WO2013044777A1 - Matériau métallique poreux médical permettant de remplacer un os de l'alvéole dentaire et procédé de préparation correspondant - Google Patents

Matériau métallique poreux médical permettant de remplacer un os de l'alvéole dentaire et procédé de préparation correspondant Download PDF

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WO2013044777A1
WO2013044777A1 PCT/CN2012/081863 CN2012081863W WO2013044777A1 WO 2013044777 A1 WO2013044777 A1 WO 2013044777A1 CN 2012081863 W CN2012081863 W CN 2012081863W WO 2013044777 A1 WO2013044777 A1 WO 2013044777A1
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temperature
powder
rate
vacuum
240min
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PCT/CN2012/081863
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Chinese (zh)
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节云峰
叶雷
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重庆润泽医药有限公司
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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
    • A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/08—Alloys with open or closed pores
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/02—Alloys based on vanadium, niobium, or tantalum
    • 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
    • A61L2430/12—Materials or treatment for tissue regeneration for dental implants or prostheses
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/11—Making porous workpieces or articles
    • B22F3/1121—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers
    • B22F3/1125—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers involving a foaming process

Definitions

  • the invention relates to a porous medical metal implant material and a preparation method thereof, in particular to a medical porous metal implant material which replaces dense bone tissue and a preparation method thereof.
  • Porous medical metal implant materials have important and special applications for treating bone tissue wounds, femoral tissue necrosis, and replacing dense bone tissues such as teeth. Common materials such as porous metal stainless steel and porous metal titanium are common materials.
  • the porosity should be 30 ⁇ 80%, and the pores are preferably all connected and evenly distributed, or as needed to conform to the bone tissue growth of the human body. , and reduce the weight of the material itself, suitable for human implant use.
  • the refractory metal ⁇ / ⁇ due to its excellent biocompatibility, its porous material is expected to replace the traditional medical metal biomaterials mentioned above. Because metal ruthenium/ruthenium is harmless to the human body, non-toxic, no side effects, and with the rapid development of medicine at home and abroad, the understanding of ⁇ / ⁇ as a human implant material is further deepened. The demand for ⁇ / ⁇ materials is becoming more and more urgent, and the requirements for them are getting higher and higher. Among them, as a porous medical implant metal ⁇ / ⁇ , if it can have a high uniform distribution of connected pores and physical and mechanical properties compatible with the human body, it is expected to be a new type of bone tissue replacement material.
  • porous metal material for medical implantation it is basically a powder sintering method as a general porous metal material, in particular, a metal in a powder sintering method for obtaining a porous metal foam structure with pore communication and uniform distribution. Drying of the powder slurry on the organic foam after drying and sintering is referred to as foam impregnation.
  • the porous metal material obtained by powder sintering generally has a very good metal mechanical property, and the main reason is how to arrange the support and elimination relationship of the pore-forming medium and the collapse problem in the sintering process of the metal powder.
  • porous ruthenium/ruthenium by metal powder sintering, and in particular, the porous ruthenium/iridium powder sintering method for the purpose of obtaining medical implant materials has been reported in the literature.
  • the porous metal obtained is either used as a filter material, or used for aerospace and other high temperature applications rather than as a medical metal implant material, and the porous metal processed is also non-porous.
  • porous tantalum US5282861 discloses an open-celled tantalum material for use in cancellous bone implants, cells and tissue receptors and its preparation.
  • the porous crucible is made of pure commercial crucible.
  • the carbon skeleton obtained by thermal degradation of the polyurethane precursor is a scaffold.
  • the carbon skeleton has multiple dodecahedrons, and the inside is a grid-like structure.
  • Hole, high porosity Up to 98%, the commercial pure ruthenium is bonded to the carbon skeleton by chemical vapor deposition and permeation to form a porous metal microstructure, which is simply referred to as a chemical deposition method.
