AU639981B2 - Bioactive vitreous composition for bone implants, filaments made therefrom and method - Google Patents
Bioactive vitreous composition for bone implants, filaments made therefrom and method Download PDFInfo
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- AU639981B2 AU639981B2 AU71491/91A AU7149191A AU639981B2 AU 639981 B2 AU639981 B2 AU 639981B2 AU 71491/91 A AU71491/91 A AU 71491/91A AU 7149191 A AU7149191 A AU 7149191A AU 639981 B2 AU639981 B2 AU 639981B2
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- 239000000203 mixture Substances 0.000 title claims description 67
- 210000000988 bone and bone Anatomy 0.000 title claims description 46
- 239000007943 implant Substances 0.000 title claims description 13
- 238000000034 method Methods 0.000 title claims description 13
- 230000000975 bioactive effect Effects 0.000 title claims description 9
- 239000000470 constituent Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 230000007547 defect Effects 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004744 fabric Substances 0.000 claims description 5
- 230000004927 fusion Effects 0.000 claims description 5
- 238000002513 implantation Methods 0.000 claims description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 229920000742 Cotton Polymers 0.000 claims description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- GFIKIVSYJDVOOZ-UHFFFAOYSA-L calcium;fluoro-dioxido-oxo-$l^{5}-phosphane Chemical compound [Ca+2].[O-]P([O-])(F)=O GFIKIVSYJDVOOZ-UHFFFAOYSA-L 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims 2
- 241000511976 Hoya Species 0.000 claims 1
- 239000000560 biocompatible material Substances 0.000 claims 1
- 239000011247 coating layer Substances 0.000 claims 1
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 claims 1
- 239000010410 layer Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 230000003019 stabilising effect Effects 0.000 claims 1
- 239000002245 particle Substances 0.000 description 21
- 239000011521 glass Substances 0.000 description 17
- 239000011159 matrix material Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 6
- 238000007689 inspection Methods 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 5
- 238000004220 aggregation Methods 0.000 description 5
- 239000008280 blood Substances 0.000 description 5
- 210000004369 blood Anatomy 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 241001465754 Metazoa Species 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000001054 cortical effect Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000008512 biological response Effects 0.000 description 2
- 210000002449 bone cell Anatomy 0.000 description 2
- 230000010072 bone remodeling Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 2
- 230000002757 inflammatory effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 210000000963 osteoblast Anatomy 0.000 description 2
- 210000005009 osteogenic cell Anatomy 0.000 description 2
- 230000002188 osteogenic effect Effects 0.000 description 2
- 239000011236 particulate material Substances 0.000 description 2
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 210000002303 tibia Anatomy 0.000 description 2
- UOTMYNBWXDUBNX-UHFFFAOYSA-N 1-[(3,4-dimethoxyphenyl)methyl]-6,7-dimethoxyisoquinolin-2-ium;chloride Chemical compound Cl.C1=C(OC)C(OC)=CC=C1CC1=NC=CC2=CC(OC)=C(OC)C=C12 UOTMYNBWXDUBNX-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 229920002683 Glycosaminoglycan Polymers 0.000 description 1
- 206010020772 Hypertension Diseases 0.000 description 1
- 241001484259 Lacuna Species 0.000 description 1
- 241000283973 Oryctolagus cuniculus Species 0.000 description 1
- 208000006735 Periostitis Diseases 0.000 description 1
- 241000700159 Rattus Species 0.000 description 1
- 208000007536 Thrombosis Diseases 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000004125 X-ray microanalysis Methods 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000005313 bioactive glass Substances 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 230000017531 blood circulation Effects 0.000 description 1
- 210000002805 bone matrix Anatomy 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 210000002808 connective tissue Anatomy 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 210000000805 cytoplasm Anatomy 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000005337 ground glass Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000011164 ossification Effects 0.000 description 1
- 210000002997 osteoclast Anatomy 0.000 description 1
- 230000000278 osteoconductive effect Effects 0.000 description 1
- 210000003460 periosteum Anatomy 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
Landscapes
- 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)
Description
I L-
'I-
WO91/12032 PCT/EP91/00201 1 BIOACTIVE VITREOUS COMPOSITION FOR BONE IMPLANTS.
FILAMENTS MADE THEREFROM AND METHOD The present invention relates to so-called bioactive vitreous compositions or glasses for bone implantation according to the preamble of Claim 1.
