WO2004031086A1 - Composition, use and manufacture of bioactive glass - Google Patents
Composition, use and manufacture of bioactive glass Download PDFInfo
- Publication number
- WO2004031086A1 WO2004031086A1 PCT/FI2003/000715 FI0300715W WO2004031086A1 WO 2004031086 A1 WO2004031086 A1 WO 2004031086A1 FI 0300715 W FI0300715 W FI 0300715W WO 2004031086 A1 WO2004031086 A1 WO 2004031086A1
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- WO
- WIPO (PCT)
- Prior art keywords
- bioactive glass
- glass composition
- starting oxides
- composition according
- bioactive
- Prior art date
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Classifications
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- 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
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- 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
- A61L27/10—Ceramics or glasses
-
- 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
-
- 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
- C03C11/00—Multi-cellular glass ; Porous or hollow glass or glass particles
-
- 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
- C03C12/00—Powdered glass; Bead compositions
-
- 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
- C03C13/00—Fibre or filament compositions
-
- 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
- C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
-
- 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
Definitions
- This invention relates to a bioactive glass composition
- a bioactive glass composition comprising Si ⁇ 2, Na2 ⁇ , CaO, K2O, MgO, P2O5 and B2O3.
- the invention further relates to the use of said composition and devices manufactured from it.
- the invention still relates to a method for manufacturing a bioactive glass composition according to the present invention.
- bioactive glass a material that has been designed to induce specific biological activity in body tissue.
- biodegradable in this context means that it is degradable upon prolonged implantation when inserted into a mammal body.
- biomaterial a non-viable material used in a medical device is meant, a material that is intended to interact with biological systems.
- Glasses have been studied extensively for applications in medical and dental surgery and implants.
- a medical device can be implanted into any human or animal tissue. This allows local application of an active agent so that targeting of the biologically active agent release site is possible. Since only a non- crystallized glass composition shows the best bioactivity and since bioactive glass compositions are in the area near the phase separation, it is very difficult to make glass compositions that do not crystallize during repeated heat treatment, i.e. that remain bioactive.
- Bioactive glasses develop reactive layers on their surfaces resulting in bonding between the device and the host tissue. Unlike most other bioactive materials, the rate of chemical reactions of bioactive glasses can be easily controlled by changing the chemical composition of the glass. Therefore, bioactive glasses are interesting in particular in clinical applications and have indeed been used for example to replace damaged parts of a face after facial injuries, replacement of the small bones (ossicles) in the middle ear and in surgery to fill defects in bone.
- bioactive glass compositions do not support repeated heat-treatments, since reheating results in a decrease of the bioactivity. This causes great problems in the manufacturing of devices from these compositions, since they can only be shaped by molding them into the final shape already in the production step of the glass or by crushing the previously formed glass particles. The molding process only allows the production of rigid non-porous devices.
- the object of this invention is to provide a bioactive glass composition that can be repeatedly heat-treated without the crystallizing of the glass and losing its bioactive properties.
- a further object of this invention is to provide a bioactive glass composition that is suitable for manufacturing devices for technically demanding applications of bioactive glass.
- Si ⁇ 2 is 51-56 wt-% of the starting oxides
- Na2 ⁇ is 7-9 wt-% of the starting oxides
- CaO is 21-23 wt-% of the starting oxides
- K2O is 10-12 wt-% of the starting oxides
- MgO is 1-4 wt-% of the starting oxides
- P2O5 is 0,5-1,5 wt-% of the starting oxides
- B2O3 is 0-1 wt-% of the starting oxides
- the total amount of Na2 ⁇ and K2O is 17-20 wt-% of the starting oxides.
- the invention concerns a bioactive glass composition that can be heat-treated even repeatedly.
- the present invention is thus a selection invention of the above- mentioned invention disclosed in WO 96/21628. Indeed, the selected subrange is narrow compared to the range disclosed in WO 96/21628, it is far removed from the end-points of said range of WO 96/21628 and it is a purposive selection since having an unexpected technical effect.
- the amount of different oxides is given as weight percent of the starting oxides because some elements, such as sodium, evaporate during the heating.
- the amounts of the final oxides are however close to those of the starting oxides and in any case, the difference between the starting amounts and the final amounts is less than 5 percentage units, preferably less than 3 percentage units.
- the amounts of the oxides can be freely chosen within the above-mentioned limits.
