WO2013044773A1 - 一种牙骨替代医用多孔金属材料的制备方法 - Google Patents

一种牙骨替代医用多孔金属材料的制备方法 Download PDF

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WO2013044773A1
WO2013044773A1 PCT/CN2012/081851 CN2012081851W WO2013044773A1 WO 2013044773 A1 WO2013044773 A1 WO 2013044773A1 CN 2012081851 W CN2012081851 W CN 2012081851W WO 2013044773 A1 WO2013044773 A1 WO 2013044773A1
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rate
vacuum
temperature
sintering
degree
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PCT/CN2012/081851
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English (en)
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
    • B22F3/1125—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers involving a foaming process
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps

Definitions

  • the invention relates to a method for preparing a medical porous metal implant material, in particular to a method for preparing a medical implanted porous metal material instead of dense bone tissue.
  • 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 ⁇ / ⁇ 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%. 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 object of the present invention is achieved by the following technical means:
  • the invention relates to a method for preparing a medical porous metal material for replacing a dental bone, which is characterized in that: a tantalum powder is mixed with a pore forming agent and a molding agent to form a mixed powder, and then a porous tantalum material is obtained by press molding, degreasing, sintering, cooling and heat treatment.
  • the press molding is to press the mixed powder into an organic foam at a pressure of 50 to 100 MPa, and the pore forming agent is one of urea, sodium chloride, ethyl cellulose, and methyl cellulose.
  • the molding agent is any one or more of any combination of stearic acid, zinc stearate, paraffin wax, and synthetic rubber.
  • 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-mentioned pore formers and molding agents 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 p a . ⁇ 0. 56 ⁇ 0
  • the hardness is greater than 50° (most preferably the pore diameter is 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°. . 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 dental bone as described above can be obtained, the product qualification rate is not high, and the production stability is not good: Powder pressing is difficult to form, and it is prone to delamination and unevenness after pressing, 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 above-mentioned pore forming agent is 20 to 30. %, the balance is tantalum powder, in terms of volume percent (in terms of volume percent, it is directly calculated by the final porous tantalum material) 5%,
  • the above-mentioned pore-forming agent accounts for 21 ⁇ 24, and the above-mentioned forming agent accounts for 5 ⁇ 6. 5%, the above-mentioned pore-forming agent accounts for 21 ⁇ 24.
  • the balance is ⁇ powder; the pressure in the above press molding process is preferably 55 to 65 MPa; more preferably, the above molding agent accounts for 6%, the above-mentioned pore former accounts for 23%, and the balance is ⁇ powder, by volume Percentage.
  • the above degreasing process is 2 ° C / mir! ⁇ 5.
  • the temperature is gradually increased to 400 ⁇ 800 °C at a rate of 5 ° C / min, and the argon gas is introduced to form a protective atmosphere and kept for 100 min to 240 min; further preferably, the temperature is gradually increased to a rate of 3 to 3. 5 ° C / min.
  • 400 ⁇ 800 °C, argon gas is passed into the protective atmosphere and kept for 150min ⁇ 200min.
  • the temperature is gradually increased to 400 to 800 ° C at a rate of 3 ° C / min, and argon gas is introduced to form a protective atmosphere and held for 170 minutes.
  • a further feature of another aspect of the present invention is that a porous sintered body is obtained by vacuum sintering treatment at a vacuum of not less than 10 - 4 to 10 - 3 P a , a temperature of 2000 to 2200 ° C, and a holding time of 1 to 5 hours.
  • the inert gas protection can be used instead of the vacuum protection; finally, the vacuum annealing treatment is performed, wherein the vacuum annealing treatment means that the temperature is maintained at 1000 ⁇ 1250 ° C after the vacuum sintering, the holding time is 1 to 4 hours, and the vacuum degree is not low. to 10- 4 ⁇ 10- 3 Pa.
