CN1489987A - Polycrystal zirconium oxide ceramic dental material and preparation thereof - Google Patents
Polycrystal zirconium oxide ceramic dental material and preparation thereof Download PDFInfo
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- CN1489987A CN1489987A CNA031563716A CN03156371A CN1489987A CN 1489987 A CN1489987 A CN 1489987A CN A031563716 A CNA031563716 A CN A031563716A CN 03156371 A CN03156371 A CN 03156371A CN 1489987 A CN1489987 A CN 1489987A
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- 238000002360 preparation method Methods 0.000 title claims description 9
- 239000011224 oxide ceramic Substances 0.000 title abstract 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title abstract 3
- 229910001928 zirconium oxide Inorganic materials 0.000 title abstract 3
- 239000005548 dental material Substances 0.000 title description 2
- 238000005245 sintering Methods 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 12
- 239000000919 ceramic Substances 0.000 claims description 72
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 62
- 238000002156 mixing Methods 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 17
- 235000015895 biscuits Nutrition 0.000 claims description 12
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 10
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims description 10
- 230000004927 fusion Effects 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000011236 particulate material Substances 0.000 claims description 10
- 229920005596 polymer binder Polymers 0.000 claims description 10
- 239000002491 polymer binding agent Substances 0.000 claims description 10
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000001746 injection moulding Methods 0.000 claims description 7
- -1 polyethylene Polymers 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- 239000012188 paraffin wax Substances 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 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 4
- 239000004200 microcrystalline wax Substances 0.000 claims description 4
- 235000019808 microcrystalline wax Nutrition 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000013467 fragmentation Methods 0.000 claims description 2
- 238000006062 fragmentation reaction Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 abstract description 5
- 238000005452 bending Methods 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 238000005238 degreasing Methods 0.000 abstract 1
- 238000002347 injection Methods 0.000 description 10
- 239000007924 injection Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000002785 anti-thrombosis Effects 0.000 description 1
- 239000003146 anticoagulant agent Substances 0.000 description 1
- 239000003462 bioceramic Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 210000004394 hip joint Anatomy 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Dental Preparations (AREA)
- Dental Tools And Instruments Or Auxiliary Dental Instruments (AREA)
Abstract
A polycrystal zirconium oxide ceramics used as tooth pile is prepared from raw zirconium oxide ceramics powder (80-90 wt.%), high-molecular adhesive (5-10) and low-molecular assistant (5-10) through pugging, granulating, ejection moulding, hot degreasing at 500-800 deg.C and sintering at 1350-1550 deg.C. It has high bending strength (more than 600 MPa), high break toughness up to 13 MPa, high elastic modulus (140 MPa) and high Vickers hardness (1050-1200 MPa).
Description
Technical field
The present invention relates to a kind of polycrystal zirconia ceramics tooth pile material and preparation method thereof, belong to ceramic materials preparation technology field.
Background technology
The tooth stake is a kind of dental material commonly used in the Oral Repair.The tooth pile material that adopts mainly contains metal and inorfil enhancing resin two big classes at present, as the stake of rustless steel tooth, the stake of carbon fiber-reinforced resin tooth.Though the stake of metal tooth has intensity and toughness preferably, potential corrosion, ion stripping all will jeopardize the reliability of tooth stake.And fiber-reinforced resin is easily aging, and its durability and reliability also are affected.In addition, this two classes tooth pile material color and human teeth's color differ greatly, and show lead in ceramic corona, influence the aesthetic of ceramic tooth.
Adopt the engineering structure pottery can overcome the problems referred to above.Wherein, the transformation toughening polycrystalline zirconia ceramic material has following excellent properties: the bending strength (600～1000MPa) that (1) is high; (2) high fracture toughness (10～15MPam
1/2), be higher than structural ceramicss such as aluminium oxide; (3) chemical stability is good, promptly not with human body in liquid reactions, acid-alkali-corrosive-resisting; (4) good biocompatibility has antithrombotic and sterilization property.Therefore, zirconia ceramics has been applied to artificial hip joint etc. as bioceramic.The present invention adopts a kind of transformation toughening polycrystal zirconia ceramics of mechanical property and chemical-biological function admirable---and yttrium is stablized cubic polycrystal zirconia ceramics mutually (being called for short Y-TZP), as ceramic tooth pile material.
Because tooth stake size is little, complex-shaped, surface accuracy and fineness require high, and therefore, the present invention proposes to adopt injection moulding method to prepare ceramic tooth stake.This is because ceramic injection forming has following characteristics:
(1) has the ability of the various complicated shape ceramic parts of molding.
