WO2010094798A1 - Implant médical - Google Patents

Implant médical Download PDF

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Publication number
WO2010094798A1
WO2010094798A1 PCT/EP2010/052209 EP2010052209W WO2010094798A1 WO 2010094798 A1 WO2010094798 A1 WO 2010094798A1 EP 2010052209 W EP2010052209 W EP 2010052209W WO 2010094798 A1 WO2010094798 A1 WO 2010094798A1
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WIPO (PCT)
Prior art keywords
medical implant
polyester
anyone
implant according
compound
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PCT/EP2010/052209
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English (en)
Inventor
Detlef Olaf Alexander Schumann
Darren Donald Obrigkeit
Jacob Koenen
Original Assignee
Dsm Ip Assets B.V.
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Publication of WO2010094798A1 publication Critical patent/WO2010094798A1/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
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/12—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L31/125—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
    • A61L31/127—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix containing fillers of phosphorus-containing inorganic materials

Definitions

  • the invention relates to a medical implant comprising a compound of a biostable polyester and an osteoconductive filler. Osteoconductive compounds are used in medical applications.
  • osteoconductive compounds such as the Biocryl Rapide composite material of DePuy and the PLC material of Smith & Nephew, contain a calcium containing filler that stimulates tissue adhesion as well as bone cell activity.
  • the calcium containing filler is combined with biodegradable materials.
  • biodegradable materials has the disadvantage that the physical properties of the biodegradable material will change over time. Degradation of the biodegradable materials in the body can also result in degradation products that can have harmful effects in the body.
  • HA hydroxyapatite
  • PEEK polyetheretherketone
  • the polymer in the implant is biodegradable.
  • the physical properties of the implant material are of special importance when used in a medical implant. To be able to use the medical implant at positions where the implant has to bear a load, the medical implant has to be impact resistant and to resist deformation. These physical properties could not been obtained so far with the implant materials that are now commercially available.
  • Implants generally has a broad meaning, referring to any foreign object that is placed in a living human or animal body.
  • Implants can be temporary, such as implants in the form of pharmaceutical dosage forms for the controlled release of drugs, or implants that are biodegradable and are therefore used for a temporary function.
  • Implants can be permanent, such as a metal pin to support a broken leg.
  • the term “permanent” will be readily understood as referring to anything that is intended to remain indefinitely in the body. This does not mean that the implant could not be removed, e.g. surgically, or could not accidentally disappear.
  • the invention relates to such implants as are suitable for permanent implantation, hence to biostable implants rather than to implants that are bioabsorbable or biodegradable.
  • a biostable implant will remain as is, i.e. once a biologically acceptable implant is introduced into the body of a living human or animal, it is traceable which material is in fact implanted. In the case of an implant that degrades in the body, and/or is absorbed by the body, degradation, conversion or metabolic materials will eventually end up in the body. From a viewpoint of controlling the health of the subject receiving the implant, this is undesirable and represents additional clinical risk. Therefore the use of resorbable implants is typically restricted to applications where this added risk is balanced by a significant long-term clinical benefit. Moreover, a permanent implant will also be capable of indefinitely contributing to load-bearing.
  • the aim of the invention is to provide a medical implant, suitable for permanent implantation, that is capable of assuming an adequate load-bearing function and has osteoconductive properties, such that fast adhesion of the implant to adjacent tissue can be obtained.
  • the fast adhesion of the implant will lead towards a better integration of the implant in the tissue.
  • a medical implant comprising a compound of a biostable thermoplastic polyester and an osteoconductive filler.