- the amount of Si ⁇ 2 can be for example 51,5, 52, 53,5, 55 or 56 wt-% of the starting oxides
- the amount of Na2 ⁇ can be for example 7, 7,3, 7,7, 8, 8,5 or 9 wt-% of the starting oxides
- the amount of CaO can be for example 21, 21,4, 21,7, 22, 22,6 or 23 wt-% of the starting oxides
- the amount of K/jO can be for example 10, 10,5, 10,6, 11, 11,3, 11,7 or 12 wt-% of the starting oxides
- the amount of MgO can be for example 1, 1,3, 1,9, 2,4, 2,7, 3,5 or 4 wt-% of the starting oxides
- the amount of P2O5 can be for example 0,5, 0,7, 1, 1,2 or 1,5 wt-% of the starting oxides
- the amount of B2O3 can be for example 0, 0,4, 0,6, 0,9 or 1 wt-
- the amount of Si ⁇ 2 is 54-56 wt-% of the starting oxides
- the inventive glass composition further comprises AI2O3 up to 1 wt-% of the starting oxides provided that the total amount of B2O3 and AI2O3 is 0,5-2,5 wt-% of the starting oxides.
- the inventive glass composition further comprises AI2O3 0,3-1,0 wt-% of the starting oxides. It is believed that aluminium improves the mechanical properties of the bioactive glass composition.
- the decrease in the amount of Na2 ⁇ and/or K2O is compensated by the increase of the amount of AI2O3 and/or B2O3.
- bioactive glass in bone formation is two-fold: to supply Ca ⁇ + ions and to form a silica gel layer on the surface of the glass.
- This gel acts as a diffusion barrier, thus slowing down the leaching of ions from the glass and accordingly slowing down the formation of the new reaction layers and new body tissue.
- the silica gel is also acidic and may therefore irritate the tissues.
- a further advantage of the bioactive glass composition according to the invention is that the primary reaction of a device manufactured from the inventive glass composition with the body tissue is "gentle", i.e. not so aggressive as with some traditional bioactive glasses. Indeed, firstly calcium phosphate is formed in the relatively thin layer into the silica gel on the surface of the glass, typically in about 6 hours and secondly, a calcium phosphate layer is formed on the layer of silica gel, typically in about 48-72 hours. During the formation of the primary calcium phosphate, the layer of silica gel on the surface of the inventive glass composition is essentially thinner than the corresponding layer on a traditional bioactive glass, for example as the one identified above.
- the bioactive glass composition according to the invention reacts in to an appropriate extent and does not dissolve too much, which is obviously an advantage in situations in vivo.
- a device manufactured from the inventive composition remains bioactive for a long period of time.
- This adyantage of the composition allows its use in target organs that are very sensible, such as cornea.
- the inventive glass composition reacts with the tissue in a gentle way, thereby reducing the chemical irritation due to the formation of the silica gel layer, for example.
- the properties of the inventive glass composition also allow it to be used in a powder having smaller particles than the traditional compositions, thus further decreasing the irritability of the composition.
- bioactive glass composition may also advantageously be used to recreate tissues that have disappeared due to an infection.
- the bioactive glass composition according to the invention thus has an increased ability to react in a controlled and desired manner. Furthermore, it can be manufactured into any desired device according to conventional manufacturing methods and thus it may be used in applications requiring especially accurate devices and conditions.
- the bioactive glass having a composition according to the invention may be processed with any conventional methods. It may for example be firstly made into a solid glass that is further crushed.
- the composition according to the invention has the further advantage that it is possible to make granules thereof having a particularly well-controlled particle size distribution. These granules can be further heated to obtain spheres that may yet further be sintered to obtain a porous device of any desired shape. It is yet further possible to use the spheres or other particles of the bioactive glass for different casting processes such as pressure casting or for the casting of a thin sheet of glass with a process similar to the production of window glass.
- a particularly preferred method for the treatment of the present bioactive glass composition is heating with laser since it allows localized yet high temperatures to be used in the melting of the glass.
- the devices according to the invention may be in various forms, e.g., in the form of a particle, a disc, a film, a membrane, a tube, a hollow particle, a coating, a sphere, a semi sphere or a monolith, and they may have various applications.
- tissue-guiding device a device is meant that has such properties that once in place in the patient's body it guides the formation of different types of tissues on different portions of the device. It may also be a device of a desired shape having various channels through its body in order to guide the formation of a vein in these locations.
