EP0514401A1 - Composition vitree bioactive destinee aux implants osseux, filaments formes a partir de celle-ci et methode - Google Patents

Composition vitree bioactive destinee aux implants osseux, filaments formes a partir de celle-ci et methode

Info

Publication number
EP0514401A1
EP0514401A1 EP91902954A EP91902954A EP0514401A1 EP 0514401 A1 EP0514401 A1 EP 0514401A1 EP 91902954 A EP91902954 A EP 91902954A EP 91902954 A EP91902954 A EP 91902954A EP 0514401 A1 EP0514401 A1 EP 0514401A1
Authority
EP
European Patent Office
Prior art keywords
filaments
bone
vitreous
vitreous composition
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP91902954A
Other languages
German (de)
English (en)
Inventor
Emilio Vita Finzi Zalman
Bruno Locardi
Carlo Gabbi
Paolo Tranquilli Leali
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Seipi Esportazione Importazione Prodotti Industriali SpA Soc
Original Assignee
Seipi Esportazione Importazione Prodotti Industriali SpA Soc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Seipi Esportazione Importazione Prodotti Industriali SpA Soc filed Critical Seipi Esportazione Importazione Prodotti Industriali SpA Soc
Publication of EP0514401A1 publication Critical patent/EP0514401A1/fr
Withdrawn legal-status Critical Current

Links

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
    • A61L27/02—Inorganic materials
    • A61L27/12—Phosphorus-containing materials, e.g. apatite
    • 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
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
    • A61L27/32—Phosphorus-containing materials, e.g. apatite
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL 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
    • C03C4/00—Compositions for glass with special properties
    • C03C4/0007—Compositions for glass with special properties for biologically-compatible glass
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS 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
    • A61F2/00—Filters 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
    • A61F2/02—Prostheses implantable into the body
    • A61F2/28—Bones
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS 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
    • A61F2310/00—Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
    • A61F2310/00005—The prosthesis being constructed from a particular material
    • A61F2310/00179—Ceramics or ceramic-like structures
    • A61F2310/00293—Ceramics or ceramic-like structures containing a phosphorus-containing compound, e.g. apatite
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS 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
    • A61F2310/00—Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
    • A61F2310/00389—The prosthesis being coated or covered with a particular material
    • A61F2310/00592—Coating or prosthesis-covering structure made of ceramics or of ceramic-like compounds
    • A61F2310/00796—Coating or prosthesis-covering structure made of a phosphorus-containing compound, e.g. hydroxy(l)apatite
    • 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
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

