WO2013044781A1 - 一种替代承重骨组织的医用多孔金属材料的制备方法 - Google Patents

一种替代承重骨组织的医用多孔金属材料的制备方法 Download PDF

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WO2013044781A1
WO2013044781A1 PCT/CN2012/081867 CN2012081867W WO2013044781A1 WO 2013044781 A1 WO2013044781 A1 WO 2013044781A1 CN 2012081867 W CN2012081867 W CN 2012081867W WO 2013044781 A1 WO2013044781 A1 WO 2013044781A1
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rate
temperature
vacuum
furnace
sintering
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PCT/CN2012/081867
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English (en)
French (fr)
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郝莉娜
叶雷
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重庆润泽医药有限公司
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Publication of WO2013044781A1 publication Critical patent/WO2013044781A1/zh

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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
    • 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
    • B22F3/1017—Multiple heating or additional steps
    • B22F3/1021—Removal of binder or filler
    • 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
    • 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
    • B22F3/1137—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers by coating porous removable preforms
    • 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 invention relates to a preparation method of a porous medical metal implant material, in particular to a preparation method of a medical porous metal implant material for replacing bone tissue of a load-bearing part.
  • Porous medical metal implant materials have important and special applications for treating bone tissue trauma and femoral tissue necrosis. Common materials such as porous metal stainless steel and porous metal titanium are common materials. As a porous implant material for the treatment of bone tissue trauma and femoral tissue necrosis, 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 to 60 m; in the whole porous material, the helium weight accounts for about 99%, and the carbon skeleton weight accounts for about 1%.
  • 5GPa tensile strength 63MPa.
  • the tensile strength of the porous material is 50 ⁇ 70MPa, the elastic modulus is 2. 5 ⁇ 3.
  • 5GPa the tensile strength is 63MPa.
  • the mechanical properties of the material such as a porous crucible for replacing medical implant materials such as skull and bone, the mechanical properties of the material, such as ductility, have obvious deficiencies, which will affect the subsequent processing of the porous tantalum material itself, such as molded parts. Cutting, etc.
  • An object of the present invention is to provide a method for preparing a porous metal material which is suitable for replacing bone tissue of a body weight bearing portion with good mechanical strength.
  • the invention relates to a method for preparing a medical porous metal material for replacing weight-bearing bone tissue, which is characterized in that: the tantalum powder is mixed with a pore-forming agent and a molding agent, and then obtained by press molding, degreasing, sintering, cooling and heat treatment; 3°C/mir! The defrosting process is 0. 3 ° C / mir! The temperature is gradually increased to 400 ⁇ 800 ° C at a rate of ⁇ 2 ° C / min, and argon gas is introduced to form a protective atmosphere and kept for 300 min to 360 min; the pore former is ammonium hydrogencarbonate or hydrogen peroxide, and the molding agent is hard fat.
  • the sintering step is a vacuum of 10 - 4 Pa to 10 - 3 p a to 10 ⁇ 20°C/min, heat up to 1500 ⁇ 1800°C, keep warm for 120 ⁇ 240min, cool with furnace to 200 ⁇ 300°C, then heat up to 1500 ⁇ 1800°C at 10 ⁇ 20°C/min, keep warm 180 ⁇ 240min, heat up to 2000 ⁇ 2200 °C at 5 ⁇ 10 °C/min for 120 ⁇ 360min.
  • medical porous metal materials as materials for replacing weight-bearing bone tissue require a large porosity, so that human tissue can easily grow in, and biocompatibility is sufficient to fully exert its function, but
  • There are many preparation routes for medical porous tantalum but the inventors have creatively proposed to use the above steps and processes to prepare medical porous tantalum implant materials, which effectively prevent the use of the soaking method, which is easy to block, and the dipping process is difficult to control and obtain.
  • the content of the impurity is less than 0.2.
  • the impurity content of the porous enamel material is less than 0.2. %, its biocompatibility and biosafety are good, the density can reach 5. 00 ⁇ 6. 67g/cm 3 , the porosity can reach 60 ⁇ 70%, the pore diameter can reach 2 00 ⁇ 400 ⁇ m; elastic modulus up to 3. 8 ⁇ 4. 2Gpa, elongation of 9. 3 ⁇ 10. 7%, bending strength up to 125 ⁇ 150Mpa, compressive strength up to 72 ⁇ 90Mpa, its biological
  • the compatibility, strength and toughness are close to the characteristics of the human body-bearing bone tissue, and the porous crucible of the invention is very suitable for replacing the weight-bearing bone tissue. Medical implant materials.
  • 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%, which is a commercially available product; the above pore-forming agent and molding agent are also commercially available products.
  • the vacuum environment of the present invention preferably employs a vacuum condition of a vacuum of 10 - 4 Pa to 10 - 3 Pa. ⁇ 0. 56 ⁇ 0 ⁇
  • the above-mentioned organic foam is preferably a polyurethane foam, further preferably having a pore diameter of 0. 48 ⁇ 0. 89mm, a density of 0. 015 g / cm 3 ⁇ 0. 035g / cm 3 , a hardness of more than 50 ° (most preferably a pore size of 0. 56 ⁇ 0 . 72mm, density 0. 025g / cm 3 , hardness 50 ° ⁇ 80 °) in polyurethane foam.
  • the inventors further studied and found that if the above preparation is not well controlled, although the medical implant material suitable for replacing the weight-bearing bone tissue as described above can be obtained, the product qualification rate is not high, and the stability of the process is not ideal. It affects the industrial scale production: such as powder pressing and forming, it is easy to appear delamination, unevenness after pressing, and some technical problems such as cracks appear after degreasing.
  • the amount of the above-mentioned pore-forming agent is 15 to 25%
  • the amount of the molding agent is 7 to 12%
  • the balance is
  • the tantalum powder in terms of volume percent (by volume percent, the unit directly calculated by the final porous tantalum material, in the weighing of the above pore former, molding agent, solid powder or according to the corresponding substance The density is calculated by the corresponding mass weighing, of course, if it is a liquid substance, it is directly weighed by volume), and further preferably, the pore forming agent is 18% of hydrogen peroxide, the molding agent is 11% of zinc stearate, and the balance is Yttrium powder, in terms of volume percent; the pressure during the above press molding process is preferably 75 to 87 MPa.
  • the above degreasing process is 0. 3 ° C / mir!
  • the rate of ⁇ rC / min is gradually increased to 400 ⁇ 800 ° C, argon gas is introduced into a protective atmosphere and held for 330min ⁇ 350min; further preferably gradually heated to 400 ⁇ 800 ° C at a rate of 0.8 ° C / min, The argon gas was introduced to form a protective atmosphere and held for 340 minutes.
  • the above-described sintering step is preferably a vacuum degree of 10- 4 Pa ⁇ 10- 3 Pa, to 12 ⁇ 15 ° C / min Warm up to 1500 ⁇ 1800 °C, keep warm for 180 ⁇ 200min, cool to 200 ⁇ 300°C with furnace, then heat up to 1500 ⁇ 1800°C at 16 ⁇ 19°C/min, keep warm for 220 ⁇ 240min, to 5 ⁇ 8° C / min heating to 2000 ⁇ 2200 ° C, holding 250 ⁇ 320min; further preferably a vacuum of 10 - 4 Pa ⁇ 10 - 3 Pa, 13 ° C / min to 1800 ° C, holding 200min, with the furnace Cool to 200 ⁇ 300 °C, then heat up to 1800 °C at 17 °C / min, keep for 230min, heat up to 2000 ⁇ 2200 °C at 7 °C / min, and keep warm for 300min.
  • 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; Cooling rate below 5 ° C / min but not higher than 30 ° C / min 5 ⁇ 3 ⁇ Select the cooling time to the room temperature, the holding time of each section is decreasing and not more than 1. 5 h ⁇ 3h.
  • the singularity of the singularity is from 0 to 2 ° C / min.
