CN112679210A - Electric-melting zirconia ceramic slurry for photocuring 3D printing and preparation method thereof - Google Patents
Electric-melting zirconia ceramic slurry for photocuring 3D printing and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an electric-melting zirconia ceramic slurry for photocuring 3D printing and a preparation method thereof, wherein the electric-melting zirconia ceramic slurry for photocuring 3D printing comprises 75-85% of electric-melting zirconia ceramic powder and 15-25% of photosensitive resin prefabricated liquid according to mass percentage; the electric melting zirconia ceramic powder comprises electric melting zirconia and a magnesia coating layer, wherein the magnesia coating layer wraps the surface of the electric melting zirconia, and the magnesia coating layer is 5-10% of the electric melting zirconia in mass percent. According to the electric-melting zirconia ceramic slurry for photocuring 3D printing, the electric-melting zirconia is used as core powder, so that the production cost of the zirconia ceramic slurry is greatly reduced, and the preparation method of the electric-melting zirconia ceramic slurry for photocuring 3D printing is simple in process and convenient to operate, and is beneficial to preventing the electric-melting zirconia ceramic slurry from settling.
Description
Technical Field
The invention relates to the technical field of additive manufacturing, in particular to an electric-melting zirconia ceramic slurry for photocuring 3D printing and a preparation method thereof.
Background
The ceramic material has the properties of high strength, high hardness, wear resistance, corrosion resistance and the like, is an important engineering material, and has wide application in the fields of aerospace, petrochemical industry, national defense and military industry, civil use and the like. In the conventional preparation process, a powder material is generally made into a green body by using a mold, and then the green body is sintered at a high temperature to obtain a ceramic component. The preparation method is limited by the manufacture of the die, and the development requirement of refinement and complication of the ceramic component is greatly restricted.
The 3D printing technology is a new material forming technology that has been developed rapidly in recent years. The controllable rapid forming of the material is realized by a layer-by-layer stacking mode, and the controllable rapid forming is also called as an additive manufacturing technology and a dieless manufacturing technology. It is especially suitable for the precise manufacture of three-dimensional entity with complex shape and high precision. The ceramic material generally has the characteristics of high hardness, large brittleness and difficult processing, so that the 3D printing technology is used for researching fire heat in the ceramic field, and particularly is a photocuring 3D printing technology with high precision and high forming speed.
The zirconia ceramic material has excellent performances of high melting point, high hardness, high toughness, high wear resistance, high thermal shock resistance, biocompatibility and the like, and is widely applied. Zirconia is classified into chemical zirconia and fused zirconia according to different production processes. The chemical zirconia is produced by adopting the processes of chlor-alkali chemical industry and high-temperature calcination, the product has high purity and good quality, but the production process flow is longer, a large amount of acid-base reagents are consumed, and the production cost is higher; the fused zirconia is produced by a physical method of electric arc furnace smelting, has short process flow and low production cost, is generally only 1/3 of chemical zirconia, but has slightly poor purity and some physical properties.
At present, the zirconia ceramic slurry used based on the photocuring 3D printing technology mostly uses high-purity superfine nano zirconia powder produced by a chemical method as a main raw material, but the application range of the high-purity superfine nano zirconia powder is very limited due to the overhigh cost.
Disclosure of Invention
The invention aims to provide the electrofusion zirconia ceramic slurry for photocuring 3D printing, which uses electrofusion zirconia as core powder, so that the production cost of the zirconia ceramic slurry is greatly reduced, and the defects in the prior art are overcome.
The invention also aims to provide a preparation method of the electrofused zirconia ceramic slurry for photocuring 3D printing, which has the advantages of simple process and convenient operation and is beneficial to preventing the electrofused zirconia ceramic slurry from settling.
