CN110951000A - Process for preparing transparent ceramic through 3D printing - Google Patents
Process for preparing transparent ceramic through 3D printing Download PDFInfo
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- CN110951000A CN110951000A CN201911169601.4A CN201911169601A CN110951000A CN 110951000 A CN110951000 A CN 110951000A CN 201911169601 A CN201911169601 A CN 201911169601A CN 110951000 A CN110951000 A CN 110951000A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F263/00—Macromolecular compounds obtained by polymerising monomers on to polymers of esters of unsaturated alcohols with saturated acids as defined in group C08F18/00
- C08F263/02—Macromolecular compounds obtained by polymerising monomers on to polymers of esters of unsaturated alcohols with saturated acids as defined in group C08F18/00 on to polymers of vinyl esters with monocarboxylic acids
- C08F263/04—Macromolecular compounds obtained by polymerising monomers on to polymers of esters of unsaturated alcohols with saturated acids as defined in group C08F18/00 on to polymers of vinyl esters with monocarboxylic acids on to polymers of vinyl acetate
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- B28—WORKING CEMENT, CLAY, OR STONE
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- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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Abstract
The invention discloses a process for preparing transparent ceramic by 3D printing, which comprises the following steps: A. mixing silicon nitride ceramic powder, silicon carbide fiber, ethoxylated trimethylolpropane triacrylate, aliphatic polyurethane diacrylate and pentaerythritol tetrakis (3-mercaptopropionate), and then carrying out ball milling for 1-2 h in an ethanol solution in which a polymerization inhibitor, a dispersing agent and a defoaming agent are dissolved to obtain ball milling slurry; B. adding a photoinitiator into the ball-milling slurry, and uniformly mixing; adjusting the solid content to 78-85% to obtain 3D printing ceramic slurry; C. and printing the 3D printing ceramic slurry by adopting a DLP printer with the wavelength of 390-420 nm, and drying to obtain the transparent ceramic. The process for preparing the transparent ceramic by 3D printing has the advantages of high forming speed, high automation degree, capability of forming any complex shape, high dimensional precision, excellent heat-conducting property and good mechanical property of the prepared transparent ceramic.
Description
Technical Field
The invention relates to the technical field of 3D printing, in particular to a process for preparing transparent ceramic through 3D printing.
Background
As one of the important development trends of the future ceramic 3D printing technology, the ceramic SLA (stereo Lithography application) 3D printing technology based on the stereolithography principle has the advantages of high forming quality, large size range of prepared parts, close compactness to an ideal value and the like.
According to the SLA forming technology, photosensitive resin is used as a raw material, laser is controlled through a computer, point-by-point scanning is carried out on the surface of the liquid photosensitive resin according to information of each layered section of a part gas-dimensional CAD model, and resin thin layers in a scanned area generate photopolymerization reaction and are homogenized to form one thin layer of a part. After 1 layer assimilation, the workbench moves downwards by a distance of 1 layer thickness, and then 1 layer of new liquid resin is coated on the surface of the original deceive-formed resin, and scanning and curing are carried out again. And continuously circulating in turn, and overlapping layer by layer until obtaining the blue-dimensional solid model.
The SLA-3D printing process can generally be divided into 3 steps:
1) processing layered data of the 3-dimensional model, namely processing the 3-dimensional model of the part into a text with a format which can be identified by printing equipment such as STL (standard template library) and the like through special software, and performing processing such as support addition, layering and the like;
2) uniformly paving the ceramic raw materials on a workbench of a printer, performing selective photocuring on ultraviolet laser according to part hierarchical data, and then continuously paving the raw materials and printing until the ceramic blank is formed;
3) and degreasing and sintering the ceramic blank to obtain the required ceramic part.
In the SLA-3D printing ceramic process, the components, viscosity and other attributes of the ceramic paste directly influence the accuracy of the implementation of the step 2), and finally influence the performance of the ceramic 3D printing part, and the ceramic paste occupies an important position in the whole 3D printing process.