Glasses of this kind have been the subject of investigations since the '70s and are described by Larry L. Hench in an article entitled 'Ceramic Implants for Humans" in ADVANCED CERAMIC MATERIALS, Vol. 1, No. 4, 1986. pp. 306-310 and 324.
Examples of such known glasses may be found in the following patent documents: FR-A-2 243 915; US..A-4 159 358: US-A-4 171 544; US-A-4 234 972; GB-A-2 080 281; DE-A-3 248 649; EP-A-0 145 210; EP-A-O 154 513.
As well as being biocompatible, these known glasses are also biodegradable by means of an interaction mechanism which is explained below.
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 composition 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 interaction between the collagen fibrils, the mucopolysaccharides 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
I
r W091/12032 PCT/EP91/00201 2 the newly-added bone matrix.
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.
From experiments carried out, it has been found that, with the known bioactive glasses specified above.
this does not take place completely. These glasses.
cannot be reduced to filaments by being drawn through a die starting from a bath of fused glass, that is, if one tries to draw them. they become ceramic at the output of the die and give rise to a fragile product whose properties are quite different from those required-for a biodegradable glass filament or fibre.
For this reason, the only way to use these known glasses for prosthetic implants is to grind them to produce a powder. In most applications the bone defects are packed with this powder which is made into a paste with a binder. The particles of the powder are far from uniform in size, however, and are irregular in shape with dimensions ranging from a few microns to several hundreds of microns. 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 1 WO 91/12032 PCT/EP91/00201 purposes of the mechanical strength of the bone, it is desirable for the fibres to be reconstituted in a regular arrangement.
In certain applications, 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 aforementioned disadvantages.
According to the present invention, this problem is resolved by means of a vitreous composition substan tially as defined in the characterising part of Claim 1.
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.
It has been found experimentally that both K 0 and 2 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. I The amorphous condition then persists during the life of the filament.
The presence of K 0 in a bioactive vitreous composition is beneficial as- regards bioactivity. In this regard K 0 also constitutes an advantageous 2 substitute for Na 0 in implants destined to patients -1- WO 91/12032 PCT/EP91/00201 4 suffering, or liable to suffer from hypertension.
However, increasing amounts of K 0 have the property of rerdering a vitreous composition more and more soluble in water. This means that a vitreous composition containing a too high percentage of K20 will soften or even be converted to a gel if it is kept under normal ambient conditions, due to hydrolysis of K20 by interaction with atmospheric humidity. Thus, filaments of vitreous compositions having a too high percentage of K20 could be stored' and handled, e.g. woven, only in a 2 perf tly dry atmosphere, but this would be quite impractical from an industrial point of view.
The undesirable effects of K20 can be successfully mitigated by the addition of Al 203 to the vitreous 23 composition. However, increasing amounts of Al203 have the drawback of lessening the reactivity of the composition, i.e. its affinity to bone tissues.
It has been found that a vitreous composition including proportions of K20 and Al203 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 compositions containing K 2 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 K20 as an anticeramising agent. GB-A-2 080 281 and US-A 4 708 652 both disclose bioactive vitreous compositions containing indeterminate amounts from zero to 8% of AL203+ZrO 2 3 2 -r
WO
~V yll ISu3 PCT/EP91/00201 Nb 20 The percentage of Al 20 is not specified. On the one hand, Al 03 ZrO 2 and Nb 05 are described in such 23, 2 25 documents as reaction controllers in respect of bioactivity. On the other hand, Al203, ZrO 2 and Nb205 are known to be inhibitors in respect of bioactivity.
Further, the compositions disclosed by GB-A-2 080 281 and US-A-4 708 652, and containing Al203 in indeterminate amounts, are mainly of the ceramic type. In other words, such documents do not teach the use of Al 03 as an anti-ceramising agent.
According to the invention it is possible to produce filaments or fibres even with diameters of the order of 10-50 microns. From such filaments or fibres -one may obtain 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 fi'aments 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
-II
WO 91/12032 PCT/EP91/00201 I'-6 well as the felts and "cotton-wools" produced from the glass filaments of the invention behave in the same way as the bundles of fibres as regards degradation but enable the growth of bone in several preferred directions to be planned. Thus, a net or a gauze can encourage the bone tissue to form a network similar to that of the original bone tissue.
Nets and gauzes can be used in the form of bandages for binding the broken region of a bone.
