CN1256933C - Dental dummy preparation method - Google Patents
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- CN1256933C CN1256933C CN 200410023360 CN200410023360A CN1256933C CN 1256933 C CN1256933 C CN 1256933C CN 200410023360 CN200410023360 CN 200410023360 CN 200410023360 A CN200410023360 A CN 200410023360A CN 1256933 C CN1256933 C CN 1256933C
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Abstract
The present invention discloses a preparation method for a dental prosthesis. The preparation method is characterized in that the preparation method comprises the following steps: step (1), oxide nanometer micro powder is formed after being granulated by adding a binding agent or directly formed without adding the binding agent, the forming modes can be a molding mode, an isostatic pressing mode or a mode with first molding and second isostatic pressing, and manufactured ceramic biscuits are heated to 900 to 1300 DEG C for heat preservation for 1 to 5 hours and preferably from 2 to 3 hours, and naturally cooled to obtain partial calcination ceramic bodies; step (2), partial calcination ceramic blocks are processed to obtain an initial prosthesis through CAD/CAM; step (3), the heat of the initial prosthesis is kept for 1.5 to 2.5 hours at the temperature of 1350 to 1550 DEG C, and the initial prosthesis is completely sintered to obtain the final dental prosthesis. The dental prosthesis prepared by the present invention has the advantages of high mechanical strength, good beautiful appearance, color precondition, etc.
Description
Technical field
The present invention relates to a kind of preparation method of dental prosthesis, especially relate to a kind of method of making dental prosthesis with the CAD/CAM technology.
Background technology
Present stage is made the method for full-porcelain dental dummy or the attached ceramic prosthesis of Metal Melting, needs a large amount of manual operationss, and Production Time is long, and highly depends on skilled worker's level height and skills involved in the labour.And manual operations, when preserving aesthetic property, the inhomogeneous of microstructure can appear in material, influences the intensity of material and the reliability of use.
Computer aided design/computer aided machine (CAD/CAM) technology and equipment have been introduced into the field, oral cavity, in these technologies, get the digitized die earlier, promptly measure tooth jaw three-dimensional configuration and reappear the 3-D view of examining stake and nuclear stake tooth on every side, produce " the video model " of CAD.According to nuclear stake and tooth on every side, the skilled worker can select an optimum nuclear stake the corona data base in having computer, corona is optimal in place with what choose, places above the nuclear stake, so also can reach the fitness requirement of dental prosthesis.The digitalized data of dental prosthesis after promptly " digitized wax pattern " forms, is delivered to the numerical control grinding machine of an energy in a plurality of dimension operation.The grinding machine is according to the design data that provides, and cutting or grinding go out a dental prosthesis from a nugget genus or ceramic material.
Aim at the CAD/CAM of dental field design and duplicate grinding system, the Duret system of France, the Cerec system of Germany and the Rekow system of the U.S. etc. are arranged.The supporting material of commercial that use and CAD/CAM system comprises feldspar porcelain and mica-based glass ceramics, good performance attractive in appearance is arranged, but the mechanical performance of material is low, and the bending strength of the dummy that obtains is from 80-200MPa, and fracture toughness is from 1-2MPam
1/2And, make cutting and grinding tool passivation through melting the machinable material that the dental polishing powder does fully, significantly reduced the dental prosthesis manufacturing speed.Dental polishing is melted in grinding fully also may cause too much chip and thin slice, influences the accurate and final fitness between dental prosthesis and patient's natural tooth of grinding action like this.
The CAD/CAM supplementary material had both needed sufficient intensity and attractive in appearance, can reduce the passivating process of cutting or grinding tool again.Partially sinter or porous material begins to play the part of important positive role in the CAD/CAM supplementary material.
U.S. Pat Pat.5,910,273 disclose a kind of technology with CAD/CAM fabrication techniques dental materials, and the porous sintered ceramic body is processed into required form, permeate this material of densification to improve intensity with glass.The Chinese invention patent application is mentioned for No. 01144129.1 with partially sintering alumina block and is processed required form, and the homemade multiple coloured glass infiltration of reuse solves color and strength problem.The glass infiltration alumina composite material that obtains, bending strength 300-450MPa, fracture toughness 3-4.5MPam
1/2This arts demand glass permeate portion sintered alumina obtains glass infiltration alumina composite material, and it is complicated, time-consuming that operating process seems.