In the light curing molding technology system, Digital Light Processing (DLP) is a development technology used in projectors and rear projection televisions, which uses a higher resolution digital light processor to cure liquid photopolymer, which is cycled in layers until the final mold is complete.
SLA and DLP belong to the same class of light-cured forming, where SLA employs laser spot focusing on liquid photopolymer, while DLP forming techniques employ a digital light processor to illuminate the cured photopolymer. SLA is generally shaped point-to-line, line-to-face, while DLP is shaped in a face-on-face manner. Therefore, the DLP forming speed is much higher than the SLA forming speed. DLP technology is consistent with photosensitive resin adopted by SLA technology, and mainly forms ultraviolet light wave bands of 365nm and 405 nm. Most materials are modified by taking photosensitive resin as a base material, so that different properties are configured, and a proper color ratio and transparency can be selected according to needs.
However, the currently used 3D printing process has the following problems:
1. the process is complex, the conditions are harsh, the forming speed is limited, and the dimensional accuracy is low when a product with a complex shape is formed;
2. the quality of a product obtained by the 3D printing process is poor, and a defective product is easy to appear;
3. the product obtained by the 3D printing process is low in yield strength, large in elongation at break or fragile and short in service life;
4. the product obtained by the 3D printing process has poor transparency, poor wear resistance, poor user experience and short service life, and cannot be used as a dental crown material.
Based on the situation, the invention provides a process for preparing transparent ceramics by 3D printing, which can effectively solve the problems.
Disclosure of Invention
The invention aims to provide a process for preparing transparent ceramic through 3D printing. The process for preparing the transparent ceramic by 3D printing has the advantages of high forming speed, high automation degree, high dimensional accuracy, capability of forming any complex shape, high mechanical property and long service life, and can be used for improving the quality stability of products and reducing the appearance of defective products by selecting the raw material composition of the transparent ceramic, optimizing the content of each raw material, and selecting the zirconium oxide, the ethylene-vinyl acetate copolymer, the hexanediol diacrylate, the carboxyl silicon dioxide microspheres, the nano titanium dioxide, the alumina fibers, the edge graphene oxide, the photoinitiator and the dispersant in proper proportion; has good antibacterial function; and has the advantages of no toxicity, good wear resistance and the like.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a process for preparing transparent ceramics by 3D printing comprises the following steps:
A. mixing zirconium oxide, ethylene-vinyl acetate copolymer, hexanediol diacrylate, carboxyl silica microspheres, nano titanium dioxide, alumina fibers and edge graphene oxide, and then carrying out ball milling for 1-2 h in an ethanol solution in which a dispersing agent is dissolved to obtain ball milling slurry;
B. adding a photoinitiator into the ball-milling slurry, and uniformly mixing; then, adjusting the solid content to 80-85% by adding ethanol or volatilizing ethanol to obtain 3D printing ceramic slurry;
C. and printing the 3D printing ceramic slurry by adopting a DLP printer with the wavelength of 390-420 nm, and drying to obtain the transparent ceramic.
Preferably, in the step B, the solid content is adjusted to 82.5% by adding ethanol or volatilizing ethanol, so as to obtain the 3D printing ceramic slurry.
Preferably, in the step C, a DLP printer with a wavelength of 405nm is adopted to print the 3D printing ceramic slurry, and the transparent ceramic is obtained after drying.
Preferably, in the step C, a DLP printer with the wavelength of 390-420 nm is adopted to print the 3D printing ceramic slurry to obtain a transparent ceramic semi-finished product; and then immersing the transparent ceramic semi-finished product into absolute ethyl alcohol for 3-5 min, washing away substances which are not solidified on the surface, and solidifying the transparent ceramic semi-finished product until the surface is dried under the condition that the exposure is 500-700 mJ/cm2 to obtain the transparent ceramic.
Preferably, in the step C, a DLP printer with a wavelength of 390-420 nm is adopted, and the exposure time of the 3D printing ceramic slurry during printing is 5-7 min.
