WO2013044852A1 - 一种医用多孔金属植入材料的制备方法 - Google Patents

一种医用多孔金属植入材料的制备方法 Download PDF

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WO2013044852A1
WO2013044852A1 PCT/CN2012/082329 CN2012082329W WO2013044852A1 WO 2013044852 A1 WO2013044852 A1 WO 2013044852A1 CN 2012082329 W CN2012082329 W CN 2012082329W WO 2013044852 A1 WO2013044852 A1 WO 2013044852A1
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rate
vacuum
temperature
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French (fr)
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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
    • 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
    • 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

Definitions

  • the invention relates to a method for preparing a medical metal implant material, in particular to a method for preparing a medical porous metal implant material.
  • 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 dental bones. 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 ruthenium due to its excellent biocompatibility, is expected to be a substitute for the conventional medical metal biomaterials described above. Since metal ruthenium is harmless to the human body, non-toxic, has no side effects, and with the rapid development of medicine at home and abroad, the understanding of sputum as a human implant material is further deepened, and the demand for porous metal ruthenium material for human body implantation is required. It has become more and more urgent, and its requirements are getting higher and higher. Among them, as a porous medical implanted metal crucible, it is expected to be a novel substitute for bone tissue if it has a high uniform distribution of interconnected pores and physical and mechanical properties compatible with the human body.
  • 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 tantalum powder sintering 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.
  • This porous tantalum is made of pure commercial niobium, which is carbon-deposited by thermal degradation of a polyurethane precursor.
  • the scaffold is a scaffold.
  • the carbon skeleton has multiple dodecahedrons.
  • the inside of the carbon skeleton is a grid-like structure. The whole is distributed in micropores and the porosity can be as high as 98%.
  • the commercial pure rhodium is combined with carbon by chemical vapor deposition and permeation.
  • the skeleton is formed 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%. 5 ⁇ 3. 5GPa, tensile strength 63MPa, plastic deformation amount of 15%, the compressive strength of the porous material is further described. However, it is used as a porous material for medical implant materials such as bone tissue such as cement. The mechanical properties of the material such as ductility, compressive strength and flexural strength are obviously insufficient, and it will affect the subsequent porous ⁇ . Processing of the material itself, such as cutting of molded parts. Also in the products obtained by the aforementioned metal powder sintering method, there are such deficiencies.
  • the invention relates to a method for preparing a medical porous metal implant material, which comprises mixing a tantalum powder with a pore forming agent and a molding agent into a mixed powder, and then forming a substitute bone by granulation, injection molding, demoulding, degreasing, sintering and heat treatment.
  • the pore former is one or more of sodium hydrogencarbonate, urea, sodium chloride, methyl cellulose, ethyl cellulose, and the molding agent
  • the temperature is gradually increased to a temperature of 0.5 ° C / min ⁇ 3 ° C / min to one or more of polyvinyl alcohol, stearic acid, zinc stearate, paraffin, synthetic rubber; 400 ⁇ 800 °C, argon gas is passed into the protective atmosphere and kept for 60min ⁇ 240min.
  • the granulation process is at an operating temperature of 450 to 535 ° C and a working pressure.
  • the mixed powder was granulated into circular particles having a particle diameter of not more than 20 ⁇ m at 12 to 15 MPa, and the circular particles were injected into a mold at a temperature of 380 to 540 ° C and a pressure of 72 to 90 MPa.
  • 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.
  • the inventors further studied and found that if the above preparation is not well controlled, although the medical implant material suitable for replacing the dental bone as described above can be obtained, the yield of the product is not high: if the powder is pressed and formed, it is difficult. After pressing, the layer is prone to delamination, unevenness, and some problems such as cracks appear after degreasing.
  • the amount of the molding agent in the above mixed powder is 5 to 10%, and the amount of the pore forming agent is 20 to 30%.
  • the balance is ⁇ powder, in terms of volume percent (in terms of volume percent, the unit directly calculated by the final porous ruthenium material,
  • the corresponding mass weighing is calculated according to the density of the corresponding substance, and further preferably, the molding agent is 7 to 9% of the paraffin wax, and the peptizing agent is the ethyl cellulose accounting for 26 to 29%.
  • the remaining amount is bismuth powder, and more preferably 8% of paraffin, 27% of ethyl cellulose, and the balance is yttrium powder, all in terms of volume percent; the above-mentioned demolding time is preferably 6 to 9 s, further preferably 7S.
  • the degreasing process is preferred in the preparation of the porous enamel material for replacing the dental bone tissue.
  • the temperature is gradually increased to 400 to 800 ° C at a rate of 2.5 to 3 ° C / min, argon gas is introduced into a protective atmosphere and held for 150 min to 240 min, and further preferably gradually heated at a rate of 2.5 ° C / min. Up to 400 ⁇ 800 ° C, argon gas is introduced into a protective atmosphere and kept for 220 min.
  • the degreasing is raised from room temperature to 400 ° C at a rate of 1 to 3 ° C / min, and the temperature is maintained for 60 to 120 min. 5 ° C / min rate from 400 ° C to 600 ⁇ 800 ° C, holding 180 - 240min ; the above granulation process preferred temperature is 510 ⁇ 535 ° C, working pressure is 13MPa
  • the mixed powder is granulated into round particles having a particle diameter of 10 to 20 ⁇ m (more preferably 13 ⁇ m), and the temperature at which the circular particles are injection-molded is 465 to 490 ° C and the pressure is 83 to 85 MPa.
  • the invention relates to a method for preparing a medical porous metal implant material, which comprises mixing the tantalum powder with a pore forming agent and a molding agent into a mixed powder, and then granulating, injecting into a mold, demolding, degreasing, sintering and heat treatment to obtain an alternative body weight bearing.