  • a permanent implant is not biodegradable. This means that the polyester in the compound that is used to make at least a part of the medical implant must also be not biodegradable.
  • the polyester in the compound can be a thermoplastic or a thermoset polyester.
  • thermosetting polyester also known as a thermoset, is a polyester material that irreversibly cures.
  • the cure may be done through heat (generally above 200 0 C), through a chemical reaction, or irradiation.
  • thermoplastic polyester also known as thermosoftening plastic-is a polymer that turns to a liquid when heated and freezes to a very glassy state when cooled sufficiently.
  • Most thermoplastics are high-molecular-weight polymers whose chains associate through weak Van der Waals forces.
  • Thermoplastic polyesters differ from thermosetting polymers as they can, unlike thermosetting polymers, be remelted and remoulded.
  • the polyester can be a homopolymer or a copolymer. Also blends of different types of polyesters can be used.
  • polyesters are polyethyleneterephthalate (PET), polybutyleneterephthalate (PBT), polyethylenenaphthenate (PEN) and poly(cyclohexylene-dimethyleneterephthalate) (PCT).
  • PET polyethyleneterephthalate
  • PBT polybutyleneterephthalate
  • PEN polyethylenenaphthenate
  • PCT poly(cyclohexylene-dimethyleneterephthalate)
  • a polycarbonate is understood to be a polyester. Therefore a polycarbonate can also be mentioned as an example of a polyester that can be used in the compound.
  • the polyester is an ethylene terephthalate or butylene terephthalate containing polymer.
  • the polyester is a thermoplastic polyester.
  • the compound in the implant according to the invention preferably comprises an impact modifier to improve the impact resistance of the compound.
  • An impact modifier is herewith defined as an additive, usually an elastomeric polymer, that is incorporated in the compound to improve the impact resistance of a medical implant.
  • Impact resistance is the ability of the finished article to withstand a sudden load without failure.
  • Impact modifiers can be chosen from polymers with elastomeric properties, for example polybutadiene, poly(phenylene oxide), low density polyethylene (LDPE) and thermoplastic elastomers (TPE) or thermoplastic polyurethanes(TPU).
  • the medical implant according to the invention comprises a compound that preferably comprises a thermoplastic elastomer (TPE) or thermoplastic polyurethanes(TPU) comprising a hard phase, and a soft phase as the impact modifier.
  • the hard phase in the TPE comprises a rigid polymer phase with a melting temperature (T m ) or a glass transition temperature (T 9 ) higher than 35 0 C.
  • the soft phase in the TPE comprises a flexible, amorphous polymer phase with a T 9 lower than 35 0 C, preferably lower than 0 0 C.
  • the TPE comprises, for example, blends of the above-mentioned hard phase polymers with soft phase polymers and block copolymers.
  • the hard and the soft phase can comprise one polymer type, but can also be composed of a mixture of two or more of the above-mentioned polymeric materials.
  • the TPE or TPU can be used as the polyester or in combination with the polyester that is used in the compound.
  • the TPE or TPU is used as the polyester at least the hard phase of the TPE or TPU has to be a polyester.
  • the soft phase in the TPE or TPU has the function of the impact modifier.
  • the TPE or TPU is a blockcopolymer.
  • TPU is a block-copolymer
  • the TPE or TPU used in the compound comprises a polymer comprising hard blocks and soft blocks
  • the hard blocks comprise a polymer chosen from the group consisting of polyester, polycarbonate, polyamide, polystyrene, polyacrylate and polyolefin
  • the soft blocks comprise a polymer chosen from the group consisting of polyether, polyester, polyacrylate, polyolefin and polysiloxane.
  • TPE block-copolymers are block-copolyesterester, block-copolyetherester, block-copolycarbonateester, block-copolysiloxaneester, block- copolyesteramide, block-copolymer containing polybutylene terephthalate (PBT) hard blocks and poly(oxytetramethylene) soft blocks, block-copolymer containing polystyrene hard blocks and ethylene butadiene soft blocks (SEBS).
  • PBT polybutylene terephthalate
  • SEBS ethylene butadiene soft blocks
  • thermoplastic polyurethane encompasses a family of polymers that usually includes three principal components. These are a macroglycol, a diisocyanate and a chain extender. They are generally classified as polyurethanes in as much as the backbone thereof includes urethane groups and often also urea groups, which groups are recurring units within the polymer backbone.