The filaments of the vitreous composition according to the invention can be broken into pieces or small cylinders whose lengths are of the same order of magnitude as their diameters. For example, cylinders can be produced with diameters and lengths of the order of twenty microns.
A particulate product thus obtained, possibly made into a paste with a binder, 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.
Naturally, 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.
Preferably, however, 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 WO 91/12032 PCT/EP91/00201 7permanent 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. In this application, 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 temperatures 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 CaO+P 02, possibly with the addition of an inorganic oxide selected from alumina, silica, sodium oxide, iron oxide, magnesium oxide, kaolin and mixtures thereof.
Although they are wholly biocompatible and "recognised" as hydroxylapatite by the osteoblasts, these glass fibres are not biodegradable so that fabrics made of these fibres remain incorporated permanently in the reformed bone tissue.
The following are two currently preferred vitreous compositions according to the invention.
Composition I This composition is characterised essentially in that it has the following constituents in percentages by weight: SiO 50%; P05 CaO 16%; Na 0 20%; K20 MgO 1%; 2 2 5 2 2 2 Mg0 1%; a
I-
T
8 A1 2 0 2%.
Comoosition II This composition is characterised essentially in that it includes the following constituents in percentages by weight: SiO 2 50%; P205 CaO 16%; Na20 15%; K20 MgO 1%; Al 20 B203 Tolerances of 7% a- the percentage by weight of each constituent are permitted for both compositions.
From a biological point of view, the behaviour of both compositions is the same.
The 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. Preferably, to avoid the inclusion of impurities into the bath and the filaments, the crucible is of substantially pure platinum.
Composition I can be drawn into filaments very easily but within a fairly narrow temperature range of between about 9000C and 1050 0 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.
In composition II, the presence of B03 widens the temperature range within which the composition can be drawn into filaments without becoming ceramic to between 80000 and 10500C. Within this temperature range, however, the vitreous mass is yet more fluid than composition" I so that the drawing rate must be A 30 controlled precisely.
W0 91/12032 PCT/EP91/0020 9 At least traces of calcium fluoride and/or calcium fluorophosphate may be added to the compositions in small proportions to catalyse certain biological processes. 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.
After periods varying from 10 days to 7 months, the portions of bone concerned in the test were removed from animals which had been killed and were then prepared for examination by optical microscope or electron scanning microscope and for X-ray microanalysis.
In the inspections after 10 days, optical microscopic examination of the specimens obtained revealed that they had cells with basophilous 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.
In subsequent inspections at 20 and 30 days, 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 WO 91/12032 PCT!EP91/00201 10 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.
At 30 days, the cortical bone defect was completely 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.
Still at 30 days, the particles of the vitreous composition formed aggregations with irregular profiles which, nevertheless, were incorporated in the bony matrix without the interposition of connective membranes.
In the sections of the tibiae examined at subsequent time intervals (from 2 to 7 months) no changes were observed in the vitreous compositions as long as they remained incorporated in the bony matrix.
As a result of the remodelling of the bone, the inspections at 4, 5, 6 and 7 months showed resorption lacunae which extended to the bone surro i.iding the implanted material and exposed its surface. These lacunae constituted a similar number of regions which, as is desirable, were susceptible to vascularisation.
The inspections made at the same time intervals showed that the aggregations of particles of the vitreous composition and the fibres released from the bony matrix WO 91/12032 PCT/EP91/00201 11 appeared irregular and broken and were absorbed progressively by giant multinucleate cells, that is, they were progressively removed from the matrix.
The vitreous material which had not come into contact with the osteogenic bone cells, for example, the material which had migrated out of the periosteum, appeared to be surrounded by an inflammatory infiltrate constituted mainly by neutrophilous polymorphonucleates and giant multinucleate cells. The presence of the inflammatory infiltrate was evidence of a favourable intensification of the blood circulation.
As well as confirming the surface characteristics of the vitreous compositions according to the invention, the experiments carried out appear to have demonstrated their osteoconductive properties, documented histologically by fact that the material was incorporated in the bony matrix without the interposition of connective tissue, provided that a sufficient number of cf-1s differentiated towards osteogenic activity were presst at the site of the imp.ant. The fibres and particles of the vitreous composition inc- 'ted ir the cortical bone defect both showed this property. In the case of 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, however, formed compact aggregations upon contact with the blood and only the outer surface was available for bonding. Thus, althoug., WO 91/12032 PCT/EP91/00201 12 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 ph.ysical properties such as their shape and size. In general, in the experiments, the fibres were more easily manipulated than the particles and were more evenly distribued in the bone defect.