  • the porous tantalum material obtained by this method has a tantalum layer thickness of 40 60 m; in the whole porous material, the helium weight accounts for about 99%, and the carbon skeleton weight accounts for about 1%. Further, the literature further describes that the porous material has a compressive strength of 50 70 MPa, an elastic modulus of 2.5 3.5 GPa, a tensile strength of 63 MPa, and a plastic deformation amount of 15%.
  • a porous crucible for medical implant materials such as teeth, such as teeth, the mechanical properties of the material, such as ductility, are obviously insufficient, and it will affect the subsequent processing of the porous tantalum material itself, such as molded parts. Cutting, etc. Also in the products obtained by the aforementioned metal powder sintering method, there are such deficiencies.
  • Another object of the present invention is to provide a method of producing the above medical porous metal material.
  • a medical porous metal material for replacing dental bone characterized in that: the powder is mixed with polyvinyl alcohol and sodium hydrogencarbonate to form a mixed powder, and the mixed powder is pressed into an organic foam at 50 100 MPa to form and degrease.
  • the sintering step is a vacuum of 10 - 4 Pa 10 - 3 Pa, a temperature of 10 20 ° C / m in to 1500 1800 ° C, a temperature of 120 240 min, with furnace cooling Up to 200 300 ° C, then 10 20 ° C / min to 1500 1800 ° C, 180 240 min insulation, 5 10 ° C / min to 2000 2200 ° C, holding 120 360 min, the formation of porous porous material pores
  • the diameter is 15 28 m
  • the porosity is 20 35%
  • the bending strength is 130 140Mpa
  • the compressive strength is 140 170MPa.
  • the sintering is more uniform and thorough; after testing, the impurity content can be less than 0.2%, the biocompatibility and biosafety are good, the density can reach 10.84 13.34g/cm 3 , the porosity can reach 20 35%, the pore diameter Up to 15 28 ⁇ m; elastic modulus up to 4.5 6.0Gpa, flexural strength up to 130 140Mpa, compressive strength up to 140 170MPa, the porous crucible of the invention is very suitable for medical implant materials for replacing dental bone.
  • the raw material tantalum powder used in the present invention has an average particle diameter of less than 43 ⁇ m and an oxygen content of less than 0.1%, and is a commercially available product; the above polyvinyl alcohol and sodium hydrogencarbonate are also commercially available products.
  • the above polyvinyl alcohol mainly functions as a molding, but at the same time, it also has a function of pore formation, and the above sodium hydrogencarbonate functions as a pore.
  • the vacuum environment of the present invention preferably employs a vacuum condition of a vacuum of 10 - 4 Pa 10 - 3 P a .
  • the above organic foam is preferably a polyurethane foam, further preferably having a pore diameter of 0.48 0.89 mm and a density of 0.015 g/cm 3 0.035 g/cm 3 and a hardness of more than 50° (most preferably a pore diameter of 0.56 0.72 and a density of 0.025 g/cm 3 and a hardness of 50° 80°). ) in the polyurethane foam.
  • the amount of polyvinyl alcohol in the above mixed powder is 5 10%, and the amount of sodium hydrogencarbonate is 20 30%.
  • the balance is ⁇ powder, calculated by volume percent (by volume percent, the unit directly calculated by the final porous ruthenium material, and the corresponding powder is also calculated according to the density of the corresponding substance in the above-mentioned mixed powder weighing. More preferably, the polyvinyl alcohol accounts for 7 to 9%, the sodium hydrogencarbonate accounts for 26 29%, and the balance is cerium powder; the pressure during the press molding process is preferably 70 80 MPa.
  • the above degreasing process is at a rate of 0.5 ° C / mir 3 ° C / min.
  • the method for preparing the medical porous tantalum material for replacing the dental bone is formed by sintering by a molding method, and is characterized in that the powder of the tantalum powder is mixed with polyvinyl alcohol and sodium hydrogencarbonate powder to form a mixed powder, wherein the amount of polyvinyl alcohol accounts for 5 10%.
