CN113968734B - Preparation method of high-density zirconia ceramic material - Google Patents
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Abstract
A preparation method of a high-compactness zirconia ceramic material comprises the steps of carrying out high-temperature high-pressure spray drying composite modification on zirconia powder by Stearic Acid (SA) and Polyethyleneimine (PEI) to prepare zirconia ceramic slurry, carrying out ultraviolet irradiation curing to obtain a ceramic blank, carrying out five-stage degreasing treatment at the atmospheric pressure and at the temperature of 180-1000 ℃, wherein the vacuum degree is 10 ‑3 And (3) heating the Pa to 1000 ℃ for high-temperature treatment, and finally, regulating the pressure to 1000-3000 Pa by adopting nitrogen to perform segmented high-temperature sintering. The solid content of the zirconia slurry prepared by the invention is 90-94% and is 30S ‑1 The lower viscosity is 1.05-1.39 Pa.s, the prepared zirconia ceramic material has no crack and no layering defect, the shrinkage rate after degreasing and sintering is 14-18%, the sintering density reaches 98.9-99.7%, the ceramic has good uniformity, and no crack, layering and other defects are generated.
Description
Technical Field
The invention relates to the technical field of additive manufacturing, in particular to a preparation method of a high-compactness zirconia ceramic material.
Background
The zirconia ceramics are widely applied to the fields of chemical industry, machinery, electronics, aerospace, biomedicine and the like due to the excellent physical characteristics of mechanical strength, high temperature resistance, corrosion resistance, chemical stability and the like. The conventional ceramic preparation process generally comprises mixing ceramic powder with a binder or other additives, preparing the mixture into a desired shape by various methods such as injection molding, compression molding, casting, gel casting and the like, and densifying the mixture by processes such as drying, high-temperature degreasing, sintering and the like. However, most of the traditional preparation methods need to manufacture a mold in advance, so that the whole preparation period is long, and ceramic parts with highly complex structures, particularly with mesopores and porosities, cannot be prepared. With the advancement and development of science and technology, 3D printing technology is changing day by day, and the most prominent is digital light processing technology.
Digital Light Processing (DLP) 3D printing to prepare zirconia ceramics is a hotspot of additive manufacturing technology. Compared with the 3D printing technology of other ceramic materials, the DLP-3D printing technology is high in speed and high in product precision. However, DLP-3D printed ceramic materials require a high solids content low viscosity slurry. DLP-3D printing zirconia ceramic slurry contains more resin materials, because the ceramic slurry is required to have lower viscosity, the low viscosity reduces cracks and improves the uniformity of microstructure, but the low viscosity is ensured, the solid content of the prepared slurry is low, the resin material is decomposed to release a large amount of gas, internal chemical water and partial components to volatilize during high-temperature degreasing, and sintering after the high-temperature degreasing ensures that the material has larger shrinkage rate to form great deformation, the factors enable the material to easily generate the defects of cracks, layers, pores and the like, the defects can be amplified in the sintering process, the sintering density of the material is reduced, and the performance of the prepared ceramic material is influenced.
Disclosure of Invention
The invention aims to provide a preparation method of a high-density zirconia ceramic material.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a high-compactness zirconia ceramic material is characterized by comprising the following steps: performing high-temperature high-pressure spray drying composite modification on zirconium oxide powder by using Stearic Acid (SA) and Polyethyleneimine (PEI) to prepare zirconium oxide ceramic slurry, performing ultraviolet irradiation curing to obtain a ceramic blank, performing five-stage degreasing treatment at 180-1000 ℃ under atmospheric pressure, and performing vacuum degree of 10 -3 And (3) heating the Pa to 1000 ℃ for high-temperature treatment, and finally, regulating the pressure to 1000-3000 Pa by adopting nitrogen to perform segmented high-temperature sintering.
Further, the composite modification is to mix 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 mass ratio of 5: and (5) adding 95-15: 85 into an ethanol solution of SA and PEI, stirring and mixing, and then carrying out high-temperature high-pressure spray drying to obtain the modified zirconia powder.