  • the rate of 8 ° C / min is increased from 400 ° C to 600 ⁇ 800 ° C, 340 ⁇ 360 min;
  • the vacuum sintering conditions vacuum degree is 10 - 4 Pa ⁇ 10 - 3 Pa, to 12 ⁇ 15 ° C / Min heating to 1500 ⁇ 1800 °C, holding 180 ⁇ 200min, cooling with furnace to 200 ⁇ 300 °C, then heating to 1500 ⁇ 1800 °C at 16 ⁇ 19 °C/min, keeping 220 ⁇ 240min, 5 ⁇ 8 °C / min heating to 2000 ⁇ 2200 ° C, holding 250 ⁇ 320min;
  • cooling conditions after vacuum sintering also include: vacuum degree of 10 - 4 Pa ⁇ 10 - 3 P a; to 10 ⁇ 20 ° C / m in The rate is cooled to 1500 ⁇ 1600 ° C, kept for 30 ⁇ 60 min; cooled to 1200 ⁇ 1250 ° C at a rate of
  • 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 the strength thereof, is greatly improved; the preparation process of the invention makes the product qualified rate high, the production is stable, and the product qualification rate can be as high as 93%. 00 ⁇ 6.
  • Porosity can be obtained.
  • the porosity of the porous ruthenium of the present invention is uniform and continuous, and the biocompatibility is good, and the impurity content can be less than 0.2%, the density can reach 5. 00 ⁇ 6. 67g/cm 3 , the porosity can be 2 ⁇ 10. 7%, bending strength up to 125 ⁇ 150Mpa, compressive strength up to 60 ⁇ 70%, the modulus of the pores up to 200 ⁇ 400 m; The strength can reach 72 ⁇ 90Mpa, which effectively solves the contradiction that the medical porous tantalum material as a substitute bearing part requires both a large porosity and a good mechanical property.
  • the porous tantalum of the present invention is very suitable for use as a medical alternative to load-bearing bone tissue. Implant material.
  • the medical porous tantalum material for replacing the weight-bearing bone tissue is specifically selected from one or more of stearic acid, zinc stearate, paraffin wax and synthetic rubber as a forming agent, ammonium hydrogencarbonate or hydrogen peroxide as a pore former, and an average Particle size less than 43 microns, oxygen
  • the degreasing process is 0. 3
  • the degreasing process is 0. 3
  • the degreasing process is 0.30
  • the degreasing process is 0. 3 °C/mir!
  • the temperature is gradually increased to 400 ⁇ 800 ° C at a rate of ⁇ 2 ° C / min, and the argon gas is introduced to form a protective atmosphere and kept for 300 min to 360 min;
  • the sintering step is a vacuum degree of 10 - 4 Pa to 10 - 3 Pa, 10 ⁇ 20°C/min, heat up to 1500 ⁇ 1800°C, keep warm for 120 ⁇ 240min, cool with furnace to 200 ⁇ 300°C, then heat up to 1500 ⁇ 1800°C at 10 ⁇ 20°C/min, keep warm 180 ⁇ 240min, heat up to 2000 ⁇ 2200 °C at 5 ⁇ 10 °C / min, keep warm for 120 ⁇ 360min. 2 ⁇ 10 ⁇ 7% ⁇
  • the porphyrin of the porphyrin porphyrin porch porch porch is a vacuum degree of 10 - 4 Pa to 10 - 3 Pa, 10 ⁇ 20°C/min, heat up to 1500 ⁇ 1800°C, keep warm for 120 ⁇ 240min, cool with furnace to 200 ⁇ 300°C, then heat up to 1500
  • the above porous ruthenium is 7 to 12% by volume of the above-mentioned molding agent, 15 to 25% by volume of the above-mentioned pore-forming agent, and the balance of cerium powder.
  • the degreasing treatment is performed to remove the pore former, the molding agent and the polyurethane foam, wherein argon gas is introduced to remove the air in the furnace before the temperature rise, and the degreased sample is cooled with the furnace; the sample after the degreasing treatment is placed along with the tungsten device
  • the vacuum degree in the high-vacuum high-temperature sintering furnace is 10 - 4 Pa ⁇ 10 - 3 P a , 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.
  • the sample is cooled with the furnace, maintaining a certain degree of vacuum during cooling or at a certain cooling rate.
  • the section is cooled to maintain a certain temperature for a suitable period of time, and an inert gas can be used as a protective atmosphere during the heat preservation process.
  • the sample after vacuum sintering and cooling is placed in a vacuum annealing furnace with a corundum container to gradually heat up and heat-treat to perform stress relief annealing.
  • the temperature of the annealing furnace is maintained at a certain degree of vacuum before the temperature rise, and the sample after vacuum annealing is cooled with the furnace and cooled.
  • the process also maintains a certain degree of vacuum or a certain cooling rate to maintain a certain temperature for a suitable time.
  • an inert gas can be used as a protective atmosphere, and finally a conventional post-treatment is performed to obtain a porous crucible.
  • the degreasing process is gradually heated to a temperature of 400 to 800 ° ⁇ at a rate of 0.3 ° 111 / 111 ⁇ 1 ° ⁇ / 1 ⁇ 1 , argon gas is introduced into a protective atmosphere and incubated for 330 min to 350 min; further preferred The temperature was gradually increased to 400 to 800 ° C at a rate of 0.8 ° C / min, and argon gas was introduced to form a protective atmosphere and held for 340 minutes.
  • the vacuum is maintained, and the temperature is cooled to a temperature of, for example, 1500 ° C to 1600 ° C at a certain cooling rate, and the temperature is kept, and then cooled to a temperature of, for example, 1200 ° C to 1250 ° C at a certain cooling rate, and the temperature is lowered to some extent.
  • the rate is cooled to, for example, 800 ° C and then cooled with the furnace.
  • the vacuum annealing treatment is performed on the vacuum-sintered sample, and the corundum container is placed in a vacuum annealing furnace at a certain heating rate to a temperature of, for example, 1000 ° C to 1250 ° C for stress relief annealing, and the annealing furnace is heated before the temperature rise.
  • Maintain the vacuum inside increase from room temperature to 1000 °C ⁇ 1250 °C at a certain heating rate, keep warm, keep vacuum; then cool to a temperature of 1000 °C at a certain cooling rate, keep warm; then at a certain cooling rate Cool to, for example, 800 ° C, keep warm; also cool at room temperature with a certain rate of cooling.
  • a conventional post-treatment is carried out to obtain a porous crucible.
  • the inventor used metal powder sintering method mainly based on physical molding method, and did a lot of theoretical analysis and experimental test. It is proved that the porous bismuth product has been tested to have an impurity content of less than 0.2%, a density of up to 5. 00 6. 67g/cm 3 , a porosity of 60 70%, and a pore diameter of up to 200 400 ⁇ m;
  • the modulus can reach 3. 8 4. 2Gpa
  • the elongation rate is 9. 3 10. 7%, the bending strength can reach 125 150Mpa, and the compressive strength can reach 72 90Mpa.
  • Example 1 Weighing zinc stearate, an average particle size of less than 43 ⁇ m, an oxygen content of less than 0.1%, and a mixture of bismuth powder and hydrogen peroxide, wherein zinc stearate accounts for 11%, hydrogen peroxide accounts for 18%, and strontium powder accounts for 71%. %, all in volume percent.
  • Press molding The above mixed powder was placed in an injection molding machine and pressed at a pressure of 82 MPa to a polyurethane foam (pore size 0. 48 0. 89 mm, density 0. 015 g/cm 3 0. 035 g/cm 3 , hardness greater than 50.) Forming in the middle.
  • Degreasing treatment The vacuum degree is 10 - 4 Pa, the temperature is raised from room temperature to 400 ° C at a heating rate of 1.5 ° C / min, and the temperature is maintained for 320 min; and the temperature is raised from 400 ° C to 700 at a heating rate of 0.6 ° C / min. °C, holding time 350 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 ° at 17 ° C / min.