In the experiments carried out, it was observed that, once they were incorporated in the bony matrix, the fibres or the aggregations of particles of the vitreous compositions of the invention showed no further changes in the inspections up to 7 months and did not cause any cell reaction. This can be attributed to the fact that the incorporated material was no longer j-.
contact with the interstitial liquids, or at any rate that the interstitial circulation in the bone was not sufficient to trigger a significant degradation process.
The presence of the siliceous residue in the bony matrix did not appear to interfere wit- 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 WO 91/12032 PCT/EP91/00201 13 process of dissolution of the vitreous composition was progressing and that the fragments were being absorbed by giant polynucleate cells.
Since the remodelling of the bone consists of successive resorption and addition, the dissolution of the vitreous composition or its reincorporation in the newly-added matrix would seem to be affected by two factors: 1) the number of osteogenic cells available in the lacuna; 2) the shape and size of the vitreous material: in fact, whilst the fibres showed generalised dissolution, the aggregations of several particles also had surfaces with newly-added material.
These results -appear to confirm that, as well as being affected by the chemical characteristics of the material, the nature of the biological response is also affected by the shapes and sizes of the fibres and particles and, in particular, that the uniformity of their dimensions is beneficial.
S. h l(
Claims (14)
1. A bioactive vitreous composition for bone implant- ation, including the following appreximato percentages by weight of the following oxides: SiO, from 40 to P205 from 4 to CaO (MgO) from 20 to 40%; Na 0 and/or K 0 up to characterised in that it includes as anti-ceramising oxides a global percentage by weight between 2% and 9% of K 0 and Al 03, the percentage of Al 0 being from 2 23' 2 3-- to whereby the composition can be drawn into filaments or fibres from a fusion bath. A -vitreous f ee-fR t a cha acterised in that it has the following constituents. in perentages by weight: SiO 2 50%; P205 CaO 16%: Na 0 20%' K 0 MgO Al 0 with tolgerances of S2 \2 23 i 7% in the 'ercentage of each constituent.
3. A vitreous composition according to Claim 1, characterised in tht it has substantially the following constituents in perce tages by weight: SiO 50%; P 0, 2 2 CaO 16%; Na 0 15%; 0 MgO Al203 B 03 5% with tolerances of 7 in the percentage of each constituent.
4. A vitreous composition accor ing to any of Claims 1 to 3, characterised in that it als includes at least traces of clacium fluoride and/or calc. m fluorophos- phate.. The use of a vitreous composition accordi'g to any of Claims 1 to 4 for the formation of bone imol ts or parts thereof. FiLLtlt -PrdUCed by the drawEing of j ,jr j f s WO 91/12032 PCT/EP PCT/EP9 /40201 1 1. A bioactive vitreous composition for bone impl ation, including the following approximate pe ntages by weight of the following oxides: SiO from 40 to P205 from 4 to CaO (MgO) fro to 40%; Na20 and/or K 0 up to characterised that it includes, as stabilising oxides a gloal percentage by weight between 2% and 9.% of K- and Al203, the percentage of Al 203 being from -3 23 23 to whereby the composition can be drawn into filaments or fibroc from a fusion bath. 2. A vitreous composition according to Claim 1 characterised in that it has the following constituents. in percentages by weight: SiO 2 50%; P 0 CaO 16%: -rances 20%; K20 MgO A1203 with 4-lgor of 2 2 23 7% ,i4 the percentage of each constituent. 3. A vitreous composition according to Claim 1, characterised in that it has substantially the following constituents in percentages by weight: SiO 50%; P205 CaO 16%; Na 0 15%; K 0 MgO Al 03 B203 22 23 5% with tolerances of 7%A-4 the percentage of each constituent. 4. A vitreous composition according to any of Claims 1 to 3, characterised in that it also includes at least traces of clacium fluoride and/or calcium fluorophos- phate. The use of a vitreous composition according to any of Claims 1 to 4 for the formation of bone implants or parts thereof.
6. Filaments produced by the drawing of a vitreous <14 -(4 WO91/12032 PCT/EP91/00201 1 composition according to any of Claims 1 to 4.