Further, in the ethanol solution of SA and PEI, the ethanol is absolute ethanol, the mass ratio of SA, PEI and absolute ethanol is 1: 0.4-0.6: 8.5-10, and the mass ratio of the zirconia powder to the ethanol solution of SA and PEI is 1: 4.5-5.
Further, the high-temperature and high-pressure spray drying is carried out under the pressure of 10-12 MPa, the air inlet temperature is 220-230 ℃, the air outlet temperature is 60-80 ℃, the rotation frequency of a fan is 40-50 Hz, and the rotation speed of a peristaltic pump is 60-70 mL/h.
In the modification process, carboxyl in SA reacts with hydroxyl on the high-surface maintenance to generate monomolecular acid on the surface, so that internal friction is reduced, the fluidity of the zirconia powder is enhanced, the carboxyl on the surface of SA is activated in a high-temperature and high-pressure spraying environment, the carboxyl reacts with amino in PEI, the space steric hindrance is formed on the long chain of SA coated on the surface of the zirconia in SA-PEI, the monomolecular acid on the surface of the zirconia promotes the protonation of the amino, so that the surface of the powder has positive charges, and the zirconia powder is uniformly dispersed in slurry and does not have the phenomena of agglomeration, caking and the like under the action of electrostatic repulsion.
In addition, the zirconia powder with two specific particle sizes is combined, the zirconia powder with a larger particle size forms a slurry system with lower viscosity, the zirconia powder with a smaller particle size enters gaps among the zirconia powder with a larger particle size to form secondary filling, the modified zirconia powder is effectively spheroidized by spray drying at high temperature and high pressure, the crystal boundary of zirconia is reduced, so that the contact area among powder particles is reduced, the binding force is reduced, the friction among the powder particles is further reduced, and the relative motion among the powder is increased, so that the viscosity of the system can not be increased while the solid content of the slurry is increased, the zirconia ceramic slurry with high solid content and low viscosity is obtained, the solid content is high, the volume is reduced in the heat treatment process, the crystal particles grow more compactly, the gaps among the particles are smaller, and the density of the finished ceramic material is higher, the higher the relative density is, the foundation is laid for the subsequent preparation of the high-density zirconia ceramic material.
Further, the zirconia ceramic slurry is a premixed solution formed by polyurethane acrylate (PUA) and 1, 6-hexanediol diacrylate (HDDA), and the modified zirconia powder, the dispersant and the photoinitiator are sequentially added.
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 percentage content of each component in the zirconia ceramic slurry is that the modified zirconia powder is 90-94%, the dispersant is 1-3%, the photoinitiator is 0.5-1.2%, and the rest is the premixed liquid.
Further, the wavelength of the ultraviolet light is 405nm, and the light intensity is 283mW/cm 2 And the irradiation time is 10-30 s.
Further, the five-stage degreasing treatment comprises the following steps: starting from room temperature, heating to 180 ℃ within 180min, keeping the temperature for 60min, heating to 375 ℃ within 195min, keeping the temperature for 120min, heating to 440min within 65min, keeping the temperature for 120min, heating to 620min within 180min, keeping the temperature for 240min, heating to 1000 ℃ within 190min, keeping the temperature for 30min, and then cooling to room temperature along with the furnace.
Because the ceramic slurry has higher solid content and slower heat transfer, the invention adopts five-stage degreasing, in the first stage of 185-375 ℃, hydroxyethyl acrylate is mainly dissociated from PUA, the degradation of urethane bonds is mainly carried out when the temperature is kept at 375-440 ℃, the degradation of urea bonds is mainly carried out above 440 ℃, and HDDA is also decomposed from 440-620 ℃. 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.
Further, the high temperature treatment in the vacuum is 10 -3 Heating to 1000 ℃ within 325min under the vacuum condition of Pa, and preserving heat for 60 min.
Further, the step sintering treatment comprises: heating to 1350 ℃ within 175min, keeping the temperature for 30min, heating to 1600 ℃ within 125min, keeping the temperature for 60min, cooling to 1400 ℃ within 110min, keeping the temperature for 30min, and then cooling to room temperature along with the furnace.