  • a medical porous metal implant material for bone tissue characterized in that: the pore former is ammonium hydrogencarbonate, and the molding agent is one of polyvinyl alcohol, stearic acid, zinc stearate, paraffin, and synthetic rubber. Or a variety of; the degreasing process is 0. 3 ° C / mir!
  • the temperature was gradually increased to 400 ⁇ 800 °C at a rate of ⁇ 2 °C/min, and argon gas was introduced to form a protective atmosphere and kept for 300 min to 360 min.
  • the above granulation process is working at a working temperature of 480 to 525 ° C.
  • the mixed powder is granulated into circular particles having a particle diameter of not more than 30 ⁇ m under a pressure of 5 to 7 MPa, and the circular particles are injected into a mold at a temperature of 500 to 600 ° C and a pressure of 60 to 70 MPa.
  • 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.
  • the inventors further studied and found that if the above preparation is not well controlled, although the medical implant material suitable for replacing the dental bone as described above can be obtained, the yield of the product is not high: if the powder is pressed and formed, it is difficult. After pressing, the layer is prone to delamination, unevenness, and some problems such as cracks appear after degreasing.
  • the amount of the molding agent in the above mixed powder is 7 to 12%, and the amount of the pore forming agent is 15 to 25%.
  • the balance is ⁇ powder, calculated by volume percent (by volume percent, the unit directly calculated by the final porous enamel material, and the corresponding powder is also calculated according to the density of the corresponding substance in the above-mentioned mixed powder weighing. Quality weighing), further preferred
  • the molding agent is 11% stearic acid, 18% ammonium hydrogencarbonate, and the balance is bismuth powder, and the volume is preferably 5 to 6 s, and more preferably 5 s.
  • the above degreasing process is preferably 0. 3 ° C / mir! in order to make the body of the degreasing process more stable, reduce the part of the body body deformation, the pore size is not uniform, and further improve the yield and quality stability.
  • 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, and further preferably gradually heated to 400 ⁇ 800 ° C at a rate of 0.8 ° C / min 8° 0. 8° 0. 8° 0. 8° 0. 8° 0. 8° 0. 3° 0.
  • the rate of C/min is increased from 400 ° C to 600 to 800 ° C, and the temperature is maintained at 340 to 360 min; the above granulation process preferably has a temperature of 500 to 525 ° C and a working pressure of 6 MPa to granulate the mixed powder into pellets.
  • the circular particles having a diameter of 20 to 30 ⁇ m are injection-molded at a temperature of 560 to 600 ° C and a pressure of 63 to 65 MPa.
  • a further feature of another aspect of the present invention is that: the vacuum sintering conditions further include: a vacuum of not less than 10 - 3 p a , and a temperature increase rate of from 10 to 20 ° C / min from room temperature to 1200 ° C to 1500 °C, after lh ⁇ 2h, heat up to 2000 ⁇ 2200°C at a temperature increase rate lower than 20°C/min, and keep at least 2h ⁇ 4h.
  • 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 heat treatment (vacuum annealing) conditions further 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 time to a room temperature of not 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 conditions further include: increasing from room temperature to 1200 to 1250 ° C at a rate of 10 to 15 ° C / min, holding for 30 to 60 minutes, and having a vacuum of 10 - 4 Pa to 10 - 3 Pa; 10 ⁇ 20 ° C / min rate was raised to 1500 ° C, holding 30 ⁇ 60min, the degree of vacuum of 10- 4 Pa ⁇ 10- 3 Pa, at 6 ⁇ 20 ° C / min rate was raised to 2000 ⁇ 2200 ° C , insulation 120 ⁇ 240min, the degree of vacuum of 10- 4 Pa ⁇ 10- 3 P a; cooling conditions after the vacuum sintering further comprises: a degree of vacuum of 10- 4 Pa ⁇ 10- 3 P a; to 10 ⁇ 20 ° C Cool down to 1500 ⁇ 1600 °C at a rate of /min, keep warm for 30 ⁇ 60min; cool to 1200 ⁇ 1250°C at a rate of 12 ⁇ 20°C/min, keep warm for 60 ⁇ 90min; at a rate of 10 ⁇ 20°C/min Cooled
  • the properties of metal ruthenium and osmium are very similar, and the above methods are also suitable for the preparation of medical porous ruthenium materials.
  • the preparation method of the porous metal material of the invention adopts an injection 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 granulation, injection molding, degreasing, sintering and the present invention are The process conditions of the annealing step are optimized, so that the yield is high, the uniformity of the finished pore diameter is better, the preparation process is more stable, the quality stability is good, the thermal stress is effectively eliminated, the structure of the porous tantalum material is more uniform, and the porous is further improved.
  • the mechanical properties such as strength and toughness of niobium are simultaneously improved.
  • the qualification rate and production stability of products are determined by human operation factors and the process route itself, and the human operation will eventually be at a high standardization level. Therefore, the stability of production quality is mainly determined by its own process. 2% ⁇ 96. 3% ⁇
  • the pass rate is high, the production is stable, the product qualification rate is as high as 94.2% to 96.3%.
  • the porous enamel prepared by the invention has uniform pore distribution and good communication and good biocompatibility.
  • the porosity of the porous bismuth material may be less than 0.2%, the density may be 11.67 ⁇ 13.