  • block polyurethane copolymers comprising hard and soft polymer blocks.
  • the hard blocks of the block copolymer may preferably have a molecular weight of about 160 to 10,000, and more preferably about 200 to 2,000.
  • the molecular weight of the soft segment is typically about 200 to 1 ,000,000 and preferably about 400 to 9000.
  • block polyurethane copolymers and methods to prepare these copolymers are described in, for instance, US 4739013, US 4810749, US 5133742 and US 5229431. These block polyurethane copolymers have a hard polycarbonate phase and are biostable.
  • the hard blocks in the TPE or TPU consist of a rigid polymer, as described above, with a T m or T 9 higher than 35 0 C.
  • the different polymers as described above can be used as the hard blocks.
  • copolymers of esters, amides, styrenes, acrylates and olefins can be used as the hard polymer block as long as the T m or T 9 of the hard polymer block is higher than 35 0 C.
  • the hard block of the TPE or TPU is a polyester block or a polycarbonate block.
  • the hard block When the hard block is a polycarbonate block the hard block consists of repeating units derived from at least one alkylene glycol and at least one aromatic dicarboxylic acid or an ester thereof.
  • the alkylene group generally contains 2-6 carbon atoms, preferably 2-4 carbon atoms.
  • Preferable for use as the alkylene glycol are ethylene glycol, propylene glycol and in particular butylene glycol.
  • Terephthalic acid, 2,6-naphthalenedicarboxylic acid and 4,4'-diphenyldicarboxylic acid are very suitable for use as the aromatic dicarboxylic acid. Combinations of these dicarboxylic acids, and/or other dicarboxylic acids such as isophthalic acid may also be used. Their effect is to influence the crystallisation behaviour, e.g. melting point, of the hard polyester blocks.
  • the soft blocks in the TPE or TPU consist of a flexible polymer, as described above, with a T 9 lower than 35 0 C.
  • the polymers as described above can be used as the soft blocks.
  • copolymers can be used as the soft polymer block as long as the T 9 of the soft polymer block is lower than 35 0 C.
  • the soft block comprises a polyester or a polyether; more preferably an aliphatic polyester or polyether.
  • TPE's comprising polyester, or polyether soft blocks is that aliphatic polyesters, and polyethers feature a high chemical stability.
  • alkylene carbonates and aliphatic polyesthers are preferred as the soft block, which result in thermoplastic elastomers with particularly low moisture sensitivity and favourable adhesive properties.
  • the compound in the implant according to the invention preferably comprises an ethylene terephthalate or a butylene terephthalate containing polymer as the polyester. More preferably, the compound comprises an ethylene terephthalate or a butylene terephthalate blockcopolymer.
  • the blockcopolymer comprises a hard phase consisting of polyethylene terephthalate or polybutylene terephthalate and soft phase comprising a polymer chosen from the group consisting of polyether, polyester, polyacrylate, polyolefin and polysiloxane.
  • the hard phase is the polyester phase and the soft phase of the blockcopolymer functions as the impact modifier.
  • the compound in the implant according to the invention also comprises an osteoconductive filler.
  • Osteo means “bone”. Osteoconduction refers to the ability of certain fillers to serve as a scaffold on which bone cells can attach, migrate (meaning move or “crawl”), and grow and divide. In this way, the bone healing response is "conducted”.
  • osteoconductive fillers are, for example, calcium hydroxyapatite, monocalcium phosphate, dicalcium phosphate, ⁇ -tricalcium phosphate ( ⁇ -TCP), ⁇ -tricalcium phosphate ( ⁇ -TCP), octacalcium phosphate, tetracalcium phosphate, dicalcium phosphate, fluoroapatite, calcium sulphate, calcium fluoride and calcium oxide.
  • Calcium phosphate materials can be apatitic materials. These apatitic materials have been described, for example, in US-6117456, US-6953594, US- 6013591 and US-6972130.
  • Examples of calcium phosphate apatites are Ca 5 (PO 4 , CO 3 F) 3 R; Ca 5 (PO 4 CO 3 OH)OH; Ca 5 (PO-O 3 CI; Ca 5 (PO 4 ) 3 F; Ca 5 (PO 4 ) 3 OH; Cai 0 (PO 4 ) 6 CO 3 ;
  • Nanocrystalline apatite material is commercially available, for example, from Berkeley Advanced Biomaterials Inc.