  • the vacuum sintering conditions further include: a vacuum degree of not less than 10 - 3 P a , rising from room temperature to 1200 ° C to 1500 ° C at a heating rate of 10 to 20 ° C / m in after holding for 1 h to 2 h; The temperature is raised to 2000 ⁇ 2200 ° C at a temperature increase rate lower than 20 ° C / min, and at least 2 h to 4 h.
  • the cooling conditions after vacuum sintering further include: a vacuum degree of not less than 10 - 3 P a , a cooling capacity of not less than 25 ° C / min, not less than 10 ° C / min, and a sintered porous body
  • the section is cooled to 800 ° C, and the holding time of each section is 30 min to 90 min, and then cooled to room temperature with the furnace.
  • the vacuum annealing conditions also include: the vacuum degree is not lower than 10 - 4 Pa, and the temperature is raised to 1000 to 1250 ° C at a rate of not higher than 30 ° C / m in , and the temperature is kept for 4 h to 6 h; 5 ⁇ 3 ⁇ Select a cooling rate of less than 5 ° C / min but not more than 30 ° C / min.
  • the degreasing treatment conditions further include: gradually increasing the temperature to 600 to 800 ° C, specifically by using pure argon gas (99.9999%) to form a protective atmosphere, to l 2
  • the rate of °C/min is raised from room temperature to 400 ° C, kept at 100 ⁇ 120min, raised from 400 °C to 600 ⁇ 800 °C at a rate of 2 ⁇ 3 °C/min, and kept at 200 ⁇ 240min;
  • the 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; to 10 to 20 °
  • the rate of C/min is raised to 1500 ° C, the temperature is kept for 30 to 60 minutes, the degree of vacuum is 10 - 4 Pa to 10 - 3 Pa, and the temperature is raised to 2000 to 2200 ° C at a rate of 6 to 20 ° C / min.
  • the degree of vacuum is 10 - 4 Pa ⁇ 10 - 3 P a
  • the cooling conditions after vacuum sintering further include: a degree of vacuum of 10 - 4 Pa ⁇ 10 - 3 P a; at a rate of 10 to 20 ° C / min Cool to 1500 ⁇ 1600 °C, keep warm for 30 ⁇ 60min; cool at 12 ⁇ 20°C/min But to 1200 ⁇ 1250 ° C, keep warm 60 ⁇ 90min; cool to 800 ° C at a rate of 10 ⁇ 20 ° C / min, and then cool with the furnace; the vacuum annealing conditions also include: at 15 ⁇ 30 ° C / min rate was raised to 1000 ⁇ 1250 ° C, insulation 240 ⁇ 480min, the degree of vacuum of 10- 4 Pa ⁇ 10- 3 Pa, and then cooled to 1000 ° C at a rate of 5 ⁇ 10 ° C / min, and incubated 90 ⁇ 180min , the degree of vacuum is 10 - 4 Pa ⁇ 10 - 3 Pa; cooled to 800 ° C
  • 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 further improving the mechanics of porous tantalum The performance, such as strength and toughness, are simultaneously improved.
  • the preparation process of the invention has high yield and stable production, and the product qualification rate can be as high as 93%.
  • the porosity of the porous ruthenium obtained by the present invention is uniform and continuous, and the biocompatibility is good.
  • the impurity content may be less than 0.2%, the density may be 11.67 ⁇ 13. 34 g /cm 3 , porosity Up to 20 ⁇ 30%, pore diameter up to 5 ⁇ 30 ⁇ ⁇ ; elastic modulus up to 4. 5 ⁇ 6. 0Gpa, bending strength up to 110 ⁇ 130Mpa, compressive strength up to 100 ⁇ 130Mpa, porous in the invention ⁇ Ideal for medical implant materials that replace dental bones.