  • the amount of sodium bicarbonate is 20 30%, and the balance is strontium powder, in terms of volume percent; and the mixed powder is pressed into the organic foam at 50 100 MPa to form, degrease, vacuum sintering, cooling and heat treatment.
  • the porous tantalum material is prepared; the sintering step is to increase the temperature to 10,500 ° C / min to 1500 1800 ° C, the temperature is 120 240 min, and the furnace is cooled to 200 300 ° C under a vacuum of 10 - 4 Pa 10 - 3 Pa. Then heat up to 1500 1800 ° C at 10 20 ° C / min, keep warm for 180 240 min, heat up to 2000 2200 ° C at 5 10 ° C / min, keep warm for 120 360 min
  • the raw material tantalum powder has an average particle diameter of less than 43 ⁇ m and an oxygen content of less than 0.1%; and the mixed powder preferably has a polyvinyl alcohol content of 79%, sodium hydrogencarbonate accounts for 26 29%, and the balance is a tantalum powder, and more preferably a polycondensation. Vinyl alcohol accounts for 8%, sodium bicarbonate accounts for 27%, and the balance is tantalum powder, based on volume percent.
  • the above organic foam is preferably a polyurethane foam, and more preferably has a pore diameter of 0.48 0.89 and a density of 0.015 g/cm 3 and 0.035 g/cm 3 and a hardness of more than 50. (The most preferred is a polyurethane foam having a pore diameter of 0.56 0.72 and a density of 0.025 g/cm 3 and a hardness of 50 ° 80 °).
  • the pressure used in the above pressing process is preferably 70 80 MPa; preferably 0.5° in the above degreasing process.
  • the rate of C/min 3 ° C / min is gradually increased to 400 800 ° C, argon gas is introduced into a protective atmosphere and kept for 60 min and 240 min, and further preferably gradually heated to 400 800 ° C at a rate of 2.5 3 ° C / min.
  • the argon gas is introduced into a protective atmosphere and kept for 150 minutes and 240 minutes, and further preferably gradually heated to 400 800 ° C at a rate of 2.5 ° C / min, and argon gas is introduced to form a protective atmosphere and kept for 220 minutes.
  • the degree of vacuum is 10 - 4 Pa to 10 - 3 Pa
  • the temperature is raised to 1500 to 1800 ° C at 12 to 15 ° C / min
  • the temperature is maintained for 180 to 200 minutes
  • the furnace is cooled to 200 to 300 ° C
  • 16 ⁇ 19 ° C / min was heated to 1500 ⁇ 1800 ° C
  • insulation 220 ⁇ 240min, at 5 ⁇ 10 ° C / min was heated to 2000 ⁇ 2200 ° C, insulation 250 ⁇ 320min
  • the temperature was raised to 2000 ⁇ 2200 °C at °C/min and the temperature
  • the cooling conditions after vacuum sintering further include: a vacuum degree of not less than 10 - 3 P a , a cooling capacity of not less than 25 ° C / min, not less than 10 ° C / min, and a sintered porous body
  • the section is cooled to 800 ° C, and the holding time of each section is 30 min to 90 min, and then cooled to room temperature with the furnace.
  • the vacuum annealing conditions also include: the vacuum degree is not lower than 10 - 4 Pa, and the temperature is raised to 1000 to 1250 ° C at a rate of not higher than 30 ° C / m in , and the temperature is kept for 4 h to 6 h; 5 ⁇ 3 ⁇ Select a cooling rate of less than 5 ° C / min but not more than 30 ° C / min.
  • the degreasing treatment conditions further include: gradually increasing the temperature to 600 to 800 ° C, specifically by using pure argon gas (99.9999%) to form a protective atmosphere, to 1-3
  • the rate of °C/min is raised from room temperature to 400 ° C, and kept at 60 to 120 min, at a rate of 1.5 to 2. 5 ° C / min from 400 ° C to 600 to 800 ° C, and the temperature is 180 to 240 min.