  • C is kept for 230min, heated to 2000 2200°C at 7°C/min, and kept for 300min.
  • the sintering process is filled with argon gas. After removing the product, the surface dust and dirt are removed.
  • the prepared sample is subjected to conventional post-treatment to obtain porous ⁇ . Finished product.
  • the inventor is tested according to the standard of GB/T5163_2006 GB/T5249_1985 GB/T6886-2001 and other standards for the porous material, the porosity, the porosity, the pore diameter and the various mechanical properties: the impurity content is less than 0.2%, the pores Uniform distribution, density 6.56g/cm 3 , porosity 65%, average pore diameter 300 m, elastic modulus 4. 0Gpa, elongation 10.02%, flexural strength 145MPa, compressive strength 89MPa
  • Example 2 Weighing stearic acid, an average particle size of less than 43 microns, an oxygen content of less than 0.1% of strontium powder and ammonium bicarbonate mixed uniformly into a mixed powder, wherein stearic acid accounted for 12%, ammonium bicarbonate accounted for 23% ⁇ 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 size 0. 48 0. 89 density 0. 015 g/cm 3 0. 035 g/cm 3 , hardness greater than 50°) forming.
  • Degreasing treatment The degree of vacuum was 10 - 4 Pa, and the temperature was raised from room temperature to 500 ° C at a heating rate of 0.3 ° C / min, and the temperature was maintained for 360 minutes.
  • Vacuum sintering The vacuum degree is 10 - 3 Pa, the temperature is raised to 1500 ° C at 10 ° C / min, the temperature is kept for 150 min, the furnace is cooled to 200 300 ° C, and then heated to 1600 ° C at 20 ° C / min, and the temperature is kept for 240 min. The temperature is raised to 2000 2200 ° C at 10 ° C / min, and the temperature is kept for 120 min.
  • the sintering process is filled with argon gas to remove the surface dust and dirt after the product is taken out, and the prepared sample is subjected to conventional post-treatment to obtain a porous tantalum product.
  • the inventor is tested according to the standard of GB/T5163_2006 GB/T5249_1985 GB/T6886-2001 and other standards for the porous material, the porosity, the porosity, the pore diameter and the various mechanical properties: the impurity content is less than 0.2%, the pores Uniform distribution, density 6.25g/cm 3 , porosity 61%, average pore diameter 200 m, elastic modulus 3. 8Gpa, elongation 9.3%, flexural strength 125MPa, compressive strength 75MPa
  • Example 3 Weighing paraffin, the average particle size is less than 43 micrometers, and the oxygen content is less than 0.1%.
  • the tantalum powder and the hydrogen peroxide are uniformly mixed, wherein paraffin accounts for 7%, hydrogen peroxide accounts for 25%, and tantalum powder accounts for 68%, all of which are in volume. Sub-content meter.
  • Press molding The above mixed powder was placed in an injection molding machine and pressed at a pressure of 52 MPa to a polyurethane foam (pore diameter 0. 48 0. 89 mm, density). 0. 015 g / cm 3 ⁇ 0. 035g / cm 3 , hardness greater than 50 °) Forming.
  • Degreasing treatment The vacuum degree is 10 - 4 Pa, and the temperature is raised from room temperature to 400 ° C at a heating rate of 2 ° C / min, and the temperature is maintained for 300 min.
  • Vacuum sintering The vacuum degree is 10 - 4 Pa, the temperature is raised to 1600 ° C at 20 ° C / min, the temperature is kept for 120 min, the furnace is cooled to 200 ⁇ 300 ° C, and then heated to 1500 ° C at 10 ° C / min, and the temperature is kept. 180min, the temperature is raised to 2000 ⁇ 2200°C at 5°C/min, and the temperature is kept for 360min.
  • the sintering process is filled with argon gas, cooled and discharged, and the surface dust and dirt are removed.
  • the prepared sample is subjected to conventional post-treatment to obtain porous ⁇ . Finished 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 6.55g/cm 3 , the porosity is 70%, the average pore diameter is 400 m, the elastic modulus is 3. 9Gpa, the elongation is 9.8%, the bending strength is 133MPa, and the compressive strength is 85MPa.
  • Example 4 Weighing isoprene rubber, the average particle size is less than 43 ⁇ m, and the oxygen content is less than 0.1%.
  • the niobium powder and the ammonium bicarbonate are uniformly mixed, wherein the isoprene rubber accounts for 9%, the ammonium bicarbonate accounts for 15%, and the niobium powder 76%, both in volume percent.
  • Pressing and forming The above mixed powder is added to an injection molding machine and pressed to a polyurethane foam at a particle size of 96 MPa (pore diameter 0. 48 ⁇ 0. 89 mm, density 0. 015 g/cm 3 to 0. 035 g/cm 3 , hardness greater than 50). .) Forming.
  • Degreasing treatment The degree of vacuum was 10 - 4 Pa, and the temperature was raised from room temperature to 400 ° C at a heating rate of 0.8 ° C / min, and the temperature was maintained for 340 min.
  • Vacuum sintering The degree of vacuum is 10 - 4 Pa, the temperature is raised to 1700 ° C at 15 ° C / min, the temperature is maintained for 180 min, cooled to 200 ⁇ 300 ° C with the furnace, and then heated to 1700 ° C at 19 ° C / min, heat preservation 220min, the temperature is raised to 2000 ⁇ 2200°C at 8°C/min, and the temperature is kept for 320min.
  • the sintering process is filled with argon gas, cooled and discharged, and the surface dust and dirt are removed.
  • the prepared sample is subjected to conventional post-treatment to obtain porous ⁇ . to make
  • Example 5 a porous crucible having a particle size of less than 43 m, an oxygen content of less than 0.1%, a mixture of stearic acid and hydrogen peroxide as a raw material, followed by compression molding, degreasing treatment, vacuum sintering, Vacuum annealing and conventional post-treatment are obtained.
  • 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. 5 ⁇ /min ; 0. 4°C/min, the temperature of the furnace is increased from the room temperature to 400 ° C, the temperature is maintained for 310 minutes, the argon gas flow rate is 0. 5L / min ; 0.
  • the sample after the degreasing treatment is heated to a high temperature and high temperature sintering furnace with the tungsten device at a certain heating rate to 220CTC vacuum sintering at a degree of vacuum sintering furnace prior to heating to achieve at least 10- 4 Pa, to 12 ⁇ 15 ° C / min was heated to 1500 ⁇ 1800 ° C, insulation 180 ⁇ 200min, with the furnace cooled to 200 ⁇ 300 ° C, then raise the temperature to 1500 ⁇ 1800 °C at 16 ⁇ 19 °C / min, keep warm for 220 ⁇ 240min, heat up to 2000 ⁇ 2200 °C at 5 ⁇ 8 °C/min, keep warm for 250 ⁇ 320min ; after sintering, vacuum degree 10 - 3 Pa, cooled to 1600 ° C at a rate of 10 to 15 ° C / min, kept for 30 min; cooled to 1200 ° C at a rate of 12 ° C / min, held for 60 min; at a rate of 10 ° C / min Cool to 800 °
  • 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%
  • pore distribution density 6. 00 ⁇ 6. 67g / cm 3, a porosity of 62 ⁇ 67%, average pore diameter 200 ⁇ 340 ⁇ m, the modulus of elasticity 3. 8 ⁇ 4.
  • the qualified rate of the preparation process of the invention can be as high as about 92%.