Duggusa company develops the Cercon system, has omitted CAD system, makes the wax pattern of dummy earlier, gather the data of dummy on the wax pattern with contact type measurement, amplify certain size, directly the processing part sintered body obtains required form then, and dense sintering obtains dental prosthesis again.The nano powder that partially sinters body and be with stabilized with yttrium oxide tetragonal phase zirconium oxide (Y-TZP) particle diameter 40-60nm is a raw material, obtains through waiting static pressure, partially sintering.The solution of dummy color problem is to contain Fe by infiltration in partially sintering body
3+, Pr
3+, V
4+Solution, the alopecia solvent liquid that volatilizees again behind the dense sintering, promptly contains above-mentioned ion and shows different colors in pottery.The intensity height of the dummy that this technology obtains is made wax pattern but this arts demand is manual earlier, also needs to solve color problem with solution soaking before dense sintering, and it is complicated, loaded down with trivial details that process seems, time-consuming length.
US Pat.6,354,836 disclose a kind of method of making dummy through CAD/CAM, and ceramic precursor powder and binding agent are mixed, and are pressed into block biscuit.Biscuit is through soft sintering, and apparent density is less than 85% of final densities.Soft sintered ceramic body obtains " initial dummy " and is sintered to final densities again through the CAD/CAM grinding, obtains the high strength dental prosthetic material.In the method, the grain diameter of oxide powder is from 0.1-100 μ m, preferred 1-30 μ m.This automation technolo degree height, the mechanical performance of the dental prosthesis that makes and surface property are still not ideal enough; In addition, this method does not also propose to solve the scheme of this major issue of dummy material color.
Summary of the invention
Purpose of the present invention just is to overcome the deficiency of above-mentioned background technology, and a kind of technology of making dental prosthesis through CAD/CAM is provided, and the dental prosthesis that uses this technology to make has mechanical strength height, performance attractive in appearance and reaches color well and advantage such as can regulate in advance.
The present invention adopts CAD/CAM processing part sintered ceramic material piece, obtains the dental materials of up-sizing required form, and sintering obtains the dental prosthesis of sufficient intensity again.Wherein ceramic material comprises the nano powder of size basically identical, does not have the cluster of grains aggressiveness substantially, and biscuit density is even, can predict the ground isotropism like this and evenly shrink in sintering process, can not produce and can be out of shape with perceiveing.Biscuit partially sinters the solid density that apparent density is 50%-85% (also can be write as 50%TD-85%TD).Partially sinter ceramic body and go out required form through the CAD/CAM grinding, for the expection sintering that compensates in sintering process shrinks, its size is amplified in proportion.This material can be aluminium oxide, cubic phase polycrystal zirconia (TZP), silicon oxide or their mixture.The color of ceramic material realizes that by adding iron sesquioxide and cerium oxide in micropowder the depth of color is regulated by the addition of iron sesquioxide and cerium oxide.This ceramic material is used for making dental prosthesis, includes but not limited to: bridge, hat, artificial tooth, veneer, inlay etc.
The preparation technology of the present invention's dental prosthesis specifically comprises the steps:
(1) preparation partially sinters ceramic body
With oxide micropowder, adding additives pelletize aftershaping or adding additives straight forming not, molding mode can be mold pressing or etc. static pressure, or first mold pressing waits static pressure again, makes biscuit of ceramics.
Biscuit of ceramics is warmed up to 900-1300 ℃, is incubated 1-5 hour (preferred 2-3 hour), and natural cooling obtains partially sintering ceramic body.
The density that partially sinters ceramic body is 50%TD-85%TD.
Described oxide is aluminium oxide (Al
2O
3), silicon oxide (SiO
2), cubic phase polycrystal zirconia (be called for short TZP or zirconium oxide) or optional wherein at least two kinds mixture.
The stabilizing agent of TZP is yittrium oxide (Y
2O
3), cerium oxide (CeO
2) or their mixture.With Y
2O
3During for stabilizing agent, Y
2O
3Content is 1.5wt%-8.0wt%; With CeO
2During for stabilizing agent, CeO
2Content is 13.0wt%-22.0wt%; With Y
2O
3And CeO
2Mixture when being stabilizing agent, both mixture content are 4wt%-18wt%, Y in the mixture
2O
3And CeO
2Ratio be 1: 0.5-12.