  • the vacuum sintering condition the degree of vacuum is 10 - 4 Pa ⁇ 10 - 3 Pa, the temperature is raised to 1500 ⁇ 1800 ° C at 12 ⁇ 15 ° C / min, the temperature is maintained for 180 ⁇ 200min, and the furnace is cooled to 200 ⁇ 300 ° C Then, the temperature is raised to 1500 ⁇ 1800 °C at 16 ⁇ 19 °C/min, the temperature is kept for 220 ⁇ 240min, the temperature is raised to 2000 ⁇ 2200 °C at 5 ⁇ 10 °C/min, and the temperature is kept for 250 ⁇ 320min; the cooling condition after vacuum sintering Also included are: vacuum degree of 10 - 4 Pa ⁇ 10 - 3 Pa; cooling at a rate of 10 to 20 ° C / min to 1500 ⁇ 1600 ° C, holding 30 ⁇ 60min; at a rate of 12 ⁇ 20 ° C / min Cooling to 1200 ⁇ 1250 ° C, keeping warm for 60 ⁇ 90min; cooling to 800 ° C at a rate of 10 ⁇ 20 °
  • metal ruthenium and osmium are very similar, and the above methods are also suitable for the preparation of medical porous ruthenium materials.
  • the porous crucible preparation method of the invention adopts a pure physical molding method, so that the content of impurities in the final porous tantalum material is extremely low, and the biocompatibility and biosafety are effectively improved; the steps of press molding, degreasing, sintering and annealing of the present invention are carried out. Optimization of process conditions, high yield, better uniformity of finished pore size, more stable preparation process, good quality stability, effectively eliminating thermal stress, making the structure of porous tantalum material more uniform, and effectively improving the mechanics of porous tantalum The performance, especially its strength is greatly improved, and the density is also effectively controlled, so that it has good comfort as a substitute material for the bone.
  • the preparation process of the invention makes the finished product have high yield and stable production, and the product qualification rate can be as high as 92%. . 2% ⁇
  • Example 1 Weighing polyvinyl alcohol, an average particle diameter of less than 43 ⁇ m, an oxygen content of less than 0.1%, and a mixture of bismuth powder and sodium hydrogencarbonate are uniformly mixed into a mixed powder, wherein polyvinyl alcohol accounts for 8% and sodium hydrogencarbonate accounts for 27%. ⁇ powder accounts for 65%, both in volume percent.
  • Press molding the above mixed powder is added to an injection molding machine and pressed at 75 MPa to a polyurethane foam (pore diameter 0. 48 0. 89 density 0. 015 g/cm 3 0. 035 g/cm 3 , hardness greater than 50°) .
  • Desalination treatment a vacuum of 10 - 4 Pa, with argon as a protective atmosphere, at a temperature increase rate of 2.0 ° C / min from room temperature to 400 ° C, holding for 90 min; and then 2. 0 ° C / m in The heating rate was raised from 40 CTC to 700 ° C and the holding time was 210 minutes.
  • Vacuum sintering The degree of vacuum is 10 - 4 Pa 10 - 3 Pa, the temperature is raised to 1800 ° C at 13 ° C / min, the temperature is kept for 200 min, cooled to 200 300 ° C with the furnace and then raised to 1800 ° C at 17 ° C / min.
  • heat preservation for 230min heat up to 2000 2200 ° C at 7 ° C / min, heat preservation for 300 min.
  • the sintering process is filled with argon gas protection. After removing the product, the surface dust and dirt are removed, and the prepared sample is subjected to conventional post-treatment to obtain a porous product. .
  • the impurity content is less than 0.2%
  • the impurity content of the porous material is less than 0.2%
  • the impurity content is less than 0.2%
  • the pore distribution is uniform, the density is 12.00g/cm 3 , the porosity is 28%, the average pore diameter is 25 m, the elastic modulus is 5.0 GPa, the bending strength is 140 MPa, the compressive strength is 165 MPa.