  • Depressurization temperature sintering atmosphere Pa) / temperature CC) / time (min) Annealing atmosphere (Pa) / liter pressure ( °C) / time temperature or cooling rate (°c (min) / min) (°C ) /
  • the temperature is raised from room temperature to 1750 ° C, 195 min, and the temperature is raised to 400 ° C, 200 ⁇ 300 ° C, and then raised to 1030 ° C at 18 ° C / min. Insulation 322min / 1620 ° C, heat preservation 240min, to 7. 5 ° C / min 480min /
  • the vacuum degree at 2 °C / min is 10 4 Pa ⁇ 10 - 3 Pa, and the temperature is raised from room temperature to 1 excitation at a rate of 10 ° C / min 10" 3 Pa / 20 ° C / min. C, warming up Up to 1650 ° C, heat preservation for 150 min, with furnace cooling
  • the obtained porous tantalum or porous tantalum product is inspected as described above.

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Abstract

一种替代承重骨组织的医用多孔金属材料的制备方法，由钽粉与造孔剂、成型剂混合，再将混合粉末压制到有机泡沫体中成型、脱脂、烧结、冷却和热处理；脱脂是以 0.3℃/min～2℃/min的速率逐步升温至400～800℃，以氩气通入构成保护气氛并保温300min～360min；烧结是在 10-4Pa～10-3Pa，以 10～20℃/min 升温至1500～1800℃、保温 120～240min、随炉冷至 200～300℃，再以 10～20℃/min 升温至 1500～1800℃、保温 180～240min，以5～10℃/min 升温至 2000～2200℃、保温 120～360min。经测试杂质含量低于 0.2%、密度可达5.00～6.67g/cm3，孔隙度可达60～70%，孔隙直径可达200～400μm；弹性模量可达3.8～4.2Gpa，弯曲强度可达 125～150Mpa、抗压强度可达 72～90Mpa，有效解决了作为替代承重部位的医用多孔钽材料既要求其孔隙率较大、又要求力学性能好的矛盾。

Description

一种替代承重骨组织的医用多孔金属材料的制备方法 技术领域
本发明涉及一种多孔医用金属植入材料的制备方法， 特别是涉及一种替代承重部位骨 组织的医用多孔金属植入材料的制备方法。
背景技术
多孔医用金属植入材料具有治疗骨组织创伤、 股骨组织坏死等重要而特殊的用途， 现 常见的这类材料有多孔金属不锈钢、 多孔金属钛等。 作为骨组织创伤和股骨组织坏死治疗 使用的多孔植入材料， 其孔隙度应达 30〜80%， 而且孔隙最好全部连通与均匀分布， 或根 据需要使之既与人体的骨组织生长相一致， 又减轻了材料本身的重量， 以适合人体植入使 用。
而难熔金属钽 /铌， 由于它具有优秀的生物相容性， 其多孔材料有望作为替代前述等 传统医用金属生物材料。 由于金属钽 /铌对人体的无害、 无毒、 无副作用， 以及随着国内 外医学的飞速发展， 对钽 /铌作为人体植入材料认知的进一步深入， 人们对人体植入用多 孔金属钽 /铌材料的需求变得越来越迫切， 对其要求也越来越高。 其中作为多孔医用植入 金属钽 /铌， 如果能具有很高的均匀分布连通孔隙以及与人体相适应的物理机械性能， 则 其有望作为一种新型的骨组织替代材料。
作为医用植入的多孔金属材料就像一般的多孔金属材料那样基本上是以粉末烧结法 为主要的加工方法， 特别是为获取孔隙连通与均匀分布的多孔金属泡沫结构采用粉末烧结 法中的金属粉末浆料在有机泡沫体上的浸渍后干燥再烧结简称泡沫浸渍法居多。 关于粉末 烧结所获得的多孔金属材料通常其金属力学性能并不是很好， 其主要原因是工艺上如何安 排成孔介质的支撑与消除关系、 金属粉末烧结过程中的塌陷问题。 而已知的文献报道中均 没有很好的解决方法而放任自然。
采用金属粉末烧结法制造多孔钽 /铌的文献报道很少， 特别是以获得医用植入材料用 为目的的多孔钽 /铌粉末烧结法文献报道几乎没有。 可以参考的是公开号为 CN200510032174, 名称 "三维通孔或部分孔洞彼此相连多孔金属泡沫及其制备方法" 以及 CN200710152394, 名称 "一种新型多孔泡沫钨及其制备方法" 。 然而其所获得的多孔金属 或是为过滤材料用， 或是为航空航天及其它高温场合用而非作为医用金属植入材料使用， 再者所加工的多孔金属也非多孔钽 /铌。
关于多孔钽， US5282861 公开了一种应用于松质骨植入体、 细胞和组织感受器的开孔 钽材料及其制备。 这种多孔钽由纯商业钽制成， 它以聚亚氨酯前体进行热降解得到的碳骨 架为支架， 该碳骨架呈多重的十二面体， 其内为网格样结构， 整体遍布微孔， 孔隙率可高 达 98%， 再将商业纯钽通过化学蒸气沉积、 渗透的方法结合到碳骨架上以形成多孔金属微 结构， 简称为化学沉积法。 这种方法所获得的多孔钽材料其表面的钽层厚度在 40〜60 m 之间； 在整个多孔材料中， 钽重约占 99%， 而碳骨架重量则占 1%左右。 文献进一步记载， 该多孔材料的抗压强度 50〜70MPa， 弹性模量 2. 5〜3. 5GPa, 抗拉强度 63MPa。 但是将它作 为替代承重骨组织如颅骨等医用植入材料的多孔钽， 其材料的力学性能如延展性有明显不 足之处， 会影响到后续的对多孔钽材料本身的加工， 例如成型件的切割等。 同样在前述的 金属粉末烧结法所获得的产品也均存在这样的不足。 再由于其制备方法的局限， 获得的成 品纯度不够， 有碳骨架残留物， 导致生物安全性降低。
发明内容
本发明的目的在于提供一种力学强度好的适用于替代人体承重部位骨组织的多孔金 属材料的制备方法。
本发明的目的是通过如下技术手段实现的：
一种替代承重骨组织的医用多孔金属材料的制备方法，其特征在于： 由钽粉与造孔剂、 成型剂混合， 再经压制成型、 脱脂、 烧结、 冷却和热处理制得的； 所述压制成型是将所述 混合粉末压制到有机泡沫体中成型，其压力为 50〜100Mpa，所述脱脂过程是以 0. 3°C/mir！〜 2°C/min的速率逐步升温至 400〜800°C，以氩气通入构成保护气氛并保温 300min〜360min; 所述造孔剂为碳酸氢铵或双氧水， 所述成型剂为硬脂酸、 硬脂酸锌、 石蜡、 合成树脂 （优 选为丁苯橡胶或异戊橡胶） 中的一种或多种； 所述烧结步骤是真空度为 10— 4Pa〜10— 3pa， 以 10〜20°C/min升温至 1500〜1800°C、 保温 120〜240min、 随炉冷至 200〜300°C， 再以 10〜20°C/min升温至 1500〜1800°C、 保温 180〜240min， 以 5〜10°C/min升温至 2000〜 2200 °C 保温 120〜360min。
