CA1266685A - Controlled pore size ceramics particularly for orthopaedic and dental applications - Google Patents

Controlled pore size ceramics particularly for orthopaedic and dental applications

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Publication number
CA1266685A
CA1266685A CA000552590A CA552590A CA1266685A CA 1266685 A CA1266685 A CA 1266685A CA 000552590 A CA000552590 A CA 000552590A CA 552590 A CA552590 A CA 552590A CA 1266685 A CA1266685 A CA 1266685A
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Canada
Prior art keywords
ceramic
glass
particles
ceramic composite
ceramic particles
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CA000552590A
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French (fr)
Inventor
George Arthur Graves Jr.
Dale E. Mccullum
Steven M. Goodrich
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University of Dayton
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University of Dayton
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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00Compositions for glass with special properties
    • C03C4/0007Compositions for glass with special properties for biologically-compatible glass
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61CDENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
    • A61C8/00Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools
    • A61C8/0012Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools characterised by the material or composition, e.g. ceramics, surface layer, metal alloy
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61CDENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
    • A61C8/00Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools
    • A61C8/0012Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools characterised by the material or composition, e.g. ceramics, surface layer, metal alloy
    • A61C8/0013Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools characterised by the material or composition, e.g. ceramics, surface layer, metal alloy with a surface layer, coating
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02Prostheses implantable into the body
    • A61F2/30Joints
    • A61F2/30767Special external or bone-contacting surface, e.g. coating for improving bone ingrowth
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00Preparations for dentistry
    • A61K6/15Compositions characterised by their physical properties
    • A61K6/17Particle size
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00Preparations for dentistry
    • A61K6/70Preparations for dentistry comprising inorganic additives
    • A61K6/71Fillers
    • A61K6/74Fillers comprising phosphorus-containing compounds
    • A61K6/75Apatite
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00Preparations for dentistry
    • A61K6/80Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/802Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
    • A61K6/807Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics comprising magnesium oxide
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00Preparations for dentistry
    • A61K6/80Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/802Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
    • A61K6/818Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics comprising zirconium oxide
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00Preparations for dentistry
    • A61K6/80Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/831Preparations for artificial teeth, for filling teeth or for capping teeth comprising non-metallic elements or compounds thereof, e.g. carbon
    • A61K6/836Glass
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02Inorganic materials
    • A61L27/10Ceramics or glasses
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02Inorganic materials
    • A61L27/12Phosphorus-containing materials, e.g. apatite
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/56Porous materials, e.g. foams or sponges
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00Glass compositions
    • C03C3/12Silica-free oxide glass compositions
    • C03C3/16Silica-free oxide glass compositions containing phosphorus
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00Glass compositions
    • C03C3/12Silica-free oxide glass compositions
    • C03C3/23Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron
    • C03C3/247Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron containing fluorine and phosphorus
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00Compositions for glass with special properties
    • C03C4/0007Compositions for glass with special properties for biologically-compatible glass
    • C03C4/0014Biodegradable glass
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B32/00Artificial stone not provided for in other groups of this subclass
    • C04B32/005Artificial stone obtained by melting at least part of the composition, e.g. metal
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/0038Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by superficial sintering or bonding of particulate matter
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02Prostheses implantable into the body
    • A61F2/30Joints
    • A61F2/3094Designing or manufacturing processes
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02Prostheses implantable into the body
    • A61F2/30Joints
    • A61F2002/30001Additional features of subject-matter classified in A61F2/28, A61F2/30 and subgroups thereof
    • A61F2002/30108Shapes
    • A61F2002/30199Three-dimensional shapes
    • A61F2002/30242Three-dimensional shapes spherical
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2230/00Geometry of prostheses classified in groups A61F2/00 - A61F2/26 or A61F2/82 or A61F9/00 or A61F11/00 or subgroups thereof
    • A61F2230/0063Three-dimensional shapes
    • A61F2230/0071Three-dimensional shapes spherical
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2310/00Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
    • A61F2310/00005The prosthesis being constructed from a particular material
    • A61F2310/00179Ceramics or ceramic-like structures
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2310/00Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
    • A61F2310/00005The prosthesis being constructed from a particular material
    • A61F2310/00179Ceramics or ceramic-like structures
    • A61F2310/00185Ceramics or ceramic-like structures based on metal oxides
    • A61F2310/00203Ceramics or ceramic-like structures based on metal oxides containing alumina or aluminium oxide
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2310/00Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
    • A61F2310/00005The prosthesis being constructed from a particular material
    • A61F2310/00179Ceramics or ceramic-like structures
    • A61F2310/00293Ceramics or ceramic-like structures containing a phosphorus-containing compound, e.g. apatite
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2310/00Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
    • A61F2310/00389The prosthesis being coated or covered with a particular material
    • A61F2310/00928Coating or prosthesis-covering structure made of glass or of glass-containing compounds, e.g. of bioglass
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00836Uses not provided for elsewhere in C04B2111/00 for medical or dental applications
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991Coated
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991Coated
    • Y10T428/2993Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]

Abstract

Abstract The present invention provides a ceramic composite having an open porous network and a controlled pore size comprising a plurality of ceramic particles having a fused glass coating and a method for producing the same. The ceramic particles are enveloped by and bonded to adjacent ceramic particles at their interfaces by the glass coating.

Description

~, .
CONTROLLED PORE SIZE CERAMICS PARTIC~LARLY
FOR ORTHOPAEDIC AND DENTAL APPLICATIONS
Background of the Invention The present invention relates to a ceramic having a controlled pore size and, more particularly, to a con-trolled pore structure, liquid phase sintered ceramics for orthopaedic and dental applications.
Ceramic materials which are useful as bone sub-stitutes are used in nu~erous orthopaedic and dental ap-plications including as implants. Examples of such bone substitutes are described in U~S. Patent Nos. 4,097,935 to Jarcho; 4,113,500 to Ebihara et al; 4,149,893 to Aoki et al and 4,330,514 to Nagai et al.
Two bone substitute materials, hydroxyapatite and tricalcium phosphate, have been approved for general dental implant use, and in some selected instances, orthopaedi-c- ~' clinical trials. Howev'e~r,''~'hës'ë''ma'~'erla~s''arë''only avair-able in particulate or solid bulk closed cell forms.
~'~ Thus, the use of such materials in orthopaedic and dental applications has been limited.
Bone substitutes such as hydroxyapatite have been combined with other agents in various medical applications.
~` 20 Surgical cements including hydroxyapatite as the bone substitute are used in numerous orthopaedic and dental applications including repairing bone fractures, in at-~; taching bone plates and other prostheses, in bridging comminuted ractures, and in filling or aligning dental ~ ~ 25 cavities. Examples of such compositions are described in ;' U.S. Patent Nos. 4,518,430 to Brown et al; and 4r542,167 :-:"
~.