- Especially interesting forms of the present bioactive glass composition are fibre rovings, a perforated plate or sheet and a woven tissue having a precise profile.
- a perforated plate or sheet may be manufacture by casting or weaving and the diameter of the perforations is typically in the range of 10-500 ⁇ m.
- a woven tissue having a precise profile it is meant a tissue wherein the position of the fibres is determined with a precision of micrometers.
- the bioactive glass composition according to the invention may also be used for the coating of a device. The coating may be performed either by casting or dipping or a device may be coated with crushed particles of bioactive glass that is then sintered.
- the bioactive glass composition according to the invention may especially advantageously be used in the coating of ceramic materials since the heat expansion coefficients of the glass and ceramics do not significantly deviate from each other. It is also possible to use the present bioactive glass composition for the coating of metal such as titanium. A further advantage of the present composition is that it undergoes the treatment without crystallizing.
- Tooth-implants hip-implants, knee-implants, mini plates, external fixation pins, stents (e.g. for use in repair of blood vessels) or any other implants can be coated with the inventive glass composition.
- the glass according to the present invention is advantageously prepared in atmospheric pressure and at temperatures of about 1360 °C.
- the heating time for making the glass melt is typically three hours. No protection gas is needed.
- a porous device may also be manufactured by injecting pressurized gas into the glass melt, for example during the casting of the glass. If pressurized air is used, the conventional glass crystallizes due to the low temperature of the air. This problem does however not occur with the inventive glass composition and therefore both open- and closed-celled structures may be formed.
- the pores may further be filled by some active agents. Porosity of the bioactive glass does not only noticeably increase the total reacting surface of the glass but also allows a three-dimensional formation of the healing bone tissue.
- the inventive glass composition can further be used in the manufacturing of different composites and devices consisting of at least two materials, such as a combination of bioactive glass and a metal or a ceramic material.
- the bioactive glass composite may comprise different materials such as polymers, metals or ceramics.
- biopolymers Either polymers based on renewable raw materials, e.g. cellulose, or synthetic polymers that are biodegradables, e.g. polylactides are meant by "biopolymer”.
- a composite may be formed using the inventive bioactive glass composition as a matrix and a ceramic material as reinforcing component.
- the inventive composition is especially suitable for matrix due to its crystallization properties.
- the inventive composition also glues the reinforcing particles or fibers strongly together.
- An implant manufactured from such a composite quickly becomes porous once in contact with the body tissue, a property that is desired in some applications, such as devices for tissue engineering.
- the additives or reinforcements used in the composites may be in various forms such as fibres, woven or nonwoven mats, particles or hollow particles. They may also be porous or dense materials, and it is obvious that they are preferably biocompatible.
- the present glass composition may be drawn to a fibre at higher temperatures than the known bioactive glass compositions.
- the manufacturing temperature may be even 100 °C higher than for the conventional bioactive glass compositions.
- Higher manufacturing temperatures lead to fibres having a smaller diameter since the viscosity of the glass melt decreases with increasing temperature.
- the manufacturing temperature is critical for the resulting fibre product since it is close to the softening temperature of the glass, thus close to the crystallization temperature.
- a fibre manufactured from the present composition has then been heat-treated three times and it still has the described properties.
- a further advantage of the present glass composition is its better stability during storage. Indeed, the glass composition may react with the humidity of air during storage. Therefore, a glass composition according to the present invention which has a homogeneous structure will react uniformly and the product after storage still has predictable properties.
- the present invention further relates to a method for manufacturing a repeatedly heat-treatable bioactive glass composition according to the present invention, the method being characterized in that it comprises the steps of
- the method according to the present invention thus comprises two steps of melting or heating the composition in order to obtain a homogeneous mixture.
- the final bioactive glass composition can be cast or mold to any desired shape such as directly into the form of a sheet or a rod that can be further made into fibre or into a solid block that is used in the conventional way, i.e. crushed into pieces and reheated to be mold.
- Figure 1 illustrates an example of a device for tissue engineering comprising the inventive glass composition.
- Figure 2 illustrates a cross-section of a bioactive fabric comprising the inventive glass composition.
- Figure 3a illustrates the reaction of a fibre made from conventional bioactive glass when in contact with a body fluid.
- Figure 3b illustrates the reaction of a fibre made from the inventive bioactive glass when in contact with a body fluid.
- Figure 4a shows a scanning electron microscope picture of a bioactive glass fiber according to the present invention at a magmfication of xlOO.
