CN113956035A - Zirconium oxide composite calcium-phosphorus ceramic slurry and preparation method and application thereof - Google Patents
Zirconium oxide composite calcium-phosphorus ceramic slurry and preparation method and application thereof Download PDFInfo
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- CN113956035A CN113956035A CN202111262643.XA CN202111262643A CN113956035A CN 113956035 A CN113956035 A CN 113956035A CN 202111262643 A CN202111262643 A CN 202111262643A CN 113956035 A CN113956035 A CN 113956035A
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- ceramic slurry
- composite calcium
- hydroxyapatite
- zirconia composite
- zirconia
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- 239000000919 ceramic Substances 0.000 title claims abstract description 40
- 239000002002 slurry Substances 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- ZQBZAOZWBKABNC-UHFFFAOYSA-N [P].[Ca] Chemical compound [P].[Ca] ZQBZAOZWBKABNC-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title claims description 20
- 229910001928 zirconium oxide Inorganic materials 0.000 title description 4
- 238000007613 slurry method Methods 0.000 title description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 25
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims abstract description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000292 calcium oxide Substances 0.000 claims abstract description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910002076 stabilized zirconia Inorganic materials 0.000 claims description 25
- 229910052727 yttrium Inorganic materials 0.000 claims description 17
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 17
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002518 antifoaming agent Substances 0.000 claims description 9
- 239000003085 diluting agent Substances 0.000 claims description 9
- 238000010146 3D printing Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 7
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims description 7
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 6
- 239000004014 plasticizer Substances 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 230000002745 absorbent Effects 0.000 claims description 5
- 239000002250 absorbent Substances 0.000 claims description 5
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 5
- 239000004068 calcium phosphate ceramic Substances 0.000 claims description 5
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 3
- 229930195725 Mannitol Natural products 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- MWKXCSMICWVRGW-UHFFFAOYSA-N calcium;phosphane Chemical compound P.[Ca] MWKXCSMICWVRGW-UHFFFAOYSA-N 0.000 claims description 3
- DROMNWUQASBTFM-UHFFFAOYSA-N dinonyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCC DROMNWUQASBTFM-UHFFFAOYSA-N 0.000 claims description 3
- 239000000594 mannitol Substances 0.000 claims description 3
- 235000010355 mannitol Nutrition 0.000 claims description 3
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005997 Calcium carbide Substances 0.000 claims description 2
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- 239000006096 absorbing agent Substances 0.000 claims 1
- 229910001882 dioxygen Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 239000000395 magnesium oxide Substances 0.000 abstract description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003381 stabilizer Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 3
- MXFQRSUWYYSPOC-UHFFFAOYSA-N (2,2-dimethyl-3-prop-2-enoyloxypropyl) prop-2-enoate Chemical class C=CC(=O)OCC(C)(C)COC(=O)C=C MXFQRSUWYYSPOC-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003832 thermite Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/15—Compositions characterised by their physical properties
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
- A61K6/818—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics comprising zirconium oxide
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/831—Preparations for artificial teeth, for filling teeth or for capping teeth comprising non-metallic elements or compounds thereof, e.g. carbon
- A61K6/838—Phosphorus compounds, e.g. apatite
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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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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
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Abstract
The invention discloses zirconia composite calcium-phosphorus ceramic slurry and a preparation method and application thereof, the invention combines the bioactivity of hydroxyapatite and the high strength and good toughness of zirconia, aluminum powder is added, then a large amount of heat is released through thermit reaction to sinter the material, magnesium oxide is generated at high temperature and the added calcium oxide is used as a stabilizer, the thermal expansion coefficient of the product is reduced, and the prepared slurry has good fluidity. The paste is matched with an SLA-3D printing program, so that the printed false tooth is similar to a natural tooth, the surface of a sample is flat and does not crack, and the paste can be widely popularized and used.
Description
Technical Field
The invention belongs to the field of 3D printing materials, and particularly relates to zirconia composite calcium-phosphorus ceramic slurry and a preparation method and application thereof.
