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WO2025083707A1 - Nouveau verre bioactif à base de borosilicate pour revêtement sur des implants ti-6al-4v et son procédé - Google Patents

Nouveau verre bioactif à base de borosilicate pour revêtement sur des implants ti-6al-4v et son procédé Download PDF

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Publication number
WO2025083707A1
WO2025083707A1 PCT/IN2024/052069 IN2024052069W WO2025083707A1 WO 2025083707 A1 WO2025083707 A1 WO 2025083707A1 IN 2024052069 W IN2024052069 W IN 2024052069W WO 2025083707 A1 WO2025083707 A1 WO 2025083707A1
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Prior art keywords
coating
glass
glasses
molar
implants
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Anustup CHAKRABORTY
Subhadip Bodhak
Kaushik Biswas
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Council of Scientific and Industrial Research CSIR
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Council of Scientific and Industrial Research CSIR
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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
    • A61L27/04—Metals or alloys
    • A61L27/06—Titanium or titanium alloys
    • 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
    • A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
    • 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
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • 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
    • 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
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/08—Frit compositions, i.e. in a powdered or comminuted form containing phosphorus
    • 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
    • A61L2420/00—Materials or methods for coatings medical devices
    • A61L2420/02—Methods for coating medical devices
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

Definitions

  • the present invention relates to novel borosilicate based bioactive glass for coating on Ti-6A1-4V implants and its process thereof.
  • the novel glass compositions yielding fast in vitro biomineralization ability, high thermal stability, and a similar thermal expansion coefficient to that of Ti-6A1-4V implants are suitable for obtaining a well adherent and crack-free coating on such implants through simple enameling technique.
  • the high thermal stability of the novel glasses helps in retaining amorphous nature even in the form of a sintered coating and thus, the biological functionalities of the parent glasses can be preserved in the applied coating.
  • metallic implants such as Ti and its alloys, stainless steel, Co-Cr etc.
  • Ti-6A1-4V is highly advantageous because of high corrosion resistance, low density, and favorable mechanical properties relevant to orthopaedic implants.
  • the released metal ions from the implant can induce genotoxicity and carcinogenesis while the lack of osseointegration can cause loosening of the implant.
  • bioactive glass coating on the surface of the metallic implant has been found very effective for improving corrosion resistance and osseointegration.
  • Bioactive glasses are well-known for their bone bonding ability while those are also capable of stimulating new bone growth.
  • bioactive glasses The bone regeneration capability of bioactive glasses is mediated by apatite crystallization on the surface which enhance bone cell proliferation. Moreover, the released ions from bioactive glass to the physiological medium may result in many beneficial functionalities such as antibacterial property, osteoinductive effect, stimulated vascularization etc.
  • bioactive glasses it is challenging to obtain an adherent coating on the metallic substrate due to an imbalance in the thermal expansion coefficient (Table 1). Additionally, the commercial bioactive glasses suffer from high crystallization tendency or devitrification tendency during processing at higher temperatures. Bioactive glass coating deposited on metallic implants often needs to be consolidated through viscous flow sintering at a temperature higher than the glass transition temperature.
  • a crystallization event during sintering results in incomplete densification because the development of crystalline phases hinders the viscous flow sintering process. Moreover, the crystalline phase dissolves at a much lower rate compared to the glassy phase when in contact with a physiological medium. The slower dissolution of the crystalline phase leads to deterioration of the osseointegration process as it depends on the concentration of the released ions in the surrounding medium.
  • Table 1 Comparison of linear thermal expansion coefficient ((0150-300) x 10 ⁇ 6 /°C) of some commercial bioactive glasses and Ti alloys
  • the glass comprises 10-25% of Sit , 10-20% of CaO, and 1-3% of P2O5., 3-8% of Na 2 O, 6-10% of K 2 O, 5-10% of MgO, 5-8% of SrO, and 30-50% of B2O3.
  • the process is quite complex and the benefit of ionic dissolution product on the tissue healing process cannot be realized completely as glass is partially converted to HCA.
