WO2000048552A1 - Ceramiques organiques - Google Patents

Ceramiques organiques Download PDF

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Publication number
WO2000048552A1
WO2000048552A1 PCT/NL2000/000094 NL0000094W WO0048552A1 WO 2000048552 A1 WO2000048552 A1 WO 2000048552A1 NL 0000094 W NL0000094 W NL 0000094W WO 0048552 A1 WO0048552 A1 WO 0048552A1
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WO
WIPO (PCT)
Prior art keywords
organoceramic
process according
powder
chosen
ceramic material
Prior art date
Application number
PCT/NL2000/000094
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English (en)
Inventor
Eric Peter Carton
Clemens Antoni Van Blitterswijk
Joost Robert De Wijn
Marianne Euphemia Corry Stuivinga
Original Assignee
Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno
Isotis B.V.
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.)
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Application filed by Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno, Isotis B.V. filed Critical Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno
Priority to AU26998/00A priority Critical patent/AU2699800A/en
Publication of WO2000048552A1 publication Critical patent/WO2000048552A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
    • A61L27/46—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with phosphorus-containing inorganic fillers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
    • A61L27/446—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with other specific inorganic fillers other than those covered by A61L27/443 or A61L27/46

Definitions

  • the invention relates to a process for preparing an organoceramic and to an organoceramic obtainable by said process .
  • Bioactive materials include calcium phosphate ceramics, such as hydroxyapatite and Bioglasses or glass-ceramics, polymers, such as polyether esters, and composites of such polymers with calcium phosphate ceramics.
  • metals and ceramics are mostly used for large restorations, while polymers and composites find application m smaller restorations.
  • composite materials as biomate ⁇ als are that the properties of two or more materials, mostly a ceramic and a polymeric material, may be combined. That way, a material is obtained which has properties which cannot be achieved by the provision of a singular material .
  • a problem encountered m composite synthesis is that only limited amounts of ceramic material can be incorporated into a polymeric material. Also, when the resulting composite material is thermally processed, e.g. sintered, the polymeric material may decompose, which leads to a loss of desired properties .
  • the present invention aims to provide a material which has a high stiffness and strength, particularly a high impact resistance. It is further aimed at that the above indicated problems of the prior art materials and their preparation are overcome.
  • the invention relates to a process for preparing an organoceramic, wherein a polymer is coupled to a ceramic material to form a composite material, which composite material is subjected to shock compaction.
  • the different components used m its preparation are substantially integrated and firmly attached to each other.
  • the material is not merely a physical mixture of two or more phases, but rather a heterogeneous compound, it is referred to herein as an organoceramic.
  • a material is obtained, which can hardly be prepared by conventional techniques, if at all.
  • the material has excellent properties, such as a high stiffness and strength, and particularly a high impact resistance.
  • the present organoceramic is prepared by starting from at least two different materials.
  • One of these is a polymeric material, the other is a ceramic material, preferably m the form of a powder.
  • the polymeric material preferably is a biocompatible and/or a biodegradable material .
  • biocompatible is intended to refer to materials which may be incorporated into a human or animal body substantially without unacceptable responses of the human or animal .
  • biodegradable refers to materials which, after a certain period of time, are broken down m a biological environment.
  • the rate of breakdown is chosen similar or identical to the rate at which the body generates autogenous tissue to replace the implant of which the biodegradable material is manufactured.
  • Suitable polymeric materials to be used m the process according to the invention include polylactic acid, polyether esters, gelatin, starch, collagen, poly (meth) acryl- ates, such as polyalkylmethacrylate and derivatives thereof. It is also possible to use mixtures of these polymers, or to use copolymers or graft polymers.
  • the ceramic material is preferably used in the form of a powder. It is preferred that a ceramic material is used which has a specific surface area of at least 60 g/m 2 .
  • the average particle size of the powder lies in the micron scale, preferably between 0.01 and 100 ⁇ m.
  • the average particle size may be measured by using laser diffraction, e.g. using a particle size measuring device of Malvern Instruments. In order to obtain an organoceramic having a particularly high relative density, it is preferred that the average particle size of the powder is higher than 0.5 ⁇ m.
  • the particle size of the ceramic powder may be used to control the ratio between the polymeric and ceramic parts of the organoceramic to be formed.
  • the ratio of the amounts of polymeric and ceramic materials preferably is selected such that the organoceramic comprises between 60 and 99 wt . % , more preferably between 75 and 95 wt . % of the ceramic material, depending on the purpose of the desired organoceramic. Surprisingly, it has been found possible to incorporate relatively large amounts of ceramic material with respect to the amount of polymeric material used. Because of this, m accordance with the invention, it is possible to suitably control the properties of the desired organoceramic .