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to Aoki et al. U.S. Patent No. 4,451,235 to Okuda et al discloses a dental root ma~erial comprising hydroxyapatite and an organic matrix such as polyethylene.
U.S. Patent No. 4,135,935 to Pfeil et al discloses a composite material useful as an implant. A first start-ing material which is preferably an apatite and a secondstarting material which is pre~erably a glass are ground, preferably jointly, to a particle size preferably between ~ about 200-500 microns. The resultant mixture is finely i 10 comminuted to a particle size preferably between about 20-50 microns. The mixture is compressed to form shaped bodies and sintered. This material does not have the open pore structure which characterizes the ceramic material of the present invention.

Summary of the Invention The present invention provides a ceramic composite having an open porous network of controlled pore size comprising a plurality of ceramic particles having a glass coating which bonds the ceramic particles at their inter-faces. While the present invention is particularly dir-ected to providing ceramics which are useful in orthopaedic and surgical applications, those skilled in the art will ;~ appreciate that the teachings herein are relevant to cera-mics generally where a controlled pore size is desired.
By varying the size of the ceramic particles and the thickness of the glass coating, the pore size of the composite ceramic can be varied.
Accordingly, one object of the present invention is to provide a ceramic material having a controlled pore s l z e .

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A further object of the present invention is to provide a ceramic composite having a controlled pore size comprising a plurality of particles of a bone ingrowth promoting material useful in dental and orthopaedic appli-¦ 5 cations.
An additional object of the present invention is ! to provide a ceramic composite having a controlled pore si7~e useful in dental and orthopaedic applications wherein the degree of resorbability can be varied.
Another object of the present invention is to provide ceramic particles having a finely divided or fused glass coating useful in providing a ceramic composite having a controlled pore size.
Still another object of the present invention is to provide a process for preparing a ceramic composite in accordance wi~h the present invention.
Other objects and advantages-o~ the--present in-vention will become apparent from the followin-g-description and the appended claims.
2~ Brief Description of the Drawings Figure l illustrates an agglomerator useful in coating the ceramic particles of the present invention with a ground glass.
Figure ~ illustrates a spray dryer useful in ; 25 coating the ceramic particles of the present invention with a ground glass.
Figure 3 illustrates the ceramic particles of the present invention with a glass powder coating prior to sintering.
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3, UVD 0~2 P2 4-Figure 4 illustrates a plurality of the ceramic particles of the present invention with a glass coating after liquid phase sintering.
Figure 5 is a scanning electron microscope photo-- 5 graph (magnification 50X) of a ceramic in accordance with the present invention showing the glass coated ceramic particles and the glass necking between them.
Yigure 6 illustrates a prosthesis carrying ceramic particles in accordance with the present invention.

Detalled Description of the Invention As stated earlier, the principal object of the present invention is to provide a ceramic composite having a controlled pore siæe. In order to achieve this object, the size of the ceramic particles must be controlled.
Knowing the size of the ceramic particle and the thickness of the glass coating, the por~ size of the ceramic-~materi-al -- ~
can be calculated by using the equation for closely packed particles. The ceramic particles used in the present invention typically have a particle size of less than about 2000 microns. If the particle size is larger than 2000 microns, the present invention can be used, but us-ually there are more expedient means available to achieve ; the desired pore size. The amount of glass necking is ;~ also less and the porous ceramic is not as strong. Pre-ferably, the ceramic particles of the present invention have a size of about lO0 to lO00 microns and, more prefer-ably 500 to lO00 microns.

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The ceramic composite of the present invention has broad application because the ceramic particles can be any of a variety of ceramic materials. It is useful in providing bone implants, surgical cements or grouts, and drug delivery devices. Outside of the biomedical field its open cell pore structure is useful in providing microporous filters.
Typical examples of useful ceramics are Al2o3, MgO, ZrO2, SiC, etc. However, the ceramic composite of the present invention is particularly useful in dental and orthopaedic applications. Ceramic particles which are useful for such dental and orthopaedic applications are a bone ingrowth promoting material. The term ~bone ingrowth promoting material" means a material, which upon im-planting into the human body, will promote or aid the growth of new bone around the ceramic material. This material may function as à scaffold for bone-growth-and-/or-~
provide nutrients which promote-bo-ne growth. - ---~ In some applications, it is anticipated that a - 20 ceramic particle of a nonresorbable bone ingrowth pro-moting material would be useful. Examples of nonresorbable bone ingrowth promoting materials are hydroxyapatite, aluminum oxide, pyrolytic carbon, etc. A preferred non-resorbable bone ingrowth promoting material is hydroxy-apatite. Examples of commer-cially available hydroxyapatite include Calcitite 20~0, a nonresorbable synthetic hydroxy-apatite available ~rom Calcitek, Inc. of San Diego, Cali-fornia and Biogel, a hydroxyapatite produced by Bio Rads Lab of Richmond, California~

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In other applications, the ceramic particles are A~ a resorbable bone ingrowth promoting material. Examples of useful resorbable bone ingrowth promoting materials include various calcium aluminates, calcium phosphates, 5 calcium aluminophosphates and calcium sulfatesO A pre-ferred resorbable bone ingrowth promoting material is ~' tricalcium phosphate. Specific examples of resorbable bone ingrowth promoting materials are the ALCAP (calcium aluminophOsphate) ceramic described in V.S. Patent No.
4,218,255 to Bajpai in ground or powdered form; calcium phosphates described in U.S. Patent No. 4,192,021; and the ALCAP ceramics described by Graves, G. A., et al, ~Resorb-able Ceramic Implants, n J Biomed. Mater. Res. Symp. 2 (Part I): 91, 1972.
Calcium aluminophosphate ceramics useful in the present invention can be obtained by mixing calcium oxide ¦ (CaO), aluminum oxide (A12o3), and phosphorus pentoxide (P2O5) in weight ratios o~--about 35-to 40%~CaO, about- ---- -- - -----45 to 55% A12o3, and about 10 to 20% P2O5; com-pressing the mixture; and calcining. A typical ceramic is ~- prepared from a 38 50 12 mixture of calcium oxide, aluminum ; oxide, and phosphorus pentoxide which is calcined at 1300C
; for 12 hours and ground.
~esorbable and nonresorbable bone ingrowth pro-;~ 25 moting materials may be combined to provide a partially resorbable ceramic. For example, in order to stimulate bone growth, it may be desirable to formulate the composi-tion such that a major or a minor portion of the ceramic is resorbed.