在医用多孔金属材料的研发过程中， 医用多孔金属材料作为替代承重骨组织的材料， 要求其孔隙率较大、 这样人体组织才易长入、 生物相容性好从而充分地发挥其作用， 但孔 隙率越大、 孔径越大， 力学性能如强度、 韧性就得不到保证； 反之， 力学性能好了又易使 孔隙率过小、 生物相容性不好、 密度也过大引起不舒适感； 医用多孔钽的制备路线众多， 但发明人创造性地提出了采用上述步骤、 工艺制备医用多孔钽植入材料， 有效防止了采用 浸浆法易出现的堵孔、 浸浆过程难控制、 制得的产品质量不均匀等问题， 特别是采用的上 述烧结工艺， 使得胚体成为了发热体， 从而烧结得更均匀、 透彻； 其制得的多孔钽材料经 过测试其杂质含量可低于 0. 2%、 其生物相容性与生物安全性好， 密度可达 5. 00〜 6. 67g/cm3,孔隙度可达 60〜70%，孔隙直径可达 200〜400 μ m;弹性模量可达 3. 8〜4. 2Gpa、 延伸率达 9. 3〜10. 7%、 弯曲强度可达 125〜150Mpa、 抗压强度可达 72〜90Mpa， 其生物相 容性、 强韧性接近于人体承重骨组织的特性， 本发明多孔钽非常适合用于替代承重骨组织 的医用植入材料。
本发明采用的原料钽粉的平均粒径小于 43微米、 氧含量小于 0. 1%， 为市售产品； 上 述造孔剂、 成型剂也均为市售产品。 本发明真空环境优选采用真空度为 10— 4Pa〜10— 3Pa 的 真空条件。上述有机泡沫体优选聚氨酯泡沫，进一步优选为孔径 0. 48〜0. 89mm,密度 0. 015 g/cm3〜0. 035g/cm3, 硬度大于 50° (最优选孔径为 0. 56〜0. 72mm, 密度 0. 025g/cm3, 硬度 50°〜80°) 的聚氨酯泡沫中。
在研发过程中发明人进一步研究发现， 若上述制备中控制不好， 虽可制得如上所述适 合用于替代承重骨组织的医用植入材料但产品合格率不高， 工艺的稳定性不够理想、 影响 其工业化规模生产： 如粉末压制成型难、 在压制后部分易出现分层、 不均匀， 脱脂后部分 会出现裂纹等技术问题。
为了使粉末压制过程中成型更容易， 从而提高成品率、 成品孔隙均匀性、 使制备过程 更稳定， 上述造孔剂的用量为 15〜25%、 成型剂的用量为 7〜12%、 余量为钽粉， 均以体积 百分含量计 （以体积百分含量计是通过最终多孔钽材料的情况直接推算的单位， 在上述造 孔剂、 成型剂的称量中固体粉末还是根据相应物质的密度计算出其对应的质量称量的、 当 然若为液体物质则直接采用体积称量）， 进一步优选为造孔剂为双氧水占 18%、成型剂为硬 脂酸锌占 11%、 余量为钽粉、 以体积百分含量计； 上述压制成型过程中的压力优选为 75〜 87Mpa。
为了使脱脂过程中胚体更稳定、 减少易出现的部分胚体变形、 孔径不均匀， 从而进一 步提高成品率、 质量稳定性， 上述脱脂过程是以 0. 3°C/mir！〜 rC/min 的速率逐步升温至 400〜800°C， 以氩气通入构成保护气氛并保温 330min〜350min; 进一步优选以 0. 8°C/min 的速率逐步升温至 400〜800°C， 以氩气通入构成保护气氛并保温 340min。
为了使得胚体烧结得更均匀、 透彻， 使制得的医用多孔钽材料力学强度更高， 上述烧 结步骤优选为真空度为 10— 4Pa〜10— 3Pa，以 12〜15°C/min升温至 1500〜1800°C、保温 180〜 200min、 随炉冷至 200〜300°C， 再以 16〜19°C/min 升温至 1500〜1800°C、 保温 220〜 240min, 以 5〜8°C/min升温至 2000〜2200°C、 保温 250〜320min; 更进一步优选为真空 度为 10— 4Pa〜10— 3Pa， 以 13°C/min升温至 1800°C、 保温 200min、 随炉冷至 200〜300°C， 再以 17°C/min升温至 1800°C、保温 230min，以 7°C/min升温至 2000〜2200°C、保温 300min。
真空烧结后的冷却条件还包括有： 真空度不低于 10— 3Pa， 以不高于 25°C/min， 不低于 10°C/min渐降冷却速率方式，对烧结多孔体分段降温冷却至 800°C，各段保温时间 30min〜 90min, 然后随炉冷却至常温。
真空退火条件还包括有：真空度不低于 10— 4Pa， 以不高于 30°C/min的速率升至 1000〜 1250°C , 保温 4h〜6h; 再以先慢后快以不低于 5°C/min但不高于 30°C/min的冷却速率分 段冷却至室温， 各段的保温时间呈递减且不超过 1. 5 h〜3h内选择。
在此基础上更进一步的特点是： 所述脱脂处理条件还包括有： 以 l〜2°C/min 的速率 从室温升至 400°C，保温 300〜330min，以 0. 3〜0. 8°C/min的速率从 400°C升至 600〜800°C， 保温 340〜360min; 所述真空烧结条件： 真空度为 10— 4Pa〜10— 3Pa， 以 12〜15°C/min升温 至 1500〜1800°C、 保温 180〜200min、 随炉冷至 200〜300°C， 再以 16〜19°C/min升温至 1500〜1800°C、保温 220〜240min，以 5〜8°C/min升温至 2000〜2200°C、保温 250〜320min; 真空烧结后的冷却条件还包括有： 真空度为 10— 4Pa〜10— 3Pa; 以 10〜20°C/min的速率冷却 至 1500〜1600°C， 保温 30〜60min; 以 12〜20°C/min的速率冷却至 1200〜1250°C， 保温 60〜90min; 以 10〜20°C/min的速率冷却至 800°C， 然后随炉冷却； 所述真空退火条件包 括有： 以 15〜30°C/min的速率升至 1000〜1250°C， 保温 240〜480min， 真空度为 10— 4Pa〜 10— 3Pa，再以 5〜10°C/min的速率冷却至 1000°C，保温 90〜180min，真空度为 10— 4Pa〜10— 3Pa; 以 10〜20°C/min的速率冷却至 800°C，保温 60〜120min，真空度为 10— 4Pa;以 20〜30°C/min 的速率冷却至室温， 真空度为 10— 4Pa〜10— 3Pa。
金属钽和铌的性质极类似， 上述方法同样也适合医用多孔铌材料的制备。
本发明多孔钽制备方法采用了纯物理模压法， 使得最终多孔钽材料中杂质的含量极 低， 有效地提高了生物相容性和生物安全性； 对本发明压制成型、 脱脂、 烧结及退火步骤 的工艺条件优化， 使得成品率高、 成品孔径均匀性更好、 使制备过程更稳定、 质量稳定性 好， 有效地消除了热应力、 使多孔钽材料的组织更均匀， 有效提高了多孔钽的力学性能， 特别是其强度得到大大提高； 本发明制备工艺使得成品合格率高、 生产稳定， 产品合格率 可高达 93%。 本发明制得的多孔钽成品孔隙分布均匀且连通， 生物相容性好， 经过测试其 杂质含量可低于 0. 2%、 密度可达 5. 00〜6. 67g/cm3, 孔隙度可达 60〜70%， 孔隙直径可达 200〜400 m; 弹性模量可达 3. 8〜4. 2Gpa、 延伸率达 9. 3〜10. 7%， 弯曲强度可达 125〜 150Mpa、 抗压强度可达 72〜90Mpa， 有效解决了作为替代承重部位的医用多孔钽材料既要 求其孔隙率较大、 又要求力学性能好的矛盾， 本发明多孔钽非常适合用于作为替代承重骨 组织的医用植入材料。
具体实施方式
下面通过实施例对本发明进行具体的描述， 有必要在此指出的是以下实施例只用于对 本发明进行进一步说明， 不能理解为对本发明保护范围的限制， 该领域的技术人员可以根 据上述本发明内容对本发明作出一些非本质的改进和调整。
