WO1998016267A1 - Matieres de substitution osseuse a systeme d'interconnexion des pores - Google Patents

Matieres de substitution osseuse a systeme d'interconnexion des pores Download PDF

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Publication number
WO1998016267A1
WO1998016267A1 PCT/IE1997/000068 IE9700068W WO9816267A1 WO 1998016267 A1 WO1998016267 A1 WO 1998016267A1 IE 9700068 W IE9700068 W IE 9700068W WO 9816267 A1 WO9816267 A1 WO 9816267A1
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WO
WIPO (PCT)
Prior art keywords
bone
abm
cancellous bone
synthetic
bone replacement
Prior art date
Application number
PCT/IE1997/000068
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English (en)
Inventor
David Tancred
Brendan Mccormack
Alun Carr
Original Assignee
University College Dublin
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University College Dublin filed Critical University College Dublin
Priority to AU46362/97A priority Critical patent/AU4636297A/en
Publication of WO1998016267A1 publication Critical patent/WO1998016267A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/56—Porous materials, e.g. foams or sponges
    • 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

  • This invention relates to bone replacement materials.
  • it relates to synthetic bone replacement materials having the macroporous structure of natural cancellous bone.
  • HA macroporous hydroxyapatite
  • beta-TCP beta-tricalcium phosphate
  • the porosity of the bone replacement material, its pore size distribution, pore morphology, and the degree of pore interconnectivity significantly influence the extent of bone ingrowth.
  • the macrostructure of the bone replacement material is similar in morphological characteristics to the inorganic matrix of the bone it is replacing. While macroporous bone replacement materials have been produced based on coralline skeletal and other generic macrostructures, it has not so far been possible to produce suitable synthetic bone replacement materials having a macroporous structure similar to that of natural cancellous bone.
  • Cancellous bone consists of a network of interconnecting rods and plates called trabeculae which form a sponge-like matrix. Individual trabeculae are typically 50-150 ⁇ m thick. Fully interconnecting spaces, ranging from tens of ⁇ m to 1 mm, the majority of which are 400-600 ⁇ m in diameter, run throughout the lattice.
  • the porosity of natural cancellous bone poses considerable difficulties in forming synthetic replicas thereof having the requisite characteristics to allow their use in non-load bearing applications. Such replicas should be easy to handle and shape without damage, have the required mechanical strength and allow bone regeneration throughout their porous structure.
  • Replacement materials for cancellous bone are generally used in non-load bearing situations so that their mechanical strength need not be very high. The primary mechanical function of cancellous bone replacement materials is to prevent prolapse of soft tissue into the defect site during bone regeneration. An implant which can fulfil this function would possess sufficient strength as a bone filler.
  • a synthetic bone replacement material having a macroporous structure similar to that of natural cancellous bone, characterized by a pore volume of 70-95%, fully interconnecting pores having a diameter in the range of from about 10 ⁇ m to 1 mm.
  • the synthetic bone replacement material of the invention may be any suitable biomaterial, examples of which include bioceramic materials such as hydroxyapatite (HA) , a calcium phosphate such as a- and ⁇ -tricalcium phosphate (TCP) , bioglass, HA/cu-or ⁇ -TCP composites, HA/glass or bioglass composites and alumina; polymeric materials such as poly- -lactid acid; and metals such as titanium.
  • bioceramic materials such as hydroxyapatite (HA) , a calcium phosphate such as a- and ⁇ -tricalcium phosphate (TCP) , bioglass, HA/cu-or ⁇ -TCP composites, HA/glass or bioglass composites and alumina
  • TCP tricalcium phosphate
  • bioglass HA/cu-or ⁇ -TCP composites
  • polymeric materials such as poly- -lactid acid
  • Bioglasses are well known, a number of which are suitable for use in the bone replacement materials of the invention, either as the sole component or as a component of a HA composite. Suitable bioglasses are described in An Introduction to Bioceramics , Vol. 1, Hench, L.L. and Wilson, J. (ed.), World Scientific, Singapore, 1993.
  • a preferred bioglass has the following composition, the percentages being mol . % of the total composition: 13.1% CaO; 4.7% P2O5 ; 52.6% Si0 2 ; 25.8% Na 2 0; 0.5% Al 2 0 3 ; and 3.0% B 2 0 3 .
  • the amount of HA in HA/TCP composites can range from 5% to 95% by weight, suitably from 20% to 70% by weight.
