CN115887753A - Ceramic denture and 3D printing method thereof - Google Patents
Ceramic denture and 3D printing method thereof Download PDFInfo
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- CN115887753A CN115887753A CN202211470408.6A CN202211470408A CN115887753A CN 115887753 A CN115887753 A CN 115887753A CN 202211470408 A CN202211470408 A CN 202211470408A CN 115887753 A CN115887753 A CN 115887753A
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- 239000000919 ceramic Substances 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000010146 3D printing Methods 0.000 title abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 20
- 239000000654 additive Substances 0.000 claims abstract description 19
- 239000002270 dispersing agent Substances 0.000 claims abstract description 7
- 239000003112 inhibitor Substances 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 17
- 239000002042 Silver nanowire Substances 0.000 claims description 17
- 235000015895 biscuits Nutrition 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000005238 degreasing Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000007639 printing Methods 0.000 claims description 8
- 238000005245 sintering Methods 0.000 claims description 8
- -1 N-nitroso-N-phenylhydroxylamine aluminum Chemical compound 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- 239000001506 calcium phosphate Substances 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 4
- 229940078499 tricalcium phosphate Drugs 0.000 claims description 4
- 229910000391 tricalcium phosphate Inorganic materials 0.000 claims description 4
- 235000019731 tricalcium phosphate Nutrition 0.000 claims description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- OIMIXJLPIJKPDM-UHFFFAOYSA-N dodeca-9,11-dien-1-ol Chemical compound OCCCCCCCCC=CC=C OIMIXJLPIJKPDM-UHFFFAOYSA-N 0.000 claims description 2
- MKVYSRNJLWTVIK-UHFFFAOYSA-N ethyl carbamate;2-methylprop-2-enoic acid Chemical compound CCOC(N)=O.CC(=C)C(O)=O.CC(=C)C(O)=O MKVYSRNJLWTVIK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- 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 description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000004250 tert-Butylhydroquinone Substances 0.000 claims description 2
- 235000019281 tert-butylhydroquinone Nutrition 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims 1
- 238000005452 bending Methods 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000844 anti-bacterial effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 5
- 210000000214 mouth Anatomy 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 238000004113 cell culture Methods 0.000 description 2
- 230000001055 chewing effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000007943 implant Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 210000005260 human cell Anatomy 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
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- Dental Preparations (AREA)
Abstract
The invention discloses a ceramic denture and a 3D printing method thereof, wherein the internal structure of the ceramic denture is in a lattice microstructure shape, the ceramic denture comprises mixed ceramic powder and additives, the mixed ceramic powder accounts for 72-90% of the mass fraction, the additives account for 10-28%, and the additives comprise active oligomer, photoinitiator, dispersant and polymerization inhibitor. The ceramic denture and the 3D printing method thereof provided by the invention can improve the bending strength and bioactivity of the ceramic denture.
Description
Technical Field
The invention relates to the field of medical treatment and health, in particular to a ceramic false tooth and a 3D printing method thereof.
Background
The artificial teeth are commonly called as false teeth, and are used for replacing teeth to perform functions when the teeth of people are missing, and the false teeth are divided into three categories, namely removable false teeth, fixed false teeth and implant false teeth. The removable denture is a denture which can be taken off and worn by oneself, and the denture is convenient for cleaning the oral cavity, but the removable denture is more complicated to operate and has poor chewing efficiency due to the need of taking off and wearing. The fixed denture is a denture which does not need to be taken off and worn by oneself, and the denture has the defect that two normal teeth need to be ground. The artificial tooth is implanted at the position of the lost tooth, and the ceramic tooth is connected on the implant, so that the artificial tooth has high chewing efficiency, good retention, comfort and beauty, and the implanted ceramic artificial tooth is favored by the people with the lost tooth.
After the ceramic denture is implanted in the oral cavity of a person with a lost tooth, the implanted ceramic denture is expected to be integrated with the oral cavity of the person with the lost tooth, and to be durable. The existing ceramic false tooth is generally solid, and cellular tissues in a human body are not easy to permeate into the ceramic false tooth, so that the ceramic false tooth cannot be well fused with the oral cavity of the human body, and the bioactivity is poor. The existing ceramic false tooth has low bending strength and large brittleness, and the ceramic false tooth is easy to crack after being used for a long time.