  • the preparation method of the medical porous metal material for replacing the dental bone is to select a molding agent and a pore forming agent (the molding agent is any one or a combination of stearic acid, zinc stearate, paraffin wax, synthetic rubber) 1% ⁇ , the pore-forming agent is one or more of urea, sodium chloride, ethyl cellulose, methyl cellulose, and any combination of an average particle size of less than 43 microns, an oxygen content of less than 0.1%
  • the mixture is mixed into a mixed powder, and the mixed powder is pressed into an organic foam at 50 to 100 MPa, and then degreased, sintered, cooled, and heat-treated to obtain a porous tantalum material.
  • the formed porous crucible has a detected porosity of 20 to 30% and a pore diameter of 5 to 30 ⁇ m.
  • the above porous ruthenium is 5 to 10% by volume of the above-mentioned molding agent, 20 to 30% by volume of the above-mentioned pore-forming agent, and the balance of cerium powder Mixing into a mixed powder, put it into an injection molding machine and press-pressing it into a polyurethane foam to form; then placing it in a tungsten furnace and putting pure argon gas (99.9999%) into the protective atmosphere furnace to gradually heat up to At a certain temperature, and dehumidified 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 tungsten is placed in a high-vacuum high-temperature sintering furnace and gradually heated to 2000 ⁇ 2200 °C, and the holding time is 1 ⁇ 5 hours.
  • the vacuum degree of the sintering furnace should be at least a suitable level before the temperature rise, the sample after vacuum sintering is cooled with the furnace, and a certain degree of vacuum is maintained during the cooling process or is cooled in stages to maintain a certain temperature at a certain cooling rate.
  • an inert gas can be used as a protective atmosphere.
  • 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 treatment For the degreasing treatment, it is placed in a tungsten furnace and placed in an atmosphere furnace to raise the temperature at a certain heating rate. Before the temperature rise, an argon gas or other inert gas is introduced to remove the air in the furnace, and the temperature control process is suitable. The heating rate is raised from room temperature to a certain temperature, and the temperature is raised, and then the temperature is raised and kept warm.
  • the vacuum sintering treatment is carried out on the degreased sample in a high-vacuum high-temperature sintering furnace, and the temperature is raised to the highest sintering temperature of the crucible at a certain heating rate for vacuum sintering, and the sintering furnace maintains a certain vacuum before the temperature rises.
  • the temperature is raised to, for example, 1200 ° C at 1250 ° C at a certain heating rate, and the temperature is kept constant.
  • the temperature is raised to a temperature of, for example, 1250 ° C and 1500 ° C at a certain heating rate, and the temperature is raised to a certain temperature increase rate to, for example, ⁇ .
  • 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 and 1250 ° C for stress relief annealing, and the furnace is annealed before heating.
  • Maintain the vacuum increase from room temperature to 1000 °C at a certain heating rate, 1250 ° C, keep warm, keep vacuum; then cool to a temperature of 1000 ° C at a certain cooling rate, keep warm; then cool to a certain cooling rate to For example, 800 ° C, heat preservation; also cooled at room temperature with a certain cooling rate.
  • a conventional post-treatment is carried out to obtain a porous crucible.
  • the inventor uses a metal powder sintering method mainly based on the physical molding method, and has carried out a large number of theoretical analysis and experimental verification, and the porous bismuth product has been tested to have an impurity content of less than 0.2% and a density of up to 11.67. 34 g / cm 3 , porosity up to 20 30%, pore diameter up to 5 30 ⁇ ⁇ ; elastic modulus up to 4. 5 6. 0Gpa, bending strength up to 110 130Mpa, compressive strength up to 100 130Mpa
  • Example 1 Weighing zinc stearate, an average particle size of less than 43 microns, an oxygen content of less than 0.1% of strontium powder and methyl cellulose are mixed uniformly into a mixed powder, wherein zinc stearate accounts for 6%, methyl fiber 23% for sputum and 71% for sputum powder, all in volume percent.
  • Press molding The above mixed powder is added to an injection molding machine and pressed at a pressure of 62 MPa to a polyurethane foam (pore diameter: 0. 48 0. 89 density 0. 015 g/cm 3 0. 035 g/cm 3 , hardness greater than 50°) forming.
