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WO2018167128A1 - Procédé de métallurgie des poudres pour réaliser une ébauche dentaire - Google Patents

Procédé de métallurgie des poudres pour réaliser une ébauche dentaire Download PDF

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Publication number
WO2018167128A1
WO2018167128A1 PCT/EP2018/056354 EP2018056354W WO2018167128A1 WO 2018167128 A1 WO2018167128 A1 WO 2018167128A1 EP 2018056354 W EP2018056354 W EP 2018056354W WO 2018167128 A1 WO2018167128 A1 WO 2018167128A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyurethane
polyester
dental blank
polycarbonate
powder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2018/056354
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German (de)
English (en)
Inventor
Berthold Reusch
Michael Sax
David Figge
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Pritidenta GmbH
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Pritidenta GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Pritidenta GmbH filed Critical Pritidenta GmbH
Publication of WO2018167128A1 publication Critical patent/WO2018167128A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
    • A61C13/00—Dental prostheses; Making same
    • A61C13/0003—Making bridge-work, inlays, implants or the like
    • A61C13/0022—Blanks or green, unfinished dental restoration parts

Definitions

  • the present invention relates to the preparation of a dental blank which optionally contains coloring substances, wherein a ceramic or metallic powder is mixed as starting material with an aqueous, aliphatic polyurethane dispersion to a compressible mass, as well as a dental blank thus produced and the use of the polyurethane Dispersions for the preparation of a dental blank.
  • a ceramic or metallic powder is mixed as starting material with an aqueous, aliphatic polyurethane dispersion to a compressible mass, as well as a dental blank thus produced and the use of the polyurethane Dispersions for the preparation of a dental blank.
  • ceramic or metallic powders for the production of dental restorations, ie dental prostheses or whole teeth, such as implants or inlays, onlays, veneers, crowns or bridges, has long been known.
  • composites of ceramics and metal so-called cermets, are well known.
  • Oxide ceramics are mainly used as scaffolding material for dental restorations, as this material is characterized by excellent biocompatibility and excellent mechanical properties. Ceramics based on partially stabilized or fully stabilized zirconium oxide have lately been used.
  • a method for producing dental restorations consists of several substeps.
  • the starting material is pressed into a green body.
  • a pre-and white firing which results in a stable dental blank for further processing, in particular a further CAD CAM machining.
  • the starting material generally contains a so-called binder to make the powder press-moldable.
  • binder known polysaccharides such as starch, sugar or cellulose derivatives, polymers such as polyvinyl acetates, polyvinyl alcohols, or polyacrylates, and alginates are used.
  • a binder should preferably have no tendency to stick with the molds, solidify the starting material such that a processing of the green body is possible, and can be burned out completely and residue-free from the blank during the firing processes again.
  • a major disadvantage of the known processes for the production of blanks from green bodies are the long process times of the heat treatment of the green bodies at high reaction temperatures. Conventional procedures require reaction times of several days at temperatures of 800 ° C to 1100 ° C.
  • EP 0 588 171 A1 describes a process for coating a water-sensitive ceramic powder, in particular aluminum nitride, with a hydrophobic coating. This powder can not be processed with water without hydrophilization by additive coating.
  • a ceramic powder is mixed with a nonionic surfactant and a binder, for example a polyester-modified polyurethane resin, pressed into a binder-containing green body, and sintered at about 1850 ° C. to form a sintered body.
  • a binder for example a polyester-modified polyurethane resin
  • the invention relates to a method for producing a dental blank which optionally contains coloring substances, the method comprising the following steps:
  • step (b) preparing a granulate from the mass obtained according to step (a);
  • step (c) producing a green body by compressing the granules obtained in step (b);