  • the porosity may be 20 ⁇ 30%, the porosity
  • the diameter can be up to 12 ⁇ 25 ⁇ m, the modulus of elasticity can be up to 4. 5 ⁇ 6. 0Gpa, the elongation is up to 12. 0 ⁇ 13. 8%, the bending strength can reach 120 ⁇ 150Mpa, the compressive strength can reach 90 ⁇ 110Mpa
  • the porosity of the porous bismuth material can be less than 0.2%, the density can reach 6.67 ⁇ 8. 69g/cm 3 , and the porosity can reach 48 ⁇ 60%.
  • the pore diameter is up to 100 ⁇ 350 ⁇ m, and the elastic modulus is up to 2. 5 ⁇ 4. 0Gpa, the elongation is 9. 3 ⁇ 11. 7%, the bending strength can reach 80 ⁇ 90Mpa, and the compressive strength can reach 65 ⁇ 75Mpa.
  • Example 1 Weighing paraffin, an average particle size of less than 43 ⁇ m, and an oxygen content of less than 0.1%, the strontium powder and the ethyl cellulose are uniformly mixed into a mixed powder, wherein paraffin accounts for 8%, and ethyl cellulose accounts for 27%, ⁇ Powder accounts for 65%, both in volume percent.
  • Granulation The mixed powder was granulated into circular particles having a particle diameter of 10 to 13 ⁇ m at an operating temperature of 510 to 520 ° C and a working pressure of 12 to 13 MPa.
  • Injection molding The temperature at which the round particles were injected into the mold was 465 to 490 ° C and the pressure was 83 to 85 MPa. Demoulding time: 6 ⁇ 7S.
  • Degreasing treatment vacuum degree of 10- 4 Pa, at a rate l ⁇ 3 ° C / min was raised to 400 ° C from room temperature, incubated 60 ⁇ 120min, at a rate of 1. 5 ⁇ 2 5 ° C / min from 400. °C rose to 600 ⁇ 800 °C, and kept at 180 ⁇ 240min.
  • Vacuum sintering Sintering in a vacuum furnace, sintering temperature 2000 ° C, holding for 2 hours, vacuum degree 10 - 4 Pa, sintering process is filled with argon gas protection, after removing the product to remove surface dust and dirt, to obtain a porous tantalum 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 12.54 g / cm 3 , the porosity is 25%, the average pore diameter is 23 ⁇ ⁇ , the elastic modulus is 5.0 GPa, the elongation is 12.3%, the bending strength is 132 MPa, and the compressive strength is 100 MPa.
  • the porous crucible is very suitable for replacing human dental bone tissue Medical implant materials.
  • 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 6% and sodium hydrogencarbonate accounts for 29%. ⁇ powder accounts for 65%, both in volume percent.
  • Granulation The mixed powder was granulated into round particles having a particle size of 20 ⁇ m at an operating temperature of 45 CTC and a working pressure of 15 MPa.
  • Injection molding The circular particles were injected into a mold at a temperature of 540 ° C and a pressure of 90 MPa. Demoulding time: 9S.
  • Degreasing treatment The vacuum degree is 10 - 4 Pa, the temperature is raised from room temperature to 400 ° C at a heating rate of rC / min, and the temperature is maintained for 60 min; and the temperature is raised from 400 ° C to 800 ° C at a heating rate of 2.5 ° C / min.
  • the holding time is 180 minutes.
  • Vacuum sintering Sintering in a vacuum furnace, sintering temperature 2100 ° C, holding for 4 hours, vacuum degree 10 - 4 Pa, argon gas protection during sintering, removing surface dust and dirt after removing the product, and preparing the sample for routine
  • the post-treatment is porous and finished.
  • 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 11.74 g / Cm 3 , a porosity of 30%, an average pore diameter of 24 ⁇ ⁇ , an elastic modulus of 4. 5 GPa, an elongation of 12.8%, a flexural strength of 133 MPa, and a compressive strength of 92 MPa.
  • the porous crucible is very suitable for use in medical implant materials that replace human dental bone tissue.
  • Example 3 a porous crucible having a particle size of less than 43 m, an oxygen content of less than 0.1%, a mixture of polyvinyl alcohol and sodium bicarbonate, followed by granulation, injection molding, and demolding. , degreasing treatment, vacuum sintering, vacuum annealing treatment.
  • polyvinyl alcohol accounts for 7%
  • sodium bicarbonate accounts for 20%
  • metal cerium powder accounts for 73%, based on volume percent
  • granulation the mixture is mixed at an operating temperature of 520 ° C and a working pressure of 14 MPa.
  • the powder is granulated into round particles having a particle size of 16 ⁇ m;
  • Injection molding and demolding The circular pellets were injected into a mold at a temperature of 468 ° C and a pressure of 76 MPa. Demoulding time: 8S;
  • 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 introduced into the pure argon gas for at least 30 minutes before the temperature rise to remove the furnace.
  • the temperature of the argon gas is 0. 5L/min; at a rate of 2.0 ° C / min, the temperature is increased from room temperature to 400 ° C, the temperature is maintained at a rate of 1. 5 ° C / min.
  • the tungsten is placed in a high-vacuum high-temperature sintering furnace and heated to 220 CTC at a certain heating rate for vacuum sintering.
  • the vacuum of the sintering furnace should be at least 10 - 4 Pa, 10 to 15 ° before the temperature rise.
  • the rate of C/min is raised from room temperature to 1200 ° C, kept for 30 min, the degree of vacuum is 10 - 4 Pa; at a rate of 10 ° C / min, it is raised to 1500 ° C, kept for 30 min, and the degree of vacuum is 10 - 4 Pa ⁇ 10- 3 Pa; at a rate of 6 ° C / min was raised to 2200 ° C, 120min incubation, the degree of vacuum of 10- 3 Pa; sintering is completed, the degree of vacuum of 10- 3 Pa, to 10 ⁇ 15 ° C / min to Rate cooling to 1600 ° C, insulation 30 min ; cooled to 1200 ° C at a rate of 12 ° C / min, held for 60 min; cooled to 800 ° C at a rate of 10 ° C / min, and then cooled 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 12.87 g/cm 3 , a porosity of 23%, an average pore diameter of 20 m, an elastic modulus of 5. 8 GPa, a bending strength of 137 MPa, and a compressive strength of 103 MPa. 4% ⁇
  • the long-term test, the qualification rate of the preparation process is as high as 95.4%.