In order to achieve the purpose, the invention adopts the following technical scheme:
the electrofusion zirconia ceramic slurry for photocuring 3D printing comprises 75-85% of electrofusion zirconia ceramic powder and 15-25% of photosensitive resin prefabricated liquid according to mass percentage;
the electric melting zirconia ceramic powder comprises electric melting zirconia and a magnesia coating layer, wherein the magnesia coating layer wraps the surface of the electric melting zirconia, and the magnesia coating layer is 5-10% of the electric melting zirconia in mass percent.
Preferably, the photosensitive resin prefabricated liquid comprises the following raw materials in parts by weight: 5-50 parts of free radical type polymer, 5-50 parts of active diluent, 0.5-5 parts of photoinitiator, 1-5 parts of dispersant and 1-5 parts of defoaming agent.
Preferably, the molecular weight of the free radical polymer is < 3000.
Preferably, the free radical type polymer is any one or combination of more of polyurethane acrylate, epoxy acrylate, polyester acrylate and bisphenol A epoxy acrylate.
Preferably, the reactive diluent is any one or a combination of more of 1, 6-hexanediol diacrylate, isobornyl acrylate, trimethylolpropane triacrylate, tripropylene glycol diacrylate and pentaerythritol triacrylate.
Preferably, the photoinitiator is any one or more of diphenyl (2,4, 6-trimethylbenzoyl) phosphine oxide, 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxy-cyclohexyl-phenyl ketone and 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone.
Preferably, the dispersant is any one or combination of more of silane coupling agent, stearic acid, oleic acid, ammonium polyacrylate, sodium polyacrylate and polyvidone.
Preferably, the defoaming agent is any one or a combination of mannitol, sodium dodecyl benzene sulfonate and polyethylene glycol.
The preparation method of the electrofusion zirconia ceramic slurry for photocuring 3D printing is used for preparing the electrofusion zirconia ceramic slurry for photocuring 3D printing and comprises the following steps:
(1) putting the fused zirconia into a magnesium nitrate solution for mixing to prepare a suspension;
(2) adding ammonia water into the suspension for mixing to obtain fused zirconia ceramic powder;
(3) mixing a free radical type polymer, a reactive diluent, a photoinitiator, a dispersant and a defoaming agent according to a ratio to obtain a photosensitive resin prefabricated liquid;
(4) adding the electric melting zirconia ceramic powder and the photosensitive resin prefabricated liquid into a ball mill according to the proportion for ball milling to obtain the electric melting zirconia ceramic slurry for photocuring 3D printing.
Preferably, in the step (4), the ball milling rotation speed in the ball milling step is 200-1000 r/min, and the ball milling time is 2-6 h.
The invention has the beneficial effects that:
1. this technical scheme provides an electric smelting zirconia ceramic thick liquids for photocuring 3D prints, and it uses electric smelting zirconia as core powder, greatly reduced zirconia ceramic thick liquids's manufacturing cost, be favorable to solving the too high problem of manufacturing cost of the zirconia ceramic thick liquids that present is used for photocuring 3D to print.
2. According to the technical scheme, the electric melting zirconia with the magnesia coating layer is used for replacing the common chemical zirconia as the core powder of the zirconia ceramic slurry, so that the problems of dispersibility and impurities caused by the electric melting zirconia powder can be effectively solved, and meanwhile, the improvement of the production cost is avoided.
3. In the technical scheme, the fused zirconia powder is wrapped by the magnesia, so that the absorption of the fused zirconia to ultraviolet light caused by impurities of the fused zirconia is reduced, the curing depth of the ceramic slurry is further improved, and the photocuring printing forming efficiency is finally improved; in addition, the surface property of the coated and modified fused zirconia powder can be optimized, so that the combination between the micron-sized fused zirconia powder and a dispersing agent in zirconia ceramic slurry is facilitated, the steric hindrance between the powder is increased, and the excellent dispersibility and stability of the micron-sized zirconia ceramic slurry are ensured.