  • step (d) heat treatment, in particular tempering or pre-firing, of the green body obtained according to step (c) for the production of the dental blank at temperatures of 60 ° C to 150 ° C; and optional
  • step (e) machining the dental blank obtained according to step (d) to produce a machined dental blank.
  • the dental blank is sintered in a further step.
  • the ceramic powder is a zirconia powder.
  • the zirconia powder is a partially stabilized zirconia powder.
  • the metallic powder is a chromium-cobalt-molybdenum sintered metal powder.
  • the polyurethane is selected from a polyester-polyurethane, polycarbonate-polyurethane, polyester-polycarbonate-polyurethane, copolymer based on a polycarbonate-polyurethane and a polyacrylate, and / or a polyether-polyurethane.
  • the polyester-polyurethane and / or the polyester-polycarbonate-polyurethane are in colloidal form.
  • the polyester-polyurethane, the polycarbonate-polyurethane, the polyester-polycarbonate-polyurethane and / or the polyether-polyurethane are in anionic form.
  • the polyurethane dispersion contains admixtures or functional groups of polyesters, polycarbonates, polyester-carbonates and / or polyethers.
  • the polyurethane dispersion has a solids content of about 20-50 wt .-%, preferably from about 29-46 wt .-%, in particular from about 31-46 wt .-%, especially from about 44-46 wt .-%.
  • the content of the aliphatic polyurethane based on the solids content of the mixture of from 0.5 wt .-% to 20 wt .-%.
  • the content of the aliphatic polyurethane based on the solids content of the mixture of from 0.5 wt .-% to 6 wt .-%.
  • the polyurethane dispersion additionally contains at least one antioxidant, at least one pressing agent, at least one lubricant and / or at least one plasticizer.
  • the present invention relates to a dental blank with optionally coloring compounds preparable by a method described herein.
  • the invention relates to the use of an aqueous, aliphatic polyurethane dispersion which is free of isocyanate groups, for the preparation of a composition of a ceramic and / or metallic powder for producing a possibly sintered dental blank, which optionally contains coloring compounds, in particular according to one of the embodiments described herein.
  • the object of the present invention was therefore to find a binder or a binder mixture which can advantageously be used in the production of a blank, in particular a dental blank.
  • Another object of the present invention was to provide a method which enables the production of a blank, in particular a dental blank, with short process times and low reaction temperatures.
  • an aqueous, aliphatic polyurethane dispersion which is free from isocyanate groups can generally be used as binder in the production of a blank, in particular a dental blank.
  • the invention therefore relates to the use of an aqueous, aliphatic polyurethane dispersion which is free of isocyanate groups, for producing a mass of a ceramic and / or metallic powder for producing an optionally sintered blank, in particular a possibly sintered dental blank, as well a method for producing a blank, in particular a dental blank, and a blank which can be produced by the method according to the invention, as claimed in the independent patent claims.
  • the blank is in particular a dental blank.
  • the particular advantages of the use according to the invention of the polyurethane dispersion described as a binder are, in particular: (a) essentially lacking tendency to stick with the molds, in particular during the press molding; (b) solidification by heat treatment enabling machining; (c) production of an extremely homogeneous green body or compact; (d) producing a green body with significantly higher green strength and thus a significantly higher edge strength than can be achieved with known binder systems, which allows for surface treatment in particular with nanoscale powders; (e) wet working the green body, since the network of binder is no longer redispersible in water; (f) good, residue-free burnout without significant odor development; and / or (g) redispersibility in alcohol, whereby process residues (recycled) can be recovered.
  • the starting material for the process according to the invention are ceramic or metallic powders.
  • the ceramic and metallic powders are commercially available.
  • Ceramic powders are zirconium oxide powders, which may be partially stabilized and fully stabilized.
  • the use of partially stabilized zirconia is particularly preferred since the flexural strength is particularly high (eg, higher than 1 .100 MPa).