  • a first step the polymeric material is coupled to the ceramic material.
  • a suitable coupling agent e.g. a alkylenednsocyanate, an aromatic dnsocyanate, an isocyanatoalkyi ester, such as isocyanatoethyl methacrylate, an isocyanatosilane, such as isocyanatopropyl t ⁇ ethoxysilane, or an organic silane.
  • the coupling agent possibly through certain functional groups m the coupling agent, is capable of reacting with hydroxyl groups which are present on the surface of a ceramic material.
  • the coupling agent is capable of reacting with functional groups of the polymeric material .
  • functional groups which may be present m the polymeric material to react with the coupling agent include, inter alia , glycidyl, vinyl, and ammoalkyl groups.
  • the coupling agent may be reacted with the ceramic material by adding said agent to a dispersion of the ceramic material m a suitable solvent and letting the resulting mixture react at elevated or ambient temperature for a period ranging from several hours to several days. At the end of this period, the excess, unreacted coupling agent is removed by washing and the modified ceramic material is retrieved.
  • the modified ceramic material On the surface of the thus obtained modified ceramic material, various kinds of polymers may be immobilized (or may be coupled thereto) .
  • the modified ceramic material is dispersed m a solution of the polymeric material, or m a liquid curing system, e.g. methylmethacrylate combined with a hardener, such as a benzoylperoxide tertiary aromatic amine system.
  • a hardener such as a benzoylperoxide tertiary aromatic amine system.
  • An alternative method to achieve the coupling of the polymeric material to the ceramic material involves co- precipitation and has been disclosed by Stupp and Ciegler m J. Biomed. Mater. Res., 26 . , 1992, pp. 169-183.
  • This alternative method is particularly applicable when a polymeric material is used which is soluble m water.
  • the ceramic material is precipitated from a solution that also contains the water soluble polymeric material .
  • the precipitation may suitable be performed by addition of an acidic and a basic material or of two salts. The addition of said materials initiates the formation of insoluble salts, which, while precipitating, lock the polymeric material m their crystal structure.
  • the composite material resulting after the coupling step is, m a second step, subjected to shock compaction.
  • a pre-compaction step prior to the shock compaction.
  • This pre-compaction may be carried out by centrifugmg the material or by subjecting it to an ultrasonic treatment or by isostatic pressure techniques (Cold Isostatic Pressing, CIP) .
  • the pre- compaction is carried out to such a degree that a material is obtained which has 80% or more of its theoretical density (TMD) .
  • TMD theoretical density
  • the density may be determined by measuring mass and volume of a sample of the material.
  • the theoretical maximal density is a weighted average of the fractions constituting the sample.
  • the shock compaction technique is described m, inter alia , US-A-5, 631, 016 and m WO-A-96/27566 and may be performed by generating a Shockwave m the material .
  • a preferred manner of performing the shock compaction is set forth m O-A-96/27566 , which is therefore incorporated herein by reference.
  • Suitable manners m which to generate a shock wave include detonation of an explosive and launching a projectile toward the material.
  • the shock wave is generated by detonation of an explosive.
  • the composite material is preferably confined m a mold cavity, which is surrounded by an explosive material .
  • Suitable explosives include nonideally detonating explosives having a low detonation velocity, typically below 6 km/s, and preferably between 2-4 km/s. It has been found that the use of this type of explosives avoids the occurrence of cracks m the compacted material due to rarefaction waves. Examples include, but are not limited to, ammonium nitrate based explosives, such as AMPA (which is a TNO melange) , ANFO (which is a mixture of ammonium nitrate and diesel oil) and T ⁇ amite.
  • AMPA which is a TNO melange
  • ANFO which is a mixture of ammonium nitrate and diesel oil
  • the amount of explosives used m relation to the amount of material to be compacted is not critical and highly dependent on the scale on which the compaction is carried out. Based on his ordinary skill, the artisan will be able to select a suitable amount of explosive to make sure that a minimal thickness of a layer of explosives is obtained to ensure proper detonation. Generally, the ratio of explosives to material to be compacted may range from 40:1 to 1:1.
  • a preferred manner for carrying out the shock compaction is the cylindrical configuration.
  • a cylindrical metal container for instance aluminum with an inner diameter of 30 mm, a wall thickness of 2.3 mm and a length of 120 mm
  • the container may then be closed by metal plugs and placed at the center of a 50 mm longer polymer or cardboard tube with a diameter 2-4 times that of the metal container.
  • the tube is filled with a powder explosive and placed in a concrete bunker where the explosive compaction is performed.
  • an electrically ignited detonator is placed on top of the configuration at the axis of symmetry. The detonator is used to initiate the detonation of the explosive. After, the compaction, the container is removed.
  • shock compaction is by manufacturing plates, analogous to the procedure described by Stuivinga et al . , 9 th CIMTEC, World Ceramics Congress & Forum on New Materials, 14-19 June, 1998, Florence Italy.
  • a layer of the material to be compacted may be brought into a metallic profile, which has the form of a flat plate.
  • the profile may be surrounded by explosives and shock compaction can further be carried out as described above.