一种替代承重骨组织的医用多孔钽材料具体是选用硬脂酸、 硬脂酸锌、 石蜡、 合成橡 胶中的一种或多种为成型剂、 碳酸氢铵或双氧水为造孔剂， 与平均粒径小于 43 微米、 氧 含量小于 0. 1%的钽粉混合， 在 50〜100Mpa下将所述混合粉末压制到有机泡沫体中成型， 再经脱脂、 烧结、 冷却和热处理而得； 所述脱脂过程是以 0. 3°C/mir！〜 2°C/min 的速率逐 步升温至 400〜800°C， 以氩气通入构成保护气氛并保温 300min〜360min; 所述烧结步骤 是真空度为 10— 4Pa〜10— 3Pa， 以 10〜20°C/min升温至 1500〜1800°C、 保温 120〜240min、 随炉冷至 200〜300°C， 再以 10〜20°C/min升温至 1500〜1800°C、 保温 180〜240min， 以 5〜10°C/min升温至 2000〜2200°C、 保温 120〜360min。 形成的医用多孔钽材料孔隙直径 为 200〜400 μ m、 孔隙度介于 60〜70%、 弹性模量为 3. 8〜4. 2Gpa 延伸率为 9. 3〜10· 7%。
更具体地说， 上述多孔钽是将 7〜12% (以体积百分含量计） 的上述成型剂、 15〜25% (以体积百分含量计） 的上述造孔剂以及余量的钽粉混合， 将其放入注塑成型机中加压压 制到聚氨酯泡沫中成型； 再置于钨器中放入纯净氩气 （99. 9999%) 通入构成的保护气氛炉 中逐步升温至一定温度， 并保温进行脱脂处理以除去造孔剂、 成型剂和聚氨酯泡沫， 其中 在升温之前先通入氩气以排除炉内空气， 脱脂后的样品随炉冷却； 对于脱脂处理后的样品 随钨器置于高真空高温烧结炉内烧结真空度为 10— 4Pa〜10— 3Pa， 以 12〜15 °C/min 升温至 1500〜1800°C、保温 180〜200min、随炉冷至 200〜300°C，再以 16〜19°C/min升温至 1500〜 1800°C、 保温 220〜240min， 以 5〜8°C/min升温至 2000〜2200°C、 保温 250〜320min， 真 空烧结后的样品随炉冷却， 冷却过程中保持一定的真空度或按一定的冷却速率分段冷却以 保持一定温度于适当的时间， 在保温过程中可以采用充惰性气体作为保护气氛。 对于真空 烧结冷却后的样品随刚玉容器置于真空退火炉中逐步升温、 保温进行去应力退火处理， 在 升温之前退火炉内的保持一定的真空度， 真空退火处理后的样品随炉冷却， 冷却过程中也 保持一定的真空度或按一定的冷却速率分段冷却以保持一定温度于适当的时间， 在保温过 程中可以采用充惰性气体作为保护气氛， 最后进行常规后处理制得多孔钽。
对于脱脂处理， 脱脂过程是以0. 3°〇/111 〜1 °〇/1^1 的速率逐步升温至400〜800°〇， 以 氩气通入构成保护气氛并保温 330min〜350min;进一步优选以 0. 8°C /min的速率逐步升温 至 400〜800°C， 以氩气通入构成保护气氛并保温 340min。 上述真空烧结完毕， 保持真空， 以一定的降温速率冷却至例如 1500°C〜1600°C， 保温， 再以一定的降温速率冷却至例如 1200°C〜1250°C， 保温， 还以一定的降温速率冷却至例如 800°C， 然后随炉冷却。 对于真 空烧结冷却后的样品进行真空退火处理， 是将其随刚玉容器置于真空退火炉中以一定的升 温速率升温至例如 1000°C〜1250°C进行去应力退火处理，在升温之前退火炉内的保持真空 度， 以一定的升温速率从室温升至 1000°C〜1250°C， 保温， 保持真空； 再以一定的降温速 率冷却至例如 1000°C， 保温； 再以一定的降温速率冷却至例如 800°C， 保温； 还以一定的 降温速率冷却室温。 最后进行常规后处理制得多孔钽。
发明人采用金属粉末烧结法主要以物理模压法为主， 做了大量的理论分析和实验验 证， 得到多孔钽产品经过测试其杂质含量可低于 0. 2%、 密度可达 5. 00 6. 67g/cm3， 孔隙 度可达 60 70%，孔隙直径可达 200 400 μ m;弹性模量可达 3. 8 4. 2Gpa 延伸率达 9. 3 10. 7%， 弯曲强度可达 125 150Mpa、 抗压强度可达 72 90Mpa
实施例 1 : 称量硬脂酸锌、 平均粒径小于 43微米氧含量小于 0. 1%的钽粉和双氧水混 合均匀， 其中硬脂酸锌占 11%， 双氧水占 18%、 钽粉占 71%， 均以体积百分含量计。 加压成 型： 将上述混合粉末加入注塑成型机中在 82Mpa 下压制到聚氨酯泡沫体 （孔径 0. 48 0. 89mm, 密度 0. 015 g/cm3 0. 035g/cm3, 硬度大于 50。)中成型。脱脂处理： 真空度 10— 4Pa 以 1. 5°C/min的升温速率从室温升温至 400°C、 保温 320min; 再以 0. 6°C/min的升温速率 从 400°C升温至 700°C， 保温时间 350分钟。 真空烧结： 真空度为 10— 4Pa 10— 3Pa， 以 13°C /min升温至 1800°C、 保温 200min、 随炉冷至 200 300°C， 再以 17°C/min升温至 1800°C 保温 230min， 以 7°C/min升温至 2000 2200°C、 保温 300min; 烧结过程充氩气保护， 取 出产品后去除表面灰尘及污物， 制得的样品再进行常规的后处理得多孔钽成品。
发明人按 GB/T5163_2006 GB/T5249_1985 GB/T6886-2001等标准对上述多孔钽成品 的多孔材料密度、 孔隙率、 孔径及各种力学性能进行检测： 其杂质含量低于 0. 2%， 其孔隙 分布均匀， 密度 6. 56g/cm3， 孔隙率 65%， 孔隙平均直径 300 m， 弹性模量 4. 0Gpa、 延伸 率 10. 02%, 弯曲强度 145MPa， 抗压强度 89MPa
实施例 2: 称取硬脂酸、 平均粒径小于 43微米氧含量小于 0. 1%的钽粉和碳酸氢铵混 合均匀成混合粉末， 其中硬脂酸占 12%、 碳酸氢铵占 23%、 钽粉占 65%， 均以体积百分含量 计。 加压成型： 将上述混合粉末加入注塑成型机中在 75Mpa下压制到聚氨酯泡沫体 （孔径 0. 48 0. 89 密度 0. 015 g/cm3 0. 035g/cm3， 硬度大于 50°) 中成型。 脱脂处理： 真空 度 10— 4Pa， 以 0. 3°C/min的升温速率从室温升温至 500°C、 保温 360min。 真空烧结： 真空 度为 10— 3Pa， 以 10°C/min升温至 1500°C、 保温 150min、 随炉冷至 200 300°C， 再以 20 °C/min升温至 1600°C、 保温 240min， 以 10°C/min升温至 2000 2200°C、 保温 120min; 烧结过程充氩气保护， 取出产品后去除表面灰尘及污物， 制得的样品再进行常规的后处理 得多孔钽成品。
发明人按 GB/T5163_2006 GB/T5249_1985 GB/T6886-2001等标准对上述多孔钽成品 的多孔材料密度、 孔隙率、 孔径及各种力学性能进行检测： 其杂质含量低于 0. 2%， 其孔隙 分布均匀， 密度 6. 25g/cm3， 孔隙率 61%， 孔隙平均直径 200 m， 弹性模量 3. 8Gpa、 延伸 率 9. 3%, 弯曲强度 125MPa， 抗压强度 75MPa
实施例 3: 称取石蜡、 平均粒径小于 43微米氧含量小于 0. 1%的钽粉和双氧水混合均 匀， 其中石蜡占 7%、 双氧水占 25%、 钽粉占 68%， 均以体积百分含量计。 加压成型： 将上 述混合粉末加入注塑成型机中在 52Mpa下压制到聚氨酯泡沫体（孔径 0. 48 0. 89mm, 密度 0. 015 g/cm3〜0. 035g/cm3， 硬度大于 50°) 中成型。 脱脂处理： 真空度 10— 4Pa， 以 2°C/min 的升温速率从室温升温至 400°C、 保温 300min。 真空烧结： 真空度为 10— 4Pa， 以 20°C/min 升温至 1600°C、 保温 120min、 随炉冷至 200〜300°C， 再以 10°C/min升温至 1500°C、 保 温 180min， 以 5°C/min升温至 2000〜2200°C、 保温 360min; 烧结过程充氩气保护， 冷却 出炉， 去除产品表面灰尘及污物， 制得的样品再进行常规的后处理得多孔钽成品。