  • osteoconductive filler materials can be used such as, for example, non-calcium phosphate apatites, such as Ba 5 (PO 4 ) 3 CI, (Sr,Ce) 5 (PO 4 ) 3 OH, (Ce,Ca) 5 (PO 4 ) 3 (OH,F), (Y,Ca) 5 (PO 4 ) 3 (OH,F), Na 3 Pb 2 (SO-O 3 CI, Na 3 Ca 2 (SO 4 ) 3 OH, Ca 5 (SiO 4 , PO 41 SO-O 3 (CI, F), Pb 5 (AsO-O 3 CI, (Ca 1 Sr) 5 (AsO 4 , PO 4 ) 3 OH, Pb(AsO 4 ) 3 CI, Ca 5 (SiO 4 ,PO 4 ,SO 4 ) 3 (F,OH,CI), Pb 3 Ca 2 (AsO-O 3 CI, Ca 5 (SiO 4 , PO 4 ,SO 4 ) 3 (OH, F 1 CI),
  • the average particle size of the osteoconductive filler has a range between 10 nm - 100 ⁇ m. This is an average particle size ranging from nanoparticles or small crystals to agglomerates of small particles or crystals.
  • the average particle size of the crystals and nanoparticles is between 1 and 50 ⁇ m which provides a compound which is good compatible with bone. More preferably the average particle size of the crystals and nanoparticles is between 1 and 10 ⁇ m.
  • Agglomerates of small particles or crystals have an average particle size that is preferably smaller than 50 ⁇ m, more preferably smaller than 10 ⁇ m.
  • the compounds as described above can be prepared by using compounding processes known by the person skilled in the art, for example by mixing, kneading, extrusion and pelletization. During compounding the average particle size of the osteoconductive filler can become smaller.
  • the amount of osteoconductive filler in the compound is lower than 40 wt. %, preferably lower than 20 wt.% and more preferably lower than 10 wt.%.
  • the amount of osteoconductive filler in the compound is higher than
  • the amount of impact modifier in the compound is lower than 95 wt.%, preferably lower than 75 wt.%, more preferably lower than 50 wt.%.
  • the amount of impact modifier in the compound is preferably higher than 1 wt.%, more preferably higher than 5 wt.%.
  • the compound can also contain other additives such as reinforcing agents, fillers, compatibilizers, flame retardants, pigments, tracing agents for e.g. radiology and other auxiliary additives like plasticizers, processing aids, such as mould release agents, stabilizers such as antioxidants and UV stabilizers, crystallization accelerating agents or nucleating agents.
  • additives such as reinforcing agents, fillers, compatibilizers, flame retardants, pigments, tracing agents for e.g. radiology and other auxiliary additives like plasticizers, processing aids, such as mould release agents, stabilizers such as antioxidants and UV stabilizers, crystallization accelerating agents or nucleating agents.
  • the compounds as described above can be used in medical applications, preferably in medical implants.
  • Examples of medical implants are screws, rods, plates, pins, shafts, anchors, rings, porous or open structures, scaffolds and spinal cages a spinal disk, a spinal body, a hip cup or a knee implant and/or components thereof.
  • the invention is also directed to a method for treating a mammal which comprises inserting a medical implant, as described here above, into an area of the mammal where bone is degenerated, damaged or missing.
  • the medical implants can be completely prepared out of the compound of a biostable polyester and an osteoconductive filler, but also only certain parts of the medical implant can be made out of the compound.
  • the medical implant can also be, at least partially, coated with the compound.
  • the surface of the medical implant is preferably activated. More preferably, the surface of the implant is activated after the implant has been given its final shape.
  • Activation is performed to roughen the surface of the implant to promote better access of the osteoconductive filler in the compound for (bone) cells to obtain better adhesion of the surrounding tissue to the medical implant.
  • Activation By activation the top layer of the compound is, partially, removed. Activation can be performed by various mechanical and chemical treatments known to the person skilled in the art; for example by milling, sanding, abrading, machining, scraping or chemical etching.
  • Arnitel ® CM551 block copolymer; hard block: polybutylene terepthalate (PBT), soft block: polycarbonate) from DSM N.V.
  • Arnitel ® EL250 (block copolymer; hard block polybutylene terepthalate (PBT), soft block: polytetramethyleneoxide (PTMO)) from DSM N.V.
  • Arnitel ® EM400 block copolymer; hard block: polybutylene terepthalate (PBT), soft block: polytetramethyleneoxide (PTMO)) from DSM N.V.
  • Arnitel ® EM460 block copolymer; hard block polybutylene terepthalate (PBT), soft block: polytetramethyleneoxide (PTMO)) from DSM N.V.