  • the glass is preferably a phosphate glass containing about 50 mol . % CaO and about 50 mol.% P 2 C>5 and is preferably present in the composite at a concentration of from 2.5 to 10% by weight .
  • the synthetic bone replacement material of the present invention may be used as a carrier matrix for a bone inductive material, such as a bone morphogenetic protein (BMP) or a non-collagenous protein (NCP) in the stimulation of bone formation.
  • a bone inductive material such as a bone morphogenetic protein (BMP) or a non-collagenous protein (NCP) in the stimulation of bone formation.
  • BMP bone morphogenetic protein
  • NCP non-collagenous protein
  • the invention also provides the use of cancellous bone in the preparation of a synthetic bone replacement material having a macroporous structure similar to that of natural cancellous bone.
  • a synthetic bone replacement material of the present invention may be obtained by a process comprising the following steps:
  • the resulting product is a positive replica of the original cancellous bone matrix.
  • a synthetic bone replacement material of the present invention may also be obtained by a process comprising the following steps :
  • the resulting product is a negative replica of the original cancellous bone matrix.
  • the above processes may be carried out by cutting cancellous bone samples to the desired shape.
  • the samples may be in particulate form wherein individual particles are about 1-3 mm in diameter, or block form wherein individual blocks preferably have a thickness of up to about 12 mm.
  • the organic material is then removed in such a way that the ABM remains intact. This may be accomplished by, for example, thermal treatment (calcination) wherein all of the organic material is burnt off by heating to a sufficiently high temperature (typically 800°C or higher) .
  • the organic material may be removed by chemical extraction with a suitable solvent, such as ethylenediamine or formamide, using a soxhlet extraction apparatus. Chemical extraction of the organic material is preferred.
  • the anorganic bone mineral should preferably be treated prior to its infiltration so as to seal its trabecular microporosity without blockage of the macroporous structure to be replicated.
  • a preferred treatment involves boiling the ABM for several minutes in sodium hypochlorite and drying the treated product without rinsing. A crystalline residue is thus formed which blocks the trabecular microporosity without alteration or blockage of the trabecular macrostructure .
  • the ABM may be coated by treatment with a suitable polymeric substance, for example, Mowiol (Trade Mark of Hoechst) prior to its infiltration.
  • the ABM is then impregnated with wax under vacuum at about 20 °C above the melting temperature of the wax.
  • Any suitable wax may be used. Suitable waxes are those which are tough, have a moderate viscosity permitting full infiltration of the ABM, solidify without excessive shrinkage resulting in pore formation within the casting, and resist degradation following exposure to the decalcifying agent .
  • Preferred waxes are Castylene B271 and Techniwax 9210 (Dussek Campbell, U.K.) and A7 machining wax (Blayson Olefines Ltd., U.K.) . Following wax solidification, the wax castings are decalcified by, for example, immersion at a temperature ranging from about 20°C to 50°C for about 24 hours to 7 days in dilute acid, for example HC1.
  • a suitable slip is one which is capable of being rendered sufficiently fluid by vibration to penetrate the wax mould completely while having as high a solids content as possible.
  • a bioceramic slip is formed by dispersing the bioceramic in powder form in a carrier fluid having a pH in the range of 7 to 13.
  • the carrier fluid may comprise water and optionally a deflocculant .
  • the deflocculant is preferably present at a concentration up to about 4% by weight of the slip.
  • the bioceramic powder preferably constitutes about 75% by weight of the slip.
  • the slip may be infiltrated into the wax mould by applying a suitable vibratory action.
  • slip infiltration may be performed by application of a vacuum.
  • the prepared slip is placed in a glass container within a vacuum chamber to which a full vacuum may be applied. Wax negative samples are immersed and secured below the surface of the slip. The vacuum chamber is then sealed and a vacuum of at least -0.9 bar applied and held for a period of about 2 minutes. The system is then allowed to back-fill to atmospheric pressure and samples are removed. Mould infiltration may also be achieved by centrifugal casting.
  • samples are recovered and dried slowly, for example at 30-35°C for 24 hours.
  • the wax is removed by slow-melting to prevent destruction of the delicate slip-infiltrated structure.