  • the porous crucible is very suitable for use in medical implant materials that replace human dental bone tissue. In the method given in the above Example 3, we can also obtain other options for various conditions among them to obtain the porous tantalum according to the present invention.
  • the porous enamel finished product obtained by the furnace is inspected as described above.
  • Compressive strength (MPa) 108 100 97 92 The above porous enamel is suitable for use as a medical implant material in place of human dental bone tissue.
  • Example 8 Weigh polyvinyl alcohol, an average particle size of less than 43 ⁇ m, and an oxygen content of less than 0.1%, and the ammonium bicarbonate is uniformly mixed into a mixed powder, wherein polyvinyl alcohol accounts for 11% and ammonium hydrogencarbonate accounts for 18%. , ⁇ powder accounted for 71%, are based on volume percent.
  • Granulation The mixed powder was granulated into round particles having a particle size of 26 ⁇ m at an operating temperature of 500 to 525 ° C and a working pressure of 6 MPa.
  • Injection molding The circular particles were injected into a mold at a temperature of 560 to 600 ° C and a pressure of 63 to 65 MPa. Demoulding time: 5S.
  • Degreasing treatment vacuum degree of 10- 4 Pa, at a rate l ⁇ 3 ° C / min was raised to 400 ° C from room temperature, incubated 60 ⁇ 120min, at a rate of 1. 5 ⁇ 2 5 ° C / min from 400. °C rose to 600 ⁇ 800 °C, and kept at 180 ⁇ 240min.
  • Vacuum sintering sintering in vacuum furnace, sintering temperature 2150 ° C, holding for 2 hours, vacuum degree 10 - 4 Pa, sintering process is filled with argon gas protection, cooling out of the furnace, removing dust and dirt on the surface of the product, and the prepared sample is further processed. Conventional post-treatment results in a porous tantalum 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 7.17g/cm 3 , the porosity is 55%, the average pore diameter is 200 m, the elastic modulus is 2. 5GPa, the elongation is 9.82%, the bending strength is 85MPa, and the compressive strength is 68MPa.
  • the porous crucible is well suited for use in medical implant materials that replace body-loaded bone tissue.
  • Example 9 a porous crucible having a particle size of less than 43 m, an oxygen content of less than 0.1%, a mixture of metal stearate, zinc stearate and ammonium bicarbonate, followed by granulation, injection molding, , demoulding, degreasing treatment, vacuum sintering, vacuum annealing treatment.
  • Injection molding and demolding The circular pellets were injected into a mold at a temperature of 620 ° C and a pressure of 60 MPa. Demoulding time: 3S;
  • Degreasing treatment Under an inert gas atmosphere or vacuum degree 10 - 4 ⁇ 10 - 3 Pa, 2. 5 ⁇ 3 ° C / m in heating to 400 ° C ⁇ 800 ° C, with argon as a protective atmosphere, insulation Time 150 ⁇ 240 minutes to remove polyvinyl alcohol and sodium bicarbonate;
  • Vacuum sintering the degree of vacuum is lower than 10 - 4 Pa ⁇ 10 - 3 Pa, the temperature is 2000 ⁇ 2200 ° C, the holding time is 1 to 5 hours, and the argon gas or other inert gas is protected during the sintering process to obtain a porous material;
  • Vacuum annealing After vacuum sintering temperature is maintained 1000 ⁇ 1250 ° C, holding time 1 ⁇ 4 hours, the degree of vacuum of 10- 4 ⁇ 10- 3 Pa, to an annealing treatment for stress relief; prepared sample was subjected to conventional The post-treatment is porous and finished. 0%, 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 are evenly distributed, having a density of 6.72 g/cm 3 , a porosity of 60%, an average pore diameter of 300 m, an elastic modulus of 2. 6 GPa, an elongation of 9.5%, a flexural strength of 80 MPa, and a compressive strength of 66 MPa.
  • the porous crucible is well suited for use in medical implant materials that replace body-loaded bone tissue.