(2) size Control precision height, injection molded article have nearly clean shape feature.
(3) the ceramic member surface smoothing of molding, outward appearance is good.
(4) forming process mechanization degree height is made good repetitiveness in batches.
Contrast other forming process of ceramics manufacture method, as dry-pressing formed, injection forming and cold isostatic compaction, the ceramic injection forming technology is better than other manufacture method aspect ceramic part dimensional accuracy, density uniformity, complex-shaped property and mass serialization production.
Summary of the invention
The purpose of this invention is to provide a kind of precision height, mechanical property is good, is suitable for polycrystal zirconia ceramics tooth pile material of suitability for industrialized production and preparation method thereof.
The polycrystal zirconia ceramics tooth pile material that the present invention proposes, it is characterized in that: the initial feed that described material uses contains zirconia ceramics powder, high polymer binder, low molecule auxiliary agent, its proportioning is: zirconia ceramics powder 80～90wt%, high polymer binder 5～10wt%, low molecule auxiliary agent 5～10wt%.
In above-mentioned polycrystal zirconia ceramics tooth pile material, described high polymer binder is one or more in polyethylene, polypropylene, polystyrene, the polymethyl methacrylate.
In above-mentioned polycrystal zirconia ceramics tooth pile material, described low molecule auxiliary agent is one or more in paraffin, microcrystalline wax, diethyl phthalate, dioctyl phthalate, the dibutyl phthalate.
The preparation method of the polycrystal zirconia ceramics tooth pile material that the present invention proposes, it is characterized in that: described method is followed successively by:
(1) mixing granulator: elder generation transfers to 130 ℃～180 ℃ with the temperature of mixing roll, adds high polymer binder, after the fusion, adds low molecule auxiliary agent and zirconia ceramics powder, and after the fully mixing nothing that stirs was reunited, cooling obtained flaky mixture block, fragmentation again;
(2) ejection formation: pour in the injector barrel through the good particulate material of mixing granulator above-mentioned, divide four sections in the barrel and heat, temperature is 130 ℃～180 ℃, penetrates pressure in 150MPa, carries out injection moulding, obtains ceramic tooth stake green compact body;
(3) hot defat: the ceramic tooth stake green compact body that above-mentioned ejection formation obtains is put into crucible, then it is put to stove, with 10～30 ℃/h speed rise to 500～800 ℃, the stove internal cooling is to room temperature, remove whole organic binder bonds, obtain ceramic tooth stake biscuit;
(4) sintering: the ceramic tooth stake biscuit of above-mentioned defat is placed in the high temperature furnace, rise to sintering temperature with 2～5 ℃/minute programming rates, temperature range is 1350～1550 ℃, and constant temperature is 1～3 hour under this temperature, and the stove internal cooling is to room temperature.
In above-mentioned preparation method, the described sintering process of step (4) adopts normal pressure-sintered, carries out in air atmosphere.
Polycrystal zirconia ceramics tooth pile material that the present invention proposes and preparation method thereof has following characteristics and effect:
Injection moulding organic binder bond system has the advantage of good fluidity, molding blank density height (relative density 52-58%), thereby, guaranteed sintering after ceramic product density greater than 6.0g/cm
3
It is little that the molding blank sintering shrinks, and total linear shrinkage ratio is 15-19%, is out of shape for a short time, guaranteed the product size precision;
Prepared ceramic tooth stake good combination property: bending strength is greater than 600MPa, and fracture toughness is up to 13MPa.m
1/2, elastic modelling quantity 140MPa, Vickers hardness 1050～1200MPa.
Experimental results show that: manufacturing process good reproducibility of the present invention, constant product quality, dependable performance are convenient to suitability for industrialized production.
The specific embodiment
Introduce technical scheme of the present invention in detail below in conjunction with embodiment:
The present invention's pottery tooth stake injection moulding manufacturing mainly comprises the following steps: mixing granulator, ejection formation, defat, these 4 committed steps of sintering.