- Figure 4b shows a scanning electron microscope picture of a bioactive glass fiber according to the present invention at a magnification of x500.
- Figure 5a shows a scanning electron microscope picture of a bioactive glass fiber according to the present invention at a magmfication of x 100 and after immersion in Tris for 7 days.
- Figure 5b shows a scanning electron microscope picture of a bioactive glass fiber according to the present invention at a magmfication of x500 and after immersion in Tris for 7 days.
- Figures 6a and 6b show a scanning electron microscope picture of a bioactive glass fiber prepared according to Example 2.
- Figures 7a and 7b show a scanning electron microscope picture of a bioactive glass fiber prepared according to Example 2, after immersion in Tris for 3 days.
- Figures 8a and 8b show a scanning electron microscope picture of a bioactive glass fiber prepared according to Example 2, after immersion in Tris for 5 days.
- Figures 9a and 9b show a scanning electron microscope picture of a bioactive glass fiber prepared according to Example 2, after immersion in Tris for 7 days.
- Figures 10a and 10b show a scanning electron microscope picture of a bioactive glass fiber prepared according to the Comparative example.
- Figures 11a, lib, 12a and 12b show a scanning electron microscope picture of a bioactive glass fiber prepared according to the Comparative example, after immersion in Tris for 3 days.
- Figures 13a and 13b show a scanning electron microscope picture of a bioactive glass fiber prepared according to the Comparative example, after immersion in Tris for 5 days.
- Figures 14a and 14b show a scanning electron microscope picture of a bioactive glass fiber prepared according to the Comparative example, after immersion in Tris for 7 days.
- FIG. 1 illustrates an example of a device for tissue engineering comprising the inventive glass composition.
- the device 1 comprises glass particles or short fibers 2 manufactured from the glass composition according to the present inventive bioactive glass composition and a matrix formed of a biopolymer 3.
- the degradation rate of the biopolymer is preferably superior to the dissolution rate of the bioactive glass. Therefore, the biopolymer 3 degrades and allows the formation of body tissues such as blood vessels whereas the bioactive glass remains essentially of a constant shape and size.
- This kind of tissue engineering device allows the formation of new tissues at the desired rate and shape while maintaining unchanged the cavity wherein the device is implanted.
- the biopolymer may also comprise a biological molecule such as growth hormone.
- Figure 2 illustrates a cross-section of a bioactive fabric comprising the inventive glass composition.
- the fabric consists, in this embodiment, of three layers of fibers and can be either woven or nonwoven.
- the respective layers 4, 5 and 6 are manufactured from at least two different compositions of bioactive glass, each composition having a different bioactivity.
- the layer 4 may be manufactured from the inventive glass composition that maintains its bioactivity unchanged through the manufacturing of the fabric.
- the layers 5 and 6 may then be manufactured from glass compositions which bioactivities are either altered by the manufacturing process of the fabric or that are not bioactive at all.
- Figure 3a illustrates the reaction of a fiber 7 made from conventional bioactive glass when in contact with a body fluid.
- the Figure shows that the fiber has a heterogeneous structure consisting of a partially crystallized part 8 and an amorphous part 9.
- the amorphous part 9 has dissolved at a greater rate than the crystallized part 8 thus leading to an uneven cross-section of the reaction layers on the fiber.
- Figure 3b illustrates the reaction of a fiber 10 made from the inventive bioactive glass when in contact with a body fluid.
- the homogeneous structure of the inventive material is clearly shown by the essentially even cross-section of the reaction layers on the fiber after reaction with a body fluid.
- composition consisting of:
- the crushed glass material was reheated to a temperature of 1360 °C and maintained in this temperature for a period of three hours.
- the resulting softened glass composition was cast into a mold and allowed to cool down to ambient temperature overnight. 300 g of bioactive glass according to the present invention was obtained.
- the composition of the glass was the following:
- the bioactive glass composition obtained was used for drawing of a fiber by standard method and manufacturing a bioactive glass fabric by a nonwoven method.
- the fibers were bonded to each other by using a thin layer of an aqueous solution of starch. Said solution also acted as a sizing agent thus increasing the strength of the fabric.
- the resulting product was tested by immersing the fabric in Tris for 3, 5 and 7 days, respectively. Precipitation of calcium phosphate occurred at 5-7 days. Optical and X-ray analysis showed no crystals on or in the fibers.
- Figures 4a to 5b illustrate the results of the testing.