In the invention, zirconia ceramic slurry with high solid content and low viscosity is formed by zirconia components with specific particle sizes after composite modification in the slurry, substances in PUA are mainly removed in sections at the beginning of a sectional degreasing process at a lower degreasing temperature, substances in HDDA are mainly removed along with the gradual rise of the temperature, in the process, components in resin are slowly and completely decomposed in sections, formed pores are small and highly dispersed, the volume of a blank is reduced and the shape is reduced due to the high solid content of the slurry, in addition, in the sintering process, closed pores are formed by sintering at the temperature of 1000 ℃ under low vacuum degree firstly, then, after the pressure is regulated to rise, the pressure difference is formed inside and outside the closed pores, the material is sintered at the sectional high temperature to form uniform and stable shrinkage, and the zirconia with double particle sizes reduces the pores in the ceramic material through grain boundary diffusion and densification in a system, under a specific sintering environment, the zirconia with smaller grain size is diffused by carrying air holes through grain boundary growth, and the zirconia with larger grain size shrinks the air holes through densification, so that the density of the material is effectively improved, and the internal defects of the material are reduced.
Most specifically, the preparation method of the high-density zirconia ceramic material is characterized by comprising the following steps:
(1) preparation of ceramic slurry
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 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: 0.4-0.6: 8.5-10, 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 1-3 wt%, the photoinitiator is 0.5-1.2 wt%, and the balance is the premixed liquid, and the dispersing agent is any one of DISPERBYK-110, DISPERBYK-W969 and DISPERBYK-2020;
(2) curing treatment
The zirconia ceramic slurry is coated according to the layer thickness of 30-70um, and the light intensity is 283mW/cm 2 Exposing for 10-30s under an ultraviolet light area source with the wavelength of 405nm, and curing to obtain a zirconia ceramic blank;
(3) degreasing treatment
Heating the printed ceramic blank to 180 ℃ in 180min from room temperature under atmospheric pressure, and keeping the temperature for 60 min; heating to 375 ℃ in 195min, and keeping the temperature for 120 min; heating to 440 deg.C for 65min, and maintaining the temperature for 120 min; heating to 620 ℃ in 180min, and keeping the temperature for 240 min; heating to 1000 deg.C for 190min, and holding for 30 min. Then cooling to room temperature along with the furnace;
(4) sintering treatment
At 10 -3 Heating the degreased zirconia ceramic blank to 1000 ℃ for 325min under the vacuum condition of Pa, and preserving the temperature for 60 min; then introducing nitrogen, and adjusting the pressure to 1000-3000 Pa; heating to 1350 deg.C in 175min, and maintaining for 30 min; heating to 1600 deg.C for 125min, and maintaining the temperature for 60 min; cooling to 1400 ℃ in 110min, and keeping the temperature for 30 min; then the temperature is cooled to the room temperature along with the furnace.
The invention has the following technical effects:
the solid content of the prepared solid-phase catalyst is 90-94% and is 30S -1 The zirconia ceramic material prepared by combining the zirconia slurry with the lower viscosity of 1.05-1.39 Pa.s with the specific five-section degreasing process and the sectional sintering process has no cracks and no layering defects, the shrinkage rate after degreasing and sintering is 14-18%, the sintering density reaches 98.9-99.7%, the uniformity of the ceramic is good, and no cracks, layering and other defects are generated.
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 zirconia ceramic material prepared by the invention.