  • Example 2 Weighing polyvinyl alcohol, an average particle diameter of less than 43 ⁇ m, an oxygen content of less than 0.1%, and a mixture of bismuth powder and sodium hydrogencarbonate are uniformly mixed into a mixed powder, wherein polyvinyl alcohol accounts for 5% and sodium hydrogencarbonate accounts for 20%. ⁇ powder accounts for 75%, both in volume percent.
  • Press molding The above mixed powder is added to an injection molding machine and pressed at 80 MPa to a polyurethane foam (pore diameter 0. 48 0 ⁇ 89 mm, density 0. 015 g/cm 3 0. 035 g/cm 3 , hardness greater than 50). forming.
  • Degreasing treatment vacuum degree 10 - 4 Pa, argon gas as a protective atmosphere, temperature rising from room temperature to 400 ° C at a heating rate of 0.5 ° C / min, heat preservation for 60 min vacuum sintering: vacuum degree of 10 - 4 Pa 10 - 3 Pa, heat up to 1500 ° C at 10 ° C / min, keep warm for 120 min, cool with furnace to 200 300 ° C, then raise the temperature to 1600 ° C at 20 ° C / min, keep warm for 180 min, heat up at 10 ° C / min To 2000 2200.
  • the inventors have finished the above porous concrete according to GB/T5163_2006, GB/T5249_1985, GB/T6886-2001 and other standards.
  • Material density, porosity, pore size and various mechanical properties of porous detected impurity content of less than 0.2%, a uniform pore distribution, density of 13. 34g / Cm 3, a porosity of 20%, an average pore diameter of 15 ⁇ ⁇ , elastic modulus 6. 0GPa, bending strength 133MPa, compressive strength 147MPa.
  • Example 3 Weigh polyvinyl alcohol, an average particle size of less than 43 microns, an oxygen content of less than 0.1%, and a mixture of bismuth powder and sodium bicarbonate to form a mixed powder, wherein polyvinyl alcohol accounts for 10% and sodium bicarbonate accounts for 30%. ⁇ powder accounts for 60%, both in volume percent. Pressing and forming: The above mixed powder is added to an injection molding machine and pressed at 95 MPa to a polyurethane foam (pore diameter: 0. 48 to 0. 89 mm, density: 0.15 g/cm 3 to 0. 035 g/cm 3 , hardness: 50 or more. ) Forming.
  • Degreasing treatment The vacuum degree is 10 - 4 Pa, and the temperature is raised from room temperature to 700 ° C at a heating rate of 3 ° C / min with a argon atmosphere as a protective atmosphere, and the temperature is maintained for 240 minutes.
  • Vacuum sintering The degree of vacuum is 10 - 4 Pa ⁇ 10 - 3 Pa, the temperature is raised to 1600 ° C at 20 ° C / min, the temperature is kept for 240 min, the furnace is cooled to 200 ⁇ 300 ° C, and then heated to 10 ° C / min to 1500 °C, heat preservation 240min, heat up to 2000 ⁇ 2200 V at 5 °C/min, heat preservation for 120min, argon gas protection during sintering, remove surface dust and dirt after taking out the product, and then prepare the sample for routine post-treatment The porous product is obtained.
  • the impurity content is less than 0.2%
  • the impurity content of the porous material is less than 0.2%
  • the impurity content is less than 0.2%
  • the pores have a uniform distribution, a density of 10.84 g / Cm 3 , a porosity of 35%, an average pore diameter of 28 ⁇ ⁇ , an elastic modulus of 4. 5 GPa, a bending strength of 136 MPa, and a compressive strength of 155 MPa.
  • Example 4 Weigh polyvinyl alcohol, an average particle size of less than 43 ⁇ m, and an oxygen content of less than 0.1%, and the sodium bicarbonate and the sodium bicarbonate are uniformly mixed into a mixed powder, wherein polyvinyl alcohol accounts for 9% and sodium hydrogencarbonate accounts for 26%. ⁇ powder accounts for 65%, both in volume percent. Pressing and forming: the above mixed powder is added to an injection molding machine and pressed at a pressure of 67 MPa to a polyurethane foam (pore diameter of 0. 48 to 0. 89 mm, density of 0.105 g/cm 3 to 0. 035 g/cm 3 , hardness of more than 50 .) Forming.