- Figure 4a shows a scanning electron microscope (SEM) picture of a bioactive glass fiber according to the present invention at a magnification of x 100 and
- Figure 4b shows the same sample at a magnification of x500, i.e. the clean surface for comparison.
- SEM scanning electron microscope
- Figure 5a shows a scanning electron microscope picture of a bioactive glass fiber according to the present invention at a magnification of x 100 and after immersion in Tris for 7 days and Figure 5b shows the same sample at a magnification of x500.
- Figures 5a and 5b one can see a clear, irregular reaction surface that, in a mineral analysis, was identified as containing calsium phosphate (CaP) and silicon (Si).
- CaP calsium phosphate
- Si silicon
- step I heating speed 15 °C/min final temperature 340 °C duration 10 min
- step II heating speed 12,5 °C/min final temperature 850 °C duration 10 min
- step III heating speed 10 °C/min final temperature 900 °C duration 10 min
- step IV heating speed 10 °C/min final temperature 960 °C duration 180 min
- the process showed no problems.
- the diameter of the fibers was 0,3 mm.
- the samples for hydrolysis studies were prepared at the beginning of the process, from falling drops, in order to have thicker fibers for better SEM images.
- the fibers were tested by immersing them in Tris for 3, 5 and 7 days, respectively. Clear precipitation of calcium phosphate occurred at 3-7 days. The precipitation occurred as large flakes and started already to decay at 7 days.
- Figures 6a to 9b illustrate the results of the immersion tests.
- the Figures are SEM-pictures (scanning electron microscope) and Figures 6a, 7a, 8a and 9a are taken at a smaller enlargement than Figures 6b, 7b, 8b and 9b. From Figures 6a and 6b, it can be seen that at time 0, there is no precipitation of calcium phosphate. From Figures 7a to 9b, it can be seen that there is precipitation at times 3 days ( Figures 7a and 7b), 5 days ( Figures 8a and 8b) and 7 days ( Figures 9a and 9b). The precipitations are evenly distributed at the surface of the fibers and this shows the high uniformity of the material.
- Example 2 Samples for hydrolysis studies were prepared as in Example 2 and the hydrolysis study was carried out as in Example 2. At 3 days, one out of two samples showed precipitation of calcium phosphate, the other not. At 5 days, there was no precipitation of calcium phosphate and at 7 days, there was a clear precipitation of calcium phosphate in both samples. The precipitation occurred as small flakes, clearly smaller than in Example 2. It is believed that the irregular results in the formation of the precipitation are due to partial crystallization of the glass during the fiber making process.
- Figures 10a to 14b illustrate the results of the immersion tests.
- the Figures are SEM-pictures (scanning electron microscope) and Figures 10a, 11a, 12a, 13a and 14a are taken at a smaller enlargement than Figures 10b, lib, 12b, 13b and 14b.
- Figures 11a, lib and 12a, 12b are SEM- pictures of two different samples at time 3 days. It can be seen that in the sample shown in Figure 11a and lib, there has occurred essentially no precipitation and that in the sample shown in Figures 12a and 12b, there has occurred precipitation. This kind of discrepancy was not encountered with the samples prepared according to Example 2.
- Figures 13a and 13b show that at both samples, there was no precipitation at time 5 days, and Figures 14a and 14b show that there was precipitation at time 7 days.