Background
In terms of materials, when the zirconia composite calcium-phosphorus ceramic is used as an oral material, the composite ceramic system has good biocompatibility, chemical stability, corrosion resistance, thermal conductivity and mechanical properties similar to those of natural teeth. In addition, the ceramics themselves have similar light refraction and scattering coefficients to those of tooth tissues, and can reproduce transparency, color depth and tissue texture of natural teeth. Therefore, the zirconia composite calcium-phosphorus system ceramic is an ideal oral material, and is incomparable with metal materials or other high polymer materials. The composite system ceramic not only can be used as an implant material, but also can be prepared into an all-ceramic crown with the color similar to that of natural teeth. Among them, zirconia composite ceramics are more and more favored by dentists and patients due to the advantages of unique stress induced phase transition toughening effect, corrosion resistance, good chemical stability, no sensitization, high room temperature toughness, low thermal conductivity, beautiful appearance and the like.
In the aspect of forming, the ceramic 3D printing technology based on the stereo Lithography principle SLA (stereo Lithography application) has the advantages of high forming quality, large size range of prepared parts, density close to a theoretical value and the like, so that the SLA technology becomes one of important trends in the development of future ceramic 3D printing technologies. In the SLA-3D printing ceramic technology, ceramic raw materials are generally mixed slurry of powdery solid particles, liquid photosensitive resin, diluted monomers and other additives, and the composition, the flowability, the dispersion uniformity and the like of ceramic powder in the slurry and the performance of a final composite ceramic product under printing conditions. Therefore, research and development of the slurry suitable for SLA-3D printing and the performance of the ceramic slurry used for printing are always hot research at home and abroad.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide zirconia composite calcium phosphate ceramic slurry and a preparation method and application thereof. The zirconium oxide composite calcium-phosphorus ceramic slurry prepared by the invention has good fluidity and moderate thermal expansion coefficient, and the printed product has no crack.
The purpose of the invention is realized by the following technical scheme:
a preparation method of zirconia composite calcium phosphorus ceramic slurry comprises the following steps:
(1) adding hydroxyapatite and yttrium stabilized zirconia into a reactor, adding manganese dioxide, aluminum powder and potassium chlorate, and evacuating air in the reactor; the mass ratio of the hydroxyapatite to the yttrium-stabilized zirconia is 11-12: 15-16;
(2) adding the ignited magnesium strips into a reactor, introducing oxygen into the reactor, reacting for 1-2 h, adding calcium oxide, introducing calcium carbide gas, continuing to react for 2-3 h, and cooling to room temperature; ball-milling the cooled product to obtain hydroxyapatite/yttrium stabilized zirconia nano powder;
(3) mixing and ultrasonically dispersing an active diluent, a prepolymer and a light absorbent to obtain a photosensitive premixed solution, adding an organic solvent, a plasticizer and a defoaming agent into the photosensitive premixed solution, and uniformly stirring to obtain an organic solution containing photosensitive resin;
(4) and (3) mixing and stirring the hydroxyapatite/yttrium stabilized zirconia nano powder in the step (2) and the organic solution containing the photosensitive resin in the step (3), then heating to 40-180 ℃ to remove redundant solvent, and finally cooling to room temperature.
Preferably, the mass ratio of the manganese dioxide, the aluminum powder and the potassium chlorate in the step (1) is 15-25: 10-15: 5 to 8.
Preferably, the mass ratio of the hydroxyapatite to the aluminum powder in the step (1) is 10-12: 2 to 3.
Preferably, the evacuation of the air in the reactor in the step (1) is performed by: and introducing mixed gas of nitrogen and oxygen for evacuation.
Preferably, the introduction rate of the oxygen in the step (2) is 5-8 mL/min.
Preferably, the mass ratio of the calcium oxide in the step (2) to the hydroxyapatite in the step (1) is 3-4: 5 to 6.
Preferably, the introducing speed of the acetylene gas in the step (2) is 20-25 mL/min.
Preferably, the reactive diluent in the step (3) is at least one of propoxylated neopentyl glycol diacrylate and ethoxylated trimethylolpropane triacrylate. (note: when storing the reactive diluent, quinone polymerization inhibitor, such as 0.01-0.1 wt% Satsugao quinone, is added)
Preferably, the prepolymer in the step (3) is ditrimethylolpropane acrylate.
Preferably, the light absorbent in the step (3) is at least one of UV-328, UV-531 and UV-1084 NQ.
Preferably, the mass ratio of the reactive diluent to the prepolymer in the step (3) is 82: 23.3.
preferably, the mass of the light absorbent in the step (3) is 5% of the total mass of the reactive diluent and the prepolymer.
Preferably, the mass ratio of the organic solvent to the photosensitive premix in the step (3) is 4.07: 1.00.
preferably, the mass ratio of the plasticizer, the defoaming agent and the organic solvent in the step (3) is 1: 1: 60.
preferably, the organic solvent in step (3) is ethanol.