  • the product of the above described process has extremely favorable properties, which for a large extent may be controlled by the parameters discussed above.
  • the organoceramic has a density of at least 90%, more preferably at least 95% of its theoretical maximal density.
  • the organoceramic preferably has mechanical properties, such as an elasticity modulus, closely resembling those of bone or dental tissue.
  • the organoceramic of the present invention may, depending on its chemical composition, suitably be used for the production of medical or dental implants.
  • the ceramic powder is hydroxyapatite and the polymer is collagen
  • the organoceramic may be useful in restorative dental operations, or as crown or inlay material having a color similar to the color of natural teeth.
  • the organoceramic may be of use in electro-optical applications, where specific optical properties in combination with a high stiffness and strength, particularly a high impact resistance are desired.
  • 66 g/m 2 is dispersed in 500 ml thoroughly dried dimethylformamide (DMF) by magnetical stirring.
  • DMF dimethylformamide
  • ICM isocyanatoethylmethacrylate
  • 0.5 ml stannous octoate and 0.2 g hydroquinone are added.
  • the vessel is placed in a waterbath and heated to 50 °C and stirred at this temperature during 24 hrs while maintaining an atmosphere of dry N 2 over the reaction mixture. After this period the solvent is removed by filtering and excess reagents further removed by successive washings with DMF and chloroform. Finally, the powder is dried.
  • the obtained hydroxyapatite contains 6% of organic matter coupled thereto as measured by thermogravimetric analysis.
  • a suitable reaction vessel 10 g of finely powdered and thoroughly dried hydroxyapatite (surface area: 66 g/m 2 ) is dispersed in 100 ml dry toluene and 3.1 ml of methacryloxypropyl - trimethoxysilane (TMPS) and 40 mg hydroquinone are added. The mixture is stirred and heated to the boiling point of toluene (110 °C) maintaining an atmosphere of dry N 2 over the reaction mixture. After 24 hrs the powder is filtered off, washed several times with toluene and acetone, and dried. Typically the powder will contain 1 - 5 wt % of organic material as measured by TGA.
  • TMPS methacryloxypropyl - trimethoxysilane
  • Example 3 50 grams of hydroxyapatite powder coupled with pendant methacrylate groups as obtained in example 2 is added to a 150 grams room temperature curing methylmethacrylate/ poly-methylmethacrylate (MMA/PMMA) resin. After curing the composite blocks are dissolved in acetone. The undissolved powder is separated by centrifuging and repeatedly washed by acetone to remove all unbound PMMA and finally dried. Typically the powder contains 20 - 30 weight percent of organic matter as measured by TGA and, judging from FTIR spectra of the powder, identified as PMMA.
  • MMA/PMMA room temperature curing methylmethacrylate/ poly-methylmethacrylate
  • hydroxyapatite powder coupled to pendant isocyanate groups as obtained in example 1 is added to a 500 ml of a 10 % percent chloroform solution of a poly(ether- ester) called PolyActive (which consists of blocks of polyethyleneglycol (PEG) and blocks of polybutylene- terephtalate (PBT) ) .
  • PolyActive which consists of blocks of polyethyleneglycol (PEG) and blocks of polybutylene- terephtalate (PBT)
  • the mixture is stirred during 137 hrs at room temperature after which time the powder is separated by centrifuging and decanting. By washing the powder repeatedly with chloroform the excess of unbound polymer is removed. After drying a powder is obtained containing 7 - 10 percent by weight of organic powder as measured by TGA and which by FTIR spectroscopy is identified as mainly PolyActive.
  • PMMA-hydroxyapatite powder having a specific mass of 2.205 g/cm 3 , an average particle size smaller than 1 ⁇ m and which was prepared as described in Example 3 was shock compacted in a cylindrical configuration.
  • the powder was put in an aluminum tube having an inner diameter of 9.5 mm and a thickness of 2.25 mm.
  • the tube was closed at both ends with metal plugs.
  • Filling was done in batches of about 5 mm height by mechanically tapping (50 times at 2 Hz) and uniaxially pressing at 310 MPa . In this manner, a starting density of 85% of the TMD was obtained.
  • the aluminum tube was placed in the middle of a larger PVC tube.
  • the 16 mm space between these tubes was filled with an explosive, AMPA 2, a mixture of ammonium nitrate, TNT and aluminum, having a detonation velocity of 3.6 km/s. Above the tube, a 5 cm thick layer of the explosive was present. By detonation of the explosive with a detonator, the powder was densified to 94% of its TMD. Slices of about 4 mm thick of the obtained material were shown to be transparent to visible light.
  • AMPA 2 a mixture of ammonium nitrate, TNT and aluminum
  • E can be determined from formula (4) .
  • Table I shows the density and Young's modulus (E) of the shock compacted material compared to those of the PMMA and hydroxyapatite starting materials. It is particularly interesting to note that the elasticity modulus of the prepared organoceramic is almost identical with the known elasticity modulus of cortical bone tissue.
  • a powder of PBMA coupled to hydroxyapatite (prepared analogous to the procedure of Example 3, except that butyl- methacrylate was used instead of methylmethacrylate) was precompacted analogous to the procedure described in Example 5 to a density of 89% of its TMD.
  • the powder was placed in a stainless steel tube having an internal diameter of 9.5 mm and a wall thickness of 2.25 mm. Around the tube, a 14 mm thick layer of AMPA 2 was placed, which was subsequently detonated using a detonator.
  • the organoceramic thus obtained had a density of 100% of its TMD.
  • a scanning electron- microscopy photograph of the obtained material is shown in Figure 1.