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 preparation method of a high-density zirconia ceramic material comprises the following steps:
(1) preparation of ceramic slurry
Mixing yttrium-stabilized zirconia powder 1 with the particle size of 30nm and zirconia powder 2 with the 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 12MPa, the air inlet temperature is 220 ℃, the air outlet temperature is 60 ℃, 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 1:0.4:8.5, 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 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 300prm, and the ball-milling time is 5 hours to obtain zirconia ceramic slurry, wherein the percentage content of each component is 90wt% of zirconia powder, the dispersing agent accounts for 3wt% of the total mass, the photoinitiator accounts for 0.5wt%, the rest is the premixed liquid, and the dispersing agent is DISPERBYK-110;
(2) curing treatment
The zirconia ceramic slurry is coated according to the thickness of 30um under the condition that the light intensity is 283mW/cm 2 Exposing for 10-30s under an ultraviolet light area source with the wavelength of 405nm, and curing to obtain a zirconia ceramic blank;
(3) degreasing treatment
Heating the printed ceramic blank to 180 ℃ in 180min from room temperature under atmospheric pressure, and keeping the temperature for 60 min; heating to 375 ℃ in 195min, and keeping the temperature for 120 min; heating to 440 deg.C for 65min, and maintaining the temperature for 120 min; heating to 620 ℃ in 180min, and keeping the temperature for 240 min; heating to 1000 deg.C for 190min, and holding for 30 min. Then cooling to room temperature along with the furnace;
(4) sintering treatment
At 10 -3 Heating the degreased zirconia ceramic blank to 1000 ℃ for 325min under the vacuum condition of Pa, and preserving the temperature for 60 min; then introducing nitrogen, and adjusting the pressure to 1000-3000 Pa; heating to 1350 deg.C in 175min, and maintaining for 30 min; heating to 1600 deg.C for 125min, and maintaining the temperature for 60 min; cooling to 1400 ℃ in 110min, and keeping the temperature for 30 min; then the temperature is cooled to the room temperature along with the furnace.
The zirconia ceramic slurry prepared in this example had a solid content of 90wt% and 30S -1 The viscosity of the zirconia ceramic material is 1.08 pas at the shear rate, the viscosity is reduced along with the increase of the shear rate, the uniformity is excellent, the phenomena of agglomeration, caking, uneven dispersion and the like are avoided, the shrinkage rate of the prepared zirconia ceramic material is 16.3 percent, the relative density is 99.4 percent, the uniformity of the ceramic is good, and no crack is generated.
Example 2
A preparation method of a high-density zirconia ceramic material comprises the following steps:
(1) preparation of ceramic slurry
Mixing yttrium-stabilized zirconia powder 1 with the particle size of 40nm and zirconia powder 2 with the particle 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 10MPa, the air inlet temperature is 230 ℃, the air outlet temperature is 80 ℃, the fan rotation frequency is 50Hz, and the peristaltic pump rotation speed is 70 mL/h; the mass ratio of SA, PEI and absolute ethyl alcohol is 1:0.6: 10, 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 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 350prm, the ball-milling time is 4 hours to obtain zirconia ceramic slurry, the percentage content of each component is that the zirconia powder is 94wt%, the dispersing agent accounts for 1wt%, the photoinitiator is 1.2wt%, and the balance is the premixed liquid, and the dispersing agent is DISPERBYK-W969;
(2) curing treatment
The zirconia ceramic slurry is coated according to the thickness of 60um under the condition that the light intensity is 283mW/cm 2 Exposing for 10-30s under an ultraviolet light area source with the wavelength of 405nm, and curing to obtain a zirconia ceramic blank;
(3) degreasing treatment
Heating the printed ceramic blank to 180 ℃ in 180min from room temperature under atmospheric pressure, and keeping the temperature for 60 min; heating to 375 ℃ in 195min, and keeping the temperature for 120 min; heating to 440 deg.C for 65min, and maintaining the temperature for 120 min; heating to 620 ℃ in 180min, and keeping the temperature for 240 min; heating to 1000 deg.C for 190min, and holding for 30 min. Then cooling to room temperature along with the furnace;
(4) sintering treatment
At 10 -3 Heating the degreased zirconia ceramic blank to 1000 ℃ for 325min under the vacuum condition of Pa, and preserving the temperature for 60 min; then introducing nitrogen, and adjusting the pressure to 1000-3000 Pa; heating to 1350 deg.C in 175min, and maintaining for 30 min; heating to 1600 deg.C for 125min, and maintaining the temperature for 60 min; cooling to 1400 ℃ in 110min, and keeping the temperature for 30 min; then the temperature is cooled to the room temperature along with the furnace.