Preferably, the transparent ceramic is prepared from the following raw materials in parts by weight:
170-195 parts of zirconium oxide,
240-270 parts of ethylene-vinyl acetate copolymer,
160-175 parts of hexanediol diacrylate,
30-37 parts of carboxyl silicon dioxide microspheres,
10-14 parts of nano titanium dioxide,
15-20 parts of alumina fiber,
9-12 parts of edge graphene oxide,
1.2 to 1.5 parts of photoinitiator,
5-7 parts of a dispersing agent.
Preferably, the transparent ceramic is prepared from the following raw materials in parts by weight:
183 portions of zirconium oxide,
255 parts of ethylene-vinyl acetate copolymer,
168 portions of hexanediol diacrylate,
34 parts of carboxyl silicon dioxide microspheres,
12 portions of nano titanium dioxide,
17 parts of alumina fiber,
11 parts of edge graphene oxide,
1.4 parts of photoinitiator,
6 parts of a dispersing agent.
Preferably, the particle size of the carboxyl silicon dioxide microspheres is 150-300 nm.
Preferably, the relative content of carboxyl in the edge graphene oxide is 32.5-37.5%.
Preferably, the ethylene-vinyl acetate copolymer is a mixture comprising a transparent ethylene-vinyl acetate copolymer having a VA content of 25, a transparent ethylene-vinyl acetate copolymer having a VA content of 32, and a transparent ethylene-vinyl acetate copolymer having a VA content of 40.
Preferably, the ethylene-vinyl acetate copolymer is a mixture formed by mixing a transparent ethylene-vinyl acetate copolymer with a VA content of 25, a transparent ethylene-vinyl acetate copolymer with a VA content of 32 and a transparent ethylene-vinyl acetate copolymer with a VA content of 40.
Preferably, the ethylene-vinyl acetate copolymer is a mixture formed by mixing a transparent ethylene-vinyl acetate copolymer with a VA content of 25, a transparent ethylene-vinyl acetate copolymer with a VA content of 32 and a transparent ethylene-vinyl acetate copolymer with a VA content of 40, wherein the mass ratio of the three is 10: (13-16): (5-7).
Preferably, the photoinitiator is Irgacure 819 from basf chemicals, inc.
Preferably, the dispersant is a mixture of ammonium polymethacrylate and oleic acid.
Preferably, the mass ratio of ammonium polymethacrylate to oleic acid in the mixture of ammonium polymethacrylate and oleic acid is 1: 0.35 to 0.42.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the process for preparing the transparent ceramic by 3D printing has the advantages of high forming speed, high automation degree, high dimensional accuracy, capability of forming any complex shape, high mechanical property and long service life, and can be used for improving the quality stability of products and reducing the appearance of defective products by selecting the raw material composition of the transparent ceramic, optimizing the content of each raw material, and selecting the zirconium oxide, the ethylene-vinyl acetate copolymer, the hexanediol diacrylate, the carboxyl silicon dioxide microspheres, the nano titanium dioxide, the alumina fibers, the edge oxidized graphene, the photoinitiator and the dispersant in proper proportion; has good antibacterial function; and has the advantages of no toxicity, good wear resistance and the like.