  • Suitable stabilizing substances are oxides such as calcium oxide (CaO), magnesium oxide (MgO), yttrium oxide (Y2O3), erbium oxide (Er 2 Os) or cerium oxide (CeO 2).
  • the content of the stabilizing oxides may be in the range of 2.5 mol% to 6 mol%, preferably in the range of 2.5 mol% to 5 mol% relative to the total content of zirconium oxide and the stabilizing oxide.
  • Yttrium-fully stabilized or yttrium-partially stabilized zirconium oxide has proven particularly advantageous.
  • the optional presence of alumina (AI2O3) may vary depending on Need to increase strength and decrease light transmission (translucency).
  • the relative content of alumina preferably ranges from 0% by weight (no alumina) to 0.3% by weight, preferably in a range from 0.05% by weight to 0.25% by weight.
  • the optional presence of silica (S1O2) can further reduce translucency.
  • the content is preferably less than 0.02 wt .-%.
  • Chromium oxide (Cr 2 O 3 ), erbium oxide (Er 2 O), iron oxide (Fe 2 O), praseodymium oxide (Pr 6 On), manganese oxide (Mn 2 O 3) or cobalt oxide (CO 2 O 3) are examples of optionally available coloring substances.
  • the presence of iron oxide gives a more yellowish hue, the presence of erbia a rather reddish hue and the presence of cobalt oxide a rather gray hue. Based on suitable color mixtures, the color or the color gradient of a natural tooth can thus be largely reproduced.
  • the content of the coloring substances may generally be less than 1% by weight, preferably in a range of 0.03 to 0.6% by weight.
  • Zirconia powders are generally available commercially.
  • suitable zirconia powders have the following compositions: zirconia (above 90 and 94% by weight, respectively) with hafnium oxide (below 3% by weight), yttria (5 to 9.5% by weight) and alumina (0.05 to 0.3% by weight) at a total content in the mixture of more than 99.9% by weight; with further additions of silicon oxide ( ⁇ 0.02 wt .-%), iron oxide ( ⁇ 0.01 wt .-%) and optionally erbium oxide (0.1 wt .-% to 0.6 wt .-%).
  • light transmittances of 10% to 35% and brightnesses of 65-90 (L * value) can be set. Further examples can be found, for. In US 9,212,065 or EP 1 900 341.
  • Cobalt-chromium mixtures have proved particularly suitable as metallic powders.
  • the powder mixtures usually contain 50-70% by weight of cobalt and 20-30% by weight of chromium and, if appropriate, further metals such as molybdenum, manganese, silicon, tungsten or iron and, if appropriate, minimum amounts of carbon, in order to increase the strength if necessary increase.
  • An example of a suitable metallic powder is a chromium-cobalt-molybdenum sintered metal powder which is also commercially available.
  • an antioxidant or an antioxidant in order to suppress a chemical reaction of the metal powder with water from the binder dispersion.
  • Suitable antioxidants are, for example, oxidation inhibitors for aqueous carbide preparation, such as Metamax 1-15 from Zschimmer & Schwarz GmbH & Co. KG, Lahnstein.
  • aqueous, aliphatic polyurethane dispersions which are free of isocyanate groups and which serve as a so-called binder.
  • the polyurethane dispersions may contain functional groups or admixtures of polyesters, Polycarbonates, polyester-carbonates or polyethers possess.
  • the polyurethane dispersions may be free of organic solvents but may also contain organic solvents such as alcohol. They can be anionic or neutral depending on the functional group.
  • the properties may be viscous or low viscous and / or colloidal.
  • the aliphatic, isocyanate-free polyurethanes are preferably generally known polyester-polyurethanes, polyether-polyurethanes, polycarbonate-polyurethanes, polyester-polycarbonate-polyurethanes or copolymers of a polycarbonate-polyurethane and a polyacrylate.
  • the solids content in the dispersion moves, for example, at about 20-50% by weight, preferably at about 29-46% by weight, in particular at about 31-46% by weight, especially at about 44% by weight. 46% by weight.
  • the pH is usually 7.0-9.0.
  • the viscosity is 10-1,000 mPa generally 's.
  • a preferred polyurethane dispersion is an aqueous, anionic, aliphatic polyether polyurethane dispersion without free isocyanate groups having a solids content of 44-46% by weight, a pH of 7.0-8.0 and a viscosity of 100-1000 mPa ' s.
  • Other usable polyurethane dispersions can be found in the table below.
  • the aqueous polyurethane dispersions are generally available commercially. However, preparation examples are also found, for example, in EP 1 717 284 or EP 1 773 919.