The zirconia ceramic slurry prepared in this example had a solid content of 94wt%, 30S -1 The viscosity of the zirconia ceramic material is 1.39 Pa.s at the shear rate, the viscosity is reduced along with the increase of the shear rate, the uniformity is excellent, the phenomena of agglomeration, caking, uneven dispersion and the like are avoided, the shrinkage rate of the prepared zirconia ceramic material is 17.6 percent, the relative density is 98.9 percent, the uniformity of the ceramic is good, and no crack is generated.
Example 3
A preparation method of a high-density zirconia ceramic material comprises the following steps:
(1) preparation of ceramic slurry
Mixing yttrium-stabilized zirconia powder 1 with the particle size of 35nm and zirconia powder 2 with the particle size of 80nm according to the weight ratio of 10: 90 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 225 ℃, the air outlet temperature is 70 ℃, the fan rotation frequency is 45Hz, and the peristaltic pump rotation speed is 65 mL/h; the mass ratio of the SA to the PEI to the absolute ethyl alcohol is 1:0.5:9, and the mass ratio of the zirconia powder to the ethanol solution of the SA to the 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 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 320prm, the ball-milling time is 4.5 hours, and the zirconia ceramic slurry is obtained, wherein the percentage content of each component is 93wt% of the zirconia powder, the dispersing agent accounts for 2wt% of the total mass, the photoinitiator accounts for 0.8wt%, the balance is the premixed liquid, and the dispersing agent is DISPERBYK-2020;
(2) curing treatment
The zirconia ceramic slurry is coated according to the thickness of 70um under the condition that the light intensity is 283mW/cm 2 Exposing for 10-30s under an ultraviolet light area source with the wavelength of 405nm, and curing to obtain a zirconia ceramic blank;
(3) degreasing treatment
Heating the printed ceramic blank to 180 ℃ in 180min from room temperature under atmospheric pressure, and keeping the temperature for 60 min; heating to 375 ℃ in 195min, and keeping the temperature for 120 min; heating to 440 deg.C for 65min, and maintaining the temperature for 120 min; heating to 620 ℃ in 180min, and keeping the temperature for 240 min; heating to 1000 deg.C for 190min, and holding for 30 min. Then cooling to room temperature along with the furnace;
(4) sintering treatment
At 10 -3 Heating the degreased zirconia ceramic blank to 1000 ℃ for 325min under the vacuum condition of Pa, and preserving the temperature for 60 min; then introducing nitrogen, and adjusting the pressure to 1000-3000 Pa; heating to 1350 deg.C in 175min, and maintaining for 30 min; heating to 1600 deg.C for 125min, and maintaining the temperature for 60 min; cooling to 1400 ℃ in 110min, and keeping the temperature for 30 min; then the temperature is cooled to the room temperature along with the furnace.
The zirconia ceramic slurry prepared in this example had a solid content of 93wt%, 30S -1 The viscosity at the shear rate of the ceramic material is 1.28 Pa.s (the viscosity difference detected by different viscosity detectors is larger, the viscosity is detected by using a rotational rheometer AR 1500ex, TA Instruments and US in the invention), the viscosity is reduced along with the increase of the shear rate, the uniformity is excellent, the phenomena of agglomeration, uneven dispersion and the like do not exist, the appearance of the white interface after photocuring is shown in figure 1, the shrinkage rate of the degreased and sintered zirconia ceramic material is 14.2 percent, the relative density is 99.7 percent, the ceramic uniformity is good, and pores and cracks are not generated as shown in figure 3.