In the raw materials of the transparent ceramic, zirconia with a proper proportion is selected and matched with other components to play a good synergistic effect, so that the transparent ceramic has high yield strength, moderate elongation at break (close to alloy dental crown materials), good mechanical property and long service life; has good antibacterial function; the wear-resistant rubber also has the advantages of no toxicity, good wear resistance and the like;
in the raw materials of the transparent ceramic, the ethylene-vinyl acetate copolymer and the hexanediol diacrylate in proper proportion are selected as the photocuring monomer or prepolymer, are matched with each other to play a good synergistic effect, and are matched with other components, so that the transparent ceramic has the advantages of high yield strength, moderate elongation at break (close to alloy crown materials), good mechanical property and long service life; has good antibacterial function; the wear-resistant rubber also has the advantages of no toxicity, good wear resistance and the like; the ethylene-vinyl acetate copolymer is a mixture formed by mixing a transparent ethylene-vinyl acetate copolymer with the VA content of 25, a transparent ethylene-vinyl acetate copolymer with the VA content of 32 and a transparent ethylene-vinyl acetate copolymer with the VA content of 40, wherein the mass ratio of the ethylene-vinyl acetate copolymer to the transparent ethylene-vinyl acetate copolymer is 10: (13-16): (5-7); the three materials are reasonably matched, and after photocuring crosslinking, the transparent ceramic has high yield strength, moderate elongation at break (close to alloy dental crown materials), good mechanical property and long service life; and the processing performance is good;
in the raw materials of the transparent ceramic, carboxyl silicon dioxide microspheres with a proper proportion are selected, have good compatibility with ethylene-vinyl acetate copolymer, hexanediol diacrylate and the like, are matched with each other, play a good role in synergy, and greatly improve the wear resistance and hardness of the transparent ceramic;
in the raw materials of the transparent ceramic, alumina fibers with proper proportion are selected and matched with each other, so that a good synergistic effect is achieved, the effects of reducing the thermal conductivity and the heating shrinkage rate of the transparent ceramic are mainly achieved, almost no thermal conductivity is achieved, and the oral cavity sensitivity is effectively prevented when hot food is eaten; the heating shrinkage rate is low, so that the thermal deformation can be reduced, the damage caused by excessive thermal deformation when hot food is eaten can be effectively prevented, and the service life is prolonged;
in the raw materials of the transparent ceramic, the nano titanium dioxide and the edge graphene oxide in a proper proportion are selected to play a good antibacterial effect, and the edge graphene oxide has good compatibility in the raw material system and also can play a good reinforcing role;
in the raw materials of the transparent ceramic, a proper proportion of a dispersing agent (preferably, the dispersing agent is a mixture of ammonium polymethacrylate and oleic acid, preferably, the mass ratio of the ammonium polymethacrylate to the oleic acid in the mixture of the ammonium polymethacrylate and the oleic acid is 1: 0.35-0.42.), and for the raw material system, zirconia, carboxyl silica microspheres, nano-titanium dioxide, alumina fibers and edge oxidized graphene can be uniformly dispersed in the mixture of ethylene-vinyl acetate copolymer and hexanediol diacrylate, so that each part of the transparent ceramic is uniform in components, high in dimensional accuracy, smooth in surface, further high in yield strength, moderate in elongation at break (close to alloy crown materials), good in mechanical property and long in service life; has good antibacterial function; and has the advantages of no toxicity, good wear resistance and the like.
The preparation method has the advantages of simple process, simple and convenient operation and high forming speed.
Detailed Description
In order that those skilled in the art will better understand the technical solutions of the present invention, the following description of the preferred embodiments of the present invention is provided in connection with specific examples, which should not be construed as limiting the present patent.
The test methods or test methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials, unless otherwise indicated, are conventionally obtained commercially or prepared by conventional methods.
Example 1:
a process for preparing transparent ceramics by 3D printing comprises the following steps:
A. mixing zirconium oxide, ethylene-vinyl acetate copolymer, hexanediol diacrylate, carboxyl silica microspheres, nano titanium dioxide, alumina fibers and edge graphene oxide, and then carrying out ball milling for 1-2 h in an ethanol solution in which a dispersing agent is dissolved to obtain ball milling slurry;
B. adding a photoinitiator into the ball-milling slurry, and uniformly mixing; then, adjusting the solid content to 80-85% by adding ethanol or volatilizing ethanol to obtain 3D printing ceramic slurry;
C. and printing the 3D printing ceramic slurry by adopting a DLP printer with the wavelength of 390-420 nm, and drying to obtain the transparent ceramic.
Preferably, in the step B, the solid content is adjusted to 82.5% by adding ethanol or volatilizing ethanol, so as to obtain the 3D printing ceramic slurry.
Preferably, in the step C, a DLP printer with a wavelength of 405nm is adopted to print the 3D printing ceramic slurry, and the transparent ceramic is obtained after drying.