Preferably, the plasticizer in step (3) is at least one of di (2-ethylhexyl) phthalate, dioctyl phthalate, dibutyl phthalate and dinonyl phthalate.
Preferably, the prepolymer in the step (3) is ditrimethylolpropane acrylate.
Preferably, the defoaming agent in the step (3) is at least one of stearic acid, a defoaming agent XS-02 and mannitol.
Preferably, the volume ratio of the hydroxyapatite/yttrium-stabilized zirconia nanopowder and the organic solution containing the photosensitive resin in the step (4) is 1: 1.
The zirconia composite calcium phosphate ceramic slurry is prepared by the preparation method of the zirconia composite calcium phosphate ceramic slurry.
The zirconia composite calcium-phosphorus ceramic slurry is applied to preparing SLA-3D printing slurry.
Compared with the prior art, the invention has the beneficial effects that:
the invention combines the bioactivity of hydroxyapatite and the high strength and good toughness of zirconia, a large amount of heat is released through thermite reaction after adding aluminum powder to sinter the material, magnesium oxide generated at high temperature and added calcium oxide are jointly used as a stabilizer, the thermal expansion coefficient of the product is reduced, and the prepared slurry has good fluidity. The slurry disclosed by the invention is matched with an SLA-3D printing program, the artificial tooth printed by the zirconia composite calcium-phosphorus ceramic slurry used as the slurry for 3D printing is similar to a natural tooth, and the surface of a sample is flat and does not crack.
Drawings
FIG. 1 is an XRD diffraction pattern of yttrium stabilized zirconia nanopowder used in step (1) of example 1.
FIG. 2 is an infrared spectrum of yttrium-stabilized zirconia nanopowder used in step (1) of example 1.
FIG. 3 is a view showing the state where the slurry of the zirconium oxide composite calcium phosphorus ceramic prepared in example 1 flows on a bracket of an apparatus.
Fig. 4 is a model diagram of a denture prepared using the zirconia composite calcium-phosphorus ceramic slurry described in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Nitrogen in the mixed gas of nitrogen and oxygen: the volume ratio of oxygen is 1: 1.
yttria stabilized zirconia was purchased from new materials ltd, jippon, zhejiang.
Example 1
A preparation method of zirconia composite calcium-phosphorus ceramic slurry comprises the following steps:
(1) adding 55.0g of hydroxyapatite and 75.0g of yttrium stabilized zirconia into a reactor, adding 20.0g of manganese dioxide, 12.5g of aluminum powder and 7.0g of potassium chlorate, and introducing mixed gas of nitrogen and oxygen at the speed of 5mL/min to empty the air in the reactor;
(2) adding the ignited magnesium strip into a reactor, introducing oxygen into the reactor at the speed of 8mL/min, adding 35.0g of calcium oxide after reacting for 1.5h, introducing acetylene gas at the speed of 25mL/min, continuing to react for 2.5h, and cooling to room temperature; ball-milling the cooled product to obtain hydroxyapatite/yttrium stabilized zirconia nano powder;
(3) 164.0g of ethoxylated neopentyl glycol diacrylate, 46.6g of ditrimethylolpropane acrylate and 10.53g of UV-531 are mixed and ultrasonically dispersed for 2 hours at the temperature of 40 ℃ to obtain a photosensitive premix, 900g of ethanol, 15g of dioctyl phthalate and 15g of stearic acid are added into the photosensitive premix and uniformly stirred to obtain an organic solution containing photosensitive resin;
(4) mixing the hydroxyapatite/yttrium stabilized zirconia nano powder in the step (2) and the organic solution containing the photosensitive resin in the step (3) according to the volume ratio of 1:1, stirring for 20 hours, heating to 120 ℃ to remove redundant solvent, and cooling to room temperature.