~, : ' ~ ' : . - .~ . - .. . - .
- . . .
. . .

.;

~VD 082 P2 -7-The ceramic particles of the present invention are enveloped by a fusible glass and are bonded to adjacent ceramic particles at their interfaces by the fusible glass.
Any glass is useful in the ceramic material of the present invention, but preferably, a biocompatible glass having a melting point in the range of about 500 to 1000C is used.
In many biological applications~ the fusible glass is resorbable. A particularly useful resorbable glass comprises calcium oxide ~CaO) and phosphorus pent-oxide (P2O5). Other ingredients such as calciumfluoride (CaF2), water (H2O), and other metal oxides containing cations such as magnesium, zinc, strontium, sodium, potassium, lithium, silicon, boron and aluminum oxides may also be incorporated in small amounts. In terms of the binary mixture, the preferred Ca:P mole ratio ranges from about 0.25 to 0.33. Preferably, the glass ; ~ comprises by weight 5-50~ CaO, 50-95~ P2O5, 0-5%
CaF2, 0-5~ H2O and 0 10% of a metal oxide selected from the group consisting of magnesium, zinc, strontium, Sodium, potassium, lithium, and aluminum oxides. In a preferred embodiment, the calcium oxide (CaO) is present by weight in the amount of 15-25%; the phosphorus pentoxide (P2O5) is present by weight in the amount of 65-90~
while either calcium fluoride (CaF2) or water (H2O) is present by weight in the amount of 0.1-4%.
Comparable to the ceramic particles, the degree of resorbability of the glass coating can be controlled.
For example, as the amount of CaO increases, the degree of resorbability decreases. Also, as the amount of Na2o :
., . . ~ ~ . .. .... . . . . . . . . . . . ... . . .. . ..
.
: ~ ' ' . , ' . , . , 6~i increases, the degree of resorbability decreases. Addi-tions of potassium, aluminum or zinc oxide can also be made to achieve varying degrees of resorption in body fluids. The glass compositions can be formulated to have a range of solubility rates or be virtually insoluble.
In Table 1 below, glass compositions are provided in order of increasing resorbability:

10 Example CaO P2o5 Na20 K2o ~1203 MgO ZnO SiO2 . _ . ~ . _ _ . . .. _ . ... _ ..... .. .. _ . _ _ _ B -- 58 -- 37 5 -~
C -- 56 21 20 -- -- 3.0 --D __ 63 - 30 _ _ 7 In making the ceramic material of the present invention, the glass is ground to a particle size of about 10 to 50 microns and coa~ed on the surface of the larger ceramic particles. The particle size should be as uniform as possible.
Typically the glass is adhered to the ceramic particles as a slurry in a solution of a binder such as polyvinyl alcohol (PVA). When the ceramic is subsequently sintered, the binder burns off. The coating is typically ~- about the thickness of the glass particle, although thicker coatings may also be useful. The weight ratio of the ceramic par~icles to the glass coating is about 8:1 to :`

' ' ' . , ' ' ` ` - , ' ' , , ,, , ~ .
, ..
, ' ' 0 :, . ~ : ' ..
, ~:G6685;

14:1 and preferably about 10:1 to 12:1. In a preferred embodiment~ ~he ratio which provides a desirable thin coating with good porosity and good necking between the ceramic particles is about 11:1. Of coursel this will vary with the particle size of the ceramic.
Methods for obtaining hydroxyapatite and trical-cium phosphate particles are known in the art. Two rel~
atively new techniques can also be used. One is sol-gel processing, a method of preparing solid materials that result when certain combinations of chemicals are mixed and precipitated from solution. The sol-gel, if dried slowly, can yield very fine grained ceramics which sinter to high density. The second is a process that provides particles of well controlled size and shape by using spray drying and agglomeration techniques which, until now, were used primarily in the food and drug industry. A slurry of the ceramic and a binder such as PVA is fed to a spray dryer (e.g., a Bowen Ceramic Spray Dryer, Bowen Engineering, Inc. Somerville, N.J.) where it is atomized into fine droplets which are rapidly dried to yield :
; relatively uniform spheres of the ceramic which are sintered for example in a tunnel kiln. Both techniques after sintering provide dense, spherical shaped ceramic particles such as hydroxyapatite or tricalcium phosphate in controlled sizes which may be used to form the porous ceramic of the invention. These materials are also avail-j~ able commercially.
Figure 1 illustrates an agglomerator 10 useful incoating the ceramic particles of the present invention with glass. Ceramic particles 12 are fed by air through , ~' : .
: .
.
: ,, ' :
.. ';

~ o,~

tube 14 into the agglomerator 10. A slurry of a glass powder 1~ in a binder is fed to a rotary disc 18 through tube 17. As the disc 18 rotates, the glass powder 16 collides with and coats ceramic particles 12. The glass coated particles roll off the plate 18 and are dried in a hot air stream and collected. The resulting glass coated ceramic particles 20 appear as schematically illustrated in Figure 3.
Figure 2 illustrates a spray dryer 22 useful in coating the ceramic particles 12 with the glass powder slurry 160 Glass powder 16 is fed through a tube 24 into spray dryer 22. The ceramic particles 12 are dropped through tube 26 into the spray dryer 22. The ceramic ; particles 12 and the glass powder 16 collide and the glass powder 16 coats the ceramic particles 12 to produce the glass coated ceramic particles 20 of Figure 3~
The glass coated ceramic ~articles 20 of Figure 3 are lightly compacted into a desired shape and then sin-tered. The particles may be compacted in a mold under pressures of about 5 to 1000 psi. Virtually any simple shape can be produced. Upon sintering, surface tension causes the glass powder 16 to melt and flow on the surface ~ of the ceramic particles 12 to form the ceramic material ;~ 28 of Figure 4. Typically, the glass coated ceramic particles 20 are sintered at temperatures of about 600 to 1200C (other temperatures can also be used) for about 5 to 30 minutes. The glass powder 16 envelops the ceramic particles 12 and bonds the adjacent ceramic particles 12 at their interfaces by necking between the ceramic particles 12. Pores 30 form in the ceramic material 28~

~. ' . ' ' ,' ` ' - , . , ' ' ' . ' ` , ' '. -'~ ' ' ' '' , ' . ' ` ` ' ' ,' ' '. ~ . ` ' ' :.