Preferably, in the step C, a DLP printer with the wavelength of 390-420 nm is adopted to print the 3D printing ceramic slurry to obtain a transparent ceramic semi-finished product; and then immersing the transparent ceramic semi-finished product into absolute ethyl alcohol for 3-5 min, washing away substances which are not solidified on the surface, and solidifying the transparent ceramic semi-finished product until the surface is dried under the condition that the exposure is 500-700 mJ/cm2 to obtain the transparent ceramic.
Preferably, in the step C, a DLP printer with a wavelength of 390-420 nm is adopted, and the exposure time of the 3D printing ceramic slurry during printing is 5-7 min.
Preferably, the transparent ceramic is prepared from the following raw materials in parts by weight:
170-195 parts of zirconium oxide,
240-270 parts of ethylene-vinyl acetate copolymer,
160-175 parts of hexanediol diacrylate,
30-37 parts of carboxyl silicon dioxide microspheres,
10-14 parts of nano titanium dioxide,
15-20 parts of alumina fiber,
9-12 parts of edge graphene oxide,
1.2 to 1.5 parts of photoinitiator,
5-7 parts of a dispersing agent.
Preferably, the transparent ceramic is prepared from the following raw materials in parts by weight:
183 portions of zirconium oxide,
255 parts of ethylene-vinyl acetate copolymer,
168 portions of hexanediol diacrylate,
34 parts of carboxyl silicon dioxide microspheres,
12 portions of nano titanium dioxide,
17 parts of alumina fiber,
11 parts of edge graphene oxide,
1.4 parts of photoinitiator,
6 parts of a dispersing agent.
Preferably, the particle size of the carboxyl silicon dioxide microspheres is 150-300 nm.
Preferably, the relative content of carboxyl in the edge graphene oxide is 32.5-37.5%.
Preferably, the ethylene-vinyl acetate copolymer is a mixture comprising a transparent ethylene-vinyl acetate copolymer having a VA content of 25, a transparent ethylene-vinyl acetate copolymer having a VA content of 32, and a transparent ethylene-vinyl acetate copolymer having a VA content of 40.
Preferably, the ethylene-vinyl acetate copolymer is a mixture formed by mixing a transparent ethylene-vinyl acetate copolymer with a VA content of 25, a transparent ethylene-vinyl acetate copolymer with a VA content of 32 and a transparent ethylene-vinyl acetate copolymer with a VA content of 40.
Preferably, the ethylene-vinyl acetate copolymer is a mixture formed by mixing a transparent ethylene-vinyl acetate copolymer with a VA content of 25, a transparent ethylene-vinyl acetate copolymer with a VA content of 32 and a transparent ethylene-vinyl acetate copolymer with a VA content of 40, wherein the mass ratio of the three is 10: (13-16): (5-7).
Preferably, the photoinitiator is Irgacure 819 from basf chemicals, inc.
Preferably, the dispersant is a mixture of ammonium polymethacrylate and oleic acid.
Preferably, the mass ratio of ammonium polymethacrylate to oleic acid in the mixture of ammonium polymethacrylate and oleic acid is 1: 0.35 to 0.42.
Example 2:
a process for preparing transparent ceramics by 3D printing comprises the following steps:
A. mixing zirconium oxide, ethylene-vinyl acetate copolymer, hexanediol diacrylate, carboxyl silicon dioxide microspheres, nano titanium dioxide, alumina fibers and edge graphene oxide, and then carrying out ball milling for 1h in an ethanol solution in which a dispersing agent is dissolved to obtain ball milling slurry;
B. adding a photoinitiator into the ball-milling slurry, and uniformly mixing; then, adjusting the solid content to 80% by adding ethanol or volatilizing ethanol to obtain 3D printing ceramic slurry;
C. and printing the 3D printing ceramic slurry by adopting a DLP printer with the wavelength of 390nm, and drying to obtain the transparent ceramic.
In this embodiment, in the step C, a DLP printer with a wavelength of 390nm is used to print the 3D printing ceramic slurry, so as to obtain a transparent ceramic semi-finished product; and then immersing the transparent ceramic semi-finished product in absolute ethyl alcohol for 3min, washing out uncured substances on the surface, and curing to dry the surface under the condition that the exposure is 500mJ/cm2 to obtain the transparent ceramic.