7. Filaments according to Claim 5, characterised in that their diameters are between 10 and 50 microns.
8. A bundle constituted by a plurality of filaments according. to Claim 7 or Claim 8, for implantation in a bone defect.
9. A fabric, particularly a net or gauze, formed of filaments according to Claim 6 or Claim 7, for repairing a bone defect.
10. A felt or "cotton-wool" formed of filaments according to Claim 6 or Claim 7, for repairing a bone defect.
11. A particulate product produced from filaments according to Claim 6 or Claim 7, for implantation in a b-ne defect or for use in the preparation of products for bone implants.
12. A particulate product according to Claim 11, constituted by pieces or small cylinders produced by the shredding of the filaments.
13. A particulate product according to Claim 11. in the form of a powder produced by the grinding of the filaments.
14. A permanent bone prosthesis constituted by a solid body of biocompatible material, characterised in that the surface of the body is at least partially coated with a layer produced by the application of a parti- Sculate product according to any of Claims 11 to 13. A prosthesis according to Claim 14, in which the coating layer is produced by the application of the particulate product by the "plasma spray" technique. r WO 91/12032 PCT/EP91/00201 r r7
16. A method for the production of filaments of a bioactive vitreous composition for bone implantation, by drawing the molten composition through a die from a fusion bath, characterised in that use is made of a vitreous composition according to any of Claims 1 to 3.
17. A method according to Claim 16, characterised in that a crucible of substantially pure platinum is used for containing the fusion bath. 'p -f I; :II I INTERNATIONAL SEARCH REPORT International Application No PCT/EP 91/00201 I 1- I. CLASSIFICATION OF SUBJECT MATTER (if several classification symbols apply, Indicate all) According to International Patent Claseification (IPC) or to both National Classification and IPC. IPC A 61 L 27/00, C 03 C 4/00, C 03 C 3/097, C 03 C 13/00 II. FIELDS SEARCHED Minimum Documentation Searched 7 Classification System Classlfication Symbols A 61 L Documentation Searched other than Minimum Documentation to the Extent that such Documents are Included in the Fields Searched a IIl. DOCUMENTS CONSIDERED TO BE RELEVANT' Category Citation of Document, i with indication, where appropriate, of the relevant passages 12 Relevant to Claim No. 13 P,X DE, A, 3939831 (TETZNER, V) 1 7 June 1990 see page 2, lines-47-56; table 1; claims Y FR, A, 2243915 (ERNST LEITZ GmbH) 1-17 11 April 1975 see page 2, lines 35-40; page 3, line 1; claims cited in the application Y GB, A, 2080281 (NIPPON KOGAKU 1-17 3 February 1982 see page 2, lines 115-130; claims 1-6 cited in the application Special categories of cited documents: 1o later document published after the International filing date document definin the general itate of the art which Is not or priority date and not in conflict with the application but considered to be of particular relevance cited to understand the principle or theory underlying the E" earlier document but pu b l ished on or after the Internationl X" document of particular relevanc: i nhe claimed invention iling date cannot be considered novel or cannot be conideret to document which may throw doubts on priority claim(s) or involve an inventive step which is cited to establish the publication date of another document of particular relevance; the claimed invention citation or other special reason (as specified) canneo be considered to Involve an inventive step when the document referring to an oral discloaure, use, exhibition or document is combined with one or more other euch docu- other means menta, such combination being obvious to a person skilled document published prior to the international filing date but in the art. later than the priority date claimed document member of the same patent family IV. CERTIFICATION Date of the Actual Completion of the International Search Date of Mailing of this International Search Report 19th March 1991 26. 