1. mixing granulator step
Temperature with mixing roll transfers to 130 ℃～180 ℃ earlier.At first add high polymer binder 5～10wt.%.This class binding agent comprises a kind of in polyethylene, polypropylene, polystyrene, the polymethyl methacrylate or more than one.After treating the high polymer binder fusion, add plasticizer and the lubricant of 5～10wt.% then, as wherein a kind of in paraffin, microcrystalline wax, diethyl phthalate, dioctyl phthalate, the dibutyl phthalate or more than one.The Y-Zr0 that adds 80～90wt.% again
2Ceramics.Abundant then mixing stirring, through 30～60 minutes, treat that the mixing even nothing of zirconia ceramics powder and organic additive is reunited after, cooling obtains flaky mixture block simultaneously again.Be broken into particulate material then, pack is preserved.
3. ejection formation step
Pour in the injector barrel through the good particulate material of mixing granulator above-mentioned, divide four sections in the barrel and heat, temperature penetrates pressure in 150MPa from 130 ℃～180 ℃, carries out injection moulding, obtains ceramic tooth stake green compact body.
4. hot defatting step
The ceramic tooth stake green compact body that ejection formation obtains is put into ceramic crucible, fills emergy and quartz sand at tooth stake base substrate and crucible gap location, promptly buries powder.Then crucible is put as in the Muffle furnace, with 10～30 ℃/h speed rise to 500～800 ℃.The stove internal cooling can remove whole organic binder bonds to room temperature then, obtains ceramic tooth stake biscuit.
5. sintering step
The ceramic tooth stake biscuit of finishing defat is placed in the high temperature furnace, programming rate with 2～5 ℃/minute rises to sintering temperature, temperature range is 1350～1550 ℃, constant temperature is 1～3 hour under this temperature, in stove, be cooled to room temperature again and take out the ceramic tooth stake that sinters, whole sintering process adopts normal pressure-sintered, carries out in air atmosphere.
For further setting forth concrete technology contents of the present invention, with specific embodiment each step that zirconia ceramics tooth stake injection moulding is made is described below.
Embodiment 1
Adopt Y-ZrO
2Ceramics, mean diameter are 0.4 μ m.Earlier mixing roll is heated to 150 ℃, the polyethylene (PE) of 7wt.% percentage by weight is added mixing roll, add paraffin (5wt.%) and diethyl phthalate (DEP) more slowly (3wt.%), treat complete fusion after.Add the zirconia ceramic powder again, ceramics accounts for the percetage by weight of 85wt.%.Mixing about 30 minutes, reach fully evenly no aggregating state.The material that will mix at last takes out cooling, carries out broken pelletize again, obtains particulate material.
With about 500 grams of the particulate material after the above-mentioned pelletize, add fusion in the injection (mo(u)lding) machine barrel slowly, under the injection pressure of 120MPa, the fusion feeding is injected mould, cooled off 2 minutes, get final product the green compact body that the demoulding obtains the stake of zirconia ceramics tooth.
The green compact body is put into alumina crucible, and fill emergy around sample, the programming rate with 25 ℃/hour in Muffle furnace rises to 700 ℃, is incubated after 1 hour furnace cooling.Organic substance is all discharged and is obtained wanting agglomerating biscuit of ceramics in the green compact body.
Above-mentioned ceramic tooth stake biscuit is put into silicon order rod electric furnace, rise to 1500 ℃ with 2 ℃/minute programming rates, be incubated 2 hours, furnace cooling obtains fine and close intact ceramic tooth stake then.
Embodiment 2
Adopt Y-ZrO
2Ceramics, mean diameter are 0.2 μ m.Earlier double roll mill is heated to 135 ℃, with the polystyrene adding mixing roll of 8wt.% percentage by weight, about 5 minutes of melting mixing.Slowly add paraffin (8wt.%) and dibutyl phthalate (DBP) again (4wt.%).Add the zirconia ceramic powder again, ceramics accounts for weight 80wt.%.Mixing 35 minutes, reach fully evenly.The material that will mix at last takes out cooling, carries out broken pelletize again, obtains particulate material.
With about 500 grams of the particulate material after the above-mentioned pelletize, add fusion in the injection (mo(u)lding) machine barrel slowly, under the injection pressure of 80MPa, the fusion feeding is injected mould, cooled off 3 minutes, get final product the green compact body that the demoulding obtains the stake of zirconia ceramics tooth.
The green compact body is put into alumina crucible, and fill emergy around sample, the programming rate with 20 ℃/hour in Muffle furnace rises to 550 ℃, is incubated after 2 hours furnace cooling.Organic substance is all discharged and is obtained wanting agglomerating biscuit of ceramics in the green compact body.
Above-mentioned ceramic tooth stake biscuit is put into silicon order rod electric furnace, rise to 1400 ℃ with 3 ℃/minute programming rates, be incubated 2 hours, furnace cooling obtains fine and close intact ceramic tooth stake then.
