GB1581063A - Bioglass coated a12o3 ceramics - Google Patents
Bioglass coated a12o3 ceramics Download PDFInfo
- Publication number
- GB1581063A GB1581063A GB336677A GB336677A GB1581063A GB 1581063 A GB1581063 A GB 1581063A GB 336677 A GB336677 A GB 336677A GB 336677 A GB336677 A GB 336677A GB 1581063 A GB1581063 A GB 1581063A
- Authority
- GB
- United Kingdom
- Prior art keywords
- glass
- biologically active
- ceramic
- coating
- expansion
- 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.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- 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
- C03C4/00—Compositions for glass with special properties
- C03C4/0007—Compositions for glass with special properties for biologically-compatible glass
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5022—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with vitreous materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/86—Glazes; Cold glazes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Transplantation (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Molecular Biology (AREA)
- Dermatology (AREA)
- Medicinal Chemistry (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Geochemistry & Mineralogy (AREA)
- Epidemiology (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Materials For Medical Uses (AREA)
- Glass Compositions (AREA)
- Prostheses (AREA)
Abstract
The process consists in employing a glass whose thermal expansion coefficient is different from that of the ceramic. A first vitreous coating (2) is deposited on the ceramic (1) and is heated to ensure welding of the coating onto the ceramic by ion diffusion. The whole is cooled to create microfissures (3) in the vitreous coating layer as a result of the thermomechanical stresses which are generated therein. This first coating is covered with at least one additional layer (5) of biologically active glass, which is welded onto the first layer. The product obtained by making use of this process can be employed for the production of internal prostheses capable of replacing at least a part of a bone and requiring no cement. <IMAGE>
Description
(54) BIOGLASS COATED Al203 CERAMICS
(71) We, THE BOARD OF REGENTS, University of Florida, a body corporate established by virtue of the laws of the United States of America, having an office at 107 West Gaines Street, Tallahassee, Florida 32304, United
States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- The strength, anti-friction and high wear resistance properties of Awl203 ceramics make them ideal for use in the construction of artificial protheses and orthopedic devices.The biological inactivity of Awl203 ceramic surfaces, however, makes it extremely difficult, if not impossible, to achieve cement-free implantation of the prothesis since bone tissue will not bond or grow thereon.
Various techniques have recently been suggested for activating the ceramic surfaces in order to enhance the bone-tissue bonding capabilities of the Al203 prothesis. However, all of these techniques are either extremely expensive and time-consuming or result in ceramic structures of decreased mechanical strength, anti-friction properties and wear resistance.
It is an aim of the present invention to provide a cement-free bone prothesis implant comprising a bioactive Awl203 ceramic and a method for the preparation thereof which is inexpensive and does not result in a decrease of the mechanical strength, anti-friction and wear resistance properties of the Awl203 ceramic material.
The present invention comprises a method of coating a compacted alumina ceramic surface with a biologically active glass having a thermal coefficient of expansion different from that of the ceramic comprising:
1) Contacting the glass with the alumina ceramic surface at a temperature and for a time sufficient to bond the glass to the alumina ceramic surface by ion diffusion,
2) Causing or allowing the coated substrate to cool to a temperature sufficient to produce interconnected microcracks of less than 1 micron in width in the glass coating as a result of the thermomechanical stresses induced by the difference in thermal coefficients of expansion of said alumina ceramic and glass, and,
3) Overcoating the micro-cracked glass coating with at least one additional coating of the biologically active glass.
The invention also relates to the product of the above-described process.
The biologically active glass coated compacted Awl203 ceramic of the present invention comprises a ceramic surface coated with at least two layers of biologically active glass having a thermal coefficient of expansion different from that of the Awl203 ceramic wherein the first layer is bonded to the ceramic surface by ion diffusion and is characterized by having interconnected thermomechanical stress induced micro-cracks of less than 1 micron in width therein and wherein the subsequent layer or layers are coated thereover.
The invention also relates to a cement-free bone prothesis implant comprising the above-described bioactive glass coated Awl203 ceramic.
It is well known that when applying a glaze of higher thermal expansion to a body of lower thermal expansion, thermal stresses will arise upon cooling. Since these thermal stresses result in an overall weakening of the coated structure, it is conventional according to prior art practices to attempt to match the thermal coefficients of expansion of the respective materials as closely as possible in order to minimize these stresses. This necessarily results in a drastic reduction in the number and variety of coatings which can be applied to a particular substrate.