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Abstract

一种医用多孔金属植入材料的制备方法，将钽粉与造孔剂、成型剂混合成混合粉末，再经造粒、注射入模具成型、脱模、脱脂、烧结和热处理制得替代牙骨组织的医用多孔金属植入材料；所述造孔剂为碳酸氢钠、尿素、氯化钠、甲基纤维素、乙基纤维素中的一种或多种，所述成型剂为聚乙烯醇、硬脂酸、硬脂酸锌、石蜡、合成橡胶中的一种或多种；所述脱脂过程是以 0.5℃/min～3℃/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 60min～240min。经过测试其制得的多孔钽材料杂质含量可低于 0.2%、密度可达 11.67～13.34g/cm3，孔隙度可达 20～30%，孔隙直径可达 12～25μm、弹性模量可达 4.5～6.0Gpa、延伸率达 12.0～13.8%、弯曲强度可达 120～150Mpa、抗压强度可达 90～ 110Mpa。

Description

一种医用多孔金属植入材料的制备方法 技术领域
本发明涉及一种医用金属植入材料的制备方法， 尤其是涉及一种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、 股骨组织坏死和替代致密骨组织如牙骨 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， 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， 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。
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， 塑性变形量 15%。 但是将它作为致密骨组织如牙骨等医用植入材料的多孔钽， 其材料的力学性能如延 展性、 抗压强度、 弯曲强度等有明显不足之处， 而且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。
发明内容
本发明的目的在于提供一种生物相容性与力学性好的医用多孔金属植入材料的制备 方法。
本发明的目的是通过如下技术手段实现的：
一种医用多孔金属植入材料的制备方法， 将钽粉与造孔剂、 成型剂混合成混合粉末， 再经造粒、 注射入模具成型、 脱模、 脱脂、 烧结和热处理制得替代牙骨组织的医用多孔金 属植入材料； 其特征在于： 所述造孔剂为碳酸氢钠、 尿素、 氯化钠、 甲基纤维素、 乙基纤 维素中的一种或多种， 所述成型剂为聚乙烯醇、 硬脂酸、 硬脂酸锌、 石蜡、 合成橡胶中的 一种或多种； 所述脱脂过程是以 0. 5°C/min〜3°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 60min〜240min。
为了使制得的替代牙骨组织的多孔钽材料孔隙率合适、 以使生物相容性优异， 同时提 高其材料的力学性能， 上述造粒过程是在工作温度为 450〜535°C、 工作压力为 12〜15MPa 下将所述混合粉末造粒成粒径不高于 20μηι的圆形颗粒， 将所述圆形颗粒注射入模具的温 度为 380〜540°C、 压力为 72〜90MPa。
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。
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 合用于替代牙骨的医用植入材料但产品合格率不高： 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， 上述混合粉末中成型剂的用量为 5〜10%、造孔剂的用量为 20〜30%、余量为钽粉， 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 上述混合粉末称量中还是根据相应物质的密度计算出其对应的质量称量的）， 进一步优选 为成型剂为石蜡占 7〜9%、 造孔剂为乙基纤维素占 26〜29%、 余量为钽粉， 更进一步优选 为石蜡占 8%、 乙基纤维素占 27%、 余量为钽粉， 均以体积百分含量计； 上述脱模时间优选 为 6〜9S， 进一步优选为 7S。
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、 生产质量稳定性， 在上述替代牙骨组织的多孔钽材料的制备中脱脂过程优 选以 2. 5〜3°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 150min〜240min， 更进一步优选以 2. 5°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 220min， 最优选地， 上述脱脂是以 l〜3°C/min 的速率从室温升至 400 °C ,保温 60〜120min，以 1. 5〜2. 5°C/min的速率从 400°C升至 600〜800°C，保温 180— 240min; 上述造粒过程优选的温度为 510〜535°C、工作压力为 13MPa下将所述混合粉末造 粒成粒径 10〜20μηι (更优选为 13μηι) 的圆形颗粒， 将所述圆形颗粒注射成型的温度为 465〜490°C、 压力为 83〜85MPa。
一种医用多孔金属植入材料的制备方法， 将钽粉与造孔剂、 成型剂混合成混合粉末， 再经造粒、 注射入模具成型、 脱模、 脱脂、 烧结和热处理制得替代人体承重骨组织的医用 多孔金属植入材料； 其特征在于： 所述造孔剂为碳酸氢铵， 所述成型剂为聚乙烯醇、 硬脂 酸、 硬脂酸锌、 石蜡、 合成橡胶中的一种或多种； 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。
为了使制得的替代人体承重骨组织的多孔钽材料孔隙率合适、 以使生物相容性优异， 同时提高其材料的力学性能， 上述造粒过程是在工作温度为 480〜525°C、 工作压力为 5〜 7MPa下将所述混合粉末造粒成粒径不高于 30μηι的圆形颗粒， 将所述圆形颗粒注射入模具 成型的温度为 500〜600°C、 压力为 60〜70MPa。
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。
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 合用于替代牙骨的医用植入材料但产品合格率不高： 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， 上述混合粉末中成型剂的用量为 7〜12%、造孔剂的用量为 15〜25%、余量为钽粉， 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 上述混合粉末称量中还是根据相应物质的密度计算出其对应的质量称量的）， 进一步优选 为成型剂为硬脂酸占 11%、 碳酸氢铵占 18%、 余量为钽粉， 均以体积百分含量计； 上述脱 模时间优选为 3〜6S， 进一步优选为 5S。
