WO1999012864A1 - Injection molding of structural zirconia-based materials by an aqueous process - Google Patents
Injection molding of structural zirconia-based materials by an aqueous process Download PDFInfo
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- WO1999012864A1 WO1999012864A1 PCT/US1998/018663 US9818663W WO9912864A1 WO 1999012864 A1 WO1999012864 A1 WO 1999012864A1 US 9818663 W US9818663 W US 9818663W WO 9912864 A1 WO9912864 A1 WO 9912864A1
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
- C04B35/486—Fine ceramics
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
- C04B35/486—Fine ceramics
- C04B35/488—Composites
- C04B35/4885—Composites with aluminium oxide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/636—Polysaccharides or derivatives thereof
Definitions
- This invention relates to a process for shaping ceramic parts from powder and to molding compositions used therein. More particularly, the invention is directed to molding processes and molding compositions that form high quality, net shape and near netshape complex parts of structural ZrO 2 based materials which can be fired to full density and high strength.
- ZrO 2 Upon cooling from elevated, usually sintering, temperatures, ZrO 2 undergoes a martensitic transformation from a tetragonal crystal structure to a monoclinic crystal structure. The transformation results in a volume and anisotropic shape change. Under controlled conditions, the tetragonal phase is maintained at room temperature, and is only transformed when a crack intersects with the grain. The subsequent transformation puts a closure force on the crack, thereby increasing the crack resistance of the material.
- stabilizers such as Y 2 O 3 , can have profound effects on the stability of the tetragonal phase.
- pure yttrium- stabilized tetragonal polycrystalline zirconia (Y-TZP) materials can be sintered to high strength or fracture toughness, depending on the Y O 3 concentration, grain size, and sintering treatments (e.g. pressureless vs. HTP'ing).
- a fine grain size in Y-TZP materials provides the high strength materials, while the instability of the tetragonal phase (depending on the Y O 3 concentration) determines the toughness.
- Such materials are disclosed by Masaki & Shingo in US 4,742,030, Cassidy et al. in US 4, 866,014 and Ghoshid et al. in US 5,336,282.
- One of the main drawbacks of Y-TZP materials is their environmental degradation.
- ZrO 2 based ceramics are widespread and include metal forming tools, automotive applications, textile applications, and consumer applications such as knifes, scissors, golf clubs and the like.
- the ceramic components utilized in most of these applications are manufactured using powder pressing or slip cast forming techniques.
- One objective of any forming method is to produce articles in the unfired state with a certain density and particle packing (hereinafter called "green" parts, forming, density, etc.) which can be sintered to a shape that is reproducible to close dimensional tolerances and is free from defects.
- green-forming and sintering cracks, distortions and other defects can arise due to the shrinkage associated with the particle consolidation processes. It is generally recognized that these defect-producing processes are mitigated by producing homogeneous green bodies having adequate green strength
- Another objective of shape-forming methods is to produce articles having net shape, eliminating or minimizing the need for downstream operations, such as machining, to obtain final part dimensions. Dry pressing involves compaction of powder in a die.
- injection molding comprisesd the step of mixing ceramic powder with a dispersant and a thermoplastic organic binder of variable composition.
- the molten powder/binder mixture was heated during the injection molding process and injected into a relatively cold mold. After solidification, the part was ejected in a manner similar to plastic parts. Subsequently, the binder was removed and the part was densified by a high temperature heat treatment. There were a number of critical stages in this process, which included the initial mixing of the powder and binder, the injection of the mixture into the mold, and the removal of the organic matrix material.
- PLM initial powder injection molding
- One of the main disadvantages of the initial powder injection molding (PLM) process is the removal of the organic vehicle. At present, with the PLM process the cross section limit for fine particle sizes is 0.5-0.75 inch. If the particle sizes exceed that limit, the binder removal process will lead to defects, pinholes, cracks, blisters etc.
- Binder removal takes place by slow heat treatments that can take up to several weeks. During debinding at elevated temperatures, the binder becomes a liquid which can result in distortion of the green part due to capillary forces. Another disadvantage of the initial PLM process is the tendency for the relatively high molecular weight organic to decompose throughout the green body, causing internal or external defects.
- solvent extraction wherein a part of the organic is removed using an organic or supercritical liquid, sometimes minimizes defect formation. Solvent extraction encounters difficulties because the remainder still needs to be removed at elevated temperatures. However, the solvent extraction process allows for the formation of porosity throughout the part, with the result that removal of the remaining organic is facilitated.