Comparative example 1
Mixing polyurethane acrylate (PUA) and 1, 6-hexanediol diacrylate (HDDA) according to a mass ratio of 7:3 to form a premixed liquid, adding zirconium oxide powder with the particle size of 80nm for multiple times while stirring, then sequentially adding a dispersing agent and a phenyl bis (2,4, 6-Trimethylbenzoyl) Phosphine Oxide (TPO) photoinitiator to form a mixture and zirconium oxide grinding balls, wherein the ball milling rotation speed is 320prm, the ball milling time is 4.5h to obtain zirconium oxide ceramic slurry, the percentage content of each component is 85wt% of zirconium oxide powder, the total mass of the dispersing agent is 2wt%, the total mass of the photoinitiator is 0.8wt%, the balance is the premixed liquid, and the dispersing agent is DISPERBYK-2020;
the zirconia ceramic slurry was subjected to the curing treatment, degreasing treatment and sintering treatment in the same manner as in example 3.
The zirconia ceramic slurry prepared in comparative example 1 has a solid content of 85wt%, a viscosity of 5.79 pas, a shrinkage of 28.9% and a relative density of 87.4%, and has significant microcracks, and the prepared ceramic material has poor structural uniformity.
Comparative example 2
Adding zirconium oxide powder with the particle size of 80nm into ethanol solution of SA heated in a water bath to 65 ℃ to form mixed solution, and then performing spray drying to obtain modified zirconium oxide powder, wherein the spray drying is performed under the condition of 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 to absolute ethyl alcohol is 1: 9, and the mass ratio of the zirconia powder to the ethanol solution of SA is 1: 5;
preparing the modified zirconia powder into ceramic slurry by adopting the step (1) of the embodiment 3;
the zirconia ceramic slurry was subjected to the same curing, degreasing and sintering treatments as in example 3 in this order in a layer thickness of 70 um.
The zirconia ceramic slurry prepared in comparative example 2 had a solid content of 93wt%, a viscosity of 3.62 Pa · s, a shrinkage of 22.9% and a relative density of 92.4%, and very few microcracks occurred.
Comparative example 3
Preparing zirconia ceramic slurry in sequence according to the steps (1) and (2) which are the same as those in the embodiment 3, and curing to obtain a zirconia ceramic blank;
(3) degreasing treatment
Heating the printed ceramic blank to 1000 ℃ from room temperature at a speed of 1 ℃/min under atmospheric pressure, keeping the temperature for 1h when the temperature rises by 100 ℃, and then cooling to room temperature along with the furnace;
(4) sintering treatment
At 10 -3 Heating to 1350 ℃ in 500min under Pa vacuum, and keeping the temperature for 90 min; heating to 1600 deg.C for 125min, and maintaining the temperature for 60 min; then the temperature is cooled to the room temperature along with the furnace.
The zirconia ceramic material prepared in comparative example 3 had a shrinkage of 24.7% and a relative density of 94.3%, had significant porosity, and had significant delamination and cracking during degreasing.
Claims (8)
1. A preparation method of a high-compactness zirconia ceramic material is characterized by comprising the following steps: hard zirconia powderPerforming high-temperature high-pressure spray drying composite modification on fatty acid (SA) and Polyethyleneimine (PEI) to prepare zirconia ceramic slurry, performing ultraviolet irradiation curing to obtain a ceramic blank, performing five-stage degreasing treatment at 180-1000 ℃ under atmospheric pressure, and performing vacuum degree of 10 -3 Heating Pa to 1000 ℃ for high-temperature treatment, and finally adopting nitrogen to adjust the pressure to 1000-3000 Pa for high-temperature sintering in sections; the step sintering treatment comprises the following steps: heating to 1350 ℃ within 175min, preserving heat for 30min, heating to 1600 ℃ within 125min, preserving heat for 60min, cooling to 1400 ℃ within 110min, preserving heat for 30min, and then cooling to room temperature along with the furnace; in the ethanol solution of the SA and the PEI, the ethanol is absolute ethanol, the mass ratio of the SA, the PEI and the absolute ethanol is 1: 0.4-0.6: 8.5-10, and the mass ratio of the zirconia powder to the ethanol solution of the SA and the PEI is 1: 4.5-5.