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， 上述脱脂过程优选 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，更进一步优选以 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，最优选地，以 1〜 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; 上述造粒过程优选的温度为 500〜525°C、 工作压力 为 6MPa下将所述混合粉末造粒成粒径 20〜30μηι (更优选为 26μηι) 的圆形颗粒， 将所述 圆形颗粒注射成型的温度为 560〜600°C、 压力为 63〜65MPa。
本发明另一方面的进一步的特点是： 真空烧结条件还包括有： 真空度不低于 10— 3pa， 以 10〜20°C/min 的升温速率从室温升至 1200 °C〜 1500 °C， 保温 lh〜2h 后； 再以低于 20°C/min的升温速率升温至 2000〜2200°C， 至少保温 2h〜4h。
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。
热处理（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：逐步升温至 600〜800°C， 具体是以纯净氩气（99. 9999%)通入构成保护气氛，以 l〜3°C/min的速率从室温升至 400°C， 保温 60〜120min，以 1. 5〜2. 5°C/min的速率从 400°C升至 600〜800°C，保温 180〜240min; 所述真空烧结条件还包括有：以 10〜15°C/min的速率从室温升至 1200〜1250°C，保温 30〜 60min, 真空度为 10— 4Pa〜10— 3Pa; 以 10〜20°C/min的速率升至 1500°C， 保温 30〜60min， 真空度为 10— 4Pa〜10— 3Pa， 以 6〜20°C/min的速率升至 2000〜2200°C， 保温 120〜240min， 真空度为 10— 4Pa〜10— 3Pa; 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； 所述热处理条件还包括有： 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。 本发明多孔金属材料制备方法采用了注射成型法， 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； 对本发明造粒、 注射成型、 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， 以进一步提高多孔钽的 力学性能如强度、 韧性同时都得到提高。 众所周知， 产品的合格率、 生产稳定性由人为操 作因素决定和工艺路线本身决定、 人为操作终归会处于高标准化趋于正常水平， 因此生产 质量稳定性主要由本身工艺决定， 本发明制备工艺其成品合格率高、 生产稳定， 产品合格 率高达 94. 2%〜96. 3%。 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。 对 于制得的替代牙骨组织的多孔钽材料，经过测试其杂质含量可低于 0. 2%、密度可达 11. 67〜 13. 34g/cm3, 孔隙度可达 20〜30%， 孔隙直径可达 12〜25 μ m、弹性模量可达 4. 5〜6. 0Gpa、 延伸率达 12. 0〜13. 8%、 弯曲强度可达 120〜150Mpa、 抗压强度可达 90〜110Mpa; 对于制 得的替代承重骨组织的多孔钽材料， 经过测试其杂质含量可低于 0. 2%、 密度可达 6. 67〜 8. 69g/cm3,孔隙度可达 48〜60%，孔隙直径可达 100〜350 μ m、弹性模量可达 2. 5〜4. 0Gpa、 延伸率达 9. 3〜11. 7%、 弯曲强度可达 80〜90Mpa、 抗压强度可达 65〜75Mpa。
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。
实施例 1 : 称取石蜡、 平均粒径小于 43微米氧含量小于 0. 1%的钽粉和乙基纤维素混 合均匀成混合粉末， 其中石蜡占 8%、 乙基纤维素占 27%、 钽粉占 65%， 均以体积百分含量 计。 造粒： 在工作温度为 510〜520°C、 工作压力为 12〜13MPa下将所述混合粉末造粒成粒 径 10〜13μηι的圆形颗粒。 注射成型： 将所述圆形颗粒注射入模具的温度为 465〜490°C、 压力为 83〜85MPa。 脱模时间： 6〜7S。 脱脂处理： 真空度 10— 4Pa， 以 l〜3°C/min的速率 从室温升至 400°C，保温 60〜120min，以 1. 5〜2. 5°C/min的速率从 400°C升至 600〜800°C， 保温 180〜240min。 真空烧结： 在真空炉中烧结， 烧结温度 2000°C， 保温 2小时， 真空度 10— 4Pa， 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 12. 54g/cm3， 孔隙率 25%， 孔隙平均直径 23 μ ιιι， 弹性模量 5. 0GPa， 延伸 率 12. 3%， 弯曲强度 132MPa， 抗压强度 100MPa。 该多孔钽非常适合用于替代人体牙骨组织 的医用植入材料。
实施例 2: 称取聚乙烯醇、 平均粒径小于 43微米氧含量小于 0. 1%的钽粉和碳酸氢钠 混合均匀成混合粉末， 其中聚乙烯醇占 6%、 碳酸氢钠占 29%、 钽粉占 65%， 均以体积百分 含量计。造粒：在工作温度为 45CTC、工作压力为 15MPa下将所述混合粉末造粒成粒径 20μηι 的圆形颗粒。 注射成型： 将所述圆形颗粒注射入模具的温度为 540°C、 压力为 90MPa。 脱 模时间： 9S。 脱脂处理： 真空度 10— 4Pa， 以 rC/min的升温速率从室温升温至 400°C、 保 温 60min; 再以 2. 5°C/min的升温速率从 400°C升温至 800°C， 保温时间 180分钟。 真空烧 结： 在真空炉中烧结， 烧结温度 2100°C， 保温 4小时， 真空度 10— 4Pa， 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 11. 74g/Cm 3， 孔隙率 30%， 孔隙平均直径 24 μ πι， 弹性模量 4. 5GPa， 延伸 率 12. 8%， 弯曲强度 133MPa， 抗压强度 92MPa。 该多孔钽非常适合用于替代人体牙骨组织 的医用植入材料。