- part slumping can pose problems, especially for the larger particle sizes if the green density/strength is not high enough.
- PLM offers certain advantages for high volume automation of net shape, high dimensional control and complex parts, but the limitation of part size and the very long binder removal times combined with their environmental impact has not resulted in the expected growth of the use of this technique.
- aqueous-based binders contain either polyethyelene glycols, PVA copolymers, or COOH-containing polymers.
- BASF has developed a polyacetal based system that is molded at moderately high temperatures after which the binder is removed by a heat treatment with gaseous formic or nitric acid. The low temperature excludes the formation of a liquid phase and thus distortion of the green part due to viscous flow. The gaseous catalyst does not penetrate the polymer and the decomposition only takes place at the interface of the gas and binder, thereby preventing the formation of internal defects.
- the present invention provides an aqueous, zirconia-based molding compound and a method for compounding its constituent materials into a homogeneous mixture and format that is useful for low cost manufacture of ceramic articles by injection molding.
- zirconia-based means compositions containing 50 - 100 wt% zirconium oxide in the fired ceramic.
- the molding compounds of the present invention advantageously contain, as a homogeneous mixture, ingredients which (i) are essential for shape-forming parts by injection molding, and (ii) yield zirconia-based ceramic materials after firing.
- a molding compound comprising essentially the ceramic precursors, zirconium oxide, yttrium oxide and alumina in a form that is suitable for fabricating articles by injection molding.
- the ready moldable zirconia-based compound of the invention obviates the need for high molding pressures and special de-binding furnaces.
- the molding compound of the invention uses water as the liquid carrier and can be molded at low machine pressure below about 1,000 psi. Furthermore molded parts are dried before sintering by evaporation of the water, and the lengthy and complex de-binding step, typical of polymer- based molding systems, is eliminated. After firing, a ZrO 2 material is obtained having full density and high strength.
- Fig. 1 is a schematic representation depicting the basic steps of one embodiment of the invention.
- the ceramic powders are initially mixed with a gel-forming powder and a solvent for the gel-forming material.
- zirconia ceramics require a stabilizing additive to prevent catastrophic destruction of the article due to the occurrence of a monoclinic phase transition upon cooling from the sintering temperature.
- Any of the stabilizers known to those skilled in the art of fabricating zirconia ceramics can be used in the process.
- Common stabilizers comprise oxides of the elements Y, Ce, Ca, and Mg or compounds such as carbonates, nitrates, oxylates and the like, which produce oxides of those elements during high temperature processing.
- the amount of stabilizer can be chosen to produce the tetragonal, cubic or monoclinic or a mixture of phases .
- Yttria is the preferred stabilizer.
- the presence of alumina produces certain desired effects, such as an improvement in the environmental stability.
- the average particle size should be below 1 ⁇ m.
- the average particle size ranges from about 0.1-0.9 ⁇ m, and more preferably from about 0.3-0.5 ⁇ m.
- the term 'particle size means equivalent spherical diameter.
- the invention provides a ceramic molding compound consisting essentially of zirconium oxide as the major phase with lesser amounts of other metal inorganic compounds, water, binder (selected from class of polysaccharides) and minor amounts of other additives that improve the processability of the molding feed-stocks.
- the invention further provides a method for producing a ready-moldable feed-stock from the constituent ceramic powders, binder, carrier and other processing aids. It is customary to represent the ceramic constituents of a fired ceramic body in terms of the constituent metal oxide compounds irrespective of the actual phases present after firing.
- the ceramic constituents of the molding compounds disclosed herein may be represented by the formula [ZrO 2 ] a [Y 2 O 3 ] b [Al 2 O 3 ] c wherein a ranges from about 50 -95 wt and b ranges from about 4 to 6 wt. % and c ranges from about 0-45 wt. %.
- An example of a second preferred molding compound in terms of starting ceramic powders contains about 95 wt. % zirconium oxide and 5 wt. % yttrium oxide.
- the amount of powder in the mixture is between about 50 and about 95 percent by weight of the mixture.
- the powders constitute between about 75 and about 90 percent by weight of the mixture, and most preferably constitute between about 83 and about 86 percent by weight of the mixture.
- the preferred and most preferred amounts are quite useful in producing net and near net shape injection molded parts.
- the molding compound provides a binder which provides the mechanism for allowing the fluid material to set in a mold and be removed as a self-supporting structure.
- this role is served by a compound derived from the category of polysaccharides known as agaroids.