According to the present invention, extreme mismatches between the relative
thermal coefficients of expansion are relied upon to induce thermo-mechanical
stresses in the biologically active glass glaze coating. Upon cooling, the glaze
cracks in order to relieve the stresses due to thermal mismatch, thereby resulting in
isolated islands of biologically active glass coating separated by small
interconnected flaws or micro-cracks. These cracks are less than 1 micron in width,
and in particular may range from 0.05 to 0.8 microns wide.The small islands of
biologically active glass are bonded to the compacted Al2O3 ceramic surface by a
large diffusional bond which is developed by processing at elevated temperatures (1100 C#1350 C). The diffusional bond is a chemical bond between the Al2O3
substrate and the biologically active glass coating thereby eliminating a well
defined A12O3-biologically active glass interface and results in an enhancement of
the overall strength characteristics of the ceramic.
Multiple coatings of biologically active glass can then be applied over the micro-cracked glaze with no danger of inducing thermo-mechanical stresses in the structure. This is due to the fact that the second and subsequent glass layers are bonded to the first biologically active glass layer and not to the Al2O3 substrate.
Thus, the second glass layer has physical properties identical to the first glass layer with no mismatch in the respective coefficients of thermal expansion.
The resulting structure has the capacity to bond living tissues to an implant material comprised of the coated ceramic substrate due to the properties of the biologically active glass. In addition, the coating process does not deleteriously affect the mechanical strength of the Al2O3 ceramic since all thermo-mechanical stresses are relieved during the first coating operation and no further stresses are induced by the second and subsequent glass coating steps.
Since no regard need be given to the thermal coefficient of expansion match, a wider variety of biologically active glass materials can be coated upon the ceramic surface than by the techniques presently prevalent in the prior art.
Indeed, by carefully controlling the coating procedure, the strength of the compacted Al2O3 ceramic can actually be enhanced. By maintaining the size of the flaws or micro-cracks at below 1 micron, the strength and fatigue resistance of the
Al2O3 ceramic is increased.
Any biologically active glass may be employed for the purposes of the present invention. It will be understood by those skilled in the art that any suitable biologically active glass, depending upon the ultimate use for which the coated ceramic is intended, may be utilized. The biologically active glass is one capable of bonding to living tissue and may contain, by weight:
SiO2 4062/ Na2O 10##32% CaO 1320/, P2Os 3-9% CaF2 l8% B203 0##7.5% Ea2O+CaO should preferably be above 30% to achieve bonding to live tissue.
Suitable specific glasses include those of the following compositions:
A. SiO2 45.0% Na2O 24.5 /n CaO 24.5 /n P205 6.0 /n B. SiO2 42.940/, Na2O 23.37 /n CaO 11.69 P,O, 5.72 /n CaF2 16.26 /n C.SiO2 40.0 Na2O 24.5 /n CaO 24.5 /n P2O5 6.0 /n B 2 3 5.0 In order to achieve the micro-cracked glass coating, it is generally preferred to
employ a compacted Al2O3 ceramic having a thermal coefficient of expansion (0- 1,000 C) in the range 35-75x 10-7 in/in/ C. and a biologically active glass having a thermal coefficient of expansion (0--1,000"C.) in the range 95-145x 10-7 in/in/ C.
The biologically active glasses are first melted (e.g., in platinum crucibles) for 3-12 hours to ensure homogeneity. The melting temperatures range from 13000C.
to 15500C. After melting, the biologically active glass is quenched in water and ground in a ball mill into glass frit of the desired particle size. Generally, a particle size of less than about 74 microns is preferred. The frit is then mixed with an organic binder (e.g., organic polymers such as a mixture of 20% polyvinylacetate and 80 /n polyvinylalcohol) and a suitable organic solvent (e.g., toluene, acetone, xylene) to form a slurry. The amount of binder used depends upon the particle size of the frit employed. Generally, larger particles require greater amounts of binder to achieve adequate coverage. The amount of solvent employed is varied to control the viscosity of the slurry and the thickness of the ultimate coating.Generally, the slurry will contain from 35 to 80 percent glass frit, from 1 to 10 percent binder, and from 20 to 65 percent organic solvent, all percentages being by weight.