发明人按 GB/T5163_2006、 GB/T5249_1985、 GB/T6886-2001等标准对上述多孔钽成品 的多孔材料密度、 孔隙率、 孔径及各种力学性能进行检测： 其杂质含量低于 0. 2%， 其孔隙 分布均匀， 密度 6. 55g/cm3， 孔隙率 70%， 孔隙平均直径 400 m， 弹性模量 3. 9Gpa、 延伸 率 9. 8%， 弯曲强度 133MPa, 抗压强度 85MPa。
实施例 4: 称取异戊橡胶、 平均粒径小于 43微米氧含量小于 0. 1%的铌粉和碳酸氢铵 混合均匀， 其中异戊橡胶占 9%、 碳酸氢铵占 15%、 铌粉占 76%， 均以体积百分含量计。 加 压成型： 将上述混合粉末加入注塑成型机中在 96Mpa下压制到聚氨酯泡沫体（孔径 0. 48〜 0. 89mm, 密度 0. 015 g/cm3〜0. 035g/cm3, 硬度大于 50。)中成型。脱脂处理： 真空度 10— 4Pa， 以 0. 8°C/min的升温速率从室温升温至 400°C、 保温 340min。 真空烧结： 真空度为 10— 4Pa， 以 15°C/min升温至 1700°C、 保温 180min、 随炉冷至 200〜300°C， 再以 19°C/min升温至 1700°C、 保温 220min， 以 8°C/min升温至 2000〜2200°C、 保温 320min; 烧结过程充氩气 保护， 冷却出炉， 去除产品表面灰尘及污物， 制得的样品再进行常规的后处理得多孔铌成
P
ΡΠ。
发明人按 GB/T5163-2006、 GB/T5249_1985、 GB/T6886-2001等标准对上述多孔铌成品 的多孔材料密度、 孔隙率、 孔径及各种力学性能进行检测： 其杂质含量低于 0. 2%， 其孔隙 分布均匀， 密度 2. 74g/cm3， 孔隙率 68%， 孔隙平均直径 238 μ ιιι， 弹性模量 2. 6Gpa、 延伸 率 10. 03%， 弯曲强度 92MPa， 抗压强度 81MPa。
实施例 5: —种多孔钽， 它以粒径小于 43 m、 氧含量小于 0. 1%的金属钽粉， 硬脂酸 和双氧水混合粉为原料， 再经压制成型、 脱脂处理、 真空烧结、 真空退火及常规后处理制 得。
其中， 硬脂酸占 10%、 双氧水占 19%、 金属钽粉占 71%， 以体积百分含量计； 压制成型： 将原料混合粉末加入注塑成型机中在 83Mpa下压制到聚氨酯泡沫体 （孔径
0. 48〜0. 89mm, 密度 0. 015 g/cm3〜0. 035g/cm3, 硬度大于 50。) 中成型；
压制成型后将混合粉末放入非氧化气氛炉中以一定的升温速率升温至 800°C， 保护气 氛为 99. 999%氩气进行脱脂处理， 其在升温之前先通入纯净氩气至少 30min以排除炉内空 气，控温过程：以 1. 3°C/min的速率从室温升至 400°C，保温 310min，氩气通入量 0. 5L/min; 以 0. 4°C/min的速率从 400°C升至 800°C， 保温 358min， 氩气通入量 lL/min; 再关闭电源， 脱脂后的样品随炉冷却， 氩气通入量 lL/min， 直至冷却至室温时关闭氩气； 对于脱脂处理后的样品随钨器置于高真空高温烧结炉内以一定的升温速率升温至 220CTC进行真空烧结， 在升温之前烧结炉的真空度至少要达到 10— 4Pa， 以 12〜15°C/min升 温至 1500〜1800°C、 保温 180〜200min、 随炉冷至 200〜300°C， 再以 16〜19°C/min升温 至 1500〜1800°C、 保温 220〜240min， 以 5〜8°C/min升温至 2000〜2200°C、 保温 250〜 320min;烧结完毕， 真空度为 10— 3Pa， 以 10〜15°C/min的速率冷却至 1600 °C ,保温 30min; 以 12°C/min的速率冷却至 1200°C， 保温 60min; 以 10°C/min的速率冷却至 800°C， 然后 随炉冷却；
对于真空烧结冷却后的样品随刚玉容器置于真空退火炉中以一定的升温速率升温至 125CTC进行去应力退火处理，在升温之前退火炉内的真空度至少要达到 10— 4Pa，以 15°C/min 的速率从室温升至 1250°C， 保温 240min, 真空度为 10— 4Pa〜10— 3Pa; 再以 5°C/min的速率 冷却至 1000°C， 保温 180min, 真空度为 10— 4Pa〜10— 3Pa; 以 10°C/min的速率冷却至 800°C， 保温 120min， 真空度为 10— 4Pa; 以 20°C/min的速率冷却至室温， 真空度为 10— 4Pa。 最后进 行常规后处理制得多孔钽。
发明人按 GB/T5163_2006、 GB/T5249_1985、 GB/T6886-2001等标准对上述多孔钽成品 的多孔材料密度、 孔隙率、 孔径及各种力学性能进行检测： 其杂质含量低于 0. 2%， 其孔隙 分布均匀， 密度 6. 00〜6. 67g/cm3， 孔隙率 62〜67%， 孔隙平均直径 200〜340 μ m， 弹性模 量 3. 8〜4. 0Gpa、 延伸率 9. 3〜9. 9%， 弯曲强度 128〜136MPa， 抗压强度 75〜86MPa。 经计 算本发明制备工艺产品合格率可高达 92%左右。
在上述实施例 5给出的方法中， 我们还可以对其中的各种条件作其他选择同样能得到 本发明所述的多孔钽或多孔铌。
Figure imgf000009_0001
实 压制成型的 脱脂温度 烧结气氛（Pa) /温度 CC) /时间 （min) 退火气氛（Pa) /升 施 压力 ( °C ) /时间 温或降温速率 （°c 例 (min) /min)温度 （°C ) /
保温时间（min)
6 76MPa 以 rC/min的 真空度为 104Pa〜10-3Pa，以 14 °C /min升 10 Pa/
速率从室温 温至 1750°C、保温 195min、 随炉冷至 15°C/min的速率升 升至 400°C， 200〜300°C， 再以 18°C/min 升温至 至 1030 °C， 保温 保温 322min/ 1620°C、 保温 240min， 以 7. 5°C/min 480min/
0.3°C/min的 升温至 2000〜2200°C、 保温 266min; 5°C/min的速率 速率从 400°C 真空度为 104Pa〜10— 3Pa，以 irC/min的速 至 1000 °C， 保温 升至 600°C， 率 至 1520 °C， 保温 60min; 180min/
保温 352min 以 13°C/min的速率) f¾至 1200 °C， 保温 以 irC/min的速率
90min; 至 800°C，保温 以 13°C/min的速率 至 800°C， 然后随 108min/
炉 21 °C/min的速率冷 却至室温
7 85MPa 1.8°C/min的 真空度为 104Pa〜10— 3Pa， 以 17/min 10"3Pa/17 °C/min 的 速率从室温 升温至 1600°C、保温 208min、 随炉冷 速率升至 1050 °C， 升至 400°C， 至 200〜300°C，再以 12°C/min升温至 保温 450min/ 保温 300min/ 1720°C、 保温 190min, 以 6°C/min升 6°C/min的速率
0.8°C/min的 温至 2000〜2200°C、 保温 300min; 至 1000 °c， 保温 速率从 400°C 真 ¾S为 104Pa〜10— 3Pa; 以 12°C/min 150min/