  • the product is sintered by increasing the temperature step-wise, for example by increasing the temperature by l-15°C/min., to sintering temperature where it is held for three hours followed by step-wise cooling to room temperature.
  • the resulting product is a positive replica of the original cancellous bone.
  • the ABM is impregnated with a viscous melt of a suitable biomaterial, for example a polymeric material.
  • a vacuum may be applied to aid full infiltration of the porous matrix by the biomaterial.
  • the samples are allowed to cool to room temperature and solidify. Decalcification is then carried out as described above, the resulting product being a negative replica of the original cancellous bone.
  • the cancellous bone may be derived from any suitable source, bovine cancellous bone being preferred.
  • Cancellous bone suitable for replication should be of similar porosity to the bone being replaced and should not include any cortical bone, growth plate or defects. Furthermore, variations in porosity should be minimal within a block.
  • Bovine bone is a suitable source for the supply of bone samples due, not only to its availability and the relatively large size of each bone, but also due to its close structural similarity to human cancellous bone. Bovine cancellous bone from the distal femoral condyles, below the growth plate, was found to be particularly useful in the present invention.
  • Samples of bone used preferably have a maximum thickness of about 12 mm.
  • HA hydroxyapatite
  • ⁇ -TCP ⁇ -tricalcium phosphate
  • the glass frit was crushed and dry-milled in a five litre Al 2 0 milling pot, with 12.5 mm diameter cylpeb magnesia-stabilised zirconia milling media. Powders were dry-milled for one hour. The powder was graded by passing through 250, 106, and 45 ⁇ m sieves. Particles above 45 ⁇ m were returned for further ball-milling.
  • Bioceramic slips were prepared from the bioceramic powders described above having the composition shown in Table 2, in which the following abbreviations are used:
  • Composites are referred to according to the nomenclature ⁇ AXY, where X is ⁇ -TCP, PG or BG and Y is the glass or ⁇ -TCP addition (in wt.%) .
  • Table 2 also shows the sintering temperature range for each material and the actual sintering temperature used.
  • the powders of bioceramics 1-12 were subjected to a wet milling process in which 60 g of each powder or composite powder were added to 500 ml wide-mouth polypropylene bottles (Nalgene, Trade Mark) , together with 180 ml isopropyl alcohol (IPA) and approximately 650 g of 7 mm diameter cylpeb magnesia-stabilised zirconia milling media. Milling bottles were shaken vigorously to disperse the powder and then wet milled on ball-mill rollers at approximately 140 rpm for 1 hour.
  • IPA isopropyl alcohol
  • Slips were recovered and passed through a 38 ⁇ m sieve to remove possible contamination resulting from chipping of the milling media. Each slip was placed in an evaporating dish and allowed to dry to a powder cake in a fume hood. Final drying to a constant weight was done in a vacuum oven at approximately 70°C. The dry powders were passed through a 106 ⁇ m sieve to break up any agglomerates formed on drying. Powders were stored in a desiccator until required.
  • the organic matrix of the bone samples was removed by treating them with ethylenediamine (ED) (approx. 95% pure) in a Wheaton 1 litre soxhlet apparatus. Samples were placed in the soxhlet chamber and treated for 48 hours, at a rate of approximately three cycles per hour.
  • ED ethylenediamine
  • a large soxhlet apparatus of the type used is capable of producing 60-70 cubic specimens of 10 mm side length per charge.
  • the bone mineral was rinsed in flowing water for three hours. It was then replaced into the soxhlet extractor for about 18 hours and cycled with deionised water. Following treatment, the bone matrix was chalky white and extremely brittle. Measurement by microanalysis showed there was no detectable residual nitrogen (i.e. organic material) present (below 0.05%) following ethylenediamine treatment.
  • ABSM anorganic bone mineral
  • the resulting anorganic bone mineral (ABM) specimens were immersed in an aqueous solution of 14% sodium hypochlorite in a wide mouth, round bottom flask, fitted with a condenser, at a ratio of 20 ml solution to 1 cm 3 of ABM.
  • the temperature was raised to boiling point and held for two minutes.
  • the samples were removed and placed directly (without rinsing) onto absorbent paper to allow draining, and were then dried in a conventional oven at approximately 70 °C and stored in a desiccator until required.