~ 6~
ll V D 1) f3 2 P 2 In ~t(l(lit l.on to coatLng lar~Jer ceralllic particles w:ltll a lm~ .3r ~u~L~).Le c3.las;i~ pow(ler, other meEIns are also a ~3nvi~3Lorltlcl eor provicJLn~J ~Jlcl.3r3 co ited ceramLc particles ~ olul ln eorlllLrl(J tl~ porc~uC3 CeralniC3 o~ tn~3 present in-rj vcrltLotl. In uart Lcular, ceralnic particlt s ~uch a~ E~A and I.CP, w~lt~n eormI~d t~y r~pray clryin-J or acJc31OIneration~ are ~3:LIltt.~rt3cl pr:Lor t:o coat:Lnc~ with cJIa3~3 rll.is sintering i~3 ~I~;u7~].ly pt3reormti~d by ~he manu~ac~urer o commerci.~lly ~lval.laL).le mal:t3i-ial.q. ~lowevt~r, a contLnuous proce~;s ic3 I 10 t3nvl~Lc)ned in whictl ~ht3 ~:lntt.~ced partLcl~ ai-e elUidiZt3d ancl c onr~act.ecl w~l th t.lle cJ.lac3~ powdcr while they are at an 1ev.ltt~cl kt)mperaturc~ ~luctl tl~at t~le gla.r3s r~ilm~3 out directly on cc-~ntac~t wllh tt~e ~urfrlce ol tlle~ particle.
I rrc~ ~romot~ bone inlJrow~h, ~he ceramtc material of h~ pr~sen~ lnvantioll stlould h~lve, or acquire through r~ orp~:Lorl, a ps)re~ ~tze oE at least abo~lt 100 microns.
.Inc 1uclLng oth~r app.lications~ the ceralnic mat~rial has a pore ~I~.e Oe c~i~out 20 to 15n micron~, anc3 pre~erablY, ~rom t~bout. 100 t.o I!iQ m L~rons.
In ~ld.Lt Lon tc~ the ~la~5 compositlon and the c~ami~ p~r~ eolnpo; ltion, t~ ;la~s. thlokne~3s is a t l~a~kor in e~orl~rol:ltn~ rca~e o~ resor~abi:lity oE the c~ralni~ c0~ In ~ eréll~ Eor a s;lowly resorbable ~;~ c~r~ compo~lt~, k~le gl~s~ coatin~ i~ thi~ker than for a E~k~r ~*~;or~c~ eralnic compo~.ike.
A~ an ~ mple oE a colnp.letely nonresorbable cer ~m:l~ comp~lt~ yclroxyclpatL~e pc3rt1~1es can be cod~ed Wiktl an in~c~.lu~ ss ~ucil as ~xampl~ A in Table 1 (a typ.i~3.l ~30da llm~ t~ XE on~ theQ w~n~ed to increase .lll ~ r~sorb~bili~.y of ~h~ ~omplQt~ly nonr~sorbable cQralnic .

) UVD ~)~2 l~2 -L2-colllpoilt~, re~or~ ble cerar(lic pclrtLclec3 can be mi~ec3 with.hle tly(3rOXydp(lt' i.~,e or a re:~ort~able ylaf3s can be u~ed. An xamp:le Oe a comple~ly rescrbahLe cerarllic composite i~3 a tr:Lccllcillln pho~;~)hllte cecaw~ic ~drtic le c.~oat~d w:lth a glas~
cor~lprinln~3 Ct10 an(l P2~5 Ln a weiyhk % rat:Lo of about 20:~0. ~rlu~, th~ cer~lmic COmpQ~ite~C3 o~ the present in-c311tLOrl tlaV~ broad appllccltLon t~ecause t)le degree and rate o~ resorpt:Lc)n can ~? wiclel.y varie~ by caee~ully clloo~ing the proper colllbinal:i.on o~ ceralnic l~article composition, 1(~ glclss compositlon and it~3 ~.hickne~;f~.
When ~elect:incl a ceralnic ~article ancl glass foe n.~e :I.n ttl~3 c~ralllic corllpo~c3Lte~ tne mechanicdl s~ren~h of tl~e implant ~Ind tl~e rate o~ bone ingrowt.h sho~lld be con-c~:Ld~3red, 'l'he c~t3ra~ c pore f3ize grea~ly in~1uences both.
Gen~ra.lly~ tl cerallliC havlll~ a ~slnall pore ~:ize exhibLt~ a hi-Jh ~l~r~C3119~h t~Ut a lower rd~e o~ ingrow~.t~ compared to a c~3ramic havinl3 ~ lar~er ~ore c3iæe. I~ the ceramic and/o~
l~s iL~ re~orbable, ~he pore siæe will lncreac3e a~ the a ln 1 c a ~
I ~Q In partlclllar, i~ nkicipat~d thak a ceeamic : wi:ll bc d~ic3ncd ka tlave lligh strength initially ~In~il a :~ call~ls ~a~ forlned nround khe lmplc~nc and becolne ~ully m:ln~r~liæQ(l. ~y cde~ully desic~lllny th~ resoepkion rate a~: ~h~ cJk~s~ clndt~r khe cer~mic partic:le, the implant will onLy ~ ~t~c~b~l a~^~.er ~t~Q new bon~ ha~ enouc3h strenyth~
~h~ th~ rp~ion ra~ o~ kt~ cer~m:ic typically wi.ll be le~ han ~h~ l`A~e ak which n~w ban~ eO~n~
'rh~ c~ramlc compc)~ik~s oE t.he present inventian h~ nulil~rou.~ u~ in or~ho~aed~c nl~d d~rlk~l app.Lications.
3~ rrh~ cerc~lnlc campc)~ mc~y ~ suppli~d in a ~olid ~orm and ~ :
:

' `'` ` `, ` ` ' i,6~

cut to the desired size by the practitioner. In another application, ceramic particles coated with glass powder or the fused glass powder are sold to the surgeon who would have his own furnace and mold. The mold is filled with the ceramic particles and the ceramic material in the desired shape is sinteredO
In another application, it is anticipated that the glass coated ceramic particles could be adhered to the surface of a prosthetic device to enhance bone attachment to the device. This is accomplished by first applying a thin glass coating to the prosthesis, adhering glass coated particles to the prosthesis and then sintering. Figure 6 is an example o~ a prosthesis 40 used in hip replacements.
The shank 42 of the prosthesis is driven into the bone.
By applyiny glass-coated ceramic particles 44 to the shank, bone growth around the prosthesis and attachment of bone to the prosthesis is promoted.
The present invention is illustrated in more detail by the following non-limiting examples:

Example_l Approximately 2 g of a spherical particulate ; hydroxyapatite (HA 500, a product of Orthomatrix, Inc.) screened to 40 x 60 mesh was placed in a glass dish, 4 to
5 drops of a saturated solution of polyvinyl alcohol was added to the HA. T~le HA was coated with the PVA solution by spreading it throuyh the solution with a spatula until it is well coated (approximately 3 to 5 minutes). The PVA
coated HA was dried at 90C and separated with a spatula.
Glass composition E (Table 1) was ground to 10-40 microns :

., . . . , . . . .. . ,. .. ~ , . . . .. ... - .. . . .
. . . . . . . .

