ℃/min, and keeping the temperature for 120 min; heating to 440 ℃ at a temperature of 1 ℃/min, and keeping the temperature for 120 min; heating to 625 deg.C at 1 deg.C/min, and maintaining for 240 min; heating to 1000 ℃ at the speed of 2 ℃/min, preserving heat for 30min, and then cooling to room temperature along with the furnace;
(4) staged sintering
The degreased zirconia ceramic body is processed in a vacuum degree of 0.8 multiplied by 10-3Heating to 1000 ℃ under Pa, preserving heat for 35min, introducing nitrogen, adjusting the pressure to 2000Pa, heating to 1250 ℃, preserving heat for 35min, heating to 1450 ℃, preserving heat for 35min, cooling to 1100 ℃, preserving heat for 35min, and cooling along with the furnace.
The zirconia ceramic slurry prepared in this example had a solids content of 91wt%, 30S-1A viscosity at a shear rate of 1.19 pas, and a viscosity decreased with an increase in the shear rate,as shown in FIG. 3 (with a scale of 200 nm), the zirconia ceramic material prepared by the embodiment has excellent compactness of up to 99.4%, few defects such as holes and cracks, a grain size of 230-260 nm, a Vickers hardness of 14.1GPa, and a fracture toughness of 8.19 MPa.m1/2The flexural strength was 462.7 MPa.
Comparative example 1
Compared with the embodiment 3, unmodified zirconia powder with the particle size of 80nm is used for preparing the zirconia ceramic slurry in the step (1), the percentage content of each component is 91wt% of the zirconia powder, the dispersant accounts for 2wt% of the total mass, the photoinitiator accounts for 0.8wt%, the rest is premixed liquid, and the dispersant is DISPERBYK-2020;
the zirconia ceramic slurry was subjected to a curing treatment, a degreasing treatment and a sintering treatment in the same order as in example 3.
The ceramic slurry prepared in comparative example 1 had a solid content of 91wt%, 30S-1The viscosity at the shear rate is 8.77 Pa.s, the prepared zirconia ceramic material has excellent compactness up to 84.4 percent and obvious defects of cracks, layering and the like, the grain size of the material is 280-580 nm, the size span of the grains is large, the Vickers hardness is 8.2GPa, and the fracture toughness is 4.46 MPa.m1/2The flexural strength was 336.9 MPa.
Comparative example 2
Compared with the embodiment 3, the steps (1) to (3) are kept the same as the embodiment 3, and the step (4) of the step segmented sintering process adopts the method of directly forming the vacuum with the thickness of 0.8 multiplied by 10-3Raising the temperature to 1250 ℃ under Pa, preserving heat for 35min, raising the temperature to 1450 ℃, preserving heat for 35min, and then cooling along with the furnace.
The zirconia ceramic material prepared by the comparative example 2 has excellent compactness reaching 92.4 percent, has a small amount of defects of cracks, air holes and the like, and has the grain size of 260-350 nm, the Vickers hardness of 10.9GPa and the fracture toughness of 6.27 MPa.m1/2The flexural strength was 384.7 MPa.
Claims (8)
1. A method for preparing a high-performance zirconia ceramic material through DLP-3D printing is characterized by comprising the following steps: firstly, preparing zirconia ceramic slurry, carrying out photocuring treatment to obtain a zirconia ceramic blank, then carrying out degreasing treatment and staged sintering treatment, wherein the sintering treatment is to heat the degreased zirconia ceramic blank to 1000 ℃ in vacuum, preserving heat for 30-40 min, then introducing nitrogen, heating to 1250 ℃, preserving heat for 30min, heating to 1450 ℃, preserving heat for 30min, cooling to 1100 ℃, preserving heat for 30min, and then cooling along with a furnace.
2. The method for preparing the high-performance zirconia ceramic material by DLP-3D printing according to claim 1, wherein the method comprises the following steps: the preparation method of the ceramic slurry comprises the steps of adding zirconium oxide powder into an absolute ethyl alcohol solution of Stearic Acid (SA) and Polyethyleneimine (PEI), carrying out high-temperature and high-pressure spray drying to obtain modified zirconium oxide powder, adding a premixed solution formed by urethane acrylate (PUA) and 1, 6-hexanediol diacrylate (HDDA) according to a mass ratio of 7:3, and then adding a dispersing agent and a photoinitiator for mixing.
3. The method for preparing the high-performance zirconia ceramic material by DLP-3D printing according to claim 2, wherein the method comprises the following steps: the zirconia powder is prepared from zirconia powder with the particle size of 30-40 nm and gadolinium oxide high powder with the particle size of 70-90 nm according to the mass ratio of 5: 95-15: 85.
4. The method for preparing the high-performance zirconia ceramic material by DLP-3D printing according to claim 2 or 3, wherein the method comprises the following steps: the mass ratio of the SA to the PEI to the absolute ethyl alcohol is 1: 0.5-0.7: 8-9, and the mass ratio of the zirconia powder to the absolute ethyl alcohol solution of the SA to the PEI is 1: 4.5-5.5.