Disclosure of Invention
The invention aims to provide a ceramic denture and a 3D printing method thereof, which can improve the bending strength and bioactivity of the ceramic denture.
The invention discloses a ceramic false tooth, which is internally in a lattice microstructure shape and comprises 72-90% of mixed ceramic powder and 10-28% of additives in percentage by mass, wherein the additives comprise active oligomer, photoinitiator, dispersant and polymerization inhibitor.
Preferably, the additive further comprises silver nanowires, and the silver nanowires are located in the lattice microstructure.
Preferably, the silver nanowires have a length of 30-50 μm and a diameter of 10-20 nm.
According to a preferable scheme, the silver nano wire is 0.3-2% by mass, the active oligomer is 5-25% by mass, the photoinitiator is 2-9% by mass, the dispersant is 0.5-2% by mass, and the polymerization inhibitor is 0.2-1.7% by mass.
Preferably, the mixed ceramic powder is a mixture of one or more of hydroxyapatite, tricalcium phosphate, zirconia, silica and titanium oxide.
Preferably, the mass fraction of the zirconium oxide is 80%, the mass fraction of the titanium oxide is 5%, and the mass fraction of the tricalcium phosphate is 15%.
Preferably, the reactive oligomer comprises one or more of modified bisphenol A bis-glycidyl methacrylate, ethoxylated bisphenol A bis-glycidyl methacrylate, urethane dimethacrylate, 1, 12-dodecadienol 2-methyl-2-acrylate, triethylene glycol dimethacrylate and hydroxyethyl methacrylate.
Preferably, the photoinitiator comprises one or more of initiator ASA, photoinitiator OMTX, photoinitiator OMBP, photoinitiator CQ, photoinitiator 784, photoinitiator TPO.
Preferably, the polymerization inhibitor comprises one or more of MQ, N-nitroso-N-phenylhydroxylamine aluminum and TBHQ; the dispersant is luobozun 24000SC.
A3D printing method of a ceramic denture comprises the following steps:
s1, establishing a unit model in a hexagonal pyramid lattice structure;
s2, calculating the spatial arrangement of the unit bodies to obtain the internal crystal microstructure of the ceramic denture and the data of the ceramic denture model;
s3, importing the ceramic denture model data into a 3D printer, and printing mixed ceramic powder containing additives into a denture biscuit by the 3D printer;
s4, after cleaning and UV secondary curing are carried out on the denture biscuit, high-temperature degreasing is carried out, the high-temperature degreasing temperature is a stepped temperature rising mode, and the method specifically comprises the following steps: putting the denture biscuit into a sintering furnace, heating to 450-500 ℃ at the speed of 1-2 ℃/min, preserving the temperature for 3-4 hours, and removing resin; then heating to 1600-1850 ℃ at the speed of 12-15 ℃/min and preserving the heat for 7-8 hours to obtain the ceramic false tooth.
The ceramic denture and the 3D printing method thereof disclosed by the invention have the beneficial effects that: the internal structure of the ceramic false tooth is printed into a lattice microstructure, so that the bending strength and the biological activity of the ceramic false tooth are improved, and the antibacterial rate of the ceramic false tooth is improved by adding the silver nanowires into the ceramic false tooth.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 is a flowchart of a 3D printing method for a ceramic denture according to the present invention.
Detailed Description
The invention will be further elucidated and described with reference to a specific embodiment and the drawings of the specification:
referring to the flow of fig. 1, the following embodiments are respectively implemented:
in the case of the example 1, the following examples are given,
s1, establishing a unit model in a hexagonal pyramid lattice structure;
s2, calculating the spatial arrangement of the unit bodies to obtain the internal crystal microstructure of the ceramic denture and the data of the ceramic denture model;
and S3, importing the data of the ceramic denture model into a 3D printer, mixing the mixed ceramic powder and the additives according to the mixture ratio shown in the following tables 1 and 2, uniformly mixing the mixed ceramic powder and the additives by using a ball mill, carrying out ball milling for 6 hours, and further mixing and defoaming the slurry by using a planetary vacuum defoaming machine, wherein the processing time is 50 min, the rotating speed is 700 r/min, and the vacuum degree is-95 KPa. And then adding the processed mixed ceramic powder and the additive into a 3D printer, and printing out the denture biscuit by the 3D printer.