  • the content of the aliphatic polyurethane based on the solids content of the mixture is generally from 0.5 wt .-% to 20 wt .-%, preferably from 0.5 wt .-% to 15 wt .-%, in particular of 0.5 % By weight to 10% by weight, especially from 0.5% by weight to 6% by weight.
  • the content of the aliphatic polyurethane based on the solids content of the mixture of from 0.5 wt .-% to 5 wt .-%.
  • the polyurethane dispersions mentioned can be used as binders in both wet and dry processing.
  • a mass, also called slip, from a ceramic and / or metallic powder which advantageously has a primary particle size up to 16 m, wherein the primary particle size can be greater than 16 ⁇ , and an aqueous aliphatic polyurethane dispersion , which is free of isocyanate groups.
  • at least one antioxidant, at least one pressing or lubricating agent, at least one plasticizer, and / or fluidizing agent may be added to the composition.
  • the pressing and / or Zerspan of the green body also called powder compacts, adapted or improved.
  • Suitable pressing or slip aids are based z. B. on fatty acids or hydrocarbons such.
  • an oxide-ceramic slip for wet processing and downstream spray granulation preferably contains, in addition to the aqueous, aliphatic polyurethane dispersion usable according to the invention, the following additional components:
  • the aqueous, aliphatic polyurethane dispersion which can be used according to the invention advantageously performs several tasks simultaneously.
  • the dispersion is highly film-forming and does not show any rheological changes in the slurry viscosities, e.g. through thickening processes.
  • the downstream press molding provides optimally compacted homogeneous green bodies with higher edge strengths.
  • the option of additionally hardening the finished compact in a subsequent heat treatment process allows for exceptionally good and advantageous green processing.
  • said polyurethane dispersion behaves comparatively odorless.
  • the preparation of the mass or the slip can be carried out by mixing units with downstream sieve granulation, via a specific re-drying with subsequent granulation or via spray granulation of aqueous or alcoholic slips.
  • a granulate from the resulting mass is produced.
  • the granule size should advantageously be less than 250 ⁇ .
  • the granule size should advantageously be less than 125 ⁇ .
  • the pressing moisture of the mass is preferably 4-6%.
  • the granules by means of conventional pressing techniques z.
  • the densification is advantageously isostatic.
  • the compactness of the green body obtained is advantageously at 5.7-6.4 g / cm 3 when using metallic powders, eg. B. CrCo alloys, and at 3.3-3.4 g / cm 3 when using ceramic powders, eg. B. yttria-stabilized zirconia.
  • the green body obtained according to process step (c) is subjected to a heat treatment (process step (d)) (annealing process) in a further step for the production of the blank.
  • the heat treatment can be carried out at temperatures of 60 ° C and 150 ° C, preferably at temperatures of 80 ° C and 130 ° C, more preferably at temperatures of 100 ° C to 125 ° C.
  • the heat treatment is carried out at about 120 ° C.
  • the binder can additionally cure.
  • the holding time at these temperatures is advantageously 1-10 hours.
  • the heat treatment of process step (d) is carried out for 1 to 10 hours, for example 1 to 2 hours, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours or 10 hours.
  • a significant advantage of the method according to the invention is therefore that the heat treatment of process step (d) on the one hand in a much lower temperature range, namely at temperatures of 60 ° C and 150 ° C can be performed, as in conventional methods, which at temperatures of 800 ° C and 1000 ° C are performed.
  • the process time is significantly shorter than in conventional processes for the production of blanks, which is 3 days.
  • the energy consumption in carrying out the method according to the invention is significantly lower than in conventional methods, so that the inventive method is environmentally friendly than previously known method.
  • the blank thus obtained can then be machined wet or dry by conventional processing techniques. These include, for example, turning, milling, grinding, drilling or sawing.
  • the blank can be processed using water.
  • the milling speed can be up to four times faster than in known methods.
  • the surface quality is also significantly improved.