  • the treated bone samples were then impregnated with the wax Castylene B271 (Dussek Campbell, Kent, U.K.). This wax has a casting temperature of about 105°C, is of medium viscosity, infiltrates without void formation and is hard and shapeable.
  • Impregnation was carried out in a vacuum oven at 100-110°C as follows.
  • the wax was melted in a glass container.
  • the bone samples were placed on the wax surface and allowed to sink under their own weight, expelling air from the voids as the wax penetrated the structure.
  • a vacuum of at least 600 mm Hg was applied and held for one minute. The vacuum was released and the oven allowed to back-fill to atmospheric pressure.
  • the samples were transferred into a flexible container (e.g. weighing boat of high impact polystyrene) and allowed to cool submerged to their own depth in wax.
  • a flexible container e.g. weighing boat of high impact polystyrene
  • This provided a reservoir of molten wax during the period of solidification which prevented surface pore formation due to retraction of wax from the surface pores in a manner analogous to pipe formation in casting.
  • the samples were removed from the container and trimmed by scalpel to expose bone mineral on all sides. If required, shaping was possible at this stage as the wax-filled inorganic matrix had reasonable mechanical integrity.
  • each dried bioceramic powder prepared as described in (b) above was redispersed in a carrier fluid as described below, to form a ceramic slip. This was done by rotating at 60 rpm in an airtight glass container on ball-mill rollers for 24 hours. All slips were prepared to contain 75 wt.-% bioceramic powder with the remainder consisting of carrier fluid, i.e. 300 g of powder in 100 ml of fluid.
  • carrier fluid i.e. 300 g of powder in 100 ml of fluid.
  • the carrier fluid consisted of deionised water to which 3 wt.-% deflocculant (Darvan 811, R.T. Vanderbilt Company, Inc., USA) was added. The pH of the carrier solution was adjusted to 10 by addition of ammonia solution. For materials 7-12, the carrier fluid was deionised water without additives.
  • the samples were placed on a piece of refractory brick for removal of the wax. Wax removal must be accomplished very gently, by slow melting, to prevent destruction of the delicate unsintered slip-cast structure. If the temperature is increased too fast, the wax may melt quickly and the subsequent hot flow may destroy the delicate trabecular structure.
  • the first stage of dewaxing was done in a conventional oven. The temperature was raised at 1°C per minute to 75°C where it was held for 15 minutes. It was then raised in increments of 15°C, using a 1°C per minute ramp rate, up to 150 °C, where it was held for 1 hour. Each 15 °C increment was followed by a dwell of 15 minutes . The samples at this stage still contained a residual solid wax content, degraded due to the thermal treatment. Consequently they still retained some strength. The samples were allowed to cool and were removed from the oven. The samples were not moved from the refractory brick as handling may damage the slip infiltrated structure.
  • Kanthal (Stoke-on-Trent , U.K.) and as described in the Ph.D. thesis of David Tancred, University College, Dublin, National University of Ireland.
  • Fig. 1 is a scanning electron micrograph (SEM) of the macroporous structure of the ABM of a bovine cancellous bone sample used in the above Examples .
  • Fig. 2 is an SEM of the macroporous structure of a sintered replica based on bioglass only (Bioceramic No. 3 of Table 2) .
  • Fig. 3 is an SEM of the macroporous structure of a sintered replica based on HAPG05 (Bioceramic No. 8 of Table 2) .
  • Fig. 4 is an SEM of the macroporous structure of a sintered replica based on HABG50 (Bioceramic No. 12 of Table 2) .
  • Fig. 5 is an SEM of the macroporous structure of a sintered replica based on ⁇ -TCP (Bioceramic No. 2 of Table 2) .
  • Fig. 6 is an SEM of the macroporous structure of a sintered replica based on HA (Bioceramic No. 1 of Table 2) .
  • Samples for scanning electron microscopy were mounted on an aluminium stud with conductive carbon cement and sputter-coated with gold.
  • a JEOL 35C scanning electron microscope operating at 25 kV was used.
  • the prepared replicas based on bioceramics 1-12 of Table 2 are precise cast structural replicas (except for a shrinkage factor due to sintering, typically 15-20%) of the original starting cancellous bone.
  • Example I Following infiltration, the specimen was removed, shaped and trimmed as appropriate, and decalcified according to the procedure described in Example I .
  • All replicas prepared had adequate compressive strength (typically 1-3 MPa) , were easy to handle and shape without damage, and had good biocompatibility, thus making them particularly suitable for use as bone graft substitutes in non-load bearing applications.