实施例 3: —种多孔钽， 它以粒径小于 43 m、 氧含量小于 0. 1%的金属钽粉， 聚乙烯 醇和碳酸氢钠混合粉为原料， 再经造粒、 注射成型、 脱模、 脱脂处理、 真空烧结、 真空退 火处理制得。
其中， 聚乙烯醇占 7%、 碳酸氢钠占 20%、 金属钽粉占 73%， 以体积百分含量计； 造粒： 在工作温度为 520°C、 工作压力为 14MPa下将所述混合粉末造粒成粒径 16μηι 的圆形颗粒；
注射成型及脱模： 将所述圆形颗粒注射入模具的温度为 468°C、 压力为 76MPa。 脱模 时间： 8S;
随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. 5°C/min的速率从室温升至 400°C， 保温 88min， 氩气通入量 0. 5L/min; 以 2. 0°C/min的速率从 400°C升至 800°C， 保温 195min， 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 10〜15°C/min的 速率从室温升至 1200°C， 保温 30min， 真空度为 10— 4Pa; 以 10°C/min的速率升至 1500°C， 保温 30min， 真空度为 10— 4Pa〜10— 3Pa; 以 6°C/min的速率升至 2200°C， 保温 120min， 真 空度为 10— 3Pa; 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 12. 87g/cm3， 孔隙率 23%， 孔隙平均直径 20 m， 弹性模量 5. 8GPa， 弯曲 强度 137MPa， 抗压强度 103MPa。 经长期测试， 该制备工艺产品合格率高达 95. 4%。 该多孔 钽非常适合用于替代人体牙骨组织的医用植入材料。 在上述实施例 3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。
实 钽粉粒 造孔剂及其所 成型剂及其所 造粒温度及 注射成型 脱模时间 施 径 （微 占的体积百分 占的体积百分 压力， 所得 温度及压
例 米） /氧 比 （％) 比 （％) 圆形颗粒粒 力
含量小 径
于 （％)
4 小 于 尿素和碳酸氢 硬脂酸和石蜡， 510°C 、 465 °C 、 5.8S
38/0.1% 钠， 26% 9% 15MPa ， 86MPa
11 μ m
5 小 于 甲基纤维素， 丁苯橡胶和石 650 °C 、 380°C、 72 6S
40/0.1% 30% 蜡， 5% 13MPa ， MPa
15 μ m
6 小 于 乙基纤维素， 硬脂酸锌， 7% 450 °C 、 540 °C、 90 9S
35/0.1% 20% 12MPa ， MPa
17 m
7 小 于 尿素， 26% 异戊橡胶， 10% 535 °C 、 490 °C、 83 7.6S
Figure imgf000009_0001
Figure imgf000009_0002
炉
6 以 3°C/min的 12°C/min的速率 至 1220°。，保温 10"3Pa/20°C/min的速率升至 1100 速率从室温 55min, 真 为 104Pa; °C， 保温 420min/
升至 400°C， 以 13 °C/min的速率升至 1300 °C， 保温 7°C/min的速率) 卩至 1000 °C，保 保温 77min/ 50min; 温 130min/
2.2°C/min的 以 10°C/min的速率升至 2100°C， 保温 以 13°C/min的速率 至 800°C， 速率从 400°C 200min, 真空度为 10- 3Pa; 保温 96min/
升至 780°C， 真空度为 104Pa〜10— 3Pa;以 13°C/min的速 23°C/min的速率 至室温 保温 183min 率 至 1540 °C， 保温 50min;
以 15°C/min的速率) f¾至 1220 °C， 保温
80min;
以 15°C/min的速率 至 800°C， 然后随
炉
7 0.5°C/min的 13°C/min的速率 至 1230°。，保温 10 Pa/22°C/min的速率升至 1150 速率从室温 50min, 真 为 104Pa; °C， 保温 360min/
升至 400°C， 以 14°C/min的速率升至 1350 °C， 保温 8°C/min的速率) 卩至 1000 °C，保 保温 68min/ 45min; 温 120min/
1.8°C/min的 以 12°C/min的速率升至 2150°C， 保温 以 14°C/min的速率) f¾至 800°C， 速率从 400°C 180min, 真空度为 10—3Pa; 保温 90min/
升至 780°C， 真空度为 104Pa〜10— 3Pa;以 14°C/min的速 24°C/min的速率 至室温 保温 193min 率 至 1550 °C， 保温 45min;
以 16°C/min的速率) f¾至 1230 °C， 保温
75min;
以 16°C/min的速率 至 800°C， 然后随
炉 所得多孔钽成品按前述方法检
Figure imgf000010_0001
抗压强度 (MPa) 108 100 97 92 以上制得多孔钽适用于作为替代人体牙骨组织的医用植入材料。
实施例 8: 称取聚乙烯醇、 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， 其中聚乙烯醇占 11%、 碳酸氢铵占 18%、 钽粉占 71%， 均以体积百分 含量计。 造粒： 在工作温度为 500〜525°C、 工作压力为 6MPa下将所述混合粉末造粒成粒 径 26μηι的圆形颗粒。 注射成型： 将所述圆形颗粒注射入模具的温度为 560〜600°C、 压力 为 63〜65MPa。 脱模时间： 5S。 脱脂处理： 真空度 10— 4Pa， 以 l〜3°C/min的速率从室温升 至 400°C， 保温 60〜120min， 以 1. 5〜2. 5°C/min的速率从 400°C升至 600〜800°C， 保温 180〜240min。真空烧结：在真空炉中烧结，烧结温度 2150°C，保温 2小时，真空度 10— 4Pa， 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 7. 17g/cm3， 孔隙率 55%， 孔隙平均直径 200 m， 弹性模量 2. 5GPa， 延伸 率 9. 82%， 弯曲强度 85MPa， 抗压强度 68MPa。 该多孔钽非常适合用于替代人体承重骨组织 的医用植入材料。
实施例 9: 一种多孔钽， 它以粒径小于 43 m、 氧含量小于 0. 1%的金属钽粉， 硬脂酸 锌和碳酸氢铵混合粉为原料， 再经造粒、 注射成型、、 脱模、 脱脂处理、 真空烧结、 真空 退火处理制得。
其中， 硬脂酸锌占 7%、 碳酸氢铵占 20%、 金属钽粉占 73%， 以体积百分含量计； 造粒： 在工作温度为 480°C、 工作压力为 7MPa下将所述混合粉末造粒成粒径 30μηι的 圆形颗粒；
注射成型及脱模： 将所述圆形颗粒注射入模具的温度为 620°C、 压力为 60MPa。 脱模 时间： 3S;