  • Arnitel ® EM550 block copolymer; hard block polybutylene terepthalate (PBT), soft block: polytetramethyleneoxide (PTMO)) from DSM N.V.
  • Arnitel ® EM630 and 630-H block copolymer; hard block polybutylene terepthalate (PBT), soft block: polytetramethyleneoxide (PTMO)) from DSM N.V. (H means heat stabilized)
  • Arnitel ® EM740 block copolymer; hard block polybutylene terepthalate (PBT), soft block: polytetramethyleneoxide (PTMO)) from DSM N.V.
  • thermoplastic polyester used in accordance with the invention was capable of deforming to a much higher extent, and thus absorbed the impact energy rather than merely transmitting it to the surrounding tissue as PEEK does.
  • Example IV Growth of osteoblasts on various materials Materials
  • the ⁇ -TCP used was a ⁇ -TCP with a particle size of 1-10 ⁇ m; the agglomerates had an average particle size of 70 ⁇ m.
  • Arnitel ® CM551 block copolymer; hard block: polybutylene terepthalate (PBT), soft block: polycarbonate, modulus 140 MPa) from DSM N.V.
  • E A compound containing 65 wt% Arnitel ® CM551 as defined above and 35 wt% PBT homopolymer (Arnite ® T04201 from DSM N.V.).
  • F A compound containing 80 wt% of a compound as defined under E and 20 wt% ⁇ -TCP.
  • the materials were melted at 260 Celsius before pressing at 15OkN for 5-10min (cool down phase). From these plaques discs were punched with a diameter of 5 mm and a thickness of 1 mm. A total of 48 discs was prepared for testing.
  • One side of the discs was mechanically activated by treatment with sandpaper on a Schaublin 125 machine.
  • the sandpaper that was used was No 220.
  • the roughening was done under reproducible conditions by using a spring to control the pressure and the distance: the total force on a disc was 78.5 N, duration 1 sec, min. erosion 10 ⁇ m / max. erosion 30-40 ⁇ m.
  • the discs of materials A-F were chemically treated by submerging the discs for 12 hours in a 1.0 molar NaOH solution. The discs were washed thoroughly to remove remaining NaOH solution. The PEEK samples were cut from a rod with a diameter of 5 mm. This cutting of the discs caused a roughening of the surface of the discs. 12 PEEK discs were tested.
  • PEEK is a chemically inert material that can not be etched by using a 1.0 molar NaOH solution.
  • hOBs Primary human osteoblasts (hOBs) were suspended in a hOB growth medium.
  • the growth medium contained Alpha Modified Eagle Medium ( ⁇ -MEM) containing 10% fetal bovine serum (FBS) (Invitrogen) and 1% Penicillin/Streptomycin (Invitrogen).
  • ⁇ -MEM Alpha Modified Eagle Medium
  • FBS fetal bovine serum
  • Penicillin/Streptomycin Invitrogen
  • the osteogenic medium consisted of 100 nM dexamethasone, 50 ⁇ M ascorbic acid-2-phosphate and 5 mM ⁇ -Glycerophosphate in the hOB growth medium as described above.
  • the growth media of pre-seeded scaffolds were replaced by osteogenic media after one week and followed by subsequent weekly osteogenic media change.
  • 0.1 M cacodylate buffer was used for washing the scaffolds to remove any glutaraldehyde residue for three times at 10 minutes each.
  • the scaffolds were treated with 1 % osmium tetraoxide before dehydrated sequentially with ethanol. The dehydration process started with 2 changes of 10 minutes each with 50% ethanol, followed by 70% ethanol for 10 mins, followed by 90% for 10 minutes and subsequently 100% for 15 minutes.
  • HMDS hexamethyldisilazane
  • Alizarin Red test Alizarin Red is used in a biochemical assay to determine, quantitatively by colorimetry, the presence of calcific deposition by cells of an osteogenic lineage. As such it is an early stage marker (days 10-16 of in vitro culture) of matrix mineralisation, a crucial step towards the formation of calcified extracellular matrix associated with true bone.
  • the test is described in the following three articles: 1. H. Putchler, S. Meloan, M.S. Terry, On the history and mechanism of alizarin and alizarin red S stains for calcium, J. Histochem, Cytochem. 17 (1969) 1 10-124; 2. M. Lievremont, J. Potus, B.
  • ⁇ a surface with uneven structure is observed when enlarged 1000 times.
  • PEEK material G
  • PEEK does not promote cell adhesion and does not trigger tissue integration. It was now shown that on a mechanically activated surface of PEEK some cell growth could be observed at the site of the mechanically activated surface. No chemical etching of PEEK was possible. It also proved not to be possible to make a compound of PEEK and 20 wt% of ⁇ -TCP, as PEEK lost its mechanical integrity during compounding.