5. The method for preparing high-performance zirconia ceramic material by DLP-3D printing according to any one of claims 2 to 4, wherein: the dispersing agent is any one of DISPERBYK-110, DISPERBYK-W969 and DISPERBYK-2020, and the photoinitiator is phenyl bis (2,4, 6-Trimethylbenzoyl) Phosphine Oxide (TPO).
6. The method for preparing high-performance zirconia ceramic material by DLP-3D printing according to any one of claims 2 to 5, wherein: the zirconia ceramic slurry comprises 90-94 wt% of zirconia powder, 1.5-2.5 wt% of dispersant, 0.6-1% of photoinitiator and the balance of premixed liquid.
7. The method for preparing the high-performance zirconia ceramic material by DLP-3D printing according to claim 6, wherein the method comprises the following steps: in the degreasing step, the temperature of the cured ceramic blank is increased to 180-200 ℃ from room temperature at the speed of 1-1.5 ℃/min, and the temperature is kept for 60 min; heating to 375-385 ℃ at the speed of 1-1.5 ℃/min, and preserving the heat for 120 min; heating to 435-445 ℃ at a speed of 1-1.5 ℃/min, and keeping the temperature for 120 min; heating to 625-630 ℃ at a speed of 1-1.5 ℃/min, and keeping the temperature for 240 min; heating to 1000 ℃ at the speed of 2 ℃/min, preserving heat for 30min, and then carrying out five-stage degreasing treatment by furnace cooling to room temperature.
8. A method for preparing a high-performance zirconia ceramic material through DLP-3D printing is characterized by comprising the following steps:
(1) preparation of zirconia ceramic slurry
(a) Mixing yttrium-stabilized zirconia powder 1 with the particle size of 30-40 nm and zirconia powder 2 with the particle size of 70-90 nm according to the ratio of 5: mixing the raw materials in a mass ratio of 95-15: 85 to form zirconium oxide powder; adding SA and PEI into absolute ethyl alcohol, carrying out water bath to 60 ℃, adding zirconium oxide powder while stirring, and then carrying out spray drying to obtain composite modified zirconium oxide powder, wherein the spray drying is carried out under the conditions of 10-12 MPa, the air inlet temperature of 220-230 ℃ and the air outlet temperature of 60-80 ℃; the mass ratio of the SA to the PEI to the absolute ethyl alcohol is 1: 0.5-0.7: 8-9, and the mass ratio of the zirconia powder to the ethanol solution of the SA to the PEI is 1: 4.5-5;
(b) mixing polyurethane acrylate (PUA) and 1, 6-hexanediol diacrylate (HDDA) according to a mass ratio of 7:3 to form a premixed liquid, adding composite modified zirconia powder into the premixed liquid while stirring for multiple times, then sequentially adding a dispersing agent and a phenyl bis (2,4, 6-Trimethylbenzoyl) Phosphine Oxide (TPO) photoinitiator to form a mixture and zirconia grinding balls, wherein the ball-milling rotation speed is 300-350 prm, the ball-milling time is 4-5 h to obtain zirconia ceramic slurry, the percentage content of each component is 90-94 wt% of the zirconia powder, the dispersing agent is 1.5-2.5%, the photoinitiator is 0.6-1%, and the balance is the premixed liquid, and the dispersing agent is any one of DISPERBYK-110, DISPERBYK-W969 and DISPERBYK-2020;
(2) light curing treatment
The zirconia ceramic slurry is coated according to the layer thickness of 30-70um under the condition that the light intensity is 283mW/cm2Exposing for 10-30s under an ultraviolet light area source with the wavelength of 405nm, and curing to obtain a zirconia ceramic blank;
(3) five-stage degreasing treatment
Heating the cured ceramic blank to 180-200 ℃ at the speed of 1-1.5 ℃/min from room temperature in an atmospheric pressure environment, and keeping the temperature for 60 min; heating to 375-385 ℃ at the speed of 1-1.5 ℃/min, and preserving the heat for 120 min; heating to 435-445 ℃ at a speed of 1-1.5 ℃/min, and keeping the temperature for 120 min; heating to 625-630 ℃ at a speed of 1-1.5 ℃/min, and keeping the temperature for 240 min; heating to 1000 ℃ at the speed of 2 ℃/min, preserving heat for 30min, and then cooling to room temperature along with the furnace;
(4) staged sintering
Heating the degreased zirconia ceramic blank to 1000 ℃ in vacuum, preserving heat for 30-40 min, introducing nitrogen, heating to 1250 ℃, preserving heat for 30-40 min, heating to 1450 ℃, preserving heat for 30-40 min, cooling to 1100 ℃, preserving heat for 30-40 min, and cooling along with the furnace.
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