- An agaroid has been defined as a gum resembling agar but not meeting all of the characteristics thereof (See H.H. Selby et al., "Agar", Industrial Gums, Academic Press, New York, NY, 2nd ed., 1973, Chapter 3, p. 29).
- agaroid not only refers to any gums resembling agar, but also to agar and derivatives thereof such as agarose.
- the preferred gel-forming materials are those which are water soluble and comprise agar, agarose, or carrageenan, and the most preferred gel-forming materials consist of agar, agarose, and mixtures thereof.
- the gel-forming materials are present in an amount between 0.2 wt.% and about 6 wt.% based upon the solids in the mixture. More than about 6 wt.% of the gel-forming material may be employed in the mixture. Higher amounts are not believed to have any adverse impact on the process, although such amounts may begin to reduced some of the advantages produced by our novel composition.
- the gel-forming material comprises between about 1 percent and about 4 percent by weight of solids in the mixture.
- the molding compound also provides a liquid carrier to facilitate transport of the molding compound along the barrel of an injection molding machine to a mold.
- Water is the most preferred liquid carrier in the molding compounds because it ideally serves the dual purpose of being a solvent for the gel forming binder and liquid carrier for the solid constituents in the mixture.
- the amount of water is chosen to confer the molding compounds with the essential rheological characteristics for proper behavior in the injection molding machine.
- the proper amount of water is between about 10 wt. % and 30 wt. % of the mixture with amounts between about 15 wt. % and 20 wt. % being preferred.
- the molding compound may also contain a variety of additives which can serve any number of useful purposes.
- Additives that have been found to be very useful in the present molding compounds comprise dispersants, pH control agents, biocides and gel strength enhancing agents (e.g., metal borate compounds such as calcium borate, magnesium borate and zinc borate).
- Biocides may be used to inhibit bacterial growth in the molding compounds, especially if they are to be stored for long periods of time. It is well-known that use of dispersants and pH control can greatly improve the rheology and processabiliy of ceramic suspensions.
- dispersants based on polyacrylate and polymethylmethacrylate polymer backbones have been found useful in improving the processability of the aluminum oxide-based compositions, the amount of dispersant in the molding compound being about 0.2 wt. % to 1 wt. % and preferably 0.2 wt. % to 0.8 wt. % based on the ceramic powders.
- tetramethylammonium hydroxide has been found useful for controlling the pH of the suspensions, the useful pH range being about 8.8 to 11 and preferably 9.5 to 10.5.
- the molding compounds of the present invention combine the ceramic powders, liquid carrier, binder and processing aids in a ready-moldable form.
- a preferred composition in terms of the constituent compounds is 66.90 wt. % Zirconium oxide, 4 wt. % yttrium oxide, 11.7 wt. % aluminum oxide, 2.5 wt. % Agar, 0.33 wt. % dispersant, 0.53 wt. % tetramethylammonium hydroxide, 0.02 wt. % biocide and 14 wt. % water (where the dispersant is added as a 40 % aqueous solution and the TMA as a 25 % aqueous solution).
- the invention also provides a method for combining all of the various constituents of the molding compounds into a homogeneous mixture which will produce homogeneous molded bodies that can be fired free of cracks and other defects.
- Raw material ceramic powders are frequently highly agglomerated and require deagglomeration before they can be manufactured into useful ceramic articles, free of cracks, distortions and other defects.
- ball milling has been found convenient and useful for producing the aqueous-based molding compounds disclosed herein, the powders being simultaneously deagglomerated and homogenized in the aqueous medium.
- the useful concentration range for ball milling the ceramic powders is 50 wt. % to 85 wt. %, the preferable range being between 65 wt. % and 80 wt. %.
- Compounding of the ceramic suspension with the binder can be done in any number of efficient mixers, e.g., a sigma mixer or planetary-type mixer.
- the biocide may be blended into the composition at the compounding stage of the process or optionally near the end of the ball milling cycle.
- the blend is heated in the range 75°C to 95°C and preferably between 80°C and 90°C for a period of about 15 min to 120 min and preferably between 30 min and 60 min.
- the molding compound must be in a suitable form for charging an injection molding machine.
- the compounded, homogeneous mixture is allowed to cool below the gel point of the gel -forming agent ( ⁇ 37°C) and removed from the blender. Thereafter it is shredded into a particulate format using a rotating cutter blade typically used in food processing.
- the shredded format can be fed directly into the hopper of an injection molding machine.