S4, cleaning and UV secondary curing the denture biscuit, and then degreasing and sintering to obtain the ceramic denture; removing the organic part of the denture biscuit when the denture biscuit is degreased at high temperature to obtain the ceramic denture with the lattice microstructure; the high-temperature degreasing temperature is in a step-type heating mode, and specifically comprises the following steps: putting the denture biscuit into a sintering furnace, heating to 450 ℃ at the speed of 2 ℃/min, preserving heat for 4 hours, and removing resin; and then heating to 1850 ℃ at the speed of 12 ℃/min and preserving the heat for 8 hours, and completely sintering the ceramic and the silver nanowires to form the ceramic false tooth with the lattice microstructure shape of the silver nanowires.
TABLE 1
TABLE 2
| Mixed ceramic powder | Zirconium oxide | Titanium oxide | Tricalcium phosphate |
| Mass fraction meter | 80％ | 5％ | 15％ |
In the case of the example 2, the following examples are given,
steps S1 and S2 are the same as in example 1 above.
And S3, importing the data of the ceramic denture model into a 3D printer, mixing the mixed ceramic powder and the additives according to the mixture ratio shown in the following tables 3 and 4, uniformly mixing the mixed ceramic powder and the additives by using a ball mill, carrying out ball milling for 6 hours, and further mixing and defoaming the slurry by using a planetary vacuum defoaming machine, wherein the processing time is 50 min, the rotating speed is 700 r/min, and the vacuum degree is-95 KPa. And then adding the processed mixed ceramic powder and the additive into a 3D printer, and printing out the denture biscuit by the 3D printer.
S4, cleaning the false tooth biscuit, carrying out UV secondary curing, and carrying out degreasing sintering to obtain the ceramic false tooth; removing the organic part of the denture biscuit when the denture biscuit is degreased at high temperature to obtain the ceramic denture with the lattice microstructure; the high-temperature degreasing temperature is in a step-type heating mode, and specifically comprises the following steps: putting the denture biscuit into a sintering furnace, heating to 500 ℃ at the speed of 1 ℃/min, preserving heat for 3 hours, and removing resin; and then heating to 1600 ℃ at the speed of 15 ℃/min and preserving the heat for 7 hours, and completely sintering the ceramic and the silver nanowires to form the ceramic false tooth with the lattice microstructure shape containing the silver nanowires.
TABLE 3
TABLE 4
| Mixed ceramic powder | Zirconium oxide | Titanium oxide | Tricalcium phosphate |
| Mass fraction meter | 80％ | 5％ | 15％ |
The following comparative experiment was performed using the existing 3D printing material and method for example 1.
Comparative example 1:
s1, establishing a model of a unit body;
s2, calculating the spatial arrangement of the unit bodies to obtain ceramic denture model data;
and S3, importing the ceramic denture model data into a 3D printer, mixing the mixed ceramic powder and additives according to the mixture ratio shown in the following tables 5 and 6, adding the mixture into the 3D printer, and printing the ceramic denture of the entity by the 3D printer.
TABLE 5
TABLE 6
| Mixed ceramic powder | Zirconium oxide | Titanium oxide | Tricalcium phosphate |
| Mass fraction meter | 80％ | 5％ | 15％ |
Comparative example 2:
steps S1 and S2 are the same as comparative example 1 above.
And S3, importing the ceramic denture model data into a 3D printer, mixing the mixed ceramic powder and additives according to the mixture ratio shown in the following table 7 and table 8, adding the mixture into the 3D printer, and printing the ceramic denture of the entity by the 3D printer.
TABLE 7
TABLE 8
| Mixed ceramic powder | Zirconium oxide | Titanium oxide | Tricalcium phosphate |
| Mass fraction meter | 80％ | 5％ | 15％ |
The ceramic dentures printed in the above examples 1, 2, 1 and 2 were subjected to an antibacterial ratio test, a bending strength test and a bioactivity test, respectively, to obtain the following table 9.
TABLE 9
Wherein, the bending strength is tested by adopting the GB/T6569-86 test sample (35 multiplied by 3 multiplied by 4) standard; the antibacterial rate test adopts the antibacterial performance detection method described in GB/T28116-2011 to detect; biological activity (cell tissue permeability) test: the 3D printed gap structure provides a space for cell tissue production, and the cell tissue permeates into the 3D printed body and is combined with the 3D printed body to generate symbiosis to form a certain penetration depth; after the denture of example 1 and example 2 and the denture of comparative example 1 and comparative example 2 were subjected to cell culture in a cell culture dish for 2 weeks, the proportion of the cell structures found in the denture microstructures of the same volume was measured as an in vitro comparison basis for the cell tissue permeability.