Example 2
A preparation method of zirconia composite calcium-phosphorus ceramic slurry comprises the following steps:
(1) adding 50.0g of hydroxyapatite and 70.0g of yttrium stabilized zirconia into a reactor, then adding 15.0g of manganese dioxide, 10.0g of aluminum powder and 5.0g of potassium chlorate, and introducing mixed gas of nitrogen and oxygen at the speed of 8mL/min to evacuate air in the reactor;
(2) adding the ignited magnesium strip into a reactor, introducing oxygen into the reactor at the speed of 8mL/min, adding 30.0g of calcium oxide after reacting for 1.5h, introducing acetylene gas at the speed of 20mL/min, continuing to react for 2.5h, and cooling to room temperature; ball-milling the cooled product to obtain hydroxyapatite/yttrium stabilized zirconia nano powder;
(3) mixing 164.0g of ethoxylated neopentyl glycol diacrylate, 46.6g of ditrimethylolpropane acrylate and 10.53g of UV-1084NQ, performing ultrasonic dispersion for 2 hours at 40 ℃ to obtain a photosensitive premixed solution, adding 900g of ethanol, 15g of dibutyl phthalate and 15g of defoaming agent XS-02 into the photosensitive premixed solution, and uniformly stirring to obtain an organic solution containing photosensitive resin;
(4) mixing the hydroxyapatite/yttrium stabilized zirconia nano powder in the step (2) and the organic solution containing the photosensitive resin in the step (3) according to the volume ratio of 1:1, stirring for 20 hours, heating to 135 ℃ to remove redundant solvent, and cooling to room temperature.
Example 3
A preparation method of zirconia composite calcium-phosphorus ceramic slurry comprises the following steps:
(1) adding 60.0g of hydroxyapatite and 80.0g of yttrium stabilized zirconia into a reactor, then adding 25.0g of manganese dioxide, 15.0g of aluminum powder and 8.0g of potassium chlorate, and introducing mixed gas of nitrogen and oxygen at the speed of 8mL/min to empty the air in the reactor;
(2) adding the ignited magnesium strip into a reactor, introducing oxygen into the reactor at the speed of 8mL/min, adding 40.0g of calcium oxide after reacting for 1.5h, introducing acetylene gas at the speed of 25mL/min, continuing to react for 3h, and cooling to room temperature; ball-milling the cooled product to obtain hydroxyapatite/yttrium stabilized zirconia nano powder;
(3) 164.0g of propoxylated neopentyl glycol diacrylate, 46.6g of ditrimethylolpropane acrylate and 10.53g of UV-328 are mixed and ultrasonically dispersed for 2 hours at 40 ℃ to obtain a photosensitive premix, 900g of ethanol, 15g of dinonyl phthalate and 15g of mannitol are added into the photosensitive premix and uniformly stirred to obtain an organic solution containing photosensitive resin;
(4) mixing the hydroxyapatite/yttrium stabilized zirconia nano powder in the step (2) and the organic solution containing the photosensitive resin in the step (3) according to the volume ratio of 1:1, stirring for 20 hours, heating to 150 ℃ to remove redundant solvent, and cooling to room temperature.
Example 1 the XRD diffraction pattern of the yttrium-stabilized zirconia nanopowder used in step (1) is shown in fig. 1, from which it can be seen that: the yttrium stabilized zirconia used in the experiment has obvious peak intensity and higher purity.
Example 1 the infrared spectrum of the yttrium-stabilized zirconia nanopowder used in step (1) is shown in fig. 2, from which fig. 2 it can be seen that: as can be seen from the combination of FIG. 1, the infrared spectrum has no miscellaneous peaks, and the yttrium-stabilized zirconia used in the experiment is relatively pure.
The flowing state of the zirconia composite calcium-phosphorus ceramic slurry prepared in example 1 on the equipment bracket is shown in FIG. 3, and it can be seen from FIG. 3 that: the prepared ceramic slurry has uniform material body, and the fluidity meets the requirements of light curing equipment.
The invention utilizes the paste prepared in example 1 to prepare the denture with the following steps:
equipment: 3D-CERAM
The process of preparing the dental crown comprises the following steps: self-editing CAD-CAM software import program
Temperature: room temperature 28 deg.C
Platform temperature: 25 deg.C
Air pressure: normal atmospheric pressure 101.325kPa
Printing scraper speed: Plastic-Blade-Speed ═ 12; Scap-Speed ═ 8
And (3) drying: naturally drying
Sintering parameters: keeping the temperature for 2h at the temperature of 5 ℃/min to 600 ℃, and cooling; keeping the temperature for 2h at the temperature of 1500 ℃ at 10 ℃/min, and cooling to room temperature along with the furnace.
The denture model prepared by using the zirconia composite calcium-phosphorus ceramic slurry of example 1 is shown in fig. 4, and can be seen from fig. 4: the prepared denture has smooth and clean surface and does not crack, which shows that the paste of the invention is well matched with the printing procedure.