- the shredded feed-stock may be dried to a particular molding solids by evaporation, by exposure of the material to the atmosphere, until the desired moisture level is obtained.
- the useful solids levels in the molding compounds are in the range 75 wt. % to 88 w ⁇ % and preferably between 83 wt. % and 86 wt. %.
- the molding pressure is between 20 psi and about 3500 psi. Most preferably, the molding pressure is in the range of 40 psi to about 1500 psi.
- the mold temperature must of course be at below the gel point of the gel forming material in order to produce a self supporting body. The appropriate mold temperature can be achieved before, during or after the mixture is supplied to the mold. Ordinarily, the mold temperature is maintained at less than 40°C, and preferably between about 15 °C an about 25 °C. After the part is molded and cooled to a temperature below the gel point of the gel- forming material, the body is removed from the mold. The green body is typically sufficiently self supporting that it requires no special handling during removal from the mold.
- the part After removal from the mold, the part is dried. Similar to the drying of slip-cast parts, care needs to be taken to control the drying behavior. Depending on part size and complexity, fast drying may result in cracking. In such a case, the part may be dried in a controlled humidity environment.
- the body is sintered at an elevated temperature to produce the final product.
- the sintering time and temperature is regulated according to the powdered material employed to form the part.
- the elevated temperature at which the body is sintered is at least 1250°C, and more preferably ranges from 1300 to 1550 °C, and most preferably ranges from 1350 °C to 1500 °C.
- the sintering time at maximum temperature is less than 4 hrs., more preferably from 1-3 hrs, and most preferably from 1-2 hrs.
- the present invention can thus be used to form complex and thick net-shape or near net-shape bodies of zirconia based materials which have excellent strength properties and environmental stability.
- the physical properties of the densified ceramic from one preferred molding compound containing 20 vol.% alumina, referred to AS280, have been found excellent for a variety of structural applications, as summarized in Table I.
- Example 2 A molding feed-stock was prepared as in Example 1 , and was used to mold a variety of shapes, such as "3 -hole sensors".
- the fired parts were cylindrical in shape, nominally 0.85" in length with 3 holes, nominally 0.1" in diameter running lengthwise.
- a step divided each part into a larger diameter shoulder, 0.45" OD x 0.35" length and a smaller diameter shoulder, 0.35" OD x 0.5" length.
- Molding was performed at 85 wt. %, after which the parts were dried under ambient conditions and fired at 1450°C for 2 hrs. After firing, the average density was 5.59 ⁇ 0.012 g/cm 3 .
- the average length was 0.949 ⁇ 0.005" and the average diameter was 0.496 ⁇ 0.003".
- the average shrinkage was 21.1 ⁇ 0.5 % and 21.4 ⁇ 0.5 %, for the length and diameter respectively.
- This example represents a scale-up of the molding compound preparation described in Example 1.
- a slip was prepared from 38.4 kg HSY-3 zirconia/ytrria, 6.24 kg aluminum oxide, 14.62 kg D.I. water, 0.179 kg ammonium polyacrylate and adjusted to pH 11 with TMA. After ball milling, 55 kg of slip was transferred to a planetary type blender where it was blended ( in three separate runs) with 1.24 kg agar, 0.011 kg methyl-p-hydroxy benzoate and 0.0077 kg propyl-p-benzoate while being agitated and heated. Mixing was continued for lh after the blender reached a final temperature of 95°C. The material was put into feed- stock form by shredding.