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Transplantation (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Dermatology (AREA)
  • Medicinal Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Materials For Medical Uses (AREA)

Abstract

L'invention concerne un procédé de préparation d'une céramique organique, selon lequel un polymère est couplé à une matière céramique de façon à former un matériau composite soumis à un compactage par onde de choc. L'invention concerne également une céramique organique préparée selon ledit procédé.
PCT/NL2000/000094 1999-02-16 2000-02-15 Ceramiques organiques WO2000048552A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU26998/00A AU2699800A (en) 1999-02-16 2000-02-15 Organoceramics

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP99200449.9 1999-02-16
EP99200449 1999-02-16

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WO2000048552A1 true WO2000048552A1 (fr) 2000-08-24

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005087284A2 (fr) * 2004-03-13 2005-09-22 Dot Gmbh Materiaux composites a base d'acide polysilicique et leur procede de production
WO2006107359A1 (fr) * 2005-03-30 2006-10-12 Boston Scientific Limited Materiaux composites a base de polymere et de ceramique destines a etre utilises dans des dispositifs medicaux
WO2007040819A1 (fr) * 2005-09-16 2007-04-12 Boston Scientific Limited (Barbados Home Office) Dispositifs medicaux prepares a partir de materiaux hybrides polymeriques-inorganiques par reaction de transesterification ester-alcoxy durant un traitement par fusion
WO2008024477A2 (fr) * 2006-08-25 2008-02-28 Boston Scientific Scimed, Inc. Matériaux composites polymériques/céramiques pour une utilisation dans des dispositifs médicaux
GB2461743A (en) * 2008-07-11 2010-01-20 Smith & Nephew Medical device or composition comprising at least two inorganic components
WO2010094798A1 (fr) * 2009-02-20 2010-08-26 Dsm Ip Assets B.V. Implant médical
US8008395B2 (en) 2005-09-27 2011-08-30 Boston Scientific Scimed, Inc. Organic-inorganic hybrid particle material and polymer compositions containing same
US8980340B1 (en) 2013-10-08 2015-03-17 Benny Antony Medicinal composition of extract of seed of emblica officinalis and method of preparing the same
WO2019068903A1 (fr) 2017-10-06 2019-04-11 Dsm Intellectual Property Procédé de fabrication d'un article polymère ostéoconducteur et article polymère ostéoconducteur ainsi obtenu
US12016977B2 (en) 2017-10-06 2024-06-25 Dsm Ip Assets B.V. Method of making an osteoconductive fibrous article and a medical implant comprising such osteoconductive fibrous article

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992012698A1 (fr) * 1991-01-21 1992-08-06 Mccann, James, Michael Compositions a usage dentaire
WO1996027566A1 (fr) * 1995-03-07 1996-09-12 Nederlandse Organisatie Voor Toegepast- Natuurwetenschappelijk Onderzoek Tno Procede de fabrication d'un materiau composite
US5631016A (en) * 1992-10-28 1997-05-20 Universite De Nantes Process for the production of single- or multi-phase materials of biological interest
EP0803241A2 (fr) * 1996-04-27 1997-10-29 GC Dental Products Corporation Matériau dentaire