4. According to the technical scheme, the magnesium oxide is used as a coating material of the electric melting zirconium oxide, and on one hand, the magnesium oxide is white, so that the ultraviolet light reflectivity is high, the absorbance is low, the curing depth in the printing process is favorably improved, and the printing forming efficiency is improved; on the other hand, the introduction of the magnesia can act as a zirconia sintering aid and is helpful for high-temperature densification sintering.
5. According to the technical scheme, the coated and modified electrofusion zirconia ceramic powder is introduced into the ceramic slurry, meanwhile, the dispersing agent and the defoaming agent are introduced into the raw materials of the ceramic slurry, the addition amount of the dispersing agent and the defoaming agent is further controlled together and accurately, synergistic effects are generated among the dispersing agent and the defoaming agent, and the excellent dispersibility and stability of the micron-sized zirconia ceramic slurry are further ensured.
Detailed Description
The zirconia ceramic material has excellent performances of high melting point, high hardness, high toughness, high wear resistance, high thermal shock resistance, biocompatibility and the like, and is widely applied. At present, the zirconia ceramic slurry used based on the photocuring 3D printing technology mostly uses high-purity superfine nano zirconia powder produced by a chemical method as a main raw material, but the application range of the high-purity superfine nano zirconia powder is very limited due to the overhigh cost.
In order to solve the problem that the production cost of the existing zirconia ceramic slurry for photocuring 3D printing is too high, the technical scheme provides the electrofused zirconia ceramic slurry for photocuring 3D printing, which comprises 75-85% of electrofused zirconia ceramic powder and 15-25% of photosensitive resin prefabricated liquid in percentage by mass;
the electric melting zirconia ceramic powder comprises electric melting zirconia and a magnesia coating layer, wherein the magnesia coating layer wraps the surface of the electric melting zirconia, and the magnesia coating layer is 5-10% of the electric melting zirconia in mass percent.
The electric-melting zirconia ceramic slurry for the photocuring 3D printing, which is provided by the technical scheme, uses the electric-melting zirconia as core powder, so that the production cost of the zirconia ceramic slurry is greatly reduced. Specifically, according to the mass percentage, the electric-melting zirconia ceramic slurry for the photocuring 3D printing comprises 75-85% of electric-melting zirconia ceramic powder and 15-25% of photosensitive resin prefabricated liquid; in the electro-fused zirconia ceramic slurry for photocuring 3D printing, the higher the solid content is, the lower the content of the remaining organic matter is, the smaller the loss on ignition in the subsequent high-temperature sintering process is, the shrinkage of the product is small in the sintering process, and the cracking and deformation are not easy to occur, so that the higher the solid content in the electro-fused zirconia ceramic slurry is, the better the solid content is, and the lower limit of the solid content is limited to 75% by the technical scheme; however, if the solid content in the electrically-fused zirconia ceramic slurry is higher, the viscosity of the slurry is also higher, and the slurry with the higher viscosity is difficult to flatten in the 3D printing process, which is not beneficial to smooth 3D printing process, so that the upper limit of the solid content is limited by the technical scheme.
Zirconia is classified into chemical zirconia and fused zirconia according to different production processes. The chemical zirconia is produced by adopting the processes of chlor-alkali chemical industry and high-temperature calcination, the product has high purity and good quality, but the production process flow is longer, a large amount of acid-base reagents are consumed, and the production cost is higher; the fused zirconia is produced by a physical method of electric arc furnace smelting, has short process flow and low production cost, is generally only 1/3 of chemical zirconia, but has low purity and slightly poor physical properties. Compared with chemical zirconia, the preparation of zirconia ceramic slurry by using the electrically fused zirconia for industrial use has greater difficulty, on one hand, because the granularity of the electrically fused zirconia is generally micron-sized and is coarser than the granularity of the nanoscale chemical zirconia, the ceramic slurry prepared by using the electrically fused zirconia is easy to settle, and the slurry is not uniformly dispersed; on the other hand, the purity of the product of the electric melting zirconia is low, and the impurities brought by the electric melting zirconia easily cause the powder to have high absorbance, so that the curing depth of the zirconia ceramic slurry is reduced, and the forming efficiency of 3D photocuring printing is further reduced.