In this embodiment, in step C, a DLP printer with a wavelength of 390nm is adopted, and the exposure time when the 3D printing ceramic slurry is printed is 7 min.
In this embodiment, the transparent ceramic is prepared from the following raw materials in parts by weight:
170 parts of zirconium oxide,
240 portions of ethylene-vinyl acetate copolymer,
160 parts of hexanediol diacrylate,
30 portions of carboxyl silicon dioxide microspheres,
10 portions of nano titanium dioxide,
15 portions of alumina fiber,
9 parts of edge graphene oxide,
1.2 parts of photoinitiator,
5 parts of a dispersing agent.
In this embodiment, the particle size of the carboxyl silica microspheres is 150-250 nm.
In this embodiment, the relative content of carboxyl groups in the edge graphene oxide is 32.5%.
In this embodiment, the ethylene-vinyl acetate copolymer is a mixture of a transparent ethylene-vinyl acetate copolymer having a VA content of 25, a transparent ethylene-vinyl acetate copolymer having a VA content of 32, and a transparent ethylene-vinyl acetate copolymer having a VA content of 40.
In this embodiment, the ethylene-vinyl acetate copolymer is a mixture of a transparent ethylene-vinyl acetate copolymer with a VA content of 25, a transparent ethylene-vinyl acetate copolymer with a VA content of 32, and a transparent ethylene-vinyl acetate copolymer with a VA content of 40, where the mass ratio of the three is 10: 13: 5.
in this example, the photoinitiator is Irgacure 819 from basf chemicals, inc.
In this embodiment, the dispersant is a mixture of ammonium polymethacrylate and oleic acid; the mass ratio of ammonium polymethacrylate to oleic acid in the mixture of ammonium polymethacrylate and oleic acid is 1: 0.35.
example 3:
a process for preparing transparent ceramics by 3D printing comprises the following steps:
A. mixing zirconium oxide, ethylene-vinyl acetate copolymer, hexanediol diacrylate, carboxyl silicon dioxide microspheres, nano titanium dioxide, alumina fibers and edge graphene oxide, and then carrying out ball milling for 2 hours in an ethanol solution in which a dispersing agent is dissolved to obtain ball milling slurry;
B. adding a photoinitiator into the ball-milling slurry, and uniformly mixing; then adjusting the solid content to 85% by adding ethanol or volatilizing ethanol to obtain 3D printing ceramic slurry;
C. and printing the 3D printing ceramic slurry by adopting a DLP printer with the wavelength of 420nm, and drying to obtain the transparent ceramic.
In this embodiment, in the step C, a DLP printer with a wavelength of 420nm is used to print the 3D printing ceramic slurry, so as to obtain a transparent ceramic semi-finished product; and then immersing the transparent ceramic semi-finished product in absolute ethyl alcohol for 5min, washing out uncured substances on the surface, and curing to dry the surface under the condition that the exposure is 700mJ/cm2 to obtain the transparent ceramic.
In this embodiment, in step C, a DLP printer with a wavelength of 420nm is adopted, and the exposure time when the 3D printing ceramic slurry is printed is 5 min.
In this embodiment, the transparent ceramic is prepared from the following raw materials in parts by weight:
195 portions of zirconium oxide,
270 portions of ethylene-vinyl acetate copolymer,
175 parts of hexanediol diacrylate,
37 parts of carboxyl silicon dioxide microspheres,
14 portions of nano titanium dioxide,
20 parts of alumina fiber,
12 parts of edge graphene oxide,
1.5 parts of photoinitiator,
7 parts of a dispersing agent.
In the embodiment, the particle size of the carboxyl silica microspheres is 220-300 nm.
In this embodiment, the relative content of carboxyl groups in the edge graphene oxide is 37.5%.