  • a significant advantage of the blank obtained according to the invention lies in a significantly increased green strength, in particular in a significantly increased edge strength. As a result, much more filigree structures can be worked out.
  • zirconium oxide as the starting material, it is possible to produce significantly finer structures and thinner wall thicknesses than, for example, with pre-sintered ceramic blanks.
  • the adjustable milling speeds are also three to four times faster than with conventional manufacturing processes.
  • the chippings or the green break can then be redispersed in alcohol (eg ethanol) and essentially completely recycled and reused.
  • alcohol eg ethanol
  • recycled masses basically show no negative changes in the properties of the final product.
  • the processed blank thus obtained may further under normal sintering conditions, for. B. under oxidizing or reducing atmosphere, are sintered.
  • a so-called debinding of the binder wherein the binder according to the invention burns out completely and almost odorless.
  • metallic sintered materials found here no negative interaction reactions, eg. B. carbide formation, instead.
  • the preceding and final shapes may advantageously be computer controlled, e.g. B. by means of a CAD / CAM system or Kopierfräsvon performed.
  • aqueous, solvent-free, or solvent-containing, viscous or low-viscosity, ionic or anionic dispersions based on an aliphatic polyurethane without free isocyanate groups may also have admixtures or functional groups of polyesters, polycarbonates, polyester-carbonates or polyethers.
  • PU dispersions suitable polyurethane dispersions
  • the metal powder has a primary particle size of up to 16 ⁇ .
  • the use of the antioxidant prevents the chemical interaction of the metal powder with water from the binder.
  • the mixture was then mixed in a 20 liter Lindor Intensive Mixer for 5 to 10 minutes. After the mixing process, a screen granulate was prepared from the resulting moist mixture, which has a granule size smaller than 250 ⁇ .
  • the adjusted pressing humidity of the molding compound was 4 to 6%.
  • the sieve granules were then first biaxially pre-pressed and then isostatically densified in a shrink-wrapped plastic foil. Several series of tests showed a preferred biaxial compression pressure of 400 kp / cm 2 with a tool diameter of 92 mm.
  • the sintered metal bodies or components were fired in a protective gas sintering furnace under a reducing atmosphere as shown below.
  • Stage 1 heating from room temperature at 10 ° C / min (600 ° C / h) to 500 ° C; after that the atmospheric debinding is completed;
  • Stage 2 heating from 500 ° C at 12 ° C / min (720 ° C / h) to 1 .130 ° C
  • Stage 3 heating from 1 .130 ° C at 5 ° C / min (300 ° C / h) to 1 .280 ° C for the
  • Stage 4 Holding time of one hour on the sintering temperature
  • Step 5 Cooling from 1, 280 ° C at 10 ° C / min (600 ° C / h) to 400 ° C;
  • Gas purge is automatically turned off and the oven opens.
  • End of program - sintered parts can be removed.
  • E-modulus approx. 190 GPa
  • the content of the aliphatic polyurethane based on the solids content of the mixture is thus 2.64 wt .-% to 4.6 wt .-%. 8% by weight, ie 48 g, of solids have proven to be advantageous.
  • the slurry was again homogenized for 2 to 3 hours. After conditioning, the slurry was removed from the roll bank and sieved off the milling balls added for processing.
  • the spraying of the spray granules was carried out on a biaxial press.
  • the tool diameter was 105 mm and the biaxial pressure was 500 kgf / cm 2 .
  • the green body was again vacuum-sealed in foil and postisostatically pressed in a test series with a cold-isosatic pressing pressure of 1 to 4000 bar. As advantageous resulted in a pressing pressure of 3,000 bar.
  • the resulting green body had a compact density of 3.30 to 3.40 g / cm 3 . This was followed by annealing the compact for 1 to 2 hours in a test series in the temperature range from 60 to 150 ° C. As advantageous resulted in a tempering temperature of 120 ° C.
  • the blank or the corresponding blank could be machined wet or dry without any problems by turning, milling, grinding or sawing with conventional processing machines.
  • zirconium oxide which is fine ceramic
  • the sintering of the ceramic was carried out under atmospheric conditions and requires no change in the usual sintering conditions for the material.
  • the additive which was still in the blank or in the milled parts, burned out completely and almost odorless.