In coloured oxide micropowder, contain CeO
2And/or Fe
2O
3CeO
2Content is from 0.5wt%-22wt%, preferred 2wt%-10wt%; Fe
2O
3Content from 0.1wt%-10wt%, preferred 0.5wt%-5wt%.
Described oxide micropowder can be nano powder, mean diameter 5-100nm by wet method or dry process.
Binding agent can be polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl acetate, polrvinyl chloride, polyvinyl butyral, polystyrene or optional wherein at least two kinds mixture.
(2) partially sintering ceramic body processes through CAD/CAM
With non-contact measurement (optical measurement) or contact type measurement (mechanical measurement), scanning tooth or tooth die collect and preserve data, again by above data and corona data base, suitable on-station position, obtain the shape of " digitized wax pattern ".The size of " digitized wax pattern " is amplified in certain proportion, " initial dummy " by the dimensioned of amplifying, with the contraction of compensated part sintered ceramic material in the tight burning process.A straight line dimension, the size that finally obtains dummy is the 78%-94% of " initial dummy " size, because partially sinter density to final densities at this, linear shrinkage is 22%-6%.
(3) " initial dummy " tight burning obtains final dental prosthesis
" initial dummy " is sintered to complete density in suitable temperature, and the tight burning temperature depends on used material, is generally 1350 ℃-1550 ℃, is incubated 1.5-2.5 hour.When doing backteeth and repairing, the dummy surface finish can be used, and during dental case, also needs at the surface of dummy decorations porcelain before doing.
The dental prosthesis that uses the present invention to make has the following advantages:
Mechanical strength height, bending strength are more than 600MPa, and fracture toughness is at 4MPam
1/2More than, performance attractive in appearance is good, and zirconium oxide has certain light transmission; Color can be regulated in advance, after having added ferrum oxide or cerium oxide, repairs the different color of physical performance.
Description of drawings
The instrumentation plan of Fig. 1 pottery corona cementation surface;
The height of Fig. 2 pottery corona and the instrumentation plan of width.
The specific embodiment
The invention will be further described below in conjunction with embodiment.
The Y-TZP nano powder compression molding of embodiment 1 different-grain diameter partially sinters temperature and the relation that partially sinters body density
Adopt 3mol% stabilized with yttrium oxide tetragonal phase zirconium oxide polycrystalline material (3Y-TZP) nano powder (two kinds of self-controls that particle diameter is less, another kind of) of different-grain diameter, the specific surface area S that diameter of particle is measured with specific surface area method (BET) from the purchase of east, Guangdong zirconium industry company
BETEquivalent spherical diameter (the d that converts
BET) expression.With the poly-vinyl alcohol solution is bonding agent, and compression molding under 25MPa pressure is measured biscuit density with weight-volumetric method.To remove Organic substance, be incubated two hours in different temperature, the sintered density of measure portion sintered body at 800 ℃ of insulation 1h.Temperature programming to 1450 ℃ is incubated two hours, the sintered density and the mechanical performance of the material of test tight burning.
Adopt the three-point bending resistance method to measure the bending strength of material.Specimen size is 3mm * 2mm * 30mm, specimen surface polishing and chamfering, and span is 20mm, loading velocity is 0.05mm/min; Fracture toughness adopts the SENB method, and specimen size is 2mm * 4mm * 20mm, and otch is about 2mm deeply, and span is 15mm, and loading velocity is 0.05mm/min.
The results are shown in Table 1, table 2.
The relation that partially sinters density and temperature of table 1 different-grain diameter 3Y-TZP micropowder
| Diameter of particle and partially sinter body density (%TD) | Biscuit density (%TD) | Partially sinter temperature (℃) | ||||
| 850 | 950 | 1050 | 1100 | 1150 | ||
| d BET1＝32nm d BET2＝22nm d BET3＝17nm | 34.31 29.65 23.93 | 36.60 31.85 26.82 | 38.14 35.20 31.20 | 49.68 47.40 46.90 | 53.93 54.26 56.03 | 63.50 62.26 62.13 |
The mechanical performance of table 21450 ℃/2h pressureless sintering 3Y-TZP pottery
| Diameter of particle (nm) | Sintered density (TD%) | Bending strength (MPa) | Fracture toughness (MPam 1/2) |
| d BET1＝32 d BET2＝22 d BET3＝17 | 91.90 95.47 92.80 | 600±50.7 710±53.8 640±46.3 | 3.98±0.402 4.77±0.332 4.24±0.302 |
As can be seen from Table 1, the particle diameter of nanometer powder difference, under the condition of same molding pressure and dwell time, not only biscuit density is to have marked difference, and the process of its complete densification also is that characteristics are respectively arranged.d
BETSintering shrinks 1 powder beginning more tempestuously more than 950 ℃, and d
BET3 powder are acutely shrinking more than 850 ℃.The initial temperature that shows more little powder body contraction is low more, and sintering activity is high more, and in the sintering process, biscuit density and diameter of particle all exert an influence to densification process, and when the density of determining section sintered body, these two factors all will be taken into account.