Definitions

  • the present invention relates to so-called bio- active vitreous compositions or glasses for bone implantation according to the preamble of Claim 1.
  • these known glasses are also biodegradable by means of an inter- action mechanism which is explained below.
  • a glass of the type in question When a glass of the type in question is put into contact with the interstitial liquids of a human or animal body, it creates a gel having an ionic composi ⁇ tion similar to that of the ossification front observed in the natural bone-remodelling process.
  • the gel thus formed is recognized by the osteoblasts as a substrate for the deposition of an osteoid matrix.
  • the inter ⁇ action between the collagen fibrils, the mucopoly- saccharides of the matrix and the gel is characterised by the precipitation of hydroxylapatite crystals which enable a stable bond to be formed between the glass and the newly-added bone matrix.
  • the glass implant In many cases, it is desirable for the glass implant to degrade until it disappears completely as the bone gradually reforms and/or is remodelled to leave room for the latter.
  • the particles Because of the non-uniform sizes of the particles, most of the smallest particles are reabsorbed completely during the bone reconstitution process, whilst the largest particles are not reabsorbed or degraded and cause undesirable vitreous inclusions in the reconstituted bone. constituting corresponding discontinuities.
  • the random arrangement of the particles of different sizes encourages the bone fibres to grow in a similarly random arrangement when for the purposes of the mechanical strength of the bone, it is desirable for the fibres to be reconstituted in a regular arrangement.
  • the use of a powder in a prosthetic implant is even dangerous since, on the one hand, the blood can form a kind of mixture with the powder which constitutes a barrier against the growth of bone and, on the other hand, the powder particles may be entrained in the bloodstream and form thromboses.
  • the problem behind the present invention, in the first place, is that of providing a glass which can be used to produce bone implants without the a orementioned disadvantages.
  • the invention also relates to filaments or fibres obtained by the drawing of said vitreous composition, to products obtained from said filaments, and to a method for the production of said filaments.
  • Al 0 have the property of preventing a vitreous . composition from ceramising, by keeping it in an amorphous condition when it is drawn into a filament. The amorphous condition then persists during the life of the filament.
  • K 0 in a bioactive vitreous composition is beneficial as regards bioactivity.
  • K 0 also constitutes an advantageous substitute for Na 0 in implants destined to patients suffering, or liable to suffer from hypertension.
  • vitreous composition including proportions of K C.0 and Al.0_i within the claimed ranges performs well under both aspects of fully preventing ceramising- of the drawn filaments and fully preserving their affinity to the bone tissues.
  • FR-A-2 243 915 GB-A-2 080 281, DE-A-3 248 649 and EP-A-0 145 210 all disclose bioactive vitreous composi- tions containing K 0 in indeterminate percentages from zero (from 0.4% in ' FR-A-2 243 915) to 20%. Such documents do not teach the use of K 0 as an anti- ceramising agent.
  • GB-A-2 080 281 and US-A 4 708 652 both disclose bioactive vitreous compositions containing indeterminate amounts from zero to _,- __ .— - Nb_0_. The percentage of A1_0_ is not specified.
  • Al 0 ZrO and Nb_0_ are described in such ⁇ , __ 2 5 documents as reaction controllers in respect of bio- activity.
  • Al 0 , ZrO and Nb 0 are known to be inhibitors in respect of bioactivity.
  • the compositions disclosed by GB-A-2 080 281 and US-A-4 708 652, and containing Al 0 in indetermin ⁇ ate amounts, are mainly of the ceramic type. In other words, such documents do not teach the use of Al 0 as an anti-ceramising agent.
  • filaments or fibres even with diameters of the order of 10-50 microns.
  • products such as bundles of fibres, fabrics. particularly gauzes and nets, felts. and "cotton-wools" as well as particulate products made of shredded filaments and powders made by grinding of the filaments.
  • a bundle of filaments or fibres of a vitreous composition as claimed can be used as an implant by being inserted in a bone defect with the filaments oriented in the direction in which it is envisaged that the bone fibres will grow. thus encouraging their regular development to the benefit of the mechanical strength of the reformed bone.
  • the small diameters of the filaments or fibres ensure that they are completely degraded, that is, that they are completely replaced by. the bone tissue as it is gradually reformed and remodelled.
  • the fabrics, particularly the nets and gauzes, as well as the felts and "cotton-wools" produced from the glass filaments of the invention behave in the same way as the ' bundles of ibres as regards degradation but enable the growth of bone in several preferred direc- tions to be planned.
  • a net or a gauze can encourage the bone tissue to form a network similar to that of the original bone tissue.
  • the filaments of the vitreous composition accord ⁇ ing to the invention can be broken into pieces or small cylinders whose lengths are of the same order of magnitude as their diameters.
  • cylinders can be produced with diameters and lengths of the order of twenty microns.
  • a particulate product thus obtained can be implanted as it is by the same technique as that by which the prior-art ground glasses were implanted but with the difference that the bone defect is filled with uniformly sized particles, ensuring the degradation of the implant and its complete replacement by bone tissue over a period of time.
  • this application is justified only if there is no danger of the formation of clots with the blood and/or of the entrainment of the powder particles by the blood.
  • a particulate material of the vitreous composition according to the invention is intended to be applied as an at least partial coating, for example, by the "plasma spray” technique, to a permanent prosthesis, for example of titanium, to improve its anchorage to the surrounding bone by virtue of the progressive, and .finally complete, replacement of the coating by bone tissue.
  • a permanent prosthesis for example of titanium