Embodiment 3
Adopt Y-ZrO
2Ceramics, mean diameter are 0.6 μ m.Earlier double roll mill is heated to 180 ℃, the polymethyl methacrylate adding mixing roll with the 5wt.% percentage by weight adds microcrystalline wax (5wt.%) and dioctyl phthalate (2wt.%) more slowly after the melting.Add the zirconia ceramic powder again, ceramics accounts for the percetage by weight of total amount 88wt.%.Mixing 40 minutes, reach fully evenly.The material that will mix at last takes out cooling, carries out broken pelletize again, obtains particulate material.
With about 500 grams of the particulate material after the above-mentioned pelletize, add fusion in the injection (mo(u)lding) machine barrel slowly, under the injection pressure of 100MPa, the fusion feeding is injected mould, cooled off 2 minutes, get final product the green compact body that the demoulding obtains the stake of zirconia ceramics tooth.
The green compact body is put into alumina crucible, and fill emergy around sample, the programming rate with 5 ℃/minute in Muffle furnace rises to 800 ℃, is incubated after 2 hours furnace cooling.Organic substance is all discharged and is obtained wanting agglomerating biscuit of ceramics in the green compact body.
Above-mentioned ceramic tooth stake biscuit is put into silicon order rod electric furnace, rise to 1550 ℃ with 4 ℃/minute programming rates, be incubated 2 hours, furnace cooling obtains fine and close intact ceramic tooth stake then.
Claims (5)
1, polycrystal zirconia ceramics tooth pile material is characterized in that: the initial feed that described material uses contains zirconia ceramics powder, high polymer binder, low molecule auxiliary agent, its proportioning is: zirconia ceramics powder 80～90wt%, high polymer binder 5～10wt%, low molecule auxiliary agent 5～10wt%.
2, according to the described polycrystal zirconia ceramics tooth of claim 1 pile material, it is characterized in that: described high polymer binder is one or more in polyethylene, polypropylene, polystyrene, the polymethyl methacrylate.
3, according to the described polycrystal zirconia ceramics tooth of claim 1 pile material, it is characterized in that: described low molecule auxiliary agent is one or more in paraffin, microcrystalline wax, diethyl phthalate, dioctyl phthalate, the dibutyl phthalate.
4, a kind of method for preparing polycrystal zirconia ceramics tooth pile material as claimed in claim 1, it is characterized in that: described method is followed successively by:
(1) mixing granulator: elder generation transfers to 130 ℃～180 ℃ with the temperature of mixing roll, adds high polymer binder, after the fusion, adds low molecule auxiliary agent and zirconia ceramics powder, and after the fully mixing nothing that stirs was reunited, cooling obtained flaky mixture block, fragmentation again;
(2) ejection formation: pour in the injector barrel through the good particulate material of mixing granulator above-mentioned, divide four sections in the barrel and heat, temperature is 130 ℃～180 ℃, penetrates pressure in 150MPa, carries out injection moulding, obtains ceramic tooth stake green compact body;
(3) hot defat: the ceramic tooth stake green compact body that above-mentioned ejection formation obtains is put into crucible, then it is put to stove, with 10～30 ℃/h speed rise to 500～800 ℃, the stove internal cooling is to room temperature, remove whole organic binder bonds, obtain ceramic tooth stake biscuit;
(4) sintering: the ceramic tooth stake biscuit of above-mentioned defat is placed in the high temperature furnace, rise to sintering temperature with 2～5 ℃/minute programming rates, temperature range is 1350～1550 ℃, and constant temperature is 1～3 hour under this temperature, and the stove internal cooling is to room temperature.