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Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU93800/98A AU741599B2 (en) | 1997-09-10 | 1998-09-08 | Injection molding of structural zirconia-based materials by an aqueous process |
EP98946881A EP1027305A1 (en) | 1997-09-10 | 1998-09-08 | Injection molding of structural zirconia-based materials by an aqueous process |
JP2000510681A JP2003525828A (ja) | 1997-09-10 | 1998-09-08 | ジルコニアをベースとする構造材料の湿式法による射出成形 |
CA002303036A CA2303036A1 (en) | 1997-09-10 | 1998-09-08 | Injection molding of structural zirconia-based materials by an aqueous process |
KR1020007002533A KR100588097B1 (ko) | 1997-09-10 | 1998-09-08 | 수성공정에 의한 지르코니아계 구조재료의 사출주조법 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US92924797A | 1997-09-10 | 1997-09-10 | |
US08/929,247 | 1997-09-10 |
Publications (1)
Publication Number | Publication Date |
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WO1999012864A1 true WO1999012864A1 (en) | 1999-03-18 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/US1998/018663 WO1999012864A1 (en) | 1997-09-10 | 1998-09-08 | Injection molding of structural zirconia-based materials by an aqueous process |
Country Status (9)
Country | Link |
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EP (1) | EP1027305A1 (zh) |
JP (1) | JP2003525828A (zh) |
KR (1) | KR100588097B1 (zh) |
CN (1) | CN1290239A (zh) |
AU (1) | AU741599B2 (zh) |
CA (1) | CA2303036A1 (zh) |
MY (1) | MY119528A (zh) |
TW (1) | TWI262177B (zh) |
WO (1) | WO1999012864A1 (zh) |
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US8114383B2 (en) | 2003-08-06 | 2012-02-14 | Gruenenthal Gmbh | Abuse-proofed dosage form |
US8114384B2 (en) | 2004-07-01 | 2012-02-14 | Gruenenthal Gmbh | Process for the production of an abuse-proofed solid dosage form |
US8383152B2 (en) | 2008-01-25 | 2013-02-26 | Gruenenthal Gmbh | Pharmaceutical dosage form |
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US9629807B2 (en) | 2003-08-06 | 2017-04-25 | Grünenthal GmbH | Abuse-proofed dosage form |
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US5087595A (en) * | 1990-07-18 | 1992-02-11 | Allied-Signal, Inc. | Injection molding of zirconia oxygen sensor thimbles by an aqueous process |
EP0825159A2 (en) * | 1996-08-23 | 1998-02-25 | Eastman Kodak Company | Method of making air lubricated hydrodynamic ceramic bearings |
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JP2976226B2 (ja) * | 1989-06-08 | 1999-11-10 | 工業技術院長 | アルミナ・ジルコニア系焼結体の製造法 |
US5326518A (en) * | 1991-10-08 | 1994-07-05 | Nissan Chemical Industries, Ltd. | Preparation of sintered zirconia body |
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1998
- 1998-09-08 KR KR1020007002533A patent/KR100588097B1/ko not_active IP Right Cessation
- 1998-09-08 EP EP98946881A patent/EP1027305A1/en not_active Withdrawn
- 1998-09-08 CN CN98810795A patent/CN1290239A/zh active Pending
- 1998-09-08 WO PCT/US1998/018663 patent/WO1999012864A1/en active IP Right Grant
- 1998-09-08 JP JP2000510681A patent/JP2003525828A/ja active Pending
- 1998-09-08 AU AU93800/98A patent/AU741599B2/en not_active Ceased
- 1998-09-08 CA CA002303036A patent/CA2303036A1/en not_active Abandoned
- 1998-09-09 MY MYPI98004108A patent/MY119528A/en unknown
-
1999
- 1999-02-09 TW TW087115039A patent/TWI262177B/zh not_active IP Right Cessation
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US5087595A (en) * | 1990-07-18 | 1992-02-11 | Allied-Signal, Inc. | Injection molding of zirconia oxygen sensor thimbles by an aqueous process |
EP0825159A2 (en) * | 1996-08-23 | 1998-02-25 | Eastman Kodak Company | Method of making air lubricated hydrodynamic ceramic bearings |
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US9675610B2 (en) | 2002-06-17 | 2017-06-13 | Grünenthal GmbH | Abuse-proofed dosage form |
US8075872B2 (en) | 2003-08-06 | 2011-12-13 | Gruenenthal Gmbh | Abuse-proofed dosage form |
US10058548B2 (en) | 2003-08-06 | 2018-08-28 | Grünenthal GmbH | Abuse-proofed dosage form |
US9629807B2 (en) | 2003-08-06 | 2017-04-25 | Grünenthal GmbH | Abuse-proofed dosage form |
US10130591B2 (en) | 2003-08-06 | 2018-11-20 | Grünenthal GmbH | Abuse-proofed dosage form |