In table 2, the micropowder of three kinds of different-grain diameters is at 1450 ℃/2h, and the density and the bending strength of the ceramic material that pressureless sintering obtains are inequality, and the bending strength of the material that three kinds of micropowders obtain all is higher than 600MPa, and fracture toughness all is higher than 4MPam
1/2, than the mechanical performance height of present common feldspar porcelain and glass ceramics, illustrate these three kinds all powder body have sintering character preferably, can obtain ceramic material than high-mechanical property.
Embodiment 23Y-TZP and alumina powder isostatic compaction partially sinter temperature and the relation that partially sinters body density
With 3Y-TZP nano powder, micron order and alumina in Nano level micropowder, first compression molding, isostatic cool pressing again, hydrostatic pressure is 280MPa, pressurize 1min.Be shaped as 40mm * 35mm * 12mm behind the forming of green body.Biscuit at different temperatures lower part sintering, is used bulking value method measure portion sintered density.Measure portion sintered body mechanical performance.The gained result is as follows:
Table 33Y-TZP partially sinters temperature and the relation that partially sinters body density
| Material and partially sinter body density (%TD) | Diameter of particle (nm) | Biscuit density (%TD) | Partially sinter temperature (℃) | |||
| 1150 | 1175 | 12001 | 225 | |||
| 3Y-TZP | 32 | 54.31 | 64.27 | 67.12 | 73.23 | 80.09 |
The Al of table 4 different-grain diameter
2O
3The relation that partially sinters body density and temperature of micropowder
| Material and partially sinter body density (%TD) | Diameter of particle (μ m) | Biscuit density (%TD) | Partially sinter temperature (℃) | |||
| 1400 | 1450 | 1475 | 1500 | |||
| Al 2O 3 Al 2O 3 | 3.3 0.8 | 59.67 63.24 | 66.06 72.66 | 68.84 - | 71.34 - | 73.54 - |
From table 3 and table 4 as can be seen, the sintering activity of nano powder wants high than the sintering activity of micropowder, in relatively low sintering temperature, can obtain higher sintered density.The biscuit that obtains with compression molding compares, and it is high that density is wanted, and this is because the much bigger cause of briquetting pressure.
Table 5 partially sinters zirconic relative density and mechanical property thereof
| Partially sinter zirconium oxide density (%TD) | Bending strength (MPa) | Elastic modelling quantity (GPa) | Fracture toughness (MPam 1/2) |
| 65.28 69.72 75.47 78.14 85.17 | 117.11±1.08 161.16±0.26 222.05±7.51 232.4±10.51 284.95±0.34 | 36.38±1.33 47.61±1.35 65.70±2.26 69.69±2.97 86.90±2.21 | 1.59±0.02 1.71±0.08 2.03±0.10 2.86±0.09 2.99±0.29 |
The density that partially sinters body according to the solid-phase sintering theory of Coble, is in sintering mid-term when 65%TD is between 85%TD, sintering starts from grain growth begins mid-term, and follows the extensive formation of grain boundary face.At this moment, pore is still and is interconnected into contiguous network, and intergranular crystal boundary face is still isolated mutually and do not form contiguous network.PSZ has quite high intensity and toughness, and this is because zirconic transformation toughening is playing a role.
Embodiment 3 compression moldings partially sinter the relation of body density and machinability
With the Y-TZP ceramics, biscuit is prepared in compression molding, partially sinter the body that partially sinters that obtains different densities, prepare the cuboid of 10mm * 12mm * 15mm, on dentistry Cerec IICAD/CAM machine, carry out the experiment of machinability with inside diameter slicer processing part sintered body.With the machinable performance of cutting time evaluating material, choose the suitable Y-TZP pottery that partially sinters, process " initial dummy "-corona.