- .
: ' ' , , 66~8~

' UVD 082 P2 -14-and sprinkled over the PVA coated HA. The mixture was then vibrated to uniformly coat the H~ particles (approxi-mately 1-2 minutes ). The glass composition uniformly adhered to the HA particle surfaces. The glass coated HA
particles were placed in a ~/32 inch die on a Clifton Hydraulic Press. Enough HA was placed in the die to dis-place the plunger of the die approximately 3/8 inch. 100 microliters of the PVA solution was then added to the die and the plunger was replaced and ~he die vibrated until the PVA solution stopped running out of the die (30-60 seconds). The press was activated and the HA particles were compacted (approximately 500 psi). The compacted cylinder was removed from the die and dried at 90C for ; appoximately 4 hours. The dried cylinder was sintered at ~ 15 1000C for 5 minutes~
,~
:
Hydroxyapatite was bonded to a prosthesis using the following procedure;
~` The procedure was evenly coated with a thick slurry of a glass having composition E in Table 1 using a paint brush. The slurry on the surface of the prosthesis ¦ ~ was dried at 90C and glazed by heating at 1000C for 5 minutes. Glass coated hydroxyapatite particles were pre-pared ~s in Example 1 above and spread on the prosthesis and dried. ~he prosthesis was then fired at 1000C for 5 minutes and allowed to cool slowly.
Having described the invention in detail and by reference to preferred embodiments thereof, it will be apparent that modifications and variations are possible without departing from the scope of the invention defined in the appended claims.

; " -' ' ' '. , -, . .. - - -.
.

,, ~ ' , . :

-

Claims (24)

  1. The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
    l. A ceramic composite having an open porous network of a controlled pore size comprising a plurality of ceramic particles having a coating of a fused glass on their sur-faces, said ceramic particles being bonded to adjacent ceramic particles at their interfaces by said fused glass coating to provide an open porous network between said ceramic particles.
  2. 2. The ceramic composite of claim 1 wherein said ceramic particles are a material selected from the group consisting of Al2O3, MgO, ZrO2, and SiC.
  3. 3. The ceramic composite of claim 1 wherein said ceramic composite is useful for dental and orthopaedic implants and said ceramic particles are a bone ingrowth promoting material.
  4. 4. The ceramic composite of claim 3 wherein said ceramic particles are a nonresorbable bone ingrowth pro-moting material.
  5. 5. The ceramic composite of claim 4 wherein said nonresorbable bone ingrowth promoting material is selected from the group consisting of hydroxyapatite, aluminum oxide, and pyrolytic carbon.
  6. 6. The ceramic composite of claim 3 wherein said ceramic particles are a resorbable bone ingrowth promoting material.
  7. 7. The ceramic composite of claim 6 wherein said resorbable bone ingrowth promoting material is selected from the group consisting of calcium aluminate, calcium phosphates, calcium aluminophosphates and calcium sulfates.
  8. 8. The ceramic composite of claim 7 wherein said ceramic composite has a pore size of about 20 to 150 mi-crons.
  9. 9. The ceramic composite of claim 8 wherein said ceramic composite has a pore size of at least about 100 microns.
  10. 10. The ceramic composite of claim 9 wherein said glass is resorbable.
  11. 11. The ceramic composite of claim 10 wherein said resorbable glass comprises calcium oxide (CaO) and phos-phorus pentoxide (P2O5).
  12. 12. The ceramic composite of claim 11 wherein said resorbable glass comprises by weight:

    CaO 5-50%
    P2O5 50-95%
    CaF2 0-5%
    H2O 0-5%
    XO 0-1 0%

    wherein XO is a metal oxide selected from the group con-sisting of magnesium, zinc, strontium, sodium, potassium, lithium and aluminum oxides.
  13. 13. The ceramic composite of claim 12 wherein said ceramic particles have a particle size of less than about 2000 microns.
  14. 14. The ceramic composite of claim 13 wherein said ceramic particles have a particle size of about 500 to 1000 microns.
  15. 15. The ceramic composite of claim 14 wherein the ratio of said ceramic particles to said glass coating based on the weight of said ceramic material is about 8:1 to 14:1.
  16. 16. The ceramic composite of claim 15 wherein said ceramic material is formed by coating said ceramic part-icles with fusible glass particles, molding said fusible glass coated ceramic particles into a desired shape and sintering.
  17. 17. The ceramic composite of claim 16 wherein said ceramic particles are coated with said fusible glass part-icles in an agglomerator or a spray dryer.
  18. 18. Ceramic particles having a coating of a fused glass on the surface thereof.
  19. 19. The ceramic particles of claim 18 wherein said glass comprises calcium oxide (CaO) and phosphorus pento-xide (P2O5).
  20. 20, The ceramic particles of claim 19 wherein said particles are a bone ingrowth promoting material.
  21. 21. A process for preparing a ceramic composite having a controlled pore size comprising the steps of:
    coating ceramic particles with a glass, molding said glass coated ceramic particles into a desired shape, and sintering.
  22. 22. The process of claim 21 wherein said glass is a fusible glass powder.
  23. 23. The process of claim 22 wherein said ceramic particles are coated with said fusible glass particles in an agglomerator or a spray dryer.
  24. 24. The ceramic composite of claim 9 wherein said glass is non-resorbable.
CA000552590A 1986-11-25 1987-11-24 Controlled pore size ceramics particularly for orthopaedic and dental applications Expired - Fee Related CA1266685A (en)