升至 700°C， 的速率 至 1530 °C， 保温 55min; 以 12°C/min的速率 保温 340min 以 14°C/min的速率) f¾至 1210°C， 保温 至 800°C，保温
85min; 102min/
以 14°C/min的速率 至 800°C， 然后随 22°C/min的速率冷 炉 却至室温
8 93MPa 以 2°C/min的 真空度为 104Pa〜10—3Pa， 以 19°C/min 10"3Pa/20 °C/min 的 速率从室温 速率升至 1励。 C， 升温至 1650°C、保温 150min、 随炉冷
升至 400°C， 保温 420min/ 保温 330min/ 至 200〜300°C，再以 13°C/min升温至 7°C/min的速率
0.3°C/min的 至 1000 °C， 保温
1600°C、 保温 190min, 以 9°C/min升
速率从 400°C 130min/
温至 2000〜2200°C、 保温 180min;
升至 680°C， 以 13°C/min的速率 保温 348min 真空度为 104Pa〜10- 3Pa; 以 13°C/min 至 800°C，保温 的速率 至 1540 °C， 保温 50min;
96min/ 以 15°C/min的速率) f¾至 1220 °C， 保温
23 °C/min的速率冷
80min;
却至室温 以 15°C/min的速率 至 800°C， 然后随
炉
所得多孔钽或多孔铌成品按前述方法检
Figure imgf000011_0001

Claims

权 利 要 求 书
1、 一种替代承重骨组织的医用多孔金属材料的制备方法， 其特征在于： 由钽粉与造 孔剂、 成型剂混合， 再经压制成型、 脱脂、 烧结、 冷却和热处理制得的； 所述压制成型是 将所述混合粉末压制到有机泡沫体中成型， 其压力为 50〜100Mpa， 所述脱脂过程是以 0. 3°C/min〜2°C/min 的速率逐步升温至 400〜800°C， 以氩气通入构成保护气氛并保温 300mir！〜 360min; 所述造孔剂为碳酸氢铵或双氧水， 所述成型剂为硬脂酸、 硬脂酸锌、 石 蜡、合成树脂中的一种或多种； 所述烧结步骤是真空度为 10— 4Pa〜10— 3Pa， 以 10〜20°C/min 升温至 1500〜 1800 °C、 保温 120〜240min、 随炉冷至 200〜300°C， 再以 10〜20°C/min升 温至 1500〜1800°C、保温 180〜240min，以 5〜10°C/min升温至 2000〜2200°C、保温 120〜 360miri。
2、 如权利要求 1所述的制备方法， 其特征在于： 所述造孔剂的用量为 15〜25%、 成型 剂的用量为 7〜12%、 余量为钽粉， 均以体积百分含量计； 所述压制成型过程中的压力为 75〜87Mpa; 所述有机泡沫体为孔径 0. 56〜0. 72mm， 密度 0. 025g/cm3， 硬度 50°〜80°的聚 氨酯泡沫。
3、 如权利要求 2所述的制备方法， 其特征在于： 所述造孔剂为双氧水占 18%、 成型剂 为硬脂酸锌占 11%、 余量为钽粉、 以体积百分含量计。
4、如权利要求 1、2或 3所述的制备方法，其特征在于：所述脱脂过程是以 0. 3°C/mir！〜 l °C/min的速率逐步升温至 400〜800°C，以氩气通入构成保护气氛并保温 330min〜350min。
5、 如权利要求 4所述的制备方法， 其特征在于： 所述脱脂过程是以 0. 8°C/min的速 率逐步升温至 400〜800°C， 以氩气通入构成保护气氛并保温 340min。
6、 如权利要求 1、 2 或 3 所述的制备方法， 其特征在于： 所述烧结步骤为真空度为 10— 4Pa〜10— 3Pa，以 12〜15°C/min升温至 1500〜1800°C、保温 180〜200min、随炉冷至 200〜 300 °C , 再以 16〜19°C/min升温至 1500〜1800°C、 保温 220〜240min， 以 5〜8°C/min升 温至 2000〜2200°C、 保温 250〜320min。
7、如权利要求 1、 2或 3所述的制备方法，其特征在于： 所述烧结是真空度为 10— 4Pa〜 10— 3Pa， 以 13°C/min升温至 1800°C、 保温 200min、 随炉冷至 200〜300°C， 再以 17°C/min 升温至 1800°C、 保温 230min， 以 7°C/min升温至 2000〜2200°C、 保温 300min; 所述脱脂 过程是以 0. 3°C/min〜l °C/min的速率逐步升温至 400〜800°C， 以氩气通入构成保护气氛 并保温 330min〜350min。
8、 如权利要求 6 所述的制备方法， 其特征在于： 所述真空烧结后的冷却条件还包括 有： 真空度不低于 10— 3Pa， 以不高于 25°C/min， 不低于 10°C/min渐降冷却速率方式， 对 烧结多孔体分段降温冷却至 800°C， 各段保温时间 30mir！〜 90min， 然后随炉冷却至常温； 真空热处理条件还包括有： 真空度不低于 10— 4Pa， 以不高于 30°C/min 的速率升至 1000〜1250°C， 保温 4h〜6h; 再以先慢后快以不低于 5°C/min但不高于 30°C/min的冷却 速率分段冷却至室温， 各段的保温时间呈递减且不超过 1. 5 h〜3h内选择。
9、 如权利要求 7 所述的制备方法， 其特征在于： 所述真空烧结后的冷却条件还包括 有： 真空度不低于 10— 3Pa， 以不高于 25°C/min， 不低于 10°C/min渐降冷却速率方式， 对 烧结多孔体分段降温冷却至 800°C， 各段保温时间 30mir！〜 90min， 然后随炉冷却至常温； 真空热处理条件还包括有： 真空度不低于 10— 4Pa， 以不高于 30°C/min 的速率升至 1000〜1250°C， 保温 4h〜6h; 再以先慢后快以不低于 5°C/min但不高于 30°C/min的冷却 速率分段冷却至室温， 各段的保温时间呈递减且不超过 1. 5 h〜3h内选择。
10、 如权利要求 1、 2或 3所述的制备方法， 其特征在于： 所述脱脂处理条件还包括 有： 以 l〜2°C/min的速率从室温升至 400°C， 保温 300〜330min， 以 0. 3〜0. 8°C/min的 速率从 400°C升至 600〜800°C， 保温 340〜360min; 所述真空烧结条件： 真空度为 10— 4Pa〜 10— 3Pa， 以 12〜15°C/min升温至 1500〜1800°C、 保温 180〜200min、 随炉冷至 200〜300 °C， 再以 16〜19°C/min升温至 1500〜1800°C、 保温 220〜240min， 以 5〜8°C/min升温至 2000〜2200°C、 保温 250〜320min; 真空烧结后的冷却条件还包括有： 真空度为 10— 4Pa〜 10— 3Pa; 以 10〜20°C/min的速率冷却至 1500〜1600°C， 保温 30〜60min; 以 12〜20°C/min 的速率冷却至 1200〜1250°C， 保温 60〜90min; 以 10〜20°C/min的速率冷却至 800°C， 然 后随炉冷却； 所述热处理条件包括有： 以 15〜30°C/min的速率升至 1000〜1250°C， 保温 240〜480min，真空度为 10— 4Pa〜10— 3Pa，再以 5〜10°C/min的速率冷却至 1000°C，保温 90〜 180min，真空度为 10— 4Pa〜10— 3Pa;以 10〜20°C/min的速率冷却至 800°C，保温 60〜120min， 真空度为 10— 4Pa; 以 20〜30°C/min的速率冷却至室温， 真空度为 10— 4Pa〜10— 3Pa。
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