脱脂处理： 在惰性气体保护气氛下或真空度 10— 4〜10— 3Pa， 以 2. 5〜3°C/min 升温至 400°C〜800°C， 以氩气为保护气氛、 保温时间 150〜240 分钟以除去其中的聚乙烯醇及碳 酸氢钠；
真空烧结： 真空度低于 10— 4Pa〜10— 3Pa， 温度 2000〜2200°C， 保温时间 1〜5小时， 烧 结过程保温时充氩气或其他惰性气体保护， 以得到多孔材料；
真空退火： 经过真空烧结后继续保持温度处于 1000〜1250°C， 保温时间 1〜4小时， 真空度为 10— 4〜10— 3Pa， 以进行去应力退火处理； 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. 72g/cm3， 孔隙率 60%， 孔隙平均直径 300 m， 弹性模量 2. 6GPa， 延伸 率 9. 5%， 弯曲强度 80MPa， 抗压强度 66MPa。 该多孔钽非常适合用于替代人体承重骨组织 的医用植入材料。

Claims

权 利 要 求 书
1、 一种医用多孔金属植入材料的制备方法， 将钽粉与造孔剂、 成型剂混合成混合粉 末， 再经造粒、 注射入模具成型、 脱模、 脱脂、 烧结和热处理制得替代牙骨组织的医用多 孔金属植入材料； 其特征在于： 所述造孔剂为碳酸氢钠、 尿素、 氯化钠、 甲基纤维素、 乙 基纤维素中的一种或多种， 所述成型剂为聚乙烯醇、 硬脂酸、 硬脂酸锌、 石蜡、 合成橡胶 中的一种或多种；所述脱脂过程是以 0. 5°C/min〜3°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 60min〜240min。
2、 如权利要求 1所述的制备方法， 其特征在于： 所述造粒过程是在工作温度为 450〜 535°C、工作压力为 12〜15MPa下将所述混合粉末造粒成粒径不高于 20μηι的圆形颗粒， 将 所述圆形颗粒注射入模具的温度为 380〜540°C、 压力为 72〜90MPa。
3、 如权利要求 1或 2所述的制备方法， 其特征在于： 所述混合粉末中成型剂的用量 为 5〜10%、 造孔剂的用量为 20〜30%、 余量为钽粉， 以体积百分含量计； 所述脱模时间为 6〜9S。
4、 如权利要求 3所述的制备方法， 其特征在于： 所述成型剂为石蜡占 7〜9%、 造孔剂 为乙基纤维素占 26〜29%、 余量为钽粉， 均以体积百分含量计。
5、 如权利要求 4所述的制备方法， 其特征在于： 所述石蜡占 8%、 乙基纤维素占 27%、 余量为钽粉， 均以体积百分含量计； 所述脱模时间为 7S。
6、 如权利要求 1或 2所述的制备方法， 其特征在于： 所述替代牙骨组织的多孔钽材 料的制备中脱脂过程是以 l〜3°C/min的速率从室温升至 400°C，保温 60〜120min，以 1. 5〜 2. 5°C/min的速率从 400°C升至 600〜800°C， 保温 180〜240min; 所述造粒过程的温度为 510〜535°C、 工作压力为 13MPa下将所述混合粉末造粒成粒径 10〜20μηι的圆形颗粒， 将 所述圆形颗粒注射成型的温度为 465〜490°C、 压力为 83〜85MPa。
7、 如权利要求 4 所述的制备方法， 其特征在于： 所述替代牙骨组织的多孔钽材料的 制备中脱脂过程是以 l〜3°C/min的速率从室温升至 400°C， 保温 60〜120min， 以 1. 5〜 2. 5°C/min的速率从 400°C升至 600〜800°C， 保温 180〜240min; 所述造粒过程的温度为 510〜535°C、 工作压力为 13MPa下将所述混合粉末造粒成粒径 10〜20μηι的圆形颗粒， 将 所述圆形颗粒注射成型的温度为 465〜490°C、 压力为 83〜85MPa。
8、 如权利要求 7 所述的制备方法， 其特征在于： 所述真空烧结条件还包括有： 真空 度不低于 10— 3Pa， 以 10〜20°C/min的升温速率从室温升至 1200°C〜1500°C， 保温 lh〜2h 后； 再以低于 20°C/min的升温速率升温至 2000〜2200°C， 至少保温 2h〜4h;
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；
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 1或 2所述的制备方法， 其特征在于： 所述真空烧结条件还包括有： 以 10〜15°C/min的速率从室温升至 1200〜1250°C， 保温 30〜60min， 真空度为 10— 4Pa〜 10— 3Pa; 以 10〜20°C/min的速率升至 1500°C， 保温 30〜60min， 真空度为 10— 4Pa〜10— 3Pa， 以 6〜20°C/min的速率升至 2000〜2200°C， 保温 120〜240min， 真空度为 10— 4Pa〜10— 3Pa; 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； 所述热处理条件还包 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。
10、如权利要求 6所述的制备方法，其特征在于：所述真空烧结条件还包括有： 以 10〜 15°C/min的速率从室温升至 1200〜1250°C， 保温 30〜60min， 真空度为 10— 4Pa〜10— 3Pa; 以 10〜20°C/min的速率升至 1500°C， 保温 30〜60min， 真空度为 10— 4Pa〜10— 3Pa， 以 6〜 20°C/min的速率升至 2000〜2200°C， 保温 120〜240min， 真空度为 10— 4Pa〜10— 3Pa; 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； 所述热处理条件还包括有： 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。
11、如权利要求 7所述的制备方法，其特征在于：所述真空烧结条件还包括有： 以 10〜 15°C/min的速率从室温升至 1200〜1250°C， 保温 30〜60min， 真空度为 10— 4Pa〜10— 3Pa; 以 10〜20°C/min的速率升至 1500°C， 保温 30〜60min， 真空度为 10— 4Pa〜10— 3Pa， 以 6〜 20°C/min的速率升至 2000〜2200°C， 保温 120〜240min， 真空度为 10— 4Pa〜10— 3Pa; 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； 所述热处理条件还包括有： 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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