  • the composition of the glasses and relevant properties described in the patent significantly differ from the present invention.
  • RO 130068 describes a method of producing alkali free bioactive glass coated dental implants through radio frequency magnetron field sputtering technology.
  • the bioactive glass composition belongs to SiOi-CaO-MgO-PiOs-ZnO-SrO system and maintains the thermal expansion coefficient close to that of titanium and its alloys. The details regarding the composition range, thermal expansion coefficient values and thermal stability are not disclosed in the patent document. Moreover, the compositions are widely different than the present invention while having some additional components like MgO, ZnO and SrO.
  • Canadian patent CA2210070C discloses glass compositions with a large working range, controlled durability and chemical bonding ability with hard and soft tissues.
  • the disclosed glass compositions contain additional oxides such as K2O and MgO which are not used in the glass composition related to the present invention.
  • additional oxides such as K2O and MgO which are not used in the glass composition related to the present invention.
  • the thermal expansion coefficient and the suitability of the glass compositions for coating on metallic alloys have not been addressed in the patent document.
  • Our present invention mainly focuses on the thermal expansion behavior, devitrification resistance and in vitro bioactivity of the glass compositions that make them suitable for coating applications on Ti-6A1-4V implants.
  • JP2008518650A relates to the development of glass compositions for treatment of lesions associated with damaged or insufficient angiogenesis and for preventing avascular fibrosis.
  • the glass composition belongs to SiOi-NaiO-CaO-KiO-MgO-BiCh-PiOs system and used in the unsintered form or as fibers.
  • the patent lacks any information regarding the thermal expansion behavior and thermal stability while the glass composition is also completely different than our present invention.
  • Peddi et al. (Peddi L, Brow RK, Brown RF. Bioactive borate glass coatings for titanium alloys. Journal of Materials Science: Materials in Medicine. 2008 Sep; 19:3145- 52.) reported bioactive borate glass compositions for coating application on Ti-6A1-4V implants.
  • the glass containing NaiO, CaO, B2O3, SiCh, AI2O3, and P2O5 possess a thermal expansion coefficient close to that of Ti alloy.
  • the coating with this glass composition was achieved through enamelling technique resulting in good adhesion strength.
  • the thermal stability or the amorphous nature of the coating was not addressed while the in vitro bioactivity results highlight a delayed bioactivity (2 weeks).
  • the compositions of the reported glasses were also substantially different than the present invention.
  • the reported parent glass compositions contain similar ingredients like present invention, the proportion of different ingredients is significantly different.
  • the reported glasses comprise 25-45 mol% P2O5 and 15 mol% SiCh while glasses from the present invention contain 1-2 mol% P2O5 and 30-32 mol % SiCh.
  • the report mostly focuses on the derived glass ceramics without mentioning the important properties (linear thermal expansion coefficient, processing window or thermal stability) of parent glasses pertinent to coating application on metallic implants.
  • the bioactive glasses from prior art are having substantially different compositions compared to the present invention.
  • additional reactants like MgO, ZnO, CaFi, K2O, SrO can be noticed in most of the prior art documents.
  • MgO, ZnO, CaF2 and SrO are known to cause a delay in their in vitro biomineralization ability.
  • in vitro bioactivity and thermal stability factor of the glasses from prior art are not discussed in most of the cases.
  • the nature of coating is not reported in any of the prior art document. Therefore, it is technologically significant for commercial success to develop a bioactive glass composition with superior devitrification resistance, fast in-vitro bioactivity and a thermal expansion coefficient comparable to that of Ti-6A1-4V alloy.
  • An objective of the present invention is to provide bioactive glass compositions which have similar thermal expansion coefficient to that of Ti-6A1-4V implants and thus, eliminate or minimize the problems described in the background and prior art section.
  • Another objective of the present invention is to provide bioactive glass compositions which show considerably fast in vitro bioactivity and high enough thermal stability for retaining amorphous nature even in the sintered coating form.