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Abstract
Description
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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AU2003264666A AU2003264666B2 (en) | 2002-10-03 | 2003-10-02 | Composition, use and manufacture of bioactive glass |
CA002500823A CA2500823A1 (en) | 2002-10-03 | 2003-10-02 | Composition, use and manufacture of bioactive glass |
US10/530,043 US20060166807A1 (en) | 2002-10-03 | 2003-10-02 | Composition, use and manufacture of bioactive glass |
JP2004540837A JP2006501125A (en) | 2002-10-03 | 2003-10-02 | Bioactive glass composition, use thereof and process for its production |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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EP02079105A EP1405647B1 (en) | 2002-10-03 | 2002-10-03 | Bioactive glass composition |
EP02079105.9 | 2002-10-03 | ||
US41582002P | 2002-10-04 | 2002-10-04 | |
US60/415,820 | 2002-10-04 |
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WO2004031086A1 true WO2004031086A1 (en) | 2004-04-15 |
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US (1) | US20060166807A1 (en) |
JP (1) | JP2006501125A (en) |
AU (1) | AU2003264666B2 (en) |
CA (1) | CA2500823A1 (en) |
WO (1) | WO2004031086A1 (en) |
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WO2008099058A1 (en) | 2007-02-13 | 2008-08-21 | Vivoxid Oy | A system and method for manufacturing fibres |
WO2011001028A1 (en) * | 2009-06-29 | 2011-01-06 | Bonalive Biomaterials Oy | A bioactive glass for use in conditions relating to bone infections |
WO2018025022A1 (en) * | 2016-08-01 | 2018-02-08 | Johnson Matthey Public Limited Company | Powder and process |
WO2018025020A1 (en) * | 2016-08-01 | 2018-02-08 | Johnson Matthey Public Limited Company | Powder and process |
US10596660B2 (en) | 2015-12-15 | 2020-03-24 | Howmedica Osteonics Corp. | Porous structures produced by additive layer manufacturing |
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ES2338694T3 (en) | 2006-09-20 | 2010-05-11 | Inion Oy | COMPOSITIONS OF BIOACTIVE GLASS. |
JP5911240B2 (en) * | 2010-10-04 | 2016-04-27 | キヤノン株式会社 | Porous glass, manufacturing method thereof, optical member, and imaging apparatus |
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WO2001066479A1 (en) * | 2000-03-07 | 2001-09-13 | Itaelae Ari | A method for etching the surface of a bioactive glass |
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US3904425A (en) * | 1964-06-12 | 1975-09-09 | American Optical Corp | Absorptive glass |
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- 2003-10-02 AU AU2003264666A patent/AU2003264666B2/en not_active Ceased
- 2003-10-02 US US10/530,043 patent/US20060166807A1/en not_active Abandoned
- 2003-10-02 CA CA002500823A patent/CA2500823A1/en not_active Abandoned
- 2003-10-02 WO PCT/FI2003/000715 patent/WO2004031086A1/en active Application Filing
- 2003-10-02 JP JP2004540837A patent/JP2006501125A/en active Pending
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JP2006334406A (en) * | 2005-05-31 | 2006-12-14 | Axetis Ag | Vascular stent |
EP1872806A1 (en) * | 2006-06-28 | 2008-01-02 | Vivoxid Oy | Implant, its uses and methods for making it |
WO2008000888A2 (en) * | 2006-06-28 | 2008-01-03 | Vivoxid Oy | Implant containing a source of oxygen |
WO2008000888A3 (en) * | 2006-06-28 | 2008-10-23 | Vivoxid Oy | Implant containing a source of oxygen |
WO2008099058A1 (en) | 2007-02-13 | 2008-08-21 | Vivoxid Oy | A system and method for manufacturing fibres |
EP2448607A1 (en) * | 2009-06-29 | 2012-05-09 | BonAlive Biomaterials Oy | A bioactive glass for use in conditions relating to bone infections |
WO2011001028A1 (en) * | 2009-06-29 | 2011-01-06 | Bonalive Biomaterials Oy | A bioactive glass for use in conditions relating to bone infections |
US10596660B2 (en) | 2015-12-15 | 2020-03-24 | Howmedica Osteonics Corp. | Porous structures produced by additive layer manufacturing |
US12097657B2 (en) | 2015-12-15 | 2024-09-24 | Howmedica Osteonics Corp. | Porous structures produced by additive layer manufacturing |
WO2018025022A1 (en) * | 2016-08-01 | 2018-02-08 | Johnson Matthey Public Limited Company | Powder and process |
WO2018025020A1 (en) * | 2016-08-01 | 2018-02-08 | Johnson Matthey Public Limited Company | Powder and process |
US11628517B2 (en) | 2017-06-15 | 2023-04-18 | Howmedica Osteonics Corp. | Porous structures produced by additive layer manufacturing |
US10888362B2 (en) | 2017-11-03 | 2021-01-12 | Howmedica Osteonics Corp. | Flexible construct for femoral reconstruction |
US11890041B2 (en) | 2017-11-03 | 2024-02-06 | Howmedica Osteonics Corp. | Flexible construct for femoral reconstruction |
Also Published As
Publication number | Publication date |
---|---|
US20060166807A1 (en) | 2006-07-27 |
AU2003264666A1 (en) | 2004-04-23 |
JP2006501125A (en) | 2006-01-12 |
AU2003264666B2 (en) | 2008-08-21 |
CA2500823A1 (en) | 2004-04-15 |
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