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Families Citing this family (117)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5776353A (en) * 1996-02-16 1998-07-07 Advanced Minerals Corporation Advanced composite filtration media
US4861733A (en) * 1987-02-13 1989-08-29 Interpore International Calcium phosphate bone substitute materials
JP2702953B2 (en) * 1988-01-30 1998-01-26 オリンパス光学工業株式会社 Chemical impregnated ceramics
JP2761729B2 (en) * 1988-05-17 1998-06-04 旭光学工業株式会社 Artificial trachea
DE3831657A1 (en) * 1988-09-17 1990-03-22 Boehringer Ingelheim Kg DEVICE FOR THE OSTEOSYNTHESIS AND METHOD FOR THE PRODUCTION THEREOF
CA2029671A1 (en) * 1989-12-11 1991-06-12 Paul M. Vernon Grip surgical clip
US5266248A (en) * 1990-05-10 1993-11-30 Torao Ohtsuka Method of producing hydroxylapatite base porous beads filler for an organism
US5074916A (en) * 1990-05-18 1991-12-24 Geltech, Inc. Alkali-free bioactive sol-gel compositions
US5491082A (en) * 1991-03-18 1996-02-13 Director-General Of Agency Of Industrial Science And Technology Plasminogen activator covalently bonded to a porous body of β-tricalcium phosphate
JPH06114099A (en) * 1991-06-12 1994-04-26 Nara Kikai Seisakusho:Kk Medical material and manufacture thereof
DE4133877C1 (en) * 1991-10-12 1993-05-19 S + G Implants Gmbh, 2400 Luebeck, De
US6258137B1 (en) 1992-02-05 2001-07-10 Saint-Gobain Industrial Ceramics, Inc. CMP products
AU650382B2 (en) * 1992-02-05 1994-06-16 Norton Company Nano-sized alpha alumina particles
US5282861A (en) * 1992-03-11 1994-02-01 Ultramet Open cell tantalum structures for cancellous bone implants and cell and tissue receptors
FI91713C (en) * 1992-04-23 1994-08-10 Axidental Oy New bioactive coatings and their manufacture and use
DE4224173A1 (en) * 1992-07-22 1994-01-27 Hoechst Ceram Tec Ag Porous ceramics
CH686282A5 (en) * 1993-06-08 1996-02-29 Schuetz Dental Gmbh Ceramic composite fittings are lap.
DE4334211C2 (en) * 1993-10-07 2000-08-03 Heraeus Kulzer Gmbh & Co Kg Process for the production of a finely divided inorganic filler in the form of a composite filler made of macro-filler particles and micro-filler particles and its use
JP3362267B2 (en) * 1993-12-29 2003-01-07 日本特殊陶業株式会社 Bioimplant material and method for producing the same
US5639402A (en) 1994-08-08 1997-06-17 Barlow; Joel W. Method for fabricating artificial bone implant green parts
US6287341B1 (en) 1995-05-19 2001-09-11 Etex Corporation Orthopedic and dental ceramic implants
US6541037B1 (en) 1995-05-19 2003-04-01 Etex Corporation Delivery vehicle
US6132463A (en) 1995-05-19 2000-10-17 Etex Corporation Cell seeding of ceramic compositions
US7150879B1 (en) 1995-05-19 2006-12-19 Etex Corporation Neutral self-setting calcium phosphate paste
US6027742A (en) 1995-05-19 2000-02-22 Etex Corporation Bioresorbable ceramic composites
US6117456A (en) * 1995-05-19 2000-09-12 Etex Corporation Methods and products related to the physical conversion of reactive amorphous calcium phosphate
US5676976A (en) * 1995-05-19 1997-10-14 Etex Corporation Synthesis of reactive amorphous calcium phosphates
US6224913B1 (en) * 1996-05-09 2001-05-01 The Trustees Of The University Of Pennsylvania Conditioning of bioactive glass surfaces in protein containing solutions
US6953594B2 (en) 1996-10-10 2005-10-11 Etex Corporation Method of preparing a poorly crystalline calcium phosphate and methods of its use
US7517539B1 (en) 1996-10-16 2009-04-14 Etex Corporation Method of preparing a poorly crystalline calcium phosphate and methods of its use
AU734691B2 (en) 1996-10-16 2001-06-21 Life Science Enterprises, Inc. Bioceramic compositions
US8728536B2 (en) * 1996-10-16 2014-05-20 Etex Corporation Chemotherapeutic composition using nanocrystalline calcium phosphate paste
AU6946198A (en) * 1997-04-01 1998-10-22 Cap Biotechnology, Inc. Calcium phosphate microcarriers and microspheres
US6413660B1 (en) 1998-06-12 2002-07-02 Jeneric/Pentron, Inc. High-strength dental restorations
US20050127544A1 (en) * 1998-06-12 2005-06-16 Dmitri Brodkin High-strength dental restorations
US6533969B1 (en) * 1998-06-12 2003-03-18 Jeneric/Pentron, Inc. Method of making high-strength dental restorations
US20030114936A1 (en) * 1998-10-12 2003-06-19 Therics, Inc. Complex three-dimensional composite scaffold resistant to delimination
US6383519B1 (en) 1999-01-26 2002-05-07 Vita Special Purpose Corporation Inorganic shaped bodies and methods for their production and use
US6190643B1 (en) * 1999-03-02 2001-02-20 Patricia Stoor Method for reducing the viability of detrimental oral microorganisms in an individual, and for prevention and/or treatment of diseases caused by such microorganisms; and whitening and/or cleaning of an individual's teeth
AU6080500A (en) 1999-07-08 2001-01-30 Cap Biotechnology, Inc. Calcium-containing structures and methods of making and using the same
US6723334B1 (en) * 2000-03-01 2004-04-20 Iowa State University Research Foundation, Inc. Biologically compatible bone cements and orthopedic methods
EP1272144A4 (en) * 2000-03-27 2006-04-26 Schott Ag New cosmetic, personal care, cleaning agent, and nutritional supplement compositions comprising bioactive glass and methods of making and using the same
US6869445B1 (en) 2000-05-04 2005-03-22 Phillips Plastics Corp. Packable ceramic beads for bone repair
US6669476B2 (en) 2000-06-27 2003-12-30 David Michael Prestipino Nanophase dental prosthetics and method
GB0020610D0 (en) * 2000-08-21 2000-10-11 Dytech Corp Ltd Uses of porous carriers
US7497874B1 (en) 2001-02-23 2009-03-03 Biomet Manufacturing Corp. Knee joint prosthesis
US20020120340A1 (en) * 2001-02-23 2002-08-29 Metzger Robert G. Knee joint prosthesis
US6949251B2 (en) * 2001-03-02 2005-09-27 Stryker Corporation Porous β-tricalcium phosphate granules for regeneration of bone tissue
WO2002083194A1 (en) * 2001-04-12 2002-10-24 Therics, Inc. Method and apparatus for engineered regenerative biostructures
WO2003026714A1 (en) * 2001-09-24 2003-04-03 Millenium Biologix, Inc. Porous ceramic composite bone grafts
CA2521623C (en) * 2003-04-11 2015-03-17 Etex Corporation Osteoinductive bone material
US6993406B1 (en) * 2003-04-24 2006-01-31 Sandia Corporation Method for making a bio-compatible scaffold
US20050085922A1 (en) * 2003-10-17 2005-04-21 Shappley Ben R. Shaped filler for implantation into a bone void and methods of manufacture and use thereof
EP1742648A4 (en) * 2004-04-15 2009-03-04 Etex Corp Delayed-setting calcium phosphate pastes
US9220595B2 (en) 2004-06-23 2015-12-29 Orthovita, Inc. Shapeable bone graft substitute and instruments for delivery thereof
US8021392B2 (en) * 2004-11-22 2011-09-20 Minsurg International, Inc. Methods and surgical kits for minimally-invasive facet joint fusion