In this embodiment, the ethylene-vinyl acetate copolymer is a mixture of a transparent ethylene-vinyl acetate copolymer having a VA content of 25, a transparent ethylene-vinyl acetate copolymer having a VA content of 32, and a transparent ethylene-vinyl acetate copolymer having a VA content of 40.
In this embodiment, the ethylene-vinyl acetate copolymer is a mixture of a transparent ethylene-vinyl acetate copolymer with a VA content of 25, a transparent ethylene-vinyl acetate copolymer with a VA content of 32, and a transparent ethylene-vinyl acetate copolymer with a VA content of 40, where the mass ratio of the three is 10: 16: 7.
in this example, the photoinitiator is Irgacure 819 from basf chemicals, inc.
In this embodiment, the dispersant is a mixture of ammonium polymethacrylate and oleic acid; the mass ratio of ammonium polymethacrylate to oleic acid in the mixture of ammonium polymethacrylate and oleic acid is 1: 0.42.
example 4:
a process for preparing transparent ceramics by 3D printing comprises the following steps:
A. mixing zirconium oxide, ethylene-vinyl acetate copolymer, hexanediol diacrylate, carboxyl silicon dioxide microspheres, nano titanium dioxide, alumina fibers and edge graphene oxide, and then carrying out ball milling for 1.5h in an ethanol solution in which a dispersing agent is dissolved to obtain ball milling slurry;
B. adding a photoinitiator into the ball-milling slurry, and uniformly mixing; then, adjusting the solid content to 82.5% by adding ethanol or volatilizing ethanol to obtain 3D printing ceramic slurry;
C. and printing the 3D printing ceramic slurry by adopting a DLP printer with the wavelength of 405nm, and drying to obtain the transparent ceramic.
In this embodiment, in the step C, a DLP printer with a wavelength of 405nm is adopted to print the 3D printing ceramic slurry, so as to obtain a transparent ceramic semi-finished product; and then immersing the transparent ceramic semi-finished product in absolute ethyl alcohol for 4min, washing out uncured substances on the surface, and curing to dry the surface under the condition that the exposure is 600mJ/cm2 to obtain the transparent ceramic.
In this embodiment, in step C, a DLP printer with a wavelength of 405nm is adopted, and the exposure time when the 3D printing ceramic slurry is printed is 6 min.
In this embodiment, the transparent ceramic is prepared from the following raw materials in parts by weight:
183 portions of zirconium oxide,
255 parts of ethylene-vinyl acetate copolymer,
168 portions of hexanediol diacrylate,
34 parts of carboxyl silicon dioxide microspheres,
12 portions of nano titanium dioxide,
17 parts of alumina fiber,
11 parts of edge graphene oxide,
1.4 parts of photoinitiator,
6 parts of a dispersing agent.
In this embodiment, the particle size of the carboxyl silica microspheres is 200-250 nm.
In this embodiment, the relative content of carboxyl groups in the edge graphene oxide is 35%.
In this embodiment, the ethylene-vinyl acetate copolymer is a mixture of a transparent ethylene-vinyl acetate copolymer having a VA content of 25, a transparent ethylene-vinyl acetate copolymer having a VA content of 32, and a transparent ethylene-vinyl acetate copolymer having a VA content of 40.
In this embodiment, the ethylene-vinyl acetate copolymer is a mixture of a transparent ethylene-vinyl acetate copolymer with a VA content of 25, a transparent ethylene-vinyl acetate copolymer with a VA content of 32, and a transparent ethylene-vinyl acetate copolymer with a VA content of 40, where the mass ratio of the three is 10: 14.5: 6.
in this example, the photoinitiator is Irgacure 819 from basf chemicals, inc.
In this embodiment, the dispersant is a mixture of ammonium polymethacrylate and oleic acid; the mass ratio of ammonium polymethacrylate to oleic acid in the mixture of ammonium polymethacrylate and oleic acid is 1: 0.38.
comparative example:
the comparative example is a chinese patent application publication No. CN 105838926A.