  • a polyurethane foam pore diameter of 0. 48 to 0. 89 mm, density of 0.105 g/cm 3 to 0. 035 g/cm 3 , hardness of more than 50 .
  • Degreasing treatment vacuum degree 10 - 4 Pa, argon gas as a protective atmosphere, heating temperature from room temperature to 550 ° C at a heating rate of 2.5 ° C / min, heat preservation 220 mino vacuum sintering: vacuum degree is 10 - 4 Pa ⁇ 10 — 3 Pa, heated to 1750 ° C at 15 ° C / min, held for 180 min, cooled to 200 ⁇ 300 ° C with the furnace, then raised to 1680 ° C at 19 ° C / min, 225 min insulation, 8 ° C / The temperature is raised to 2000 ⁇ 2200°C, and the temperature is kept for 240min. The sintering process is filled with argon gas. After removing the product, the surface dust and dirt are removed, and the prepared sample is subjected to conventional post-treatment to obtain a porous product.
  • the impurity content is less than 0.2%
  • the impurity content of the porous material is less than 0.2%
  • the impurity content is less than 0.2%
  • the pores have a uniform distribution, a density of 6.51 g/cm 3 , a porosity of 24%, an average pore diameter of 21 ⁇ ⁇ , an elastic modulus of 3. 5 GPa, a bending strength of 77 MPa, and a compressive strength of 66 MPa.
  • Example 5 a porous crucible, which has a particle size of less than 43 m, an oxygen content of less than 0.1%, a mixture of polyvinyl alcohol and sodium bicarbonate as a raw material, followed by compression molding, degreasing treatment, and vacuum sintering. , vacuum annealing and conventional post-treatment. Among them, polyvinyl alcohol accounts for 7%, sodium bicarbonate accounts for 20%, and metal cerium powder accounts for 73%, based on volume percent. Press molding: The raw material mixed powder is added to an injection molding machine and pressed at 86 MPa to a polyurethane foam. (Polarization 0. 48 ⁇ 0. 89mm, density 0. 015 g/cm 3 ⁇ 0. 035g/cm 3 , hardness greater than 50.) Medium molding;
  • the mixed powder is placed in a non-oxidizing atmosphere furnace at a certain heating rate to a temperature of 800 ° C, and the protective atmosphere is 99.999% argon gas for degreasing treatment, which is first introduced into pure argon gas for at least 30 minutes before the temperature rise. exclude air furnace, temperature control process: a rate of 1. 8 ° C / min from room temperature to the 400 ° C, 76min incubation, the amount of argon passed into 0. 5L / min; to 2.
  • the tungsten is placed in a high-vacuum high-temperature sintering furnace for vacuum sintering, and the vacuum degree of the sintering furnace reaches 10 - 3 Pa before the temperature rise, and the temperature is raised to 1600 ° C at a rate of 10 to 20 ° C / min.
  • the degree of vacuum is 10 - 3 Pa; after sintering, the degree of vacuum is 10 - 3 Pa, cooled to 1600 ° C at a rate of 10 to 15 ° C / min, kept for 30 min; cooled to 1200 at a rate of 12 ° C / min °C, keep warm for 60min; cool to 800 °C at a rate of 10 °C / min, and then cool with the furnace;
  • the sample after vacuum sintering is cooled in a vacuum annealing furnace with a corundum container at a certain heating rate to 125 CTC for stress relief annealing.
  • the vacuum in the annealing furnace should be at least 10 -4 Pa to 15 ° before the temperature rise.