  • Degreasing treatment vacuum degree 10 - 4 Pa, heating from room temperature to 400 ° C at a heating rate of 1. 5 ° C / min, holding l lOmin; and then heating from 400 ° C at a heating rate of 2.5 ° C / min Up to 700 ° C, holding time 210 minutes.
  • Vacuum sintering Sintering in a vacuum furnace, sintering temperature 2000 ° C, holding for 2 hours, vacuum degree 10 - 4 Pa, argon gas protection during sintering, after taking out the product The surface dust and dirt are removed, and the prepared sample is subjected to a conventional post-treatment 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 pores have a uniform distribution, a density of 12.67 g/cm 3 , a porosity of 24%, an average pore diameter of 16 m, an elastic modulus of 6. 0 GPa, a flexural strength of 130 MPa, and a compressive strength of 130 MPa.
  • Example 2 Weighing paraffin, the average particle size is less than 43 micrometers, and the oxygen content is less than 0.1%.
  • the strontium powder and urea are uniformly mixed into a mixed powder, wherein paraffin accounts for 5%, ethyl cellulose accounts for 30%, and strontium powder accounts for 65. %, all in volume percent.
  • Press molding The above mixed powder was placed in an injection molding machine and pressed at 65 MPa to a polyurethane foam having a pore diameter of 0.56 to 0. 72 mm, a density of 025 g/cm 3 , and a hardness of 50 to 80°.
  • Degreasing treatment The vacuum degree is 10 - 4 Pa, the temperature is raised from room temperature to 400 ° C at a heating rate of 2 ° C / min, and the temperature is kept for lOOmin; and the temperature is raised from 400 ° C to 800 ° C at a heating rate of 3 ° C / min.
  • the holding time is 200 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 pore distribution is uniform, the density is 6. 00g/cm 3 , the porosity is 30%, the average pore diameter is 28 m, the elastic modulus is 2.0 GPa, the bending strength is 73 MPa, and the compressive strength is 82 MPa.
  • Example 3 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 are mixed to form a mixed powder, wherein stearic acid accounts for 10% and sodium chloride accounts for 20%. ⁇ powder accounts for 70%, both in volume percent.
  • Press molding The above mixed powder was placed in an injection molding machine and pressed at 97 MPa to a polyurethane foam having a pore diameter of 0. 56 to 0. 72 mm, dense & 0. 025 g/cm 3 , and hardness of 50 to 80.
  • 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 kept for 120 min; and the temperature is raised from 400 ° C to 750 ° C at a heating rate of 2 ° C / min. 240 minutes.
  • Vacuum sintering Sintering in a vacuum furnace, sintering temperature 2200 ° C, insulation 2. 5 hours, vacuum 10 - 3 P a , sintering process is filled with argon gas protection, cooling out of the furnace, removing dust and dirt on the surface of the product, made The sample is then subjected to conventional post-treatment 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 13.37 g/cm 3 , the porosity is 20%, the average pore diameter is 27 m, the elastic modulus is 4. 8 GPa, the bending strength is 128 MPa, and the compressive strength is 120 MPa.
  • Example 4 Weighing paraffin and zinc stearate, an average particle size of less than 43 microns, an oxygen content of less than 0.1% of strontium powder and sodium chloride are mixed uniformly into a mixed powder, wherein paraffin and zinc stearate (including paraffin and The mass ratio of zinc stearate is 1: 2. 5) 5%, sodium chloride 28%, and strontium powder 67%, both in volume percent.
  • Press molding Add the above mixed powder The injection molding machine was pressed at a pressure of 57 MPa to a pore size of 0. 56 to 0. 72 mm, a density of 0. 025 g/cm 3 , and a hardness of 50 ° to 80 ° in a polyurethane foam.
  • 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 105 min; and the temperature is raised from 400 ° C at a heating rate of 2.2 ° C / min to 800 ° C, holding time 225 minutes.