  • Yet another objective of the present invention is to provide bioactive glass compositions for coating on Ti-6A1-4V implants with a suitable balance between in vitro bioactivity, thermal stability or devitrification resistance.
  • Still another objective of the present invention is to provide an easy and economic method for coating the above-mentioned glasses on to Ti-6A1-4V substrate.
  • the present invention discloses a novel range of bioactive glass compositions exhibiting a unique combination of relevant properties like thermal expansion coefficient, thermal stability and bioactivity pertinent to coating on Ti-6A1-4V based medical implants retaining the amorphous nature.
  • the bioactive glass compositions comprise 30-32 molar % SiCh, 21-23 molar % B2O3, 1-2 molar % P2O5, 0-23 molar % Na2O, and 22-45 molar % CaO. Glasses belonging to this composition range exhibit a unique combination of properties which make them more suitable and advantageous for coating application on Ti- 6A1-4V implants compared to the compositions reported in prior art.
  • Such unique combination of properties ensures a well adherent, crack-free and amorphous coating on Ti-6A1-4V implants with the ability to integrate with the host tissue.
  • a commercially viable and simple process for coating the said glass compositions on the metallic substrate is also described. The coating has been applied through cold spraying followed by sintering technique. This coating technique is commercially viable and very simple to adopt, resulting in an amorphous coating layer on the implant.
  • the process parameters involved in slurry preparation slurry recipe, solid loading, particle size of powder, milling parameters
  • coating process spraying parameters and sintering schedule
  • Figure 1 represents DSC thermograms of the glasses from example 1 to example 5.
  • Figure 2 represents the dilatometric curves of the glasses from example 1 to example 5.
  • Figure 3 represents the XRD plots after 3 days of in vitro bioactivity study of glasses from example 1 to example 5.
  • Figure 4 represents the XRD plots of the sintered coating with commercial 45S5 glass and the glass from example 5.
  • Figure 5 represents the optical image of the sintered coating on Ti-6A1-4V substrate with the 45S5 glass (example 6) (a) and glass from example 5 (b).
  • the present invention provides novel borosilicate based bioactive glass for coating on Ti-6A1-4V implants and its process thereof which comprises 30-32 molar % SiOi, 21-23 molar % B2O3, 1-2 molar % P2O5, 0-23 molar % Na2O, and 22-45 molar % CaO as chemical constituents of the glass.
  • the invented glasses have a linear thermal expansion coefficient (0150-300) in the range of 8.5- 12.19 xlO 6 / °C.
  • the coating of commercial bioactive glasses (45S5, S53P4) on Ti-6A1-4V based medical implants comes with a spalling problem as the linear thermal expansion coefficient of those glasses varies in the range of 15-13.5 xlO 6 / °C which is a huge mismatch with the substrate.
  • the thermal expansion coefficients of novel glass compositions are similar to the substrate and hence a well adherent coating can be obtained.
  • the invented glasses exhibit a thermal stability factor (AT) of more than 145°C.
  • AT thermal stability factor
  • the thermal stability factor of commercial bioactive glasses developed so far varies in the range of 50-100°C leading to incomplete densification and deteriorated biological functionalities due to early crystallization during sintering process.
  • the higher thermal stability factor of the novel glass compositions indicates the ability of these glasses to be sintered retaining completely amorphous nature.
  • the in vitro bioactivity of the glass is comparable to that of commercial S53P4 composition which demonstrates formation of surface apatite layer within 24-72 h of immersion in stimulated body fluid when tested according to TC04 protocol.
  • the glass can be processed in to a slurry containing 30-45 vol % glass powder of 10-45 pm particle size in distilled water, ethanol or isopropanol.
  • the glass slurry can be deposited on the metal substrate by simple and commercially viable cold spraying technique using a spray gun followed by sintering at (50-70) °C above the glass transition temperature for 1-2 h.
  • the final coating was observed to be completely amorphous in nature and free from cracks.