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Transplantation (AREA)
  • Dermatology (AREA)
  • Medicinal Chemistry (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Dispersion Chemistry (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Materials For Medical Uses (AREA)

Abstract

L'invention concerne des matières de substitution osseuse synthétique présentant une structure macroporeuse similaire à celle d'un os spongieux naturel avec un volume de pores compris entre 70 et 95 % et interconnectant totalement les pores dont le diamètre est compris entre 10 νm et 1 mm. Les matières préférées sont les phosphates de calcium, le bioverre, l'acide poly-L-lactique et le titane.
PCT/IE1997/000068 1996-10-15 1997-10-15 Matieres de substitution osseuse a systeme d'interconnexion des pores WO1998016267A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU46362/97A AU4636297A (en) 1996-10-15 1997-10-15 Bone replacement materials with interconnecting pore system

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IE960728 1996-10-15
IES960728 1996-10-15

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WO1998016267A1 true WO1998016267A1 (fr) 1998-04-23

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999034845A1 (fr) * 1997-12-31 1999-07-15 Biorthex Inc. Article poreux en alliage nickel-titane
US6136030A (en) * 1999-01-12 2000-10-24 Purzer Pharmaceutical Co., Ltd. Process for preparing porous bioceramic materials
WO2000064504A3 (fr) * 1999-04-28 2001-03-22 Bruce Medical Ab Corps destine a permettre l'interposition et la croissance de tissu osseux et/ou de tissu conjonctif, et procede de fabrication
EP1363551A1 (fr) * 2000-09-14 2003-11-26 Etex Corporation Implant avec canaux d'acces
KR100452410B1 (ko) * 1999-01-15 2004-10-08 퍼저 파마수티컬 컴퍼니 리미티드 다공성 바이오세라믹 물질의 제조공정
US8101268B2 (en) 2003-08-12 2012-01-24 University Of Bath Bone substitute material
WO2012039592A1 (fr) * 2010-09-20 2012-03-29 Universite Hassan Ii Mohammedia-Casablanca Procede d'elaboration d'un ciment biphasé macroporeux a base de bioverre d'une apatite, bioactif, bioresorbable a usage biomedical
US10238507B2 (en) 2015-01-12 2019-03-26 Surgentec, Llc Bone graft delivery system and method for using same
US10687828B2 (en) 2018-04-13 2020-06-23 Surgentec, Llc Bone graft delivery system and method for using same
US11116647B2 (en) 2018-04-13 2021-09-14 Surgentec, Llc Bone graft delivery system and method for using same