US8114383B2 (en) | 2003-08-06 | 2012-02-14 | Gruenenthal Gmbh | Abuse-proofed dosage form |
US11224576B2 (en) | 2003-12-24 | 2022-01-18 | Grünenthal GmbH | Process for the production of an abuse-proofed dosage form |
US8323889B2 (en) | 2004-07-01 | 2012-12-04 | Gruenenthal Gmbh | Process for the production of an abuse-proofed solid dosage form |
US8114384B2 (en) | 2004-07-01 | 2012-02-14 | Gruenenthal Gmbh | Process for the production of an abuse-proofed solid dosage form |
US11844865B2 (en) | 2004-07-01 | 2023-12-19 | Grünenthal GmbH | Abuse-proofed oral dosage form |
US10675278B2 (en) | 2005-02-04 | 2020-06-09 | Grünenthal GmbH | Crush resistant delayed-release dosage forms |
US10729658B2 (en) | 2005-02-04 | 2020-08-04 | Grünenthal GmbH | Process for the production of an abuse-proofed dosage form |
US8722086B2 (en) | 2007-03-07 | 2014-05-13 | Gruenenthal Gmbh | Dosage form with impeded abuse |
US8383152B2 (en) | 2008-01-25 | 2013-02-26 | Gruenenthal Gmbh | Pharmaceutical dosage form |
US9750701B2 (en) | 2008-01-25 | 2017-09-05 | Grünenthal GmbH | Pharmaceutical dosage form |
US9161917B2 (en) | 2008-05-09 | 2015-10-20 | Grünenthal GmbH | Process for the preparation of a solid dosage form, in particular a tablet, for pharmaceutical use and process for the preparation of a precursor for a solid dosage form, in particular a tablet |
US9925146B2 (en) | 2009-07-22 | 2018-03-27 | Grünenthal GmbH | Oxidation-stabilized tamper-resistant dosage form |
US10080721B2 (en) | 2009-07-22 | 2018-09-25 | Gruenenthal Gmbh | Hot-melt extruded pharmaceutical dosage form |
US10493033B2 (en) | 2009-07-22 | 2019-12-03 | Grünenthal GmbH | Oxidation-stabilized tamper-resistant dosage form |
US9636303B2 (en) | 2010-09-02 | 2017-05-02 | Gruenenthal Gmbh | Tamper resistant dosage form comprising an anionic polymer |
US10300141B2 (en) | 2010-09-02 | 2019-05-28 | Grünenthal GmbH | Tamper resistant dosage form comprising inorganic salt |
US10695297B2 (en) | 2011-07-29 | 2020-06-30 | Grünenthal GmbH | Tamper-resistant tablet providing immediate drug release |
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US10201502B2 (en) | 2011-07-29 | 2019-02-12 | Gruenenthal Gmbh | Tamper-resistant tablet providing immediate drug release |
US9655853B2 (en) | 2012-02-28 | 2017-05-23 | Grünenthal GmbH | Tamper-resistant dosage form comprising pharmacologically active compound and anionic polymer |
US10335373B2 (en) | 2012-04-18 | 2019-07-02 | Grunenthal Gmbh | Tamper resistant and dose-dumping resistant pharmaceutical dosage form |
US10064945B2 (en) | 2012-05-11 | 2018-09-04 | Gruenenthal Gmbh | Thermoformed, tamper-resistant pharmaceutical dosage form containing zinc |
US10154966B2 (en) | 2013-05-29 | 2018-12-18 | Grünenthal GmbH | Tamper-resistant dosage form containing one or more particles |
US9737490B2 (en) | 2013-05-29 | 2017-08-22 | Grünenthal GmbH | Tamper resistant dosage form with bimodal release profile |
US10624862B2 (en) | 2013-07-12 | 2020-04-21 | Grünenthal GmbH | Tamper-resistant dosage form containing ethylene-vinyl acetate polymer |
US10449547B2 (en) | 2013-11-26 | 2019-10-22 | Grünenthal GmbH | Preparation of a powdery pharmaceutical composition by means of cryo-milling |
US9913814B2 (en) | 2014-05-12 | 2018-03-13 | Grünenthal GmbH | Tamper resistant immediate release capsule formulation comprising tapentadol |
US9872835B2 (en) | 2014-05-26 | 2018-01-23 | Grünenthal GmbH | Multiparticles safeguarded against ethanolic dose-dumping |
US9855263B2 (en) | 2015-04-24 | 2018-01-02 | Grünenthal GmbH | Tamper-resistant dosage form with immediate release and resistance against solvent extraction |
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Also Published As
Publication number | Publication date |
---|---|
AU9380098A (en) | 1999-03-29 |
KR100588097B1 (ko) | 2006-06-09 |
AU741599B2 (en) | 2001-12-06 |
TWI262177B (en) | 2006-09-21 |
EP1027305A1 (en) | 2000-08-16 |
MY119528A (en) | 2005-06-30 |
KR20010023855A (ko) | 2001-03-26 |
CA2303036A1 (en) | 1999-03-18 |
CN1290239A (zh) | 2001-04-04 |
JP2003525828A (ja) | 2003-09-02 |
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