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  • Health & Medical Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Dentistry (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Dental Tools And Instruments Or Auxiliary Dental Instruments (AREA)

Abstract

La présente invention concerne la réalisation d'une ébauche dentaire qui contient éventuellement des substances de coloration, une poudre céramique ou métallique en tant que matière de départ étant mélangée à une dispersion polyuréthane aliphatique aqueuse pour donner une masse compressible, et une ébauche dentaire ainsi réalisée et l'utilisation des dispersions polyuréthane pour la réalisation d'une ébauche dentaire.
PCT/EP2018/056354 2017-03-15 2018-03-14 Procédé de métallurgie des poudres pour réaliser une ébauche dentaire Ceased WO2018167128A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102017002487.1A DE102017002487A1 (de) 2017-03-15 2017-03-15 Pulvermetallurgisches verfahren zur herstellung eines rohlings
DE102017002487.1 2017-03-15

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Publication Number Publication Date
WO2018167128A1 true WO2018167128A1 (fr) 2018-09-20

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112974843A (zh) * 2021-02-07 2021-06-18 江苏创英医疗器械有限公司 一种3d打印种植体的表面处理工艺

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0588171A1 (fr) 1992-09-08 1994-03-23 Hoechst Aktiengesellschaft Procédé de transformation de poudres céramiques sensibles à l'eau en une poudre granulée apte à l'écoulement
WO2000043328A1 (fr) * 1999-01-20 2000-07-27 Siemens Aktiengesellschaft Matiere a couler ceramique aqueuse, procede de preparation et d'utilisation de ladite matiere
EP1717284A1 (fr) 2005-04-25 2006-11-02 Bayer MaterialScience AG Dispersions de polyuréthanes avec propriétés améliorées de formation de film
EP1773919A1 (fr) 2004-07-16 2007-04-18 Alberdingk Boley GmbH Dispersion aqueuse de liant comportant des nanoparticules, et son procede de production et d'utilisation
EP1900341A1 (fr) 2006-09-13 2008-03-19 Ivoclar Vivadent AG Corps moulé multicolore
US9212065B2 (en) 2013-05-02 2015-12-15 Kuraray Noritake Dental Inc. Zirconia sintered body, zirconia composition and zirconia calcined body, and dental prosthesis

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Publication number Priority date Publication date Assignee Title
DE59101468D1 (de) * 1990-02-21 1994-06-01 Basf Ag Thermoplastische Massen für die Herstellung keramischer Formkörper.
KR100458559B1 (ko) * 2000-04-07 2004-12-03 미츠이 다께다 케미칼 가부시키가이샤 수용성 폴리우레탄 및 그 용도
DE102011101661A1 (de) * 2011-05-13 2012-11-15 Wieland Dental + Technik Gmbh & Co. Kg Verfahren zur Dotierung oder zum Einfärben von Keramik, Glaskeramik oder Glas

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0588171A1 (fr) 1992-09-08 1994-03-23 Hoechst Aktiengesellschaft Procédé de transformation de poudres céramiques sensibles à l'eau en une poudre granulée apte à l'écoulement
WO2000043328A1 (fr) * 1999-01-20 2000-07-27 Siemens Aktiengesellschaft Matiere a couler ceramique aqueuse, procede de preparation et d'utilisation de ladite matiere
EP1773919A1 (fr) 2004-07-16 2007-04-18 Alberdingk Boley GmbH Dispersion aqueuse de liant comportant des nanoparticules, et son procede de production et d'utilisation
EP1717284A1 (fr) 2005-04-25 2006-11-02 Bayer MaterialScience AG Dispersions de polyuréthanes avec propriétés améliorées de formation de film
EP1900341A1 (fr) 2006-09-13 2008-03-19 Ivoclar Vivadent AG Corps moulé multicolore
US9212065B2 (en) 2013-05-02 2015-12-15 Kuraray Noritake Dental Inc. Zirconia sintered body, zirconia composition and zirconia calcined body, and dental prosthesis

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112974843A (zh) * 2021-02-07 2021-06-18 江苏创英医疗器械有限公司 一种3d打印种植体的表面处理工艺

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