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992012698A1 (fr) * 1991-01-21 1992-08-06 Mccann, James, Michael Compositions a usage dentaire
US5631016A (en) * 1992-10-28 1997-05-20 Universite De Nantes Process for the production of single- or multi-phase materials of biological interest
WO1996027566A1 (fr) * 1995-03-07 1996-09-12 Nederlandse Organisatie Voor Toegepast- Natuurwetenschappelijk Onderzoek Tno Procede de fabrication d'un materiau composite
EP0803241A2 (fr) * 1996-04-27 1997-10-29 GC Dental Products Corporation Matériau dentaire

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
HEGAZY A ABOUSREE ET AL: "SOME ASPECTS OF SHOCK CONSOLIDATION OF POLYMERIC, PVC-METALLIC AND PVC-SILICA POWDER MIXTURES", J MATER SCI DEC 1986, vol. 21, no. 12, December 1986 (1986-12-01), pages 4262 - 4268, XP002109285 *
LIU, DE WIJN AND VAN BLITTERSWIJK: "A study on the grafting reaction of isocyanates with hydroxyapatite particles", J. BIOMED. MATER. RES., vol. 40, no. 3, 1998, NEW YORK, NY; US, pages 358 - 364, XP002109709 *
LIU, DE WIJN AND VAN BLITTERSWIJK: "Composite biomaterials with chemical bonding between hydroxyapatite filler particles and PEG/PBT copolymer matrix", J. BIOMED. MATER. RES., vol. 40, no. 3, 1998, NEW YORK, NY; US, pages 490 - 497, XP002109708 *

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005087284A3 (fr) * 2004-03-13 2006-05-11 Dot Gmbh Materiaux composites a base d'acide polysilicique et leur procede de production
WO2005087284A2 (fr) * 2004-03-13 2005-09-22 Dot Gmbh Materiaux composites a base d'acide polysilicique et leur procede de production
US9125968B2 (en) 2005-03-30 2015-09-08 Boston Scientific Scimed, Inc. Polymeric/ceramic composite materials for use in medical devices
WO2006107359A1 (fr) * 2005-03-30 2006-10-12 Boston Scientific Limited Materiaux composites a base de polymere et de ceramique destines a etre utilises dans des dispositifs medicaux
WO2007040819A1 (fr) * 2005-09-16 2007-04-12 Boston Scientific Limited (Barbados Home Office) Dispositifs medicaux prepares a partir de materiaux hybrides polymeriques-inorganiques par reaction de transesterification ester-alcoxy durant un traitement par fusion
US7365126B2 (en) 2005-09-16 2008-04-29 Boston Scientific Scimed, Inc. Medical device articles formed from polymer-inorganic hybrids prepared by ester-alkoxy transesterification reaction during melt processing
US8008395B2 (en) 2005-09-27 2011-08-30 Boston Scientific Scimed, Inc. Organic-inorganic hybrid particle material and polymer compositions containing same
WO2008024477A2 (fr) * 2006-08-25 2008-02-28 Boston Scientific Scimed, Inc. Matériaux composites polymériques/céramiques pour une utilisation dans des dispositifs médicaux
WO2008024477A3 (fr) * 2006-08-25 2009-02-12 Boston Scient Scimed Inc Matériaux composites polymériques/céramiques pour une utilisation dans des dispositifs médicaux
GB2461743A (en) * 2008-07-11 2010-01-20 Smith & Nephew Medical device or composition comprising at least two inorganic components
WO2010094798A1 (fr) * 2009-02-20 2010-08-26 Dsm Ip Assets B.V. Implant médical
US8980340B1 (en) 2013-10-08 2015-03-17 Benny Antony Medicinal composition of extract of seed of emblica officinalis and method of preparing the same
WO2019068903A1 (fr) 2017-10-06 2019-04-11 Dsm Intellectual Property Procédé de fabrication d'un article polymère ostéoconducteur et article polymère ostéoconducteur ainsi obtenu
EP3974006A1 (fr) 2017-10-06 2022-03-30 DSM IP Assets B.V. Procédé de fabrication d'un article polymère ostéoconducteur et article polymère ostéoconducteur ainsi fabriqué
US11400184B2 (en) 2017-10-06 2022-08-02 Dsm Ip Assets B.V. Method of making an osteoconductive polymer article and an osteoconductive polymer article thus made
US12016977B2 (en) 2017-10-06 2024-06-25 Dsm Ip Assets B.V. Method of making an osteoconductive fibrous article and a medical implant comprising such osteoconductive fibrous article

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