  • Vacuum sintering Sintering in a 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%
  • uniform pore distribution a density of 12. 84g / Cm 3, a porosity of 23%, an average pore diameter of 26 ⁇ ⁇ , elastic modulus 5.
  • 120MPa flexural strength
  • compressive strength 125MPa.
  • Example 5 a porous crucible, which has a particle size of less than 43 m, an oxygen content of less than 0.1%, a mixture of stearic acid and ethyl cellulose as a raw material, followed by compression molding, degreasing treatment, It is obtained by vacuum sintering, vacuum annealing and conventional post treatment.
  • press molding the raw material mixed powder was added to the injection molding machine and pressed at 55 MPa to the pore size 0. 56 ⁇ 0. 72mm, density 0. 025g / cm 3 , hardness of 50 ° ⁇ 80 ° polyurethane foam molding;
  • Degreasing treatment under the inert gas protective atmosphere or vacuum degree 10 - 4 ⁇ 10 - 3 Pa, l2 ⁇ 2 / min to 400 ° C ⁇ 800 ° C, with argon as a protective atmosphere, holding time 100 ⁇ 120 minutes To remove stearic acid and ethyl cellulose; vacuum sintering: vacuum degree is lower than 10 - 4 Pa ⁇ 10 - 3 Pa, temperature 2000 ⁇ 2200 ° C, holding time 1 ⁇ 5 hours, argon filling during sintering Gas or other inert gas protection 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.
  • 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, with a density of 12.00 g/cm 3 , a porosity of 28%, an average pore diameter of 19 m, an elastic modulus of 5. 5 GPa, a flexural strength of 122 MPa, and a compressive strength of 124 MPa.
  • Example 6 a porous crucible, which has a particle size of less than 43 m, an oxygen content of less than 0.1%, a mixture of stearic acid and sodium chloride, followed by compression molding, degreasing, and vacuum. Sintering, vacuum annealing and conventional post-treatment are obtained.
  • stearic acid accounts for 10%
  • urea accounts for 30%
  • metal strontium powder accounts for 60%, based on volume percent
  • the singularity of the pore size is 0. 56 ⁇ 0. 72mm, Forming a polyurethane foam having a density of 0. 025 g/cm 3 and a hardness of 50° to 80°;
  • 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°C/min ; 2. 0°C/min ; 2. 0°C/min, the temperature of the furnace is increased from room temperature to 400 ° C, the temperature is maintained for 108 minutes, the amount of argon gas is 0.
  • 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 The rate is cooled to 1600 ° C, kept for 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 12.34 g / Cm 3 , a porosity of 26%, an average pore diameter ⁇ ⁇ ⁇ , an elastic modulus of 4. 8 GPa, a flexural strength of 117 MPa, and a compressive strength of 125 MPa.
  • the preparation process has high yield and stable production, and the product qualification rate is 90.3%.
  • ⁇ or ⁇ powder particle size (micro ⁇ powder or ⁇ powder accounted for the type of molding agent and the type of pore-forming agent and its application) / oxygen content is less than (%) volume percentage (%) accounted for the percentage of volume (% % of volume (%)
  • 13 ⁇ powder is less than 40/0.1% 62 stearic acid; 10 methyl cellulose; 28
  • 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 rate from the chamber 60min really 10 4 Pa; 15 °C / min rate rises to 400 at irC / min rate to 1250 ° C, insulation to 1030 ° C, insulation
  • vacuum is 10 - 3 Pa; to 1000 ° C, insulation rate from 400 ° C vacuum is 10 4 Pa ⁇ 10 - 3 Pa; speed of irC / min 180min /
  • the temperature is raised to 2150 ° C at 12 ° C / min, kept to 1000 ° C, the holding rate is from 400 ° C for 180 min, the vacuum is 10 - 3 Pa; 120 min / l to 780 ° C, degree of vacuum of 10 4 Pa ⁇ 10- 3 Pa; at a speed 14 ° C / min at a rate of 14 ° C / min 235min incubation rate to 1550 ° C, incubated 45min; ⁇ 800 ° C, incubated at 16 ° C / Rate of min) f3 ⁇ 4 to 1230 °C, keep warm for 90min/
  • the obtained porous tantalum or porous tantalum product is inspected as described above.