US20060111786A1 (en) * 2004-11-22 2006-05-25 Orthopedic Development Corporation Metallic prosthetic implant for use in minimally invasive acromio-clavicular shoulder joint hemi-arthroplasty
US20060111780A1 (en) * 2004-11-22 2006-05-25 Orthopedic Development Corporation Minimally invasive facet joint hemi-arthroplasty
US20060111779A1 (en) * 2004-11-22 2006-05-25 Orthopedic Development Corporation, A Florida Corporation Minimally invasive facet joint fusion
US8814567B2 (en) * 2005-05-26 2014-08-26 Zimmer Dental, Inc. Dental implant prosthetic device with improved osseointegration and esthetic features
JP5438967B2 (en) 2005-08-30 2014-03-12 ジマー デンタル, インコーポレイテッド Dental implant with improved osseointegration features
US8562346B2 (en) 2005-08-30 2013-10-22 Zimmer Dental, Inc. Dental implant for a jaw with reduced bone volume and improved osseointegration features
US8147860B2 (en) 2005-12-06 2012-04-03 Etex Corporation Porous calcium phosphate bone material
KR101417148B1 (en) * 2006-05-26 2014-07-08 백스터 인터내셔널 인코포레이티드 Injectable fibrin composition for bone augmentation
EP2040765A2 (en) 2006-06-29 2009-04-01 Orthovita, INC. Bioactive bone graft substitute
DE102006037067B4 (en) * 2006-08-08 2011-06-16 Metoxit Ag Method for producing an implant with a porous, ceramic surface layer
NL1032851C2 (en) * 2006-11-10 2008-05-14 Fondel Finance B V Kit and method for fixing a prosthesis or part thereof and / or filling bony defects.
US8163028B2 (en) 2007-01-10 2012-04-24 Biomet Manufacturing Corp. Knee joint prosthesis system and method for implantation
US8328873B2 (en) 2007-01-10 2012-12-11 Biomet Manufacturing Corp. Knee joint prosthesis system and method for implantation
US8562616B2 (en) 2007-10-10 2013-10-22 Biomet Manufacturing, Llc Knee joint prosthesis system and method for implantation
JP5448842B2 (en) 2007-01-10 2014-03-19 バイオメト マニファクチャリング コーポレイション Knee joint prosthesis system and implantation method
US8187280B2 (en) 2007-10-10 2012-05-29 Biomet Manufacturing Corp. Knee joint prosthesis system and method for implantation
US20090061003A1 (en) * 2007-03-28 2009-03-05 Doxa Ab Carriers for drug delivery
CA2686820C (en) * 2007-04-23 2016-06-28 Baxter International Inc. Fibrin compositions containing strontium compounds
EP2164535A4 (en) * 2007-06-07 2012-12-19 Smith & Nephew Inc Reticulated particle porous coating for medical implant use
EP2014259A1 (en) * 2007-07-09 2009-01-14 Astra Tech AB A bone tissue implant comprising lithium ions
EP2014319A1 (en) 2007-07-09 2009-01-14 Astra Tech AB A bone tissue implant comprising strontium ions
US9149345B2 (en) * 2007-08-30 2015-10-06 Zimmer Dental, Inc. Multiple root implant
WO2009072788A1 (en) * 2007-12-03 2009-06-11 Boo Rak Lee A implant consisting of ball and manufacturing method thereof
KR20100130178A (en) 2008-01-09 2010-12-10 이노베이티브 헬스 테크놀로지스, 엘엘씨 Implant pellets and methods for performing bone augmentation and preservation
US8899982B2 (en) 2008-07-02 2014-12-02 Zimmer Dental, Inc. Implant with structure for securing a porous portion
US8562348B2 (en) 2008-07-02 2013-10-22 Zimmer Dental, Inc. Modular implant with secured porous portion
US8231387B2 (en) 2008-07-02 2012-07-31 Zimmer, Inc. Porous implant with non-porous threads
US9095396B2 (en) 2008-07-02 2015-08-04 Zimmer Dental, Inc. Porous implant with non-porous threads
GB2461743A (en) * 2008-07-11 2010-01-20 Smith & Nephew Medical device or composition comprising at least two inorganic components
WO2010019788A1 (en) 2008-08-13 2010-02-18 Smed-Ta/Td. Llc Drug delivery implants
US20100042213A1 (en) * 2008-08-13 2010-02-18 Nebosky Paul S Drug delivery implants
US10842645B2 (en) 2008-08-13 2020-11-24 Smed-Ta/Td, Llc Orthopaedic implant with porous structural member
US9700431B2 (en) 2008-08-13 2017-07-11 Smed-Ta/Td, Llc Orthopaedic implant with porous structural member
CA2734183C (en) * 2008-08-13 2016-11-01 Smed-Ta/Td, Llc Orthopaedic implant with spatially varying porosity
US9616205B2 (en) 2008-08-13 2017-04-11 Smed-Ta/Td, Llc Drug delivery implants
WO2010025386A1 (en) * 2008-08-29 2010-03-04 Smed-Ta/Td, Llc Orthopaedic implant
US20100114314A1 (en) * 2008-11-06 2010-05-06 Matthew Lomicka Expandable bone implant
US8123815B2 (en) 2008-11-24 2012-02-28 Biomet Manufacturing Corp. Multiple bearing acetabular prosthesis
US9707058B2 (en) * 2009-07-10 2017-07-18 Zimmer Dental, Inc. Patient-specific implants with improved osseointegration
US8308810B2 (en) 2009-07-14 2012-11-13 Biomet Manufacturing Corp. Multiple bearing acetabular prosthesis
US9399086B2 (en) * 2009-07-24 2016-07-26 Warsaw Orthopedic, Inc Implantable medical devices
US8529933B2 (en) * 2009-07-27 2013-09-10 Warsaw Orthopedic, Inc. Biphasic calcium phosphate cement for drug delivery
GB0918484D0 (en) * 2009-10-22 2009-12-09 Depuy Int Ltd A medical implant device
US8602782B2 (en) 2009-11-24 2013-12-10 Zimmer Dental, Inc. Porous implant device with improved core
US20110151027A1 (en) * 2009-12-21 2011-06-23 Theodore D Clineff Strontium-doped calcium phosphate bone graft materials
US8673018B2 (en) * 2010-02-05 2014-03-18 AMx Tek LLC Methods of using water-soluble inorganic compounds for implants
US8444699B2 (en) * 2010-02-18 2013-05-21 Biomet Manufacturing Corp. Method and apparatus for augmenting bone defects
CN104922071A (en) 2010-04-09 2015-09-23 帕西拉制药有限公司 Method for formulating large diameter synthetic membrane vesicles
CA2798710C (en) 2010-05-11 2019-08-27 Venkat R. Garigapati Organophosphorous, multivalent metal compounds, & polymer adhesive interpenetrating network compositions & methods
US9050163B2 (en) 2011-03-21 2015-06-09 Endo Pharmaceuticals Inc. Urethral anastomosis device and method
WO2012158527A2 (en) 2011-05-13 2012-11-22 Howmedica Osteonics Organophosphorous & multivalent metal compound compositions & methods
US11225430B2 (en) 2012-03-26 2022-01-18 Steven Jung Bioactive glass scaffolds, and method of making
US9045362B2 (en) 2013-03-15 2015-06-02 Mosci Corp. Bioactive glass scaffolds, and method of making
US20140067082A1 (en) * 2012-09-06 2014-03-06 Xinyin Liu Bioresorbable ceramic composition for forming a three dimensional scaffold
EP2897532A1 (en) 2012-09-18 2015-07-29 Endo Pharmaceuticals Inc. Urethral anastomosis device
EP2967556A1 (en) 2013-03-14 2016-01-20 Endo Pharmaceuticals Inc. Urethral anastomosis device
US9681966B2 (en) 2013-03-15 2017-06-20 Smed-Ta/Td, Llc Method of manufacturing a tubular medical implant
US9408699B2 (en) 2013-03-15 2016-08-09 Smed-Ta/Td, Llc Removable augment for medical implant
US9724203B2 (en) 2013-03-15 2017-08-08 Smed-Ta/Td, Llc Porous tissue ingrowth structure
CN109336610B (en) * 2018-11-16 2020-08-25 南京工业大学 Silicon carbide porous ceramic and low-temperature firing method thereof
US20220009821A1 (en) * 2018-11-20 2022-01-13 Corning Incorporated Bioactive phosphate glasses