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2078696A (en) * 1980-05-28 1982-01-13 Mitsubishi Mining & Cement Co Porous Calcium Phosphate Body
WO1992021302A1 (fr) * 1991-06-03 1992-12-10 Lucocer Aktiebolag Implant
US5244577A (en) * 1990-09-06 1993-09-14 Takeda Chemical Industries, Ltd. Process for preparing osteogenesis promoting substance
DE4403509A1 (de) * 1994-02-04 1995-08-10 Draenert Klaus Werkstoff und Verfahren zu seiner Herstellung
US5492697A (en) * 1990-03-05 1996-02-20 Board Of Regents, Univ. Of Texas System Biodegradable implant for fracture nonunions

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2078696A (en) * 1980-05-28 1982-01-13 Mitsubishi Mining & Cement Co Porous Calcium Phosphate Body
US5492697A (en) * 1990-03-05 1996-02-20 Board Of Regents, Univ. Of Texas System Biodegradable implant for fracture nonunions
US5244577A (en) * 1990-09-06 1993-09-14 Takeda Chemical Industries, Ltd. Process for preparing osteogenesis promoting substance
WO1992021302A1 (fr) * 1991-06-03 1992-12-10 Lucocer Aktiebolag Implant
DE4403509A1 (de) * 1994-02-04 1995-08-10 Draenert Klaus Werkstoff und Verfahren zu seiner Herstellung

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999034845A1 (fr) * 1997-12-31 1999-07-15 Biorthex Inc. Article poreux en alliage nickel-titane
US6136030A (en) * 1999-01-12 2000-10-24 Purzer Pharmaceutical Co., Ltd. Process for preparing porous bioceramic materials
KR100452410B1 (ko) * 1999-01-15 2004-10-08 퍼저 파마수티컬 컴퍼니 리미티드 다공성 바이오세라믹 물질의 제조공정
KR100879424B1 (ko) * 1999-04-28 2009-01-19 티그란 테크놀로지즈 에이비 (피유비엘) 골조직 및/또는 결합조직의 내생 및 성장을 제공하기 위한 입자 및 이러한 입자를 제조하는 방법
WO2000064504A3 (fr) * 1999-04-28 2001-03-22 Bruce Medical Ab Corps destine a permettre l'interposition et la croissance de tissu osseux et/ou de tissu conjonctif, et procede de fabrication
US7553539B2 (en) 1999-04-28 2009-06-30 Tigran Technologies Ab Grain for providing cell growth
US7056577B1 (en) 1999-04-28 2006-06-06 Tigran Technologies Ab Body for providing ingrowth and growth of bone tissue and/or connective tissue and method of making such a body
EP1363551A4 (fr) * 2000-09-14 2006-11-29 Etex Corp Implant avec canaux d'acces
EP1363551A1 (fr) * 2000-09-14 2003-11-26 Etex Corporation Implant avec canaux d'acces
US8101268B2 (en) 2003-08-12 2012-01-24 University Of Bath Bone substitute material
WO2012039592A1 (fr) * 2010-09-20 2012-03-29 Universite Hassan Ii Mohammedia-Casablanca Procede d'elaboration d'un ciment biphasé macroporeux a base de bioverre d'une apatite, bioactif, bioresorbable a usage biomedical
US10238507B2 (en) 2015-01-12 2019-03-26 Surgentec, Llc Bone graft delivery system and method for using same
US11116646B2 (en) 2015-01-12 2021-09-14 Surgentec, Llc Bone graft delivery system and method for using same
US10687828B2 (en) 2018-04-13 2020-06-23 Surgentec, Llc Bone graft delivery system and method for using same
US11116647B2 (en) 2018-04-13 2021-09-14 Surgentec, Llc Bone graft delivery system and method for using same

Also Published As

Publication number Publication date
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