04. 91 International Searching Authority Signature of Authod rl f EUROPEAN PATENT OFFICE TORIB Form PCT/ISA/210 (second aheet) (January 1985) r! i Internatlonal Application No PCT/EP 91/00201 III. DOCUMENTS CONSIDERED TO BE RELEVANT (CONTINUED FROM THE SECOND SHEET) Category Citation of Document, I with Indication, where appropriate, of the relevant passages Relievnt to Claim No. -2- US, A, 4708652 (TAKAMITSU FUJIU et al.) 24 November 1987 see claims cited in the application, DE, A, 3248649 (NIPPON KOGAKU K.K.) 14 July 1983 see claims cited in the application EP, A, 0154513 (PFIZER HOSPITAL PRODUCTS GROUP) 11 September 1985 see page 2, lines 15-35; examples 1-3 cited in the application DE, A, 3806215 (HOYA CORP.) 8 September 1988 1-17 1-17 Form PCT/ISA 210(extra sheet) (January 1985) ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. EP 9100201 SA 44025 This annex lists the patent family members relating to the patent documents cited in the above-mentioned international search report. The members are as contained in the European Patent Office EDP file on 09/04/91 The European Patent Office is in no way liable for these particulars which are merely given for the purpose of information. Patent document Publication Patent family Publication cited in search report date member(s) date DE-A- 3939831 07-06-90 JP-A- 2149447 08-06-90 FR-A- 2243915 11-04-75 DE-A- 2346739 28-05-75 DE-A- 2434979 05-02-76 AT-B- 347021 11-12-78 BE-A- 819746 31-12-74 CH-A- 614117 15-11-79 GB-A- 1477899 29-06-77 JP-C- 1100782 18-06-82 JP-A- 50064305 31-05-75 JP-B- 56041592 29-09-81 US-A- 4135935 23-01-79 GB-A- 2080281 03-02-82 JP-C- 1380902 28-05-87 JP-A- 57003739 09-01-82 JP-B- 61046418 14-10-86 DE-A- 3123220 11-03-82 US-A- 4437192 20-03-84 US-A- 4708652 24-11-87 JP-A- 60186455 21-09-85 DE-A- 3248649 14-07-83 JP-B- 2048257 24-10-90 JP-A- 58118746 14-07-83 US-A- 4497629 05-02-85 EP-A- 0154513 11-09-85 CA-A- 1250494 28-02-89 CA-A- 1229354 17-11-87 EP-A,B 0153863 04-09-85 JP-C- 1498507 29-05-89 JP-A- 61000590 06-01-86 JP-B- 63046148 13-09-88 DE-A- 3806215 08-09-88 JP-A- 1145064 07-06-89 US-A- 4960733 02-10-90 mor- ds about th-- an N 2 SFor more details about this annex se Official Journal of the European Patent Office, No. 12/82 :e Fr more details about this annex :see Oficial Journal of the European Patent Of e No. 12/82
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IT67096A IT1240938B (en) | 1990-02-08 | 1990-02-08 | BIOACTIVE GLASS COMPOSITION FOR BONE IMPLANTS AND PRODUCTS OBTAINED WITH SUCH A COMPOSITION OR THAT INCLUDE IT |
IT67096/90 | 1990-02-08 |
Publications (2)
Publication Number | Publication Date |
---|---|
AU7149191A AU7149191A (en) | 1991-09-03 |
AU639981B2 true AU639981B2 (en) | 1993-08-12 |
Family
ID=11299541
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
AU71491/91A Ceased AU639981B2 (en) | 1990-02-08 | 1991-02-04 | Bioactive vitreous composition for bone implants, filaments made therefrom and method |
Country Status (10)
Country | Link |
---|---|
EP (1) | EP0514401A1 (en) |
JP (1) | JPH05502603A (en) |
KR (1) | KR950008173B1 (en) |
AU (1) | AU639981B2 (en) |
BR (1) | BR9106030A (en) |
CA (1) | CA2075281A1 (en) |
FI (1) | FI923561A (en) |
HU (1) | HUT61899A (en) |
IT (1) | IT1240938B (en) |
WO (1) | WO1991012032A1 (en) |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2682968B1 (en) * | 1991-10-28 | 1994-08-26 | Icmc | METHOD FOR PRODUCING A BONE IMPLANT, DEVICE FOR CARRYING OUT THE METHOD AND IMPLANT THUS CARRIED OUT |
WO1993017976A1 (en) * | 1992-03-09 | 1993-09-16 | Turku Implant Team Oy | Bioactive glass as a bone substitute |
US6121172A (en) * | 1993-11-15 | 2000-09-19 | The Trustees Of The University Of Pennsylvania | Composite materials using bone bioactive glass and ceramic fibers |