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

Abstract

La présente invention concerne un implant médical contenant un composé de polyester biostable et un support ostéoconducteur et elle concerne également le traitement d'un mammifère grâce à l'insertion de l'implant médical. Le composé peut contenir un modificateur de la résistance au choc. La surface de l'implant médical est de préférence activée avant la mise en place de l'implant dans l'organisme.
PCT/EP2010/052209 2009-02-20 2010-02-22 Implant médical WO2010094798A1 (fr)

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EP09153355.4 2009-02-20
EP09153355 2009-02-20

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Citations (11)

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US4739013A (en) 1985-12-19 1988-04-19 Corvita Corporation Polyurethanes
US4810749A (en) 1987-05-04 1989-03-07 Corvita Corporation Polyurethanes
US5133742A (en) 1990-06-15 1992-07-28 Corvita Corporation Crack-resistant polycarbonate urethane polymer prostheses
US5229431A (en) 1990-06-15 1993-07-20 Corvita Corporation Crack-resistant polycarbonate urethane polymer prostheses and the like
US6013591A (en) 1997-01-16 2000-01-11 Massachusetts Institute Of Technology Nanocrystalline apatites and composites, prostheses incorporating them, and method for their production
WO2000048552A1 (fr) * 1999-02-16 2000-08-24 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Ceramiques organiques
US6117456A (en) 1995-05-19 2000-09-12 Etex Corporation Methods and products related to the physical conversion of reactive amorphous calcium phosphate
US6953594B2 (en) 1996-10-10 2005-10-11 Etex Corporation Method of preparing a poorly crystalline calcium phosphate and methods of its use
US6972130B1 (en) 1996-10-16 2005-12-06 Etex Corporation Bioceramic compositions
US20060246397A1 (en) * 2003-11-05 2006-11-02 Friadent Gmbh Multi part non metal implant

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US4202055A (en) * 1976-05-12 1980-05-13 Battelle-Institut E.V. Anchorage for highly stressed endoprostheses
US4739013A (en) 1985-12-19 1988-04-19 Corvita Corporation Polyurethanes
US4810749A (en) 1987-05-04 1989-03-07 Corvita Corporation Polyurethanes
US5133742A (en) 1990-06-15 1992-07-28 Corvita Corporation Crack-resistant polycarbonate urethane polymer prostheses
US5229431A (en) 1990-06-15 1993-07-20 Corvita Corporation Crack-resistant polycarbonate urethane polymer prostheses and the like
US6117456A (en) 1995-05-19 2000-09-12 Etex Corporation Methods and products related to the physical conversion of reactive amorphous calcium phosphate
US6953594B2 (en) 1996-10-10 2005-10-11 Etex Corporation Method of preparing a poorly crystalline calcium phosphate and methods of its use
US6972130B1 (en) 1996-10-16 2005-12-06 Etex Corporation Bioceramic compositions
US6013591A (en) 1997-01-16 2000-01-11 Massachusetts Institute Of Technology Nanocrystalline apatites and composites, prostheses incorporating them, and method for their production
WO2000048552A1 (fr) * 1999-02-16 2000-08-24 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Ceramiques organiques
US20060246397A1 (en) * 2003-11-05 2006-11-02 Friadent Gmbh Multi part non metal implant

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Title
C.M. STANFORD; P.A. JACOBSON; E.D. EANES; L.A. LEMBKE; R.J. MIDURA: "Rapidly forming apatitic mineral in an osteoblastic cell line (UMR 106-01 BSP)", J. BIOL. CHEM., vol. 270, 1995, pages 9420 - 9428
H. PUTCHLER; S. MELOAN; M.S. TERRY: "On the history and mechanism of alizarin and alizarin red S stains for calcium", J. HISTOCHEM, CYTOCHEM., vol. 17, 1969, pages 110 - 124
KURTZ, DEVINE: "PEEK biomaterials in trauma, orthopedic, and spinal implants", BIOMATERIALS, vol. 28, 7 August 2007 (2007-08-07), pages 4845 - 4869, XP002585205 *
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M. LIEVREMONT; J. POTUS; B. GUILLOU: "Use of alizarin red S for histochemical staining of Ca2+ in the mouse; some parameters of thechemical reaction in vitro", ACTA ANAT., vol. 114, 1982, pages 268 - 280

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