  • uniform and homogenous coatings are produced because of the uniform dimensions of the glass particles. This was impossible with known biocompatible glass powders, partly because of their non-uniform particle size but particularly because these known glasses became ceramic if they were applied by spraying at the high tem ⁇ peratures of the "plasma spray" process.
  • Glass filaments or fibres, as well as fabrics produced from these fibres, are known from the document FR-A-2 548 658 and include calcium phosphate as the main constituent and not less than 80% by weight of Ca0+P 0_,
  • •_. b possibly with the addition of an inorganic oxide selected from alumina, silica, sodium oxide, iron oxide, magnesium oxide, kaolin and mixtures thereof.
  • these glass fibres are not biodegradable so that fabrics made of these fibres remain incorporated permanently in the reformed bone tissue.
  • This composition is characterised essentially in that it has the following constituents in percentages by weight: Si0 50%; P 0 6%; CaO 16%; Na 0 20%; K 0 5%; MgO 1%; 2 2 5 2. ⁇ A1 2 0 3 2%.
  • compositions are reduced to filaments by melting them in a crucible provided with a die at the bottom and drawing the molten composition through the die.
  • the crucible is of substantially pure titanium.
  • Composition I can be drawn into filaments very easily but within a fairly narrow temperature range of between about 900°C and 1050°C, in which the vitreous mass is very fluid. The only problem, therefore, is that the temperature of the fusion bath must be controlled very precisely.
  • composition II the presence of B ._-0 widens the temperature range within which the composition can be drawn into filaments without becoming ceramic to between 800°C and 1050°C. Within this temperature range, however, the vitreous mass is yet more fluid than composition I so that the drawing rate must be controlled precisely. At least traces of calcium fluoride and/or calcium fluorophosphate may be added to the compositions in small proportions to catalyse certain biological proces ⁇ ses. Compositions including these fluorides are particularly suitable for making implants for dental surgery.
  • Tests have been carried out in vivo on rats and rabbits, using compositions I and II both in fibre and powder form, according to an experimental protocol which provided for the insertion of the fibres and the powders in the marrow cavity of the tibia of each animal.
  • optical micro ⁇ scopic examination of the specimens obtained revealed that they had cells with bas ⁇ philous cytoplasm which adhered to the surfaces of the fibres and the particles and were starting to produce a bony matrix. Inter alia, this confirmed an absence of rejection.
  • both the fibres and the particulate material appeared to be completely surrounded by a bony matrix without the interposition of a connective membrane or capsule between the vitreous composition and the biological substrate. Moreover, some cells similar in appearance to primary bone cells appeared to be incorporated in the matrix near the vitreous composition. This confirmed the absence of a barrier which could arrest the growth of bone between the vitreous composition and the biological substrate.
  • the cortical bone defect was complete ⁇ ly filled with newly-formed bone.
  • the fibres of the vitreous composition incorporated in the bony matrix retained their individuality and appeared circular in histological sections taken in planes perpendicular to the major axes of the fibres and rectangular in histological sections taken in planes parallel to the major axes of the fibres.
  • the particles of the vitreous composition formed aggregations with irregular profiles which, nevertheless, were incorporated in the bony matrix without the interposition of connective mem ⁇ branes.
  • the vitreous material which had not come into contact with the osteogenic bone cells appeared to be surrounded by an inflammatory infiltrate constituted mainly by neutrophllous polymorphonucleates and giant multinucleate cells.
  • the presence of the inflammatory infiltrate was evidence of a favourable intensification of the blood circulation.
  • the experiments carried out appear to have demonstrated their osteoconductive properties, documented histo- logically by fact that the material was incorporated in the bony matrix without the interposition of connective tissue, provided that a sufficient number of cells differentiated towards osteogenic activity were present at the site of the implant.
  • the fibres and particles of the vitreous composition inserted in the cortical bone defect both showed this property.
  • the fibres when these were bathed in blood, they formed a three-dimensional network or "felt" which defined empty spaces between the fibres so that, as a whole, they offered an extensive surface for the attachment of osteogenic cells.
  • the particles of the vitreous composition of the invention formed compact aggregations upon contact with the blood and only the outer surface was available for bonding.
  • the chemical surface characteristics of the two forms of the composition that is, the fibres and the particles, are identical, their biological responses can vary according to their physical properties such as their shape and size.
  • the fibres were more easily manipulated than the particles and were more evenly distribued in the bone defect.
  • the presence of the siliceous residue in the bony matrix did not appear to interfere with the bone remodelling process so that, in the inspections made at 4 months, resorption lacunae were already observed in the region of the cortical defect which by that time was completely repaired.
  • the osteoclasts appear to cause the resorption of the matrix but do not seem to attack the fibres of the particles incorporated therein so that, when the whole of the matrix which surrounds it has been reabsorbed, the vitreous composition is, in the lacunae, in contact with the vasal and cellular components.
  • the histological appearance of the fibres at this stage showed fragmentation, suggesting that the process of dissolution of the vitreous composition was progressing and that the fragmen ⁇ ts were being absorbed by giant polynucleate cells.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Transplantation (AREA)
  • Epidemiology (AREA)
  • Dermatology (AREA)
  • Animal Behavior & Ethology (AREA)
  • Inorganic Chemistry (AREA)
  • Public Health (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Molecular Biology (AREA)
  • Materials For Medical Uses (AREA)