Table 6 partially sinters the influence of the density of ceramic body to cutting ability
| Density (%TD) | The machinability of ceramic body | Average cutting time (mins) * |
| 95.48 81.28 71.36 63.50 53.93 49.68 | Not machinable can not be cut machinable machinable machinable machinable | 14.65 10.90 10.16 9.36 |
* machine expection cutting time: 10.90min.
Three-dimensional shrinkage characteristics when embodiment 4 compression moldings partially sinter the body tight burning
Particle diameter is the compression molding of 32nm Y-TZP micropowder, density after partially sintering is that the ceramic body of 55.84%TD (T7 sample) and 67.67%TD (T8 sample) processes " initial dummy "-corona on CAD/CAM, getting the distance of the point of the several easy identifications on the corona measures, behind 1450 ℃/2h tight burning, distance between same point is measured, the three-dimensional shrinkage situation of corona behind the research tight burning.With reference to accompanying drawing, cementation surface is a cylindrical cavity, and a fixing point 2 is arranged in the outside of corona 1, and getting the diameter that extended line passes the cementation surface of fixing point 2 is d
1, perpendicular diameter is d
2, the deepest point of cementation surface is h
2, the height of high cusp is h
1, the minimum and maximum length of axial plane is designated as l
1And l
2In order to measure accurately, each condition is made three samples, gets average.
Table 7 shrinks through the three-dimensional line of ceramic tooth behind tight burning that machining becomes
| d 1 | d 2 | h 1 | h 2 | l 1 | l 2 | |
| The linear shrinkage (%) of the linear shrinkage of T7 sample (%) T8 sample | 15.36 9.68 | 15.37 9.67 | 15.34 9.69 | 15.38 9.65 | 15.35 9.63 | 15.36 9.64 |
As can be seen from Table 7, partially sinter after body processes " initial dummy ", when tight burning, its shape remains unchanged, and the contraction of each dimension is controlled, and the air line distance between several Key Points is all by shrinking with equal proportion, this is the amplification in proportion of this technology just, has established experiment basis.In sintering furnace, requiring uniformity of temperature profile, the difference in the sintering furnace between the temperature is less than ± and 10 ℃, preferably less than ± 5 ℃.
Embodiment 5 coloured micropowders and the preparation that partially sinters body
The ZrO that consists of 89wt% of oxide micropowder
2, the Y of 5.0wt%
2O
3, the CeO of 6.0wt%
2
The composition of oxide micropowder changes 99.2wt%3Y-TZP into, the Fe of 0.8wt%
2O
3
Contain CeO
2Or Fe
2O
3The zirconium oxide nano powder press embodiment 2 described technologies, promptly isostatic compaction partially sinters, preparation partially sinters body, test mechanical performance and observe color the results are shown in Table 8.
The mechanical performance that partially sinters body and the color of table 8 oxidation-containing cerium and ferrum oxide
| Contain and add the oxide kind | Partially sinter density (%TD) | Bending strength (MPa) | Elastic modelling quantity (GPa) | Fracture toughness (MPam 1/2) | Color |
| No CeO 2 Fe 2O 3 | 71.44 70.68 71.78 | 175.81 ± 2.376 155.32 ± 5.98 170.76 ± 6.67 | 52.85 ± 1.57 48.84 ± 4.36 50.90 ± 4.49 | 1.85 ± 0.06 1.65 ± 0.24 1.76 ± 0.28 | White white is yellow partially, evenly white is red partially, evenly |
As can be seen from the above table, contain cerium oxide or ferrum oxide in the nano powder after, partially sinter body surface and reveal different colors.So that can prepare a series of different colours partially sinters body for selection of clinical.Need before sintering, not go to soak by reuse solution.
Embodiment 6 is on the basis of digitized wax pattern, and up-sizing processes " initial dummy " in proportion, and tight burning obtains final dummy again.
Delivery is molded partially sinters ceramic body, and density is 67.67%TD, size 10mm * 12mm * 15mm.CAD/CAM equipment and digital converter are the system by the CAD/CAM company manufacturing of American I RVING.The tooth model elder generation digitized of making obtains the digitized wax pattern, amplifies proper proportion, and the linear shrinkage data see Table 7, with the contraction in the compensation tight burning process.According to the cad file that obtains, from ceramic body grinding " initial dummy "." initial dummy " is sintered to final densities, with following sintering schedule: 5 ℃/min, to 1150 ℃, 2 ℃/min to 1450 ℃, 1450 ℃ of insulations 2 hours.The tight burning dummy is applied on the initial model, by there being experience dentistry skilled worker to estimate its fitness, finds that its fitness is good.