The compacted Awl203 substrate to be coated is then dipped into the slurry or the slurry is hand-painted or sprayed onto the substrate. The coating is allowed to dry thoroughly.
The coated substrate is then fired following a schedule that will allow burn-off of the organic binder, followed by a softening of the glass and subsequent bonding of the glass to the substrate by ion diffusion. The high alkali content of the biologically active glass is one of the major factors that allows for good diffusional bonding between the coating and the substrate. The coated glass is then annealed to relieve mechanical stresses.
Employing the biologically active glass composition A described above and a compacted Awl203 ceramic having a thermal coefficient of expansion of 50 75x10-7 in/in C., the firing schedule set forth in Fig. 1 was employed. Although
Fig. 1 sets forth a double coated structure, it will be understood by those skilled in the art that successive coats of biologically active glass may be applied thereover following the same firing schedule, depending upon the desired surface properties
of the resulting coated system.The biologically active glass glaze ultimately coated
upon the compacted Awl203 ceramic surface contains 0.475 moles of Na2O , 0.525
moles CaO, 0.050 moles P2Os, and 0.900 moles SiO2 (normalized with respect to
alkali content).
The combination of 1) composition of the glasses (high alkali, low silica) which
allows for relatively high diffusion rates and 2) the various time-temperature firing
schedules which control the amount of diffusion permit the controlled micro
cracking of the base coat of biologically active glass. The control of these two
variables also permits regulation of the diffusion bonding which is ultimately
responsible for the success of the coated system.
The temperature to which the coated system is subjected to achieve ion
diffusion bonding depends, of course, on the particular glass and Awl203 ceramic
compositions employed. Generally, temperatures above 500"C, preferably in the
range of 900 to 1400"C, and most preferably from 11000 to 13500C, are utilized.
The first coat is applied such that the ultimate thickness thereof is from 25
100 microns. Subsequent coatings may range from 50 to 400 microns.
Fig. 2 sets forth an electron micro probe scan of sodium and aluminum in the
single coated structure set forth above. The degree of diffusional bonding is
apparent from the fact that alumina is found as far into the glass as 200 microns.
Fig. 3 sets forth an electron micro probe scan of sodium and aluminum in the
above-described double coated system. The fact that the second coating is largely
bonded to the first glass coating is apparent from the decreased intensity of the
alumina signal in the second layer of the glass coating.
Fig. 4 sets forth the strain rate dependence of the biologically active glass
coated vs. uncoated Awl203 surface. It is apparent that the fatigue resistance of the
coated material is greater as compared with the uncoated substrate.
As noted above, the application of a glaze of higher thermal expansion on a
body of lower thermal expansion will result in thermal stresses upon cooling. These
stresses can be calculated employing the following equation: ag'=E(T0-T')(ag 1 a)( 1-3 +j2) where
glaze thickness
body thickness
E=Youngs modulus TO=annealing temperature of glaze
T=final temperature [room temp. (200 C)] agl=thermal expansion of glaze ab=thermal expansion of body ag'=thermal stress (psi).
In the above-described example employing composition A:
j=0.02 T =450 C
E=8x 106 T'=200C ctgl=100x10-7 in/in/ C
αb=50x10-7 in/in/ C Substituting these parameters into the above equation, the thermal stress is found to be 8.2x 10-3 psi. It is, therefore, apparent that the degree of micro cracking can be calculated, depending upon the particular compositions employed and the firing, coating and annealing schedules followed.
Fig. 5 sets forth the coated ceramic substrate in various stages of formation.
In Fig. Sa, wherein the temperature is greater than 500 C., the ceramic substrate 1 is overcoated with the first layer of biologically active glass 2.
In Fig. Sb, wherein the system has been cooled (or allowed to cool) to room temperature, micro-cracks 3 appear in the coating 2 forming islands 4 of biologically active glass bonded, by ion diffusion, to the ceramic substrate 1.
Fig. Sc depicts a micro-cracked biologically active glass coated Awl203 ceramic substrate overcoated with a second biologically active glass layer 5.
The thus coated Al2O3 ceramic substrates are ideally adapted for the formation of cement-free bone prothesis implants of unusually high strength and capable of forming bonds with biologically active tissue.