  • the rate of C/min is raised from room temperature to 1250 ° C, heat preservation for 240 min, vacuum degree is 10 - 4 Pa ⁇ 10 - 3 Pa; then cooled to 1000 ° C at a rate of 5 ° C / min, heat preservation for 180 min, vacuum degree to 10- 4 Pa ⁇ 10- 3 Pa; cooling at a rate of 10 ° C / min to 800 ° C, 120min incubation, the degree of vacuum of 10- 4 Pa; at a rate of 20 ° C / min cooling to room temperature, the degree of vacuum It is 10 - 4 Pa.
  • a conventional post-treatment is carried out to obtain a porous crucible.
  • the impurity content is less than 0.2%
  • the impurity content of the porous material is less than 0.2%
  • the impurity content is less than 0.2%
  • the pores have a uniform distribution, a density of 13. 0 g / Cm 3 , a porosity of 22%, an average pore diameter of 17 ⁇ ⁇ , an elastic modulus of 5. 3 GPa, a flexural strength of 136 MPa, and a compressive strength of 165 MPa.
  • the yield of the preparation process product is 91.6%.
  • ⁇ powder or ⁇ powder particle size (micro ⁇ powder or ⁇ powder accounted for by the volume of sodium bicarbonate in the body of sodium bicarbonate) / oxygen content is less than (%) volume percent (%) product percentage (% ) Product percentage (%)
  • the obtained porous tantalum or porous tantalum product is inspected as described above.

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  • Materials For Medical Uses (AREA)

Abstract

La présente invention se rapporte à un matériau métallique poreux médical permettant de remplacer un os de l'alvéole dentaire et qui est obtenu par les étapes consistant à : mélanger la poudre de tantale, l'alcool polyvinylique et le bicarbonate de sodium afin de former une poudre mixte ; compacter la poudre mixte dans un corps en mousse organique et mettre en forme sous une pression de 50 à 100 MPa ; dégraisser, fritter, refroidir et effectuer des traitements thermiques ; de manière précise, l'étape de frittage consistant à : chauffer, sous une pression à vide de 10-4Pa à 10-3Pa, jusqu'à une température dans la plage de 1500 à 1800 °C à une vitesse de 10 à 20 °C/min, maintenir la chaleur pendant une période de temps comprise entre 120 et 240 min, laisser refroidir dans un four pour arriver à une température dans la plage de 200 à 300 °C ; ensuite, chauffer à nouveau jusqu'à obtenir une température comprise entre 1500 et 1800 °C à une vitesse comprise entre 10 et 20 °C/min, maintenir la chaleur pendant une période de temps de 180 à 240 min et chauffer à nouveau jusqu'à obtenir une température dans la plage de 2000 à 2200 °C à une vitesse de 5 à 10 °C/min et maintenir la chaleur pendant une période de temps de 120 à 360 min. Le matériau poreux médical à base de tantale ainsi formé présente un diamètre des pores de 15 à 28 μm, une porosité de 20 à 35 %, une résistance à la flexion de 130 à 140 MPa et une résistance à la compression de 140 à 170 MPa. Le tantale poreux de la présente invention convient spécialement comme matériau d'implant médical pour remplacer l'os de l'alvéole dentaire.
PCT/CN2012/081863 2011-09-29 2012-09-24 Matériau métallique poreux médical permettant de remplacer un os de l'alvéole dentaire et procédé de préparation correspondant WO2013044777A1 (fr)

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CN201110301061.8A CN102793946B (zh) 2011-09-29 2011-09-29 一种替代牙骨的医用多孔金属材料及其制备方法

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EP2149414A1 (fr) * 2008-07-30 2010-02-03 Nederlandse Centrale Organisatie Voor Toegepast Natuurwetenschappelijk Onderzoek TNO Procédé de fabrication d'un magnésium poreux, ou alliage de magnésium, implant biomédical ou appareil médical
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EP2149414A1 (fr) * 2008-07-30 2010-02-03 Nederlandse Centrale Organisatie Voor Toegepast Natuurwetenschappelijk Onderzoek TNO Procédé de fabrication d'un magnésium poreux, ou alliage de magnésium, implant biomédical ou appareil médical
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