In the conventional technical field using the electrically fused zirconia, when solving the problem of dispersibility of the electrically fused zirconia due to coarse particles, an auxiliary agent such as a dispersant and a surface modifier is generally added to a dispersion system to improve the dispersibility of the electrically fused zirconia in the dispersion system, but the improvement effect is limited. The grinding means has a limited effect on improving the dispersion powder, mainly because the milling process used in industry can mill the powder to be close to several microns, but the dispersion powder is still in micron-sized coarse powder, and further milling can greatly increase the industrial cost. Further, in the conventional technical field of using the electrically-fused zirconia, a technical means for solving the problem of more impurities in the electrically-fused zirconia generally is to reduce the impurity content of the electrically-fused zirconia by a chemical impurity removal means, but the improvement of the purity of the electrically-fused zirconia will correspondingly increase the production cost.
In order to effectively solve the problems of dispersibility and impurities caused by the fused zirconia powder and avoid the increase of production cost, the technical scheme adopts the fused zirconia with a magnesia coating layer, namely the fused zirconia ceramic powder. In the technical scheme, the fused zirconia powder is wrapped by the magnesia, so that the absorption of the fused zirconia to ultraviolet light caused by impurities of the fused zirconia is reduced, the curing depth of the ceramic slurry is further improved, and the photocuring printing forming efficiency is finally improved; in addition, the surface property of the coated and modified fused zirconia powder can be optimized, so that the combination between the micron-sized fused zirconia powder and a dispersing agent in zirconia ceramic slurry is facilitated, the steric hindrance between the powder is increased, and the excellent dispersibility and stability of the micron-sized zirconia ceramic slurry are ensured.
Furthermore, there are many substances, such as oxides, hydroxides or salts, etc., as the surface coating layer of the electrofused zirconia, but compared with other oxides, hydroxides or salts, the technical scheme uses the magnesia as the coating material of the electrofused zirconia, on one hand, because the magnesia is whitish, the reflectivity to ultraviolet light is very high, the absorbance is low, and the curing depth in the printing process is favorably improved, so that the printing molding efficiency is improved; on the other hand, the introduction of the magnesia can act as a zirconia sintering aid and is helpful for high-temperature densification sintering.
Furthermore, the technical scheme limits the mass of the magnesium oxide coating layer to be 5-10% of the mass of the electric melting zirconia. Specifically, the mass range of the magnesium oxide coating layer in the technical scheme is mainly limited according to the content range of the magnesium oxide coating layer as a sintering aid, namely when the content of magnesium oxide in the electric melting zirconia ceramic powder is too high, a sintered final product is not a zirconia product any more, and is a zirconia-magnesia composite product; when the content of magnesia in the electrically-fused zirconia ceramic powder is too low, the promotion effect of magnesia on sintering is reduced, and the condition of incomplete coating also exists, so that the modification effect of the electrically-fused zirconia is greatly reduced, and the problems of dispersibility and impurities caused by the electrically-fused zirconia powder are not solved.
Further, the photosensitive resin prefabricated liquid comprises the following raw materials in parts by weight: 5-50 parts of free radical type polymer, 5-50 parts of active diluent, 0.5-5 parts of photoinitiator, 1-5 parts of dispersant and 1-5 parts of defoaming agent.
The photosensitive resin prefabricated liquid in the technical scheme comprises a free radical type polymer, a reactive diluent, a photoinitiator, a dispersing agent and a defoaming agent. The radical polymer is the main reactant before photopolymerization, and the content of the radical polymer is relatively high. In particular, the polymerization reactions currently used for photocuring 3D printing are largely classified into radical type and cationic type. The free radical type reaction requires an intermediate product free radical to carry out polymerization reaction, the reaction speed is relatively high, the 3D printing forming efficiency is high, and the shrinkage is relatively large. The cationic reaction requires intermediate product cations for polymerization, and has relatively slow reaction speed, low forming efficiency and small shrinkage. Therefore, in order to improve the forming efficiency of 3D printing, the technical scheme selects a free radical type polymer for polymerization reaction.