As can be seen from table 9, in examples 1 and 2, compared to comparative examples 1 and 2, the ceramic dentures of lattice microstructures printed by examples 1 and 2 have higher antibacterial rate, flexural strength, and bioactivity than the solid ceramic dentures printed by comparative examples 1 and 2.
In conclusion, the bending strength and the bioactivity of the ceramic denture pair are greatly improved by 3D printing of the ceramic denture with the lattice microstructure; after the silver nanowires are added, the antibacterial rate of the ceramic denture is improved; and because the length of the silver nanowire is 30-50 μm, the diameter is 10-20 nm, and the silver nanowire is larger than the size of human cells by 10 μm, the silver nanowire does not cause damage to human bodies.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The ceramic false tooth is characterized in that the interior of the ceramic false tooth is in a lattice microstructure shape and comprises 72-90% of mixed ceramic powder and 10-28% of additives in percentage by mass, wherein the additives comprise active oligomer, photoinitiator, dispersant and polymerization inhibitor.
2. The ceramic denture of claim 1, wherein the additives further comprise silver nanowires, the silver nanowires being located within the lattice microstructure.
3. The ceramic denture of claim 2, wherein the silver nanowires are 30 μ ι η to 50 μ ι η in length and 10nm to 20nm in diameter.
4. The ceramic denture according to claim 2, wherein the silver nanowires are 0.3% -2%, the reactive oligomer is 5% -25%, the photoinitiator is 2% -9%, the dispersant is 0.5% -2%, and the polymerization inhibitor is 0.2% -1.7% by mass.
5. The ceramic denture of claim 1, wherein the mixed ceramic powder is a mixture of one or more of hydroxyapatite, tricalcium phosphate, zirconia, silica, and titania.
6. The ceramic denture of claim 5, wherein said zirconia is 80%, said titania is 5%, and said tricalcium phosphate is 15% by mass fraction.
7. The ceramic denture of claim 1, wherein said reactive oligomer comprises one or more of modified bisphenol a bis-glycidyl methacrylate, ethoxylated bisphenol a bis-glycidyl methacrylate, urethane dimethacrylate, 1, 12-dodecadienol 2-methyl-2 acrylate, triethylene glycol dimethacrylate, hydroxyethyl methacrylate.
8. The ceramic denture of claim 1, wherein the photoinitiator comprises one or more of initiator ASA, photoinitiator OMTX, photoinitiator OMBP, photoinitiator CQ, photoinitiator 784, photoinitiator TPO.
9. The ceramic denture of claim 1, wherein said polymerization inhibitor comprises one or more of MQ, N-nitroso-N-phenylhydroxylamine aluminum, TBHQ, and said dispersant is luobutran 24000SC.
10. A3D printing method of a ceramic denture is characterized by comprising the following steps:
s1, establishing a unit model in a hexagonal pyramid lattice structure;
s2, calculating the spatial arrangement of the unit bodies to obtain the internal lattice microstructure of the ceramic denture and the data of the ceramic denture model;
s3, importing the ceramic denture model data into a 3D printer, and printing mixed ceramic powder containing additives into a denture biscuit by the 3D printer;
s4, after cleaning and UV secondary curing are carried out on the denture biscuit, high-temperature degreasing is carried out, the high-temperature degreasing temperature is a stepped temperature rising mode, and the method specifically comprises the following steps: putting the denture biscuit into a sintering furnace, heating to 450-500 ℃ at the speed of 1-2 ℃/min, preserving the temperature for 3-4 hours, and removing resin; then heating to 1600-1850 ℃ at the speed of 12-15 ℃/min and preserving the heat for 7-8 hours to obtain the ceramic false tooth.
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| CN202211470408.6A CN115887753A (en) | 2022-11-23 | 2022-11-23 | Ceramic denture and 3D printing method thereof |
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| CN202211470408.6A CN115887753A (en) | 2022-11-23 | 2022-11-23 | Ceramic denture and 3D printing method thereof |
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