WHAT WE CLAIM IS:
1. A method of coating a compacted alumina ceramic surface with a biologically active glass, said ceramic and glass having different thermal coefficients of expansion, comprising:
1) contacting said glass with said alumina ceramic surface at a temperature and for a time sufficient to bond said glass to said alumina ceramic surface by ion diffusion,
2) causing or allowing said coated substrate to cool to a temperature sufficient to produce interconnected micro-cracks of less than 1 micron in width in said glass coating as a result of the thermo-mechanical stresses induced by the difference in thermal coefficients of expansion of said alumina ceramic and glass, and
3) overcoating said micro-cracked glass coating with at least one additional coating of biologically active glass.
2. A method according to claim 1 wherein said biologically active glass contains, by weight:
SiO2 4062% Na2O 10#32% CaO 10#32% P205 3-9% CaF2 also B203 0#7.5% 3. A method according to claim 1 wherein said biologically active glass contains, by weight:
SiO2 45.0 Na2O 24.5 /" CaO 24.5%
P2O5 6.0 /a 4. A method according to claim 1 wherein said biologically active glass contains, by weight:
SiO2 42.94% Na2O 23.37 /" CaO 11.69 /n P2O5 5.72 /" CaF2 16.26%
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (20)
1. A method of coating a compacted alumina ceramic surface with a biologically active glass, said ceramic and glass having different thermal coefficients of expansion, comprising:
1) contacting said glass with said alumina ceramic surface at a temperature and for a time sufficient to bond said glass to said alumina ceramic surface by ion diffusion,
2) causing or allowing said coated substrate to cool to a temperature sufficient to produce interconnected micro-cracks of less than 1 micron in width in said glass coating as a result of the thermo-mechanical stresses induced by the difference in thermal coefficients of expansion of said alumina ceramic and glass, and
3) overcoating said micro-cracked glass coating with at least one additional coating of biologically active glass.
2. A method according to claim 1 wherein said biologically active glass contains, by weight:
SiO2 4062% Na2O 10#32% CaO 10#32% P205 3-9% CaF2 also B203 0#7.5%
3. A method according to claim 1 wherein said biologically active glass contains, by weight:
SiO2 45.0 Na2O 24.5 /" CaO 24.5%
P2O5 6.0 /a
4. A method according to claim 1 wherein said biologically active glass contains, by weight:
SiO2 42.94% Na2O 23.37 /" CaO 11.69 /n P2O5 5.72 /" CaF2 16.26%
5. A method according to claim 1 wherein said biologically active glass contains, by weight:
SiO2 40.0%
Na2O 2455 /n CaO 24.5 P2O5 6.0/n B203 5.0
6. A method according to any of claims 1 to 5 wherein said ceramic surface has
a thermal coefficient of expansion (0##1,000 C.) in the range 50##75 x 10-7 in/in/ C.
and said glass has a thermal coefficient of expansion (0##1,000 C.) in the range 95##145x10-7 in/in/ C.
7. A method according to any of claims 1 to 6 wherein each of said coatings is
annealed.
8. A method according to any of claims I to 7 wherein said glass is bonded to
said ceramic surface at a temperature about 500"C.
9. A method according to any preceding claim wherein said glass is contacted
with said ceramic surface by coating said ceramic surface with a slurry comprising
a solvent, an organic binder, and a biologically active glass frit having a particle size
less than 74 Mm.
10. A method according to claim 9 including the steps of drying the slurry
coated ceramic substrate and firing the coated substrate to burn off said organic
binder.
Il. The product of the method according to any of claims 1 to 10.
12. A product of manufacture comprising a compacted alumina ceramic
surface coated with at least two layers of biologically active glass having a thermal
coefficient of expansion different from that of said alumina ceramic, said first layer
being bonded to said ceramic surface through ion-diffusion and having
interconnected thermo-mechanical stress induced micro-cracks of less than 1
micron in width therein, and said subsequent layer or layers being successively
bonded thereover.