The reactive diluent is a minor reactant before photopolymerization occurs, and is mainly used for reducing the viscosity of the oligomer, so that the liquid level of the slurry is easy to flatten, and the content ratio of the reactive diluent is also high. The photoinitiator is a compound for initiating photopolymerization, has high initiation efficiency and only needs low content ratio.
The dispersing agent is used for improving organic matters of the dispersion of the slurry, and the defoaming agent is used for eliminating bubbles generated in the preparation of the slurry and improving the uniformity of the slurry. According to the technical scheme, the coated and modified electrofusion zirconia ceramic powder is introduced into the ceramic slurry, and meanwhile, the dispersing agent and the defoaming agent are introduced into the raw materials of the ceramic slurry, so that the addition amount of the dispersing agent and the defoaming agent is further controlled together and accurately, a synergistic effect is generated among the dispersing agent and the defoaming agent, and the excellent dispersibility and stability of the micron-sized zirconia ceramic slurry are further ensured.
More specifically, the molecular weight of the free radical polymer is less than 3000.
When the molecular weight of the polymer is higher, the viscosity of the polymer is also higher, and in one embodiment of the technical scheme, a free radical type polymer with the molecular weight of less than 3000 is selected to be added into the photosensitive resin prefabricated liquid, so that the problem that the viscosity of the polymer is too high to increase the preparation difficulty of the slurry is favorably avoided.
Still further, the free radical polymer is any one or combination of more of urethane acrylate, epoxy acrylate, polyester acrylate and bisphenol A epoxy acrylate.
More specifically, the reactive diluent is any one or a combination of more of 1, 6-hexanediol diacrylate, isobornyl acrylate, trimethylolpropane triacrylate, tripropylene glycol diacrylate and pentaerythritol triacrylate.
More specifically, the photoinitiator is any one or combination of more of diphenyl (2,4, 6-trimethylbenzoyl) phosphine oxide, 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxy-cyclohexyl-phenyl ketone and 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone (907).
More specifically, the dispersant is any one or combination of more of silane coupling agent, stearic acid, oleic acid, ammonium polyacrylate, sodium polyacrylate and polyvidone.
More specifically, the defoaming agent is any one or a combination of mannitol, sodium dodecyl benzene sulfonate and polyethylene glycol.
The preparation method of the electrofusion zirconia ceramic slurry for photocuring 3D printing is used for preparing the electrofusion zirconia ceramic slurry for photocuring 3D printing and comprises the following steps:
(1) putting the fused zirconia into a magnesium nitrate solution for mixing to prepare a suspension;
(2) adding ammonia water into the suspension for mixing to obtain fused zirconia ceramic powder;
(3) mixing a free radical type polymer, a reactive diluent, a photoinitiator, a dispersant and a defoaming agent according to a ratio to obtain a photosensitive resin prefabricated liquid;
(4) adding the electric melting zirconia ceramic powder and the photosensitive resin prefabricated liquid into a ball mill according to the proportion for ball milling to obtain the electric melting zirconia ceramic slurry for photocuring 3D printing.
The technical scheme also provides a preparation method of the electrofused zirconia ceramic slurry for photocuring 3D printing, wherein the technical scheme utilizes an out-of-phase nucleation method to prepare the electrofused zirconia ceramic powder, the process is simple, the operation is convenient, and the production cost of the electrofused zirconia ceramic slurry can be effectively reduced. The conventional heterogeneous nucleation method mostly adopts urea, sodium hydroxide and the like as dropwise added solutions, and the technical scheme specially adopts ammonia water as the dropwise added solution, so that the pH of the slurry can be controlled to be 10 at most, Mg ions can be completely precipitated and nucleated, and the modification effect of the fused zirconia is ensured.