The following performance tests were performed on the transparent ceramics obtained in examples 2 to 4 of the present invention, and the test results are shown in table 1:
TABLE 1
As can be seen from the above table, the transparent ceramic of the present invention has the following advantages compared to the comparative example: the yield strength is high, the elongation at break is moderate (close to alloy dental crown materials), the mechanical property is good, and the service life is long; has good antibacterial function.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (10)
1. A process for preparing transparent ceramics by 3D printing is characterized by comprising the following steps:
A. mixing zirconium oxide, ethylene-vinyl acetate copolymer, hexanediol diacrylate, carboxyl silica microspheres, nano titanium dioxide, alumina fibers and edge graphene oxide, and then carrying out ball milling for 1-2 h in an ethanol solution in which a dispersing agent is dissolved to obtain ball milling slurry;
B. adding a photoinitiator into the ball-milling slurry, and uniformly mixing; then, adjusting the solid content to 80-85% by adding ethanol or volatilizing ethanol to obtain 3D printing ceramic slurry;
C. and printing the 3D printing ceramic slurry by adopting a DLP printer with the wavelength of 390-420 nm, and drying to obtain the transparent ceramic.
2. The process for preparing transparent ceramics through 3D printing according to claim 1, wherein in the step B, the solid content is adjusted to 82.5% by adding ethanol or volatilizing ethanol, so as to obtain 3D printing ceramic slurry.
3. The process for preparing transparent ceramics through 3D printing according to claim 1, wherein in the step C, a DLP printer with the wavelength of 405nm is adopted to print the 3D printing ceramic slurry, and the transparent ceramics are obtained after drying.
4. The process for preparing the transparent ceramic through 3D printing according to claim 1, wherein in the step C, a DLP printer with a wavelength of 390-420 nm is adopted to print the 3D printing ceramic slurry to obtain a transparent ceramic semi-finished product; and then immersing the transparent ceramic semi-finished product into absolute ethyl alcohol for 3-5 min, washing away substances which are not solidified on the surface, and solidifying the transparent ceramic semi-finished product until the surface is dried under the condition that the exposure is 500-700 mJ/cm2 to obtain the transparent ceramic.
5. The process for preparing transparent ceramics through 3D printing according to claim 1, wherein in the step C, a DLP printer with a wavelength of 390-420 nm is adopted, and the exposure time of printing the 3D printing ceramic slurry is 5-7 min.
6. The process for preparing transparent ceramic through 3D printing according to claim 1, wherein the transparent ceramic is prepared from the following raw materials in parts by weight:
170-195 parts of zirconium oxide,
240-270 parts of ethylene-vinyl acetate copolymer,
160-175 parts of hexanediol diacrylate,
30-37 parts of carboxyl silicon dioxide microspheres,
10-14 parts of nano titanium dioxide,
15-20 parts of alumina fiber,
9-12 parts of edge graphene oxide,
1.2 to 1.5 parts of photoinitiator,
5-7 parts of a dispersing agent.
7. The process for preparing transparent ceramic through 3D printing according to claim 6, wherein the particle size of the carboxyl silica microspheres is 150-300 nm; the photoinitiator is Irgacure 819 from Pasteur Chemicals, Inc.
8. The process for preparing transparent ceramic through 3D printing according to claim 6, wherein the relative content of carboxyl in the edge graphene oxide is 32.5-37.5%.
9. The process for preparing transparent ceramics through 3D printing according to claim 6, wherein the ethylene-vinyl acetate copolymer is a mixture of 25% of transparent ethylene-vinyl acetate copolymer, 32% of transparent ethylene-vinyl acetate copolymer and 40% of transparent ethylene-vinyl acetate copolymer, and the mass ratio of the three is 10: (13-16): (5-7).
10. The process for preparing transparent ceramics by 3D printing according to claim 6, wherein the dispersant is a mixture of ammonium polymethacrylate and oleic acid; the mass ratio of ammonium polymethacrylate to oleic acid in the mixture of ammonium polymethacrylate and oleic acid is 1: 0.35 to 0.42.
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| WO2022032817A1 (en) * | 2020-08-13 | 2022-02-17 | The Hong Kong Polytechnic University | Three-dimensional printing antimicrobial products |
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