2. The method for preparing a zirconia ceramic material with high compactness according to claim 1, wherein: and the composite modification is to add zirconia powder with the particle size of 30-40 nm and zirconia powder with the particle size of 70-90 nm into ethanol solution of SA and PEI, stir and mix, and then carry out high-temperature high-pressure spray drying to obtain the modified zirconia powder.
3. The method for preparing a zirconia ceramic material with high compactness according to claim 1 or 2, wherein: the zirconia ceramic slurry is a premixed solution formed by polyurethane acrylate (PUA) and 1, 6-hexanediol diacrylate (HDDA), and modified zirconia powder, a dispersing agent and a photoinitiator are sequentially added.
4. A method for preparing a zirconia ceramic material with high compactness according to claim 3, wherein: the zirconia ceramic slurry comprises, by percentage, 90-94% of modified zirconia powder, 1-3% of a dispersant, 0.5-1.2% of a photoinitiator, and the balance of a premixed solution.
5. A high-density zirconia ceramic material as set forth in claim 4The preparation method is characterized by comprising the following steps: the wavelength of the ultraviolet light is 405nm, and the light intensity is 283mW/cm 2 And the irradiation time is 10-30 s.
6. The method for preparing a zirconia ceramic material with high compactness according to claim 5, wherein: the five-stage degreasing treatment comprises the following steps: starting from room temperature, heating to 180 ℃ within 180min, preserving heat for 60min, heating to 375 ℃ within 195min, preserving heat for 120min, heating to 440 ℃ within 65min, preserving heat for 120min, heating to 620 ℃ within 180min, preserving heat for 240min, heating to 1000 ℃ within 190min, preserving heat for 30min, and then cooling to room temperature along with the furnace.
7. The method for preparing a zirconia ceramic material with high compactness according to claim 6, wherein: the high temperature treatment in the vacuum is 10 -3 Heating to 1000 ℃ within 325min under the vacuum condition of Pa, and preserving heat for 60 min.
8. The preparation method of the high-density zirconia ceramic material is characterized by comprising the following steps of:
(1) preparation of ceramic slurry
Mixing yttrium-stabilized zirconia powder with the particle size of 30-40 nm and zirconia powder with the particle size of 70-90 nm according to the weight 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 and the PEI to the absolute ethyl alcohol is 1: 0.4-0.6: 8.5-10, and the mass ratio of the zirconia powder to the ethanol solution of the SA and 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 for multiple times while stirring, then sequentially adding a dispersing agent and a photoinitiator to form a mixture and zirconia grinding balls, wherein the ball-milling rotation speed is 300-350 rpm, the ball-milling time is 4-5 hours, and the zirconia ceramic slurry is obtained, wherein the percentage content of each component is 90-94 wt% of the zirconia powder, the dispersing agent accounts for 1-3 wt% of the total mass, the photoinitiator accounts for 0.5-1.2 wt%, and the balance is the premixed liquid;
(2) 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/cm 2 Exposing for 10-30s under an ultraviolet light area source with the wavelength of 405nm, and curing to obtain a zirconia ceramic blank;
(3) degreasing treatment
Heating the ceramic blank obtained by curing to 180 ℃ in 180min from room temperature under atmospheric pressure, and keeping the temperature for 60 min; heating to 375 deg.C in 195min, and maintaining the temperature for 120 min; heating to 440 deg.C for 65min, and maintaining the temperature for 120 min; heating to 620 deg.C for 180min, and maintaining the temperature for 240 min; heating to 1000 deg.C for 190min, maintaining the temperature for 30min, and cooling to room temperature;
(4) sintering treatment
At 10 -3 Heating the degreased zirconia ceramic blank to 1000 ℃ for 325min under the vacuum condition of Pa, and preserving the temperature for 60 min; then introducing nitrogen, and adjusting the pressure to 1000-3000 Pa; heating to 1350 deg.C for 175min, and maintaining for 30 min; heating to 1600 deg.C for 125min, and maintaining the temperature for 60 min; cooling to 1400 deg.C in 110min, and maintaining the temperature for 30 min; then the temperature is cooled to the room temperature along with the furnace.
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