  • Example 7 8 9 10 11 12 13 Density (g/cm 3 ) 12.00 11.67 6.86 13.00 6.43 12.67 12.17 Porosity (%) 28 30 20 22 25 24 27 Aperture ( ⁇ ) 19 15 8 11 27 23 25 Elastic Modulus ( GPa) 4.5 5.0 2.6 4.8 1.5 5.0 5.7 Flexural strength (MPa) 120 115 76 130 82 122 117 Compressive strength (MPa) 118 100 55 127 67 123 107

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Abstract

一种替代牙骨的医用多孔金属材料的制备方法，以钽粉与造孔剂、成型剂混合成混合粉末，再将所述粉末压制到有机泡沫体中成型、脱脂、烧结、冷却和热处理制得多孔钽材料；压制成型采用的压力为50~100Mpa，造孔剂为尿素、氯化钠、乙基纤维素、甲基纤维素中的一种或多种任意组合，成型剂为硬脂酸、硬脂酸锌、石蜡、合成橡胶中的一种或多种任意组合。经过测试，该制备方法制成的多孔钽材料中杂质含量可低于0.2%、密度可达11.67~13.34g/cm3，孔隙度可达20~30%，孔隙直径可达5~30μm;弹性模量可达4.5~6.0Gpa、弯曲强度可达110~130Mpa、抗压强度可达100~130Mpa，该方法制备的多孔钽适合用作替代牙骨的医用植入材料。

Description

一种牙骨替代医用多孔金属材料的制备方法 技术领域
本发明涉及一种医用多孔金属植入材料的制备方法， 特别是涉及一种替代致密骨组织 的医用植入多孔金属材料的制备方法。
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 /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， 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好的牙骨替代医用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：
一种替代牙骨的医用多孔金属材料的制备方法， 其特征在于： 以钽粉与造孔剂、 成型 剂混合成混合粉末， 再经压制成型、 脱脂、 烧结、 冷却和热处理制得多孔钽材料； 所述压 制成型是将所述的混合粉末压制到有机泡沫体中， 其压力为 50〜100Mpa， 所述造孔剂为尿 素、 氯化钠、 乙基纤维素、 甲基纤维素中的一种或多种任意组合， 所述成型剂为硬脂酸、 硬脂酸锌、 石蜡、 合成橡胶中的一种或多种任意组合。
在医用多孔钽材料的研发过程中， 制备路线众多， 但发明人创造性地提出了采用上述 工艺步骤制备的医用多孔钽植入材料， 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 11. 67〜13. 34g/cm3， 孔隙度可达 20〜30%， 孔隙直径可达 5〜 30 ιιΐ; 弹性模量可达 4. 5〜6. 0Gpa、 弯曲强度可达 110〜130Mpa、 抗压强度可达 100〜 130Mpa, 本发明多孔钽非常适合用于替代牙骨的医用植入材料。
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 述的造孔剂、 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 合用于替代牙骨的医用植入材料但产品合格率不高、生产稳定性不好：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%、 上述的造孔剂用量为 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 步优选为上述的成型剂占 5〜6. 5%、 上述的造孔剂占 21〜24%、 余量为钽粉； 上述压制成 型过程中的压力优选为 55〜65Mpa; 更进一步优选为上述的成型剂占 6%、 上述的造孔剂占 23%、 余量为钽粉， 以体积百分含量计。
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 2°C/mir！〜 3. 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 100min〜240min ; 进一步优选以 3〜 3. 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 150min〜 200min。
更进一步优选以 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 170min。
本发明另一方面的进一步的特点是：在真空度不低于 10— 4〜10— 3Pa，温度 2000〜2200°C， 保温时间 1〜5 小时的真空烧结处理制得多孔烧结体。 烧结过程保温时可以充惰性气体保 护代替真空保护； 最后进行真空退火处理， 其中真空退火处理是指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， 真空度不低于 10— 4〜10— 3Pa。