Family Cites Families (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1929425A (en) * 1930-07-14 1933-10-10 Earnest T Hermann Sound absorbing material and method of making the same
GB701802A (en) * 1951-01-25 1954-01-06 Robert Wyndham Young Improvements relating to the manufacture of bricks or blocks, slabs and the like
US3787900A (en) * 1971-06-09 1974-01-29 Univ Iowa State Res Found Artificial bone or tooth prosthesis material
US3929971A (en) * 1973-03-30 1975-12-30 Research Corp Porous biomaterials and method of making same
US3981736A (en) * 1973-05-23 1976-09-21 Ernst Leitz G.M.B.H. Biocompatible glass ceramic material
US3922155A (en) * 1973-05-23 1975-11-25 Leitz Ernst Gmbh Process of making biocompatible glass ceramic
US4135935A (en) * 1973-09-17 1979-01-23 Ernst Leitz Wetzlar Gmbh Sintered composite material, a process of making same, and a method of using same
US4207306A (en) * 1974-08-02 1980-06-10 Sterling Drug Inc. Process for producing polycrystalline ceramic oxides
CH595293A5 (en) * 1975-02-20 1978-02-15 Battelle Memorial Institute
JPS5264199A (en) * 1975-11-21 1977-05-27 Tokyo Ika Shika Daigakuchiyou Artificial bone and dental root with sintered apatite and method of producing same
AT352867B (en) * 1976-05-12 1979-10-10 Battelle Institut E V BONE REPLACEMENT, BONE COMPOUND OR PROSTHESIS ANCHORING MATERIAL AND PROCESS FOR ITS PRODUCTION
US4149894A (en) * 1976-06-02 1979-04-17 Asahi Kogaku Kogyo Kabushiki Kaisha Process for producing an apatite powder having improved sinterability
JPS6050743B2 (en) * 1976-06-02 1985-11-09 旭光学工業株式会社 Apatite sintered body and its manufacturing method
US4097935A (en) * 1976-07-21 1978-07-04 Sterling Drug Inc. Hydroxylapatite ceramic
US4218255A (en) * 1976-08-30 1980-08-19 University Of Dayton Porous ceramic carriers for controlled release of proteins, polypeptide hormones, and other substances within human and/or other mamillian species and method
US4103002A (en) * 1977-02-08 1978-07-25 Board Of Regents, University Of Florida Bioglass coated A1203 ceramics
JPS53144194A (en) * 1977-05-20 1978-12-15 Kureha Chemical Ind Co Ltd Compound implanted material and making method thereof
US4156943A (en) * 1977-08-24 1979-06-05 Collier John P High-strength porous prosthetic device and process for making the same
JPS5550349A (en) * 1978-10-09 1980-04-12 Kureha Chemical Ind Co Ltd Dental compound material
US4308064A (en) * 1978-10-19 1981-12-29 Ngk Spark Plugs Co., Ltd. Phosphate of calcium ceramics
JPS5645814A (en) * 1979-09-25 1981-04-25 Kureha Chem Ind Co Ltd Hydroxyapatite, its ceramic material and its manufacture
JPS577856A (en) * 1980-06-13 1982-01-16 Mitsubishi Mining & Cement Co Manufacture of calcium phosphate porous body
US4518430A (en) * 1982-04-29 1985-05-21 American Dental Association Health Foundation Dental resptorative cement pastes
US4503157A (en) * 1982-09-25 1985-03-05 Ina Seito Co., Ltd. Sintered apatite bodies and composites thereof
US4475892A (en) * 1982-10-13 1984-10-09 Jaff Investment Company Microcellular ceramic material and process for manufacture thereof
US4576922A (en) * 1983-01-05 1986-03-18 The Regents Of The University Of Michigan High expansion dental crown core ceramic composition
US4542167A (en) * 1984-05-01 1985-09-17 Hideki Aoki Dental cement composition comprising hydroxyapatite and acrylic acid/itaconic acid copolymer hardener
EP0161578A3 (en) * 1984-05-02 1987-11-19 Rutgers, The State University Glass coated ceramic particles
DE3445731A1 (en) * 1984-12-14 1986-06-19 Klaus Dr.med. Dr.med.habil. 8000 München Draenert Material and use thereof
US4604097A (en) * 1985-02-19 1986-08-05 University Of Dayton Bioabsorbable glass fibers for use in the reinforcement of bioabsorbable polymers for bone fixation devices and artificial ligaments
US4693986A (en) * 1985-06-25 1987-09-15 Orthomatrix, Inc. Ceramic process and products

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