5, according to the preparation method of the described polycrystal zirconia ceramics tooth of claim 4 pile material, it is characterized in that: the described sintering process of step (4) adopts normal pressure-sintered, carries out in air atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03156371 CN1203830C (en) | 2003-09-05 | 2003-09-05 | Polycrystal zirconium oxide ceramic dental material and preparation thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03156371 CN1203830C (en) | 2003-09-05 | 2003-09-05 | Polycrystal zirconium oxide ceramic dental material and preparation thereof |
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| Publication Number | Publication Date |
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| CN1489987A true CN1489987A (en) | 2004-04-21 |
| CN1203830C CN1203830C (en) | 2005-06-01 |
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| CN 03156371 Expired - Fee Related CN1203830C (en) | 2003-09-05 | 2003-09-05 | Polycrystal zirconium oxide ceramic dental material and preparation thereof |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100370963C (en) * | 2005-12-15 | 2008-02-27 | 安泰科技股份有限公司 | Zirconium oxide full-porcelain dental repair material and its preparing method |
| CN100465128C (en) * | 2006-12-22 | 2009-03-04 | 詹智诚 | Grains dedicated to ceramics injection molding, and preparation method |
| CN102173791A (en) * | 2011-01-27 | 2011-09-07 | 上海高诚艺术包装有限公司 | Method for preparing zirconia ceramic bottleneck |
| CN101647730B (en) * | 2009-07-08 | 2012-07-25 | 上海上远齿科技术有限公司 | Zirconium dioxide full porcelain tooth and preparation method thereof |
| CN102843990A (en) * | 2010-04-06 | 2012-12-26 | 哈斯有限公司 | Preparation method of ceramic crowns for primary teeth, and ceramic crowns for primary teeth prepared thereby |
| CN101081735B (en) * | 2005-10-07 | 2013-03-13 | 苏舍美特科（美国）公司 | Optimized high temperature thermal heat barrier |
| CN104990412A (en) * | 2015-08-10 | 2015-10-21 | 南宁越洋科技有限公司 | Microwave hot isostatic pressure sintering furnace for dental zirconia ceramic later sintering |
| WO2017185468A1 (en) * | 2016-04-29 | 2017-11-02 | 成都贝施美医疗设备有限公司 | Zirconia ceramic prosthesis for dentistry and preparation method therefor |
| CN108066158A (en) * | 2017-12-08 | 2018-05-25 | 郑州搜趣信息技术有限公司 | High ceramic tooth material of a kind of fracture toughness and its preparation method and application |
| CN108472109A (en) * | 2015-12-15 | 2018-08-31 | 古莎有限公司 | The method for manufacturing big polymerizable dental material block |
| CN109069238A (en) * | 2016-04-22 | 2018-12-21 | 义获嘉伟瓦登特公司 | The method for being used to prepare dental prosthesis |
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| CN101081735B (en) * | 2005-10-07 | 2013-03-13 | 苏舍美特科（美国）公司 | Optimized high temperature thermal heat barrier |
| CN100370963C (en) * | 2005-12-15 | 2008-02-27 | 安泰科技股份有限公司 | Zirconium oxide full-porcelain dental repair material and its preparing method |
| CN100465128C (en) * | 2006-12-22 | 2009-03-04 | 詹智诚 | Grains dedicated to ceramics injection molding, and preparation method |
| CN101647730B (en) * | 2009-07-08 | 2012-07-25 | 上海上远齿科技术有限公司 | Zirconium dioxide full porcelain tooth and preparation method thereof |
| CN102843990A (en) * | 2010-04-06 | 2012-12-26 | 哈斯有限公司 | Preparation method of ceramic crowns for primary teeth, and ceramic crowns for primary teeth prepared thereby |
| US9458062B2 (en) | 2010-04-06 | 2016-10-04 | Hass Co., Ltd. | Method of manufacturing ceramic primary crown and ceramic primary crown manufactured by the same |
| CN102173791A (en) * | 2011-01-27 | 2011-09-07 | 上海高诚艺术包装有限公司 | Method for preparing zirconia ceramic bottleneck |
| CN104990412A (en) * | 2015-08-10 | 2015-10-21 | 南宁越洋科技有限公司 | Microwave hot isostatic pressure sintering furnace for dental zirconia ceramic later sintering |
| CN108472109A (en) * | 2015-12-15 | 2018-08-31 | 古莎有限公司 | The method for manufacturing big polymerizable dental material block |
| CN109069238A (en) * | 2016-04-22 | 2018-12-21 | 义获嘉伟瓦登特公司 | The method for being used to prepare dental prosthesis |
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| WO2017185468A1 (en) * | 2016-04-29 | 2017-11-02 | 成都贝施美医疗设备有限公司 | Zirconia ceramic prosthesis for dentistry and preparation method therefor |
| CN108066158A (en) * | 2017-12-08 | 2018-05-25 | 郑州搜趣信息技术有限公司 | High ceramic tooth material of a kind of fracture toughness and its preparation method and application |
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| CN113967959A (en) * | 2021-11-26 | 2022-01-25 | 上海陶宝陶瓷新材料开发有限公司 | Zirconia ceramic tooth injection molding process |
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