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。
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〜2°C/min的速率从室温升至 400°C， 保温 100〜120min， 以 2〜3°C/min的速率从 400°C升至 600〜800°C， 保温 200〜240min; 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； 所述真空退火条件还包括有： 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， 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，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 11. 67〜13. 34g/cm3， 孔隙度可达 20〜30%， 孔隙直径 可达 5〜30 μ πι; 弹性模量可达 4. 5〜6. 0Gpa、 弯曲强度可达 110〜130Mpa、 抗压强度可达 100〜130Mpa， 本发明多孔钽非常适合用于替代牙骨的医用植入材料。
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。
一种替代牙骨的医用多孔金属材料的制备方法， 是选用成型剂、 造孔剂 （所述成型剂 为硬脂酸、 硬脂酸锌、 石蜡、 合成橡胶中的一种或多种任意组合， 所述造孔剂为尿素、 氯 化钠、 乙基纤维素、 甲基纤维素中的一种或多种任意组合） 与平均粒径小于 43 微米、 氧 含量小于 0. 1%的钽粉混合成混合粉， 在 50〜100Mpa下将混合粉末压制到有机泡沫体中成 型，再经脱脂、烧结、冷却和热处理而得多孔钽材料。形成的多孔钽经检测孔隙度介于 20〜 30%, 孔隙直径 5〜30 μ πι。
更具体地说， 上述多孔钽是将 5〜10% (以体积百分含量计） 的上述成型剂、 20〜30% (以体积百分含量计） 的上述造孔剂以及余量的钽粉混合成混合粉， 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逐步升温至 2000〜2200°C， 保温时间 1〜5小时 进行真空烧结， 在升温之前烧结炉的真空度至少要达到合适水平， 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， 是将其置于钨器中放入气氛炉中以一定的升温速率升温， 其在升温之 前先通入氩气或其他惰性气体以排除炉内空气， 控温过程是以合适的升温速率从室温升至 一定的温度， 保温， 再升温、 保温。 对于脱脂处理后的样品进行真空烧结处理， 是将其随 钨器置于高真空高温烧结炉内以一定的升温速率升温至钽的最高烧结温度进行真空烧结， 在升温之前烧结炉保持一定的真空度， 以一定的升温速率升温至例如 1200°C 1250°C， 保 温， 保持真空； 以一定的升温速率再升温至例如 1250°C 1500°C， 保温， 再以一定的升温 速率升温至例如钽的最高烧结温度， 保温、 保持真空； 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 11. 67 13. 34g/cm3， 孔 隙度可达 20 30%， 孔隙直径可达 5 30 μ πι; 弹性模量可达 4. 5 6. 0Gpa、 弯曲强度可达 110 130Mpa、 抗压强度可达 100 130Mpa
实施例 1 : 称取硬脂酸锌、 平均粒径小于 43微米氧含量小于 0. 1%的钽粉和甲基纤维 素混合均匀成混合粉末， 其中硬脂酸锌占 6%、 甲基纤维素占 23%、 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 62Mpa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 1. 5°C/min 的升温速率从室温升温至 400°C、 保温 l lOmin; 再以 2. 5°C/min的升温速率从 400°C升温至 700°C， 保温时间 210分钟。 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 12. 67g/cm3， 孔隙率 24%， 孔隙平均直径 16 m， 弹性模量 6. 0GPa， 弯曲 强度 130MPa， 抗压强度 130MPa。
实施例 2: 称取石蜡、 平均粒径小于 43微米氧含量小于 0. 1%的铌粉和尿素混合均匀 成混合粉末， 其中石蜡占 5%、 乙基纤维素占 30%、 铌粉占 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 65Mpa下压制到孔径为 0. 56〜0. 72mm, 密度 0. 025g/cm3, 硬度 50°〜80°的聚氨酯泡沫中成型。 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 lOOmin; 再以 3°C/min的升温速率从 400°C升温至 800°C， 保温时间 200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铌成品。