Abstract

L'invention se rapporte à une composition vitrée bioactive destinée aux implantations osseuses comprenant les pourcentages en poids approximatifs des oxydes suivants: SiO2 de 40 to 55 %; P2O5 de 5 à 8 %, Cao (MgO) de 20 à 40 %; Na2 (K2O) de 20 à 30 %. La composition peut être réduite en filaments sans devenir céramique par adjonction d'un total ne dépassant pas 9 % en poids de K2O et Al2O3, le pourcentage de Al2O3 étant de 0,5 % à 2,5 %. Les filaments ainsi obtenus peuvent être utilisés pour la préparation de produits d'implantations osseuses sous forme de faisceaux de filaments, de gaze, de filets ou autres tissus, des feutres, des cotons hydrophiles et similaires, On peut réduire les filaments en particules de poudre pour application, entre autres, d'une couche de recouvrement de la composition vitrée sur une prothèse métallique permanente.
EP91902954A 1990-02-08 1991-02-04 Composition vitree bioactive destinee aux implants osseux, filaments formes a partir de celle-ci et methode Withdrawn EP0514401A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT67096A IT1240938B (it) 1990-02-08 1990-02-08 Composizione vetrosa bioattiva per impianti ossei e prodotti ottenuti con tale composizione o che la comprendono
IT6709690 1990-02-08

Publications (1)

Publication Number Publication Date
EP0514401A1 true EP0514401A1 (fr) 1992-11-25

Family

ID=11299541

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91902954A Withdrawn EP0514401A1 (fr) 1990-02-08 1991-02-04 Composition vitree bioactive destinee aux implants osseux, filaments formes a partir de celle-ci et methode

Country Status (10)