  • the glass composition comprises 30-32 molar % SiOi, 21-23 molar % B2O3, 1-2 molar % P2O5, 0-23 molar % Na2O, and 22-45 molar % CaO.
  • the micro cracks result from the different shrinkage behavior of the coating and substrate due to the mismatch in linear thermal expansion coefficients of the two materials. Any dislodged particles from such coating can lead to inflammation and other complexities.
  • the glasses from present innovation are quite well suited to mitigate such problems.
  • a well adherent coating can prevent the corrosion of metallic implants to a larger extent than a coating which is having cracks and a spalling issue.
  • the novel glasses in the form of coating on metallic implants can restrict the release of metal ions into the physiological medium and thus, minimize the risk of complex medical conditions such as genotoxicity or carcinogenesis.
  • the borosilicate glasses reported here are also more advantageous for coating application on Ti-alloys compared to the silicate compositions.
  • Such advantage stems from the possibility of formation of a Ti-boride layer at the glass-metal interface which acts as a barrier to interdiffusion and thus prevent weakening of the bonding between two materials.
  • Another aspect of the innovation is that these glasses are quite well resistant to crystallization or devitrification during processing at high temperatures. The high value (>145°C) of thermal stability factor indicates these glasses can be sintered without any hindrance from crystallization.
  • the conventional glasses are prone to crystallization and the crystallization process often interferes with the sintering process.
  • the crystallization of glasses during sintering comes with a few negative impacts on the processing and properties such as requirement of a much higher temperature for proper densification, and the loss or degradation of many biological functionalities.
  • the Ti-6A1-4V alloy undergoes phase transformation (a «->P) at such high temperatures required for proper densification of those crystallization prone glasses and thereby the alloy can get damaged.
  • the dissolution rate of glasses in physiological medium slows down when it is partially or fully converted to crystalline phase. Since all the biological functionalities are mainly governed by the released ions from the glass to the physiological medium, a deterioration of the biological functionalities can be experienced.
  • the residual glass composition does not remain same as the parent glass due to selective portioning of elements into the crystalline phase.
  • the glasses of our present invention showcase high devitrification resistance and thus, minimize the possibility of such alteration of functionalities.
  • the bioactive glass coating using the compositions of the present invention can lead to fast osseointegration which prevents loosening of the implant.
  • the in vitro bioactivity study works as an indicator for in vivo osseointegration ability.
  • a faster in vitro apatite forming ability or bioactivity is a marker of faster in vivo bone bonding ability.
  • the glasses in the present invention showcase formation of apatite layer within 1-3 days of immersion in simulated body fluid.
  • the commercial glasses like 45S5 and S53P4 take 1 day and 3 days, respectively, to exhibit the same. However, those glasses get partially crystallized during sintering which will in turn cause delayed bioactivity when applied as a coating.
  • the glasses reported here are able to retain their apatite forming ability even in the form of a sintered coating.
  • the coating of the glasses on the metallic substrate can be attained through simple cold spraying technique followed by sintering of the coating. This commercially viable process is rather simple to adopt while the sintering conditions can also be maintained well below the phase transformation temperature of Ti-6A1-4V alloy.
  • Table 2 Composition of novel borosilicate bioactive glasses
  • the glass compositions in the present invention were synthesized through conventional melt-quench technique using pure platinum crucible.
  • the thoroughly mixed batches of analytical grade raw materials such as SiCh (99.8%, Sipur Al Bremthelar Quartz - itwerk), NaiCCh (99.5%, Sigma Aldrich), CaCCh (99.5%, Sigma Aldrich), CaHPC .SHiO (98% Sigma Aldrich), and H3BO3(99.5%, Fluka) were melted at 1150-1450 °C range inside a raising hearth furnace (Kanthal).
  • the homogeneity of the glass melt was ensured by intermittent stirring with a fused silica rod during the 1.5-2.5 h melting time.