Claims (4)
1, a kind of preparation method of dental prosthesis is characterized in that, may further comprise the steps:
(1) preparation partially sinters ceramic body
With oxide micropowder, adding additives pelletize aftershaping or adding additives straight forming not, molding mode be mold pressing or etc. static pressure, or first mold pressing waits static pressure again, makes biscuit of ceramics;
Biscuit of ceramics is warmed up to 900 ℃-1300 ℃, is incubated 1-5 hour, and natural cooling obtains partially sintering ceramic body;
The density that partially sinters ceramic body is 50%TD-85%TD;
Described oxide is aluminium oxide, silicon oxide, cubic phase polycrystal zirconia or optional wherein at least two kinds mixture;
The stabilizing agent of four directions phase polycrystal zirconia is yittrium oxide (Y
2O
3), cerium oxide (CeO
2) or their mixture; With Y
2O
3During for stabilizing agent, Y
2O
3Content is 1.5wt%-8.0wt%; With CeO
2During for stabilizing agent, CeO
2Content is 13.0wt%-22.0wt%; With Y
2O
3And CeO
2Mixture when being stabilizing agent, the content of both mixture is 4wt%-18wt%, Y in the mixture
2O
3And CeO
2Ratio be 1: 0.5-12;
In the described oxide micropowder, also contain CeO
2Or/and Fe
2O
3, CeO
2Content is 0.5wt%-22wt%; Fe
2O
3Content be 0.1wt%-10wt%;
Described oxide micropowder is nano powder, mean diameter 5-100nm by wet method or dry process;
Binding agent is a polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl acetate, polrvinyl chloride, polyvinyl butyral, polystyrene or optional wherein at least two kinds mixture;
(2) partially sintering ceramic body processes through CAD/CAM
With non-contact measurement or contact type measurement, scanning tooth or tooth die collect and preserve data, again by above data and corona data base, suitable on-station position, obtain the shape of " digitized wax pattern "; The size of " digitized wax pattern " is amplified in certain proportion, " initial dummy " by the dimensioned of amplifying, with the contraction of compensated part sintered ceramic material in the tight burning process; A straight line dimension, the size that finally obtains dummy is the 78%-94% of " initial dummy " size, because partially sinter density to final densities at this, linear shrinkage is 22%-6%;
(3) " initial dummy " tight burning obtains final dental prosthesis " initial dummy " and is sintered to complete density 1350 ℃ of-1550 ℃ of temperature, is incubated 1.5-2.5 hour.
2, the preparation method of dental prosthesis according to claim 1 is characterized in that, the described biscuit of ceramics sintered heat insulating time is 2-3 hour.
3, the preparation method of dental prosthesis according to claim 1 and 2 is characterized in that, in the described oxide micropowder, and CeO
2Content is 2wt%-10wt%.
4, the preparation method of dental prosthesis according to claim 1 and 2 is characterized in that, in the described oxide micropowder, and Fe
2O
3Content be 0.5wt%-5wt%.
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|---|---|---|---|
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|---|---|---|---|
| CN 200410023360 CN1256933C (en) | 2004-06-28 | 2004-06-28 | Dental dummy preparation method |
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| CN1256933C true CN1256933C (en) | 2006-05-24 |
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| CN111803386A (en) * | 2020-06-17 | 2020-10-23 | 深圳市美鸣齿科技术有限公司 | False tooth outer crown and preparation method thereof |
| CN112250439A (en) * | 2020-10-20 | 2021-01-22 | 哈工宁伯医疗科技泰州有限公司 | Ceramic material for tooth restoration and manufacturing method thereof |
| CN113321505A (en) * | 2021-08-03 | 2021-08-31 | 中南大学湘雅医院 | Zirconia-based ceramic material and preparation method thereof |
-
2004
- 2004-06-28 CN CN 200410023360 patent/CN1256933C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101926734A (en) * | 2009-06-24 | 2010-12-29 | 四川大学 | Process for improving translucency of CAD/CAM in-ceram zirconia dental materials |
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| CN1593371A (en) | 2005-03-16 |
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