Further, in the step (4), the ball milling rotation speed in the ball milling step is 200 to 1000r/min, and the ball milling time is 2 to 6 hours.
The technical solution of the present invention is further explained by the following embodiments.
Example 1-preparation of an electrofused zirconia ceramic paste for photocuring 3D printing
(1) Putting the fused zirconia into a magnesium nitrate solution for mixing to prepare a suspension;
(2) adding ammonia water into the suspension for mixing to obtain fused zirconia ceramic powder; the fused zirconia ceramic powder comprises fused zirconia and a magnesia coating layer, and the weight of the magnesia coating layer is 6% of that of the fused zirconia according to the weight percentage;
(3) mixing 50 parts of urethane acrylate, 40 parts of 1, 6-hexanediol diacrylate, 5 parts of diphenyl (2,4, 6-trimethylbenzoyl) phosphine oxide, 4 parts of stearic acid and 1 part of sodium dodecyl benzene sulfonate to obtain a photosensitive resin prefabricated liquid;
(4) adding 80% of the electrofused zirconia ceramic powder and 20% of the photosensitive resin prefabricated liquid into a ball mill for ball milling to obtain the electrofused zirconia ceramic slurry for photocuring 3D printing.
Example 2-a method for preparing an electrofused zirconia ceramic paste for photocuring 3D printing
(1) Putting the fused zirconia into a magnesium nitrate solution for mixing to prepare a suspension;
(2) adding ammonia water into the suspension for mixing to obtain fused zirconia ceramic powder; the fused zirconia ceramic powder comprises fused zirconia and a magnesia coating layer, and the weight of the magnesia coating layer is 8% of that of the fused zirconia according to the weight percentage;
(3) mixing 50 parts of bisphenol A epoxy acrylate, 40 parts of active diluent (1, 6-hexanediol diacrylate and trimethylolpropane triacrylate are mixed according to a ratio of 1: 1), 5.5 parts of diphenyl (2,4, 6-trimethylbenzoyl) phosphine oxide, 3.5 parts of oleic acid and 1 part of polyethylene glycol to obtain a photosensitive resin preform;
(4) adding 85% of the electrofused zirconia ceramic powder and 15% of the photosensitive resin prefabricated liquid into a ball mill for ball milling to obtain the electrofused zirconia ceramic slurry for photocuring 3D printing.
Example 3-a method for preparing an electrofused zirconia ceramic paste for photocuring 3D printing
(1) Putting the fused zirconia into a magnesium nitrate solution for mixing to prepare a suspension;
(2) adding ammonia water into the suspension for mixing to obtain fused zirconia ceramic powder; the fused zirconia ceramic powder comprises fused zirconia and a magnesia coating layer, and the weight of the magnesia coating layer is 10% of that of the fused zirconia according to the weight percentage;
(3) mixing 50 parts of epoxy acrylate, 40 parts of active diluent (1, 6-hexanediol diacrylate and pentaerythritol triacrylate are mixed according to a ratio of 1: 1), 5 parts of diphenyl (2,4, 6-trimethylbenzoyl) phosphine oxide, 4 parts of a silane coupling agent and 1 part of polyethylene glycol to obtain a photosensitive resin prefabricated liquid;
(4) adding 85% of the electrofused zirconia ceramic powder and 15% of the photosensitive resin prefabricated liquid into a ball mill for ball milling to obtain the electrofused zirconia ceramic slurry for photocuring 3D printing.