  • glass melt was cast in a stainless-steel mould and the cast block was immediately transferred to a muffle furnace for annealing. Annealing was carried out for 2-3 h followed by gradual cooling to room temperature for obtaining a stress-free glass block. Finally, these annealed glass blocks were crushed and further milled in a planetary ball mill to obtain fine glass powder ( ⁇ 45 microns).
  • the thermal stability of the glasses was measured using differential scanning calorimetry (DSC) (STA 449F3, Netzsch GmbH, Selb, Germany).
  • DSC differential scanning calorimetry
  • the DSC thermograms of glass powders with below 45 pm particle size were recorded at 10 °C min 1 heating rate.
  • Thermal stability of the glass compositions described in this invention are listed in the table 3.
  • Linear thermal expansion coefficient (0150-300) of the glasses was measured utilizing a pushrod dilatometer (Netsch, DIL402PC). The Cylindrical samples having 6 mm diameter and 25 mm length was heated at 5°C/min rate and the ratio of change in length/original length (thermal strain) was recorded as a function of temperature. Linear thermal expansion coefficient of glass samples was measured from the slope of the thermal expansion versus temperature curve and the obtained values for different glasses in the 50-300 °C temperature range is reported in table 3.
  • the in vitro bioactivity indicates the time taken for formation of a crystalline apatite layer on the material’s surface when immersed in aqueous medium such as simulated body fluid, tris buffer etc.
  • a faster in vitro bioactivity of a material is a marker of faster bone bonding ability in vivo condition.
  • the in vitro bioactivity of the glasses was examined according to the TC04 protocol.
  • TC04 stands for technical committee 04 of international commission on glass (ICG) that is concerned with the glasses for medicine and biotechnology.
  • TC04 committee members conducted a round robin study across several different laboratories to develop this reliable and simple protocol for comparing bioactivity of different glasses. This protocol is frequently adopted to compare bioactivity of different samples by the bioactive glass researchers.
  • Ti-6A1-4V substrate was grit blasted using alumina powder for providing a rough surface which will allow better anchorage of the coating.
  • the grit blasted substrate was ultrasonically cleaned with ethanol.
  • the glass powder has to be taken in the form of a slurry to apply coating on the prepared substrate through the cold spraying technique.
  • the slurry was prepared by mixing fine glass powder (30-45 vol%) of 10-45 pm particle size with a solution of distilled water and poly vinyl alcohol (0.5- 1.5 weight % of glass powder). The mixing operation to obtain a stable dispersion was carried out by milling the mixture in a planetary ball mill for 1-3 h at 200-300 rpm.
  • the slurry was then sprayed on to the prepared substrate with the help of a spraying gun.
  • the coating thickness on the substrate can be controlled by changing the number of passes.
  • coated sample was dried at 110 °C in an oven.
  • the dried samples were subjected to sintering at a temperature of 550 - 720 °C (50-70 °C higher than T g ) for 1-2 h in a muffle furnace depending on their composition.
  • the sintered sample was cooled to room temperature maintaining a 2-4 °C/min cooling rate.
  • the glass comprises 31.43 molar % SiCh, 22.45 molar % B2O3, 22.21 molar % CaO, 22.21 molar % NaiO and 1.7 molar % P2O5.
  • appropriate quantity of each raw materials was mixed before charging in a platinum crucible inside raising hearth furnace.
  • the glass melting was carried out at 1150 °C and the cast block was annealed at 485 °C.
  • the linear thermal expansion coefficient (0150-300) of the glass was estimated to be 12.19 xlO’ 6 /°C.
  • the thermal stability of glass powder having below 45 pm particle size was measured to be 180 °C at 10 °C min 1 heating rate.
  • the in vitro bioactivity results highlighted formation of apatite layer after 1 day (24h) of immersion in simulated body fluid.
  • the glass comprises 31.43 molar % SiCh, 22.45 molar % B2O3, 27.76 molar % CaO, 16.66 molar % Na2O and 1.7 molar % P2O5.