The model figures of the dentures prepared by using the zirconia composite calcium-phosphorus ceramic slurry described in examples 2 and 3 were similar, and the surfaces thereof were smooth and free from cracks.
The above-described embodiments of the present invention should not be construed as limiting the scope of the present invention. Any other corresponding changes and modifications made according to the technical idea of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. The preparation method of the zirconia composite calcium-phosphorus ceramic slurry is characterized by comprising the following steps:
(1) adding hydroxyapatite and yttrium stabilized zirconia into a reactor, adding manganese dioxide, aluminum powder and potassium chlorate, and evacuating air in the reactor; the mass ratio of the hydroxyapatite to the yttrium-stabilized zirconia is 11-12: 15-16;
(2) adding the ignited magnesium strips into a reactor, introducing oxygen into the reactor, reacting for 1-2 h, adding calcium oxide, introducing calcium carbide gas, continuing to react for 2-3 h, and cooling to room temperature; ball-milling the cooled product to obtain hydroxyapatite/yttrium stabilized zirconia nano powder;
(3) mixing and ultrasonically dispersing an active diluent, a prepolymer and a light absorbent to obtain a photosensitive premixed solution, adding an organic solvent, a plasticizer and a defoaming agent into the photosensitive premixed solution, and uniformly stirring to obtain an organic solution containing photosensitive resin;
(4) and (3) mixing and stirring the hydroxyapatite/yttrium stabilized zirconia nano powder in the step (2) and the organic solution containing the photosensitive resin in the step (3), then heating to 40-180 ℃ to remove redundant solvent, and finally cooling to room temperature.
2. The preparation method of the zirconia composite calcium-phosphorus ceramic slurry according to claim 1, wherein the mass ratio of the manganese dioxide, the aluminum powder and the potassium chlorate in the step (1) is 15-25: 10-15: 5-8; the mass ratio of the hydroxyapatite to the aluminum powder in the step (1) is 10-12: 2 to 3.
3. The preparation method of the zirconia composite calcium-phosphorus ceramic slurry according to claim 1 or 2, wherein the mass ratio of the calcium oxide in the step (2) to the hydroxyapatite in the step (1) is 3-4: 5-6;
the mass ratio of the reactive diluent to the prepolymer in the step (3) is 82: 23.3; and (3) the mass of the light absorbent in the step (3) is 5% of the total mass of the reactive diluent and the prepolymer.
4. The method for preparing the zirconia composite calcium-phosphorus ceramic slurry according to claim 1 or 2, wherein the mass ratio of the organic solvent to the photosensitive premixed solution in the step (3) is 4.07: 1.00;
the mass ratio of the plasticizer, the defoaming agent and the organic solvent in the step (3) is 1: 1: 60.
5. the method for preparing a zirconia composite calcium-phosphorus ceramic slurry according to claim 1 or 2, wherein the volume ratio of the hydroxyapatite/yttrium-stabilized zirconia nanopowder and the organic solution containing the photosensitive resin in the step (4) is 1: 1.
6. The preparation method of the zirconia composite calcium-phosphorus ceramic slurry according to claim 1, wherein the oxygen gas is introduced at a rate of 5 to 8mL/min in the step (2);
the introducing speed of the acetylene gas in the step (2) is 20-25 mL/min;
the reactive diluent in the step (3) is at least one of propoxylated neopentyl glycol diacrylate and ethoxylated trimethylolpropane triacrylate;
the prepolymer in the step (3) is ditrimethylolpropane acrylate.
7. The method for preparing the zirconia composite calcium-phosphorus ceramic slurry according to claim 1, wherein at least one of the light absorbers UV-328, UV-531 and UV-1084NQ in the step (3);
the organic solvent in the step (3) is ethanol;
and (3) the plasticizer is at least one of di (2-ethylhexyl) phthalate, dioctyl phthalate, dibutyl phthalate and dinonyl phthalate.
8. The method for preparing the zirconia composite calcium-phosphorus ceramic slurry according to claim 1, wherein the prepolymer in the step (3) is ditrimethylolpropane acrylate;
the defoaming agent in the step (3) is at least one of stearic acid, defoaming agent XS-02 and mannitol.
9. The zirconia composite calcium phosphate ceramic slurry prepared by the method for preparing the zirconia composite calcium phosphate ceramic slurry according to any one of claims 1 to 8.
10. Use of the zirconia composite calcium phosphorus ceramic slurry of claim 9 in the preparation of SLA-3D printing slurry.
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