13. A product according to claim 12 wherein said biologically active glass contains, by weight:
SiO2 40##2% Na2O 10##32% CaO 1032% P2Os 3##9% CaF2 0##18% B203 0##7.5%
14. A product according to claim 12 wherein said biologically active glass
contains, by weight:
SiO2 45.0 Na2O 24.5%
CaO 24.5 P205 6.0 /n
15. A product according to claim 12 wherein said biologically active contains, by weight:
SiO2 42.94/n Na2O 23.37%
CaO 11.69 P205 5.72%
CaF2
16.26 /n 16.A product of claim 12 wherein said biologically active glass contains, by
weight:
SiO2 40.0%
Na2O 24.5%
CaO 24.5% P2O5 6.00/, B2O3 5.0%
17. A product according to any of claims 12 to 16 wherein said ceramic surface has a thermal coefficient of expansion (0##1,000 C.) in the range 50--75x10-7 in/in/ C. and said glass has a thermal coefficient of expansion (0##1,000 C.) in the range 95--145x10-7 in/in/ C.
18. A cement-free bone prothesis implant comprising the' product of the method claimed in any of claims 1 to 10.
19. A cement-free bone prothesis implant comprising the product of any of claims 12 to 17.
20. A method according to any of claims 1 to 10 substantially as herein described with reference to the accompanying drawings.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB336677A GB1581063A (en) | 1977-01-27 | 1977-01-27 | Bioglass coated a12o3 ceramics |
AT56678A AT376645B (en) | 1977-01-27 | 1978-01-26 | METHOD FOR COATING THE SURFACES OF COMPACT A12O3 CERAMIC MATERIAL WITH A BIOLOGICALLY ACTIVE GLASS |
FR7802145A FR2378733A1 (en) | 1977-01-27 | 1978-01-26 | PROCESS FOR MAKING A BIOLOGICALLY ACTIVE VITREOUS COATING ON A CERAMIC BASED ON A12O3 AND A PRODUCT THUS OBTAINED |
CH84878A CH627723A5 (en) | 1977-01-27 | 1978-01-26 | Process for coating the surface of a ceramic with a biologically active glass, product obtained by using this process and use of this product |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB336677A GB1581063A (en) | 1977-01-27 | 1977-01-27 | Bioglass coated a12o3 ceramics |
Publications (1)
Publication Number | Publication Date |
---|---|
GB1581063A true GB1581063A (en) | 1980-12-10 |
Family
ID=9756971
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB336677A Expired GB1581063A (en) | 1977-01-27 | 1977-01-27 | Bioglass coated a12o3 ceramics |
Country Status (4)
Country | Link |
---|---|
AT (1) | AT376645B (en) |
CH (1) | CH627723A5 (en) |
FR (1) | FR2378733A1 (en) |
GB (1) | GB1581063A (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4626392A (en) * | 1984-03-28 | 1986-12-02 | Ngk Spark Plug Co., Ltd. | Process for producing ceramic body for surgical implantation |
US4775646A (en) * | 1984-04-27 | 1988-10-04 | University Of Florida | Fluoride-containing Bioglass™ compositions |
JP2858126B2 (en) * | 1989-06-30 | 1999-02-17 | 京セラ株式会社 | Biological implant material and its manufacturing method |
DE102004050202A1 (en) * | 2004-10-15 | 2006-04-20 | Otto Huber | Surface preparation of difficultly-bondable ceramic parts e.g. in dentistry involves blasting, peptizing or silanizing the surface of an applied glass or glass-ceramic layer |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH613679A5 (en) * | 1973-05-23 | 1979-10-15 | Leitz Ernst Gmbh | Glass-ceramic material, and process for the production thereof |
CH595293A5 (en) * | 1975-02-20 | 1978-02-15 | Battelle Memorial Institute | |
DE2546824C2 (en) * | 1975-10-18 | 1986-05-07 | Ernst Leitz Wetzlar Gmbh, 6330 Wetzlar | Coated endoprosthesis and process for their manufacture |
-
1977
- 1977-01-27 GB GB336677A patent/GB1581063A/en not_active Expired
-
1978
- 1978-01-26 CH CH84878A patent/CH627723A5/en not_active IP Right Cessation
- 1978-01-26 FR FR7802145A patent/FR2378733A1/en active Granted
- 1978-01-26 AT AT56678A patent/AT376645B/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
AT376645B (en) | 1984-12-10 |
CH627723A5 (en) | 1982-01-29 |
FR2378733B1 (en) | 1983-06-10 |
ATA56678A (en) | 1984-05-15 |
FR2378733A1 (en) | 1978-08-25 |
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