  • appropriate quantity of each raw materials was mixed before charging in a platinum crucible inside raising hearth furnace.
  • the glass melting was carried out at 1200 °C and the cast block was annealed at 515 °C.
  • the linear thermal expansion coefficient (0150-300) of the glass was estimated to be 10.96 xlO’ 6 /°C.
  • the thermal stability of glass powder having below 45 pm particle size was measured to be 149°C at 10 °C min 1 heating rate.
  • the in vitro bioactivity results highlighted formation of apatite layer after 3 days (72h) of immersion in simulated body fluid.
  • the glass comprises 31.43 molar % SiCh, 22.45 molar % B2O3, 33.31 molar % CaO, 11.11 molar % Na2O and 1.7 molar % P2O5.
  • appropriate quantity of each raw materials was mixed before charging in a platinum crucible inside raising hearth furnace.
  • the glass melting was carried out at 1250 °C and the cast block was annealed at 545 °C.
  • the linear thermal expansion coefficient (0150-300) of the glass was estimated to be 10.07 xlO’ 6 /°C.
  • the thermal stability of glass powder having below 45 pm particle size was measured to be 169°C at 10 °C min 1 heating rate.
  • the in vitro bioactivity results highlighted formation of apatite layer after 3 days (72h) of immersion in simulated body fluid.
  • the glass comprises 31.43 molar % SiCh, 22.45 molar % B2O3, 38.87 molar % CaO, 5.55 molar % NaiO and 1.7 molar % P2O5.
  • appropriate quantity of each raw materials was mixed before charging in a platinum crucible inside raising hearth furnace.
  • the glass melting was carried out at 1300 °C and the cast block was annealed at 575 °C.
  • the linear thermal expansion coefficient (0150-300) of the glass was estimated to be 9.44 xlO’ 6 /°C.
  • the thermal stability of glass powder having below 45 pm particle size was measured to be 167°C at 10 °C min 1 heating rate.
  • the in vitro bioactivity results highlighted formation of apatite layer after 3 days (72h) of immersion in simulated body fluid.
  • the glass comprises 31.43 molar % SiCh, 22.45 molar % B2O3, 44.42 molar % CaO, and 1.7 molar % P2O5.
  • appropriate quantity of each raw materials was mixed before charging in a platinum crucible inside raising hearth furnace.
  • the glass melting was carried out at 1350 °C and the cast block was annealed at 605 °C.
  • the linear thermal expansion coefficient (0150-300) of the glass was estimated to be 8.5xl0 -6 /°C.
  • the thermal stability of glass powder having below 45 pm particle size was measured to be 187 °C at 10 °C min 1 heating rate.
  • the glass from example 5 was applied as a coating on the Ti-6A1-4V substrate.
  • the coating process has already been mentioned earlier. Briefly, an aqueous slurry containing 30-45 volume % glass powder of 10-45 pm particle size and small amount (1 weight % of glass powder) of polyvinyl alcohol as binder was prepared. The prepared slurry was then coated on to the grit blasted Ti-6A1-4V substrate through a spray gun. Finally, applied coating was sintered at 710 °C for Ih and then slowly cooled to room temperature to obtain consolidated coating. Both visual and microscopic examinations confirmed the coating is free of cracks (figure 5).
  • the sintered coating obtained from the glass composition in example 5 was noticed to be completely amorphous in nature from the x-ray diffraction technique (figure 4). Mechanical properties of the coating were investigated by the means of nano-indentation technique. The hardness and modulus of the coating comprising glass from example 5 are 99.5 GPa and 1.83 GPa, respectively.
  • the 45S5 coating exhibited crystalline nature and the crystalline phase was combeite or sodium-calcium-silicate (figure 4) whereas the sintered coating obtained from the glass composition in example 5 was noticed to be completely amorphous in nature (figure 4).
  • Table 4 Properties of the glass from example 6 and the process parameters utilized for coating on Ti-6A1-4V substrate
  • compositions can be applied as a well adherent coating on Ti-6A1-4V implants which will not show any kind spalling problems due to thermal expansion mismatch.