Country Link
EP (1) EP0514401A1 (fr)
JP (1) JPH05502603A (fr)
KR (1) KR950008173B1 (fr)
AU (1) AU639981B2 (fr)
BR (1) BR9106030A (fr)
CA (1) CA2075281A1 (fr)
FI (1) FI923561A0 (fr)
HU (1) HUT61899A (fr)
IT (1) IT1240938B (fr)
WO (1) WO1991012032A1 (fr)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2682968B1 (fr) * 1991-10-28 1994-08-26 Icmc Procede de realisation d'un implant osseux, dispositif permettant de mettre en óoeuvre le procede et implant ainsi realise.
WO1993017976A1 (fr) * 1992-03-09 1993-09-16 Turku Implant Team Oy Verre bioactif utilise comme substitut osseux
US5468544A (en) * 1993-11-15 1995-11-21 The Trustees Of The University Of Pennsylvania Composite materials using bone bioactive glass and ceramic fibers
US6121172A (en) * 1993-11-15 2000-09-19 The Trustees Of The University Of Pennsylvania Composite materials using bone bioactive glass and ceramic fibers
FI101129B (sv) * 1995-01-13 1998-04-30 Vivoxid Oy Nya bioaktiva glas och deras användning
FI110063B (fi) 1998-12-11 2002-11-29 Antti Yli-Urpo Uusi bioaktiivinen tuote ja sen käyttö
FI117963B (fi) 2001-04-26 2007-05-15 Eija Marjut Pirhonen Luuta korvaavat materiaalit
CN101454028B (zh) 2006-05-26 2014-06-04 巴克斯特国际公司 用于骨质增加的可注射纤维蛋白组合物
DE602006011323D1 (de) 2006-09-20 2010-02-04 Inion Oy Bioaktive Glaszusammensetzungen
CA2686820C (fr) 2007-04-23 2016-06-28 Baxter International Inc. Compositions de fibrine contenant des composes de strontium
US10751367B2 (en) 2016-05-27 2020-08-25 Corning Incorporated Bioactive glass microspheres
US20170342383A1 (en) 2016-05-27 2017-11-30 Corning Incorporated Lithium disilicate glass-ceramic compositions and methods thereof
CN111417603B (zh) 2017-11-28 2023-10-31 康宁股份有限公司 生物活性硼酸盐玻璃及其方法
EP3717030A1 (fr) 2017-11-28 2020-10-07 Corning Incorporated Compositions de verre bioactif et restauration de l'hypersensibilité de la dentine
CN111433165A (zh) 2017-11-28 2020-07-17 康宁股份有限公司 高液相线粘度生物活性玻璃
TWI794344B (zh) 2017-11-28 2023-03-01 美商康寧公司 經化學強化之生物活性玻璃陶瓷
CN113905993A (zh) * 2019-05-22 2022-01-07 康宁股份有限公司 生物活性玻璃组合物

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GB1477899A (en) * 1973-09-17 1977-06-29 Leitz Ernst Gmbh Manufacture of therapeutically useful composite materials
JPS573739A (en) * 1980-06-11 1982-01-09 Nippon Kogaku Kk <Nikon> Bioactive glass and glass ceramic
JPS58118746A (ja) * 1982-01-07 1983-07-14 株式会社ニコン 歯科用インプラント及びその製造方法
CA1229354A (fr) * 1984-03-01 1987-11-17 David C. Greenspan Verres a vocation biologique pour liaisonnement sur alliages
JPS60186455A (ja) * 1984-03-06 1985-09-21 株式会社ニコン アパタイトコンポジツトセラミクス
US4960733A (en) * 1987-02-28 1990-10-02 Hoya Corporation Inorganic biomaterial and process for producing the same
JPH02149447A (ja) * 1988-12-01 1990-06-08 Nippon Electric Glass Co Ltd 歯科用結晶化ガラス

Non-Patent Citations (1)

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Title
See references of WO9112032A1 *

Also Published As

Publication number Publication date
BR9106030A (pt) 1993-03-02
FI923561A (fi) 1992-08-07
JPH05502603A (ja) 1993-05-13
IT9067096A1 (it) 1991-08-08
FI923561A0 (fi) 1992-08-07
CA2075281A1 (fr) 1991-08-09
HUT61899A (en) 1993-03-29
AU7149191A (en) 1991-09-03
IT9067096A0 (it) 1990-02-08
AU639981B2 (en) 1993-08-12
WO1991012032A1 (fr) 1991-08-22
IT1240938B (it) 1993-12-27
KR950008173B1 (ko) 1995-07-26

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