Example 4-a method for preparing an electrofused zirconia ceramic paste for photocuring 3D printing
(1) Putting the fused zirconia into a magnesium nitrate solution for mixing to prepare a suspension;
(2) adding ammonia water into the suspension for mixing to obtain fused zirconia ceramic powder; the fused zirconia ceramic powder comprises fused zirconia and a magnesia coating layer, and the weight of the magnesia coating layer is 5% of that of the fused zirconia according to the weight percentage;
(3) mixing 50 parts of urethane acrylate, 40 parts of 1, 6-hexanediol diacrylate, 5 parts of diphenyl (2,4, 6-trimethylbenzoyl) phosphine oxide, 4 parts of stearic acid and 1 part of sodium dodecyl benzene sulfonate to obtain a photosensitive resin prefabricated liquid;
(4) adding 75% of the electrofused zirconia ceramic powder and 25% of the photosensitive resin prefabricated liquid into a ball mill for ball milling to obtain the electrofused zirconia ceramic slurry for photocuring 3D printing.
Comparative example 1-preparation method of electrofused zirconia ceramic slurry
(1) Mixing 50 parts of urethane acrylate, 40 parts of 1, 6-hexanediol diacrylate, 5 parts of diphenyl (2,4, 6-trimethylbenzoyl) phosphine oxide, 4 parts of stearic acid and 1 part of sodium dodecyl benzene sulfonate to obtain a photosensitive resin prefabricated liquid;
(2) adding 80% of fused zirconia and 20% of photosensitive resin prefabricated liquid into a ball mill for ball milling to obtain fused zirconia ceramic slurry.
An electrofused zirconia ceramic slurry was prepared according to the methods of the above examples and comparative examples, and the obtained electrofused zirconia ceramic slurry was placed on a photocuring 3D printer to perform a photocuring depth test in which the light wavelength used in the photocuring depth test was 405nm and the optical power density was 25mW/cm2The exposure time is 8 s; after the slurry exposure, the thickness of the cured sample in the exposed area (i.e., the curing depth) was measured with a micrometer. In addition, the obtained electrically fused zirconia ceramic slurry was placed in a beaker, allowed to stand at normal temperature and pressure for 72 hours, and the sedimentation of the slurry in the beaker was observed. The results are shown in table 1:
TABLE 1 Performance test results for different fused zirconia ceramic slurries
From the implementation results of examples 1 to 4 and comparative example 1, it can be known that the technical scheme wraps the fused zirconia powder by using the magnesia, which is beneficial to reducing the absorption of the fused zirconia to ultraviolet light caused by impurities of the fused zirconia, and further improves the curing depth of the ceramic slurry; in addition, the surface property of the coated and modified fused zirconia powder can be optimized, so that the combination between the micron-sized fused zirconia powder and a dispersing agent in zirconia ceramic slurry is facilitated, the steric hindrance between the powder is increased, and the excellent dispersibility and stability of the micron-sized zirconia ceramic slurry are ensured.
The technical principle of the present invention is described above in connection with specific embodiments. The description is made for the purpose of illustrating the principles of the invention and should not be construed in any way as limiting the scope of the invention. Based on the explanations herein, those skilled in the art will be able to conceive of other embodiments of the present invention without inventive effort, which would fall within the scope of the present invention.
Claims (10)
1. A electric smelting zirconia ceramic thick liquids for photocuring 3D prints which characterized in that: according to the mass percentage, the material comprises 75-85% of electric melting zirconia ceramic powder and 15-25% of photosensitive resin prefabricated liquid;
the electric melting zirconia ceramic powder comprises electric melting zirconia and a magnesia coating layer, wherein the magnesia coating layer wraps the surface of the electric melting zirconia, and the magnesia coating layer is 5-10% of the electric melting zirconia in mass percent.
2. An electrofused zirconia ceramic slurry for photocuring 3D printing according to claim 1 characterized by: the photosensitive resin prefabricated liquid comprises the following raw materials in parts by weight: 5-50 parts of free radical type polymer, 5-50 parts of active diluent, 0.5-5 parts of photoinitiator, 1-5 parts of dispersant and 1-5 parts of defoaming agent.