  • compositions described in this invention will be useful for coating application on Ti-6A1-4V implants.
  • the metal implants coated with the novel glasses will be able to show proper osseointegration which will in turn circumvent the issue of implant loosening in the long run.
  • novel glass compositions when applied as a coating on the metallic implants will also help in reducing the release of metal ions into the physiological medium, and thus, the risk of carcinogenesis and genotoxicity can be reduced.
  • novel compositions also exhibit high thermal stability values which indicate those will retain their amorphous nature even after sintering.
  • the amorphous coating helps in retaining the biological functionalities originating from the dissolution behavior of the parent glasses.
  • the developed glasses exhibit fast in vitro bioactivity which indicates the well adherent coating will also have fast osseointegration ability.
  • the glass composition described in this invention have been achieved through usage of less number reactants as the reactants like MgO, K2O, CaFi etc. described in the glass compositions of prior art are not incorporated.
  • the coating on the metallic substrate can be achieved through an economic and commercially viable cold-spraying technique followed by sintering.

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  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
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  • Veterinary Medicine (AREA)
  • Engineering & Computer Science (AREA)
  • Dermatology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Transplantation (AREA)
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Abstract

Tandis que l'alliage Ti -6 A1-4 V est largement préféré pour des implants orthopédiques, il est crucial de traiter les risques potentiels de génotoxicité et de desserrage d'implant provoqués par des ions métalliques libérés et l'absence d'ostéo-intégration, respectivement. Dans ce contexte, la présente invention concerne de nouvelles compositions de verre bioactif à base de borosilicate, appropriées pour une application de revêtement sur des implants Ti-6A1-4V. Les caractéristiques évaluées de ces verres présentent une stabilité thermique élevée (> 145°C), une bioactivité in vitro rapide (24-72h) et un coefficient de dilatation thermique linéaire (8,5 - 12,19 x 10-6/°C) similaire à celui de l'alliage. La combinaison favorable de propriétés permet d'obtenir un revêtement bien adhérent et amorphe sur la surface de l'alliage, assurant une capacité d'ostéo-intégration et une protection contre le risque de génotoxicité. De plus, la présente invention présente une technique de revêtement commercialement viable qui implique une pulvérisation à froid suivie d'un traitement thermique, ce qui permet d'obtenir un revêtement amorphe souhaité sur la surface d'implant. Globalement, la présente invention devrait améliorer considérablement les performances d'implants orthopédiques à base de Ti-6A1-4V.
PCT/IN2024/052069 2023-10-16 2024-10-15 Nouveau verre bioactif à base de borosilicate pour revêtement sur des implants ti-6al-4v et son procédé Pending WO2025083707A1 (fr)

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IN202311070421 2023-10-16

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009081120A1 (fr) * 2007-12-20 2009-07-02 Imperial Innovations Limited Revêtements en verre bioactif
KR20090077650A (ko) * 2008-01-11 2009-07-15 재단법인서울대학교산학협력재단 생체활성 유리 조성물 및 이를 이용한 결정화 유리의제조방법
CN104876439A (zh) * 2006-06-16 2015-09-02 帝国创新有限公司 生物活性玻璃
US9238044B2 (en) * 2011-04-05 2016-01-19 Reg4Life Regeneration Technology, S.A. Alkali-free bioactive glass composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104876439A (zh) * 2006-06-16 2015-09-02 帝国创新有限公司 生物活性玻璃
WO2009081120A1 (fr) * 2007-12-20 2009-07-02 Imperial Innovations Limited Revêtements en verre bioactif
KR20090077650A (ko) * 2008-01-11 2009-07-15 재단법인서울대학교산학협력재단 생체활성 유리 조성물 및 이를 이용한 결정화 유리의제조방법
US9238044B2 (en) * 2011-04-05 2016-01-19 Reg4Life Regeneration Technology, S.A. Alkali-free bioactive glass composition

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