US5468544A (en) * | 1993-11-15 | 1995-11-21 | The Trustees Of The University Of Pennsylvania | Composite materials using bone bioactive glass and ceramic fibers |
FI101129B (en) * | 1995-01-13 | 1998-04-30 | Vivoxid Oy | New bioactive glasses and their use |
FI110063B (en) | 1998-12-11 | 2002-11-29 | Antti Yli-Urpo | New bioactive product and its use |
FI117963B (en) | 2001-04-26 | 2007-05-15 | Eija Marjut Pirhonen | Material that replaces bone |
EP2029184B1 (en) | 2006-05-26 | 2011-02-23 | Baxter International Inc. | Injectable fibrin composition for bone augmentation |
ATE452863T1 (en) * | 2006-09-20 | 2010-01-15 | Inion Oy | BIOACTIVE GLASS COMPOSITIONS |
WO2008131154A2 (en) | 2007-04-23 | 2008-10-30 | Baxter International Inc. | Fibrin compositions containing strontium compounds |
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 |
WO2019108556A1 (en) | 2017-11-28 | 2019-06-06 | Corning Incorporated | Bioactive glass compositions and dentin hypersensitivity remediation |
EP3717426A1 (en) | 2017-11-28 | 2020-10-07 | Corning Incorporated | Chemically strengthened bioactive glass-ceramics |
WO2019108558A1 (en) | 2017-11-28 | 2019-06-06 | Corning Incorporated | High liquidus viscosity bioactive glass |
WO2019108557A1 (en) | 2017-11-28 | 2019-06-06 | Corning Incorporated | Bioactive borate glass and methods thereof |
EP3972941A1 (en) * | 2019-05-22 | 2022-03-30 | Corning Incorporated | Bioactive glass compositions |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2080281A (en) * | 1980-06-11 | 1982-02-03 | Nippon Kogaku Kk | Biologically active glass |
US4708652A (en) * | 1984-03-06 | 1987-11-24 | Nippon Kogaku K. K. | Apatite composite ceramics |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1477899A (en) * | 1973-09-17 | 1977-06-29 | Leitz Ernst Gmbh | Manufacture of therapeutically useful composite materials |
JPS58118746A (en) * | 1982-01-07 | 1983-07-14 | 株式会社ニコン | Dental implant and production thereof |
CA1229354A (en) * | 1984-03-01 | 1987-11-17 | David C. Greenspan | Biologically active glass compositions for bonding to alloys |
US4960733A (en) * | 1987-02-28 | 1990-10-02 | Hoya Corporation | Inorganic biomaterial and process for producing the same |
JPH02149447A (en) * | 1988-12-01 | 1990-06-08 | Nippon Electric Glass Co Ltd | Dental crystallized glass |
-
1990
- 1990-02-08 IT IT67096A patent/IT1240938B/en active IP Right Grant
-
1991
- 1991-02-04 HU HU9202578A patent/HUT61899A/en unknown
- 1991-02-04 BR BR919106030A patent/BR9106030A/en not_active Application Discontinuation
- 1991-02-04 EP EP91902954A patent/EP0514401A1/en not_active Withdrawn
- 1991-02-04 JP JP3503103A patent/JPH05502603A/en active Pending
- 1991-02-04 WO PCT/EP1991/000201 patent/WO1991012032A1/en not_active Application Discontinuation
- 1991-02-04 CA CA002075281A patent/CA2075281A1/en not_active Abandoned
- 1991-02-04 AU AU71491/91A patent/AU639981B2/en not_active Ceased
- 1991-02-04 KR KR1019920701897A patent/KR950008173B1/en active IP Right Grant
-
1992
- 1992-08-07 FI FI923561A patent/FI923561A/en not_active Application Discontinuation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2080281A (en) * | 1980-06-11 | 1982-02-03 | Nippon Kogaku Kk | Biologically active glass |
US4708652A (en) * | 1984-03-06 | 1987-11-24 | Nippon Kogaku K. K. | Apatite composite ceramics |
Also Published As
Publication number | Publication date |
---|---|
EP0514401A1 (en) | 1992-11-25 |
CA2075281A1 (en) | 1991-08-09 |
FI923561A0 (en) | 1992-08-07 |
IT9067096A1 (en) | 1991-08-08 |
IT9067096A0 (en) | 1990-02-08 |
JPH05502603A (en) | 1993-05-13 |
BR9106030A (en) | 1993-03-02 |
HUT61899A (en) | 1993-03-29 |
FI923561A (en) | 1992-08-07 |
KR950008173B1 (en) | 1995-07-26 |
AU7149191A (en) | 1991-09-03 |
IT1240938B (en) | 1993-12-27 |
WO1991012032A1 (en) | 1991-08-22 |
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