3. An electrofused zirconia ceramic slurry for photocuring 3D printing according to claim 2 characterized by: the molecular weight of the free radical polymer is less than 3000.
4. An electrofused zirconia ceramic slurry for photocuring 3D printing according to claim 3 characterized by: the free radical type polymer is any one or combination of more of polyurethane acrylate, epoxy acrylate, polyester acrylate and bisphenol A epoxy acrylate.
5. An electrofused zirconia ceramic slurry for photocuring 3D printing according to claim 2 characterized by: the active diluent is any one or a combination of more than one of 1, 6-hexanediol diacrylate, isobornyl acrylate, trimethylolpropane triacrylate, tripropylene glycol diacrylate and pentaerythritol triacrylate.
6. An electrofused zirconia ceramic slurry for photocuring 3D printing according to claim 2 characterized by: the photoinitiator is any one or combination of more of diphenyl (2,4, 6-trimethylbenzoyl) phosphine oxide, 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxy-cyclohexyl-phenyl ketone and 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone.
7. An electrofused zirconia ceramic slurry for photocuring 3D printing according to claim 2 characterized by: the dispersing agent is any one or combination of more of silane coupling agent, stearic acid, oleic acid, ammonium polyacrylate, sodium polyacrylate and polyvidone.
8. An electrofused zirconia ceramic slurry for photocuring 3D printing according to claim 2 characterized by: the defoaming agent is any one or combination of mannitol, sodium dodecyl benzene sulfonate and polyethylene glycol.
9. The preparation method of the electrofused zirconia ceramic slurry for photocuring 3D printing is characterized by comprising the following steps of:
(1) putting the fused zirconia into a magnesium nitrate solution for mixing to prepare a suspension;
(2) adding ammonia water into the suspension for mixing to obtain fused zirconia ceramic powder;
(3) mixing a free radical type polymer, a reactive diluent, a photoinitiator, a dispersant and a defoaming agent according to a ratio to obtain a photosensitive resin prefabricated liquid;
(4) adding the electric melting zirconia ceramic powder and the photosensitive resin prefabricated liquid into a ball mill according to the proportion for ball milling to obtain the electric melting zirconia ceramic slurry for photocuring 3D printing.
10. The method of preparing an electrofused zirconia ceramic slurry for photocuring 3D printing according to claim 9, characterized by: in the step (4), the ball milling rotation speed in the ball milling step is 200-1000 r/min, and the ball milling time is 2-6 h.
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| CN113754430A (en) * | 2021-08-05 | 2021-12-07 | 西安交通大学 | Graded zirconia paste for 3D printing and preparation method and application thereof |
| CN114368972A (en) * | 2022-01-21 | 2022-04-19 | 中国地质大学（武汉） | Visible light 3D printing photocuring ceramic slurry, preparation method and printing method |
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| CN111320480A (en) * | 2020-03-02 | 2020-06-23 | 广东省新材料研究所 | 3D printing photocuring ceramic particle and preparation method thereof |
| CN112225580A (en) * | 2020-09-14 | 2021-01-15 | 苏州沪之光智能制造科技有限公司 | Photocuring 3D printing zirconia foamed ceramic filter and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111320480A (en) * | 2020-03-02 | 2020-06-23 | 广东省新材料研究所 | 3D printing photocuring ceramic particle and preparation method thereof |
| CN112225580A (en) * | 2020-09-14 | 2021-01-15 | 苏州沪之光智能制造科技有限公司 | Photocuring 3D printing zirconia foamed ceramic filter and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113754430A (en) * | 2021-08-05 | 2021-12-07 | 西安交通大学 | Graded zirconia paste for 3D printing and preparation method and application thereof |
| CN114368972A (en) * | 2022-01-21 | 2022-04-19 | 中国地质大学（武汉） | Visible light 3D printing photocuring ceramic slurry, preparation method and printing method |
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