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 6. 00g/cm3， 孔隙率 30%， 孔隙平均直径 28 m， 弹性模量 2. 0GPa， 弯曲强 度 73MPa， 抗压强度 82MPa。
实施例 3: 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 10%、氯化钠占 20%、钽粉占 70%，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 97Mpa下压制到孔径为 0. 56〜0. 72mm, 密 & 0. 025g/cm3, 硬度 50°〜80°的聚氨酯泡沫中成型。 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 120min; 再以 2°C/min的升温速率从 400°C升温至 750 °C , 保温时间 240分钟。 真空烧结： 在真空炉中烧结， 烧结温度 2200°C， 保温 2. 5小 时， 真空度 10— 3Pa， 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 13. 37g/cm3， 孔隙率 20%， 孔隙平均直径 27 m， 弹性模量 4. 8GPa， 弯曲 强度 128MPa， 抗压强度 120MPa。
实施例 4: 称取石蜡和硬脂酸锌、 平均粒径小于 43微米氧含量小于 0. 1%的钽粉和氯 化钠混合均匀成混合粉末， 其中石蜡和硬脂酸锌 （其中石蜡与硬脂酸锌质量比为 1 : 2. 5 ) 占 5%、 氯化钠占 28%、 钽粉占 67%， 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 57Mpa下压制到孔径为 0. 56〜0. 72mm, 密度 0. 025g/cm3, 硬度 50°〜80° 的聚氨酯泡沫中成型。 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 105min; 再以 2. 2°C/min的升温速率从 400°C升温至 800°C， 保温时间 225分 钟。 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 12. 84g/Cm 3， 孔隙率 23%， 孔隙平均直径 26 μ ιιι， 弹性模量 5. 0GPa， 弯曲 强度 120MPa， 抗压强度 125MPa。
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 和乙基纤维素混合粉为原料， 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 7%、 乙基纤维素占 20%、 金属钽粉占 73%， 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 55Mpa下压制到孔径为 0. 56〜0. 72mm, 密度 0. 025g/cm3, 硬度 50°〜80°的聚氨酯泡沫中成型；
脱脂处理：在惰性气体保护气氛下或真空度 10— 4〜10— 3Pa， 以 l〜2/min升温至 400°C〜 800°C， 以氩气为保护气氛、 保温时间 100〜120分钟以除去其中的硬脂酸及乙基纤维素； 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 12. 00g/cm3， 孔隙率 28%， 孔隙平均直径 19 m， 弹性模量 5. 5GPa， 弯曲 强度 122MPa， 抗压强度 124MPa。
实施例 6: —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 和氯化钠混合粉为原料， 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%、 尿素占 30%、 金属钽粉占 60%， 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 53Mpa下压制到孔径为 0. 56〜0. 72mm, 密度 0. 025g/cm3, 硬度 50°〜80°的聚氨酯泡沫中成型；
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. 5°C/min的速率从室温升至 400°C，保温 108min，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 215min， 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. 34g/Cm 3， 孔隙率 26%， 孔隙平均直径 ΙΟ μ ιιι, 弹性模量 4. 8GPa， 弯曲 强度 117MPa， 抗压强度 125MPa。 该制备工艺使得成品合格率高、 生产稳定， 产品合格率 达 90· 3%。
在上述实施例 6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。
实 钽或铌粉粒径 （微 钽粉或铌粉占的 成型剂种类及其所 造孔剂种类及其所 施 米) /氧含量小于（％) 体积百分比 （％) 占的体积百分比(％) 占体积百分比 （％) 例
7 钽粉小于 38/0.1% 75 硬脂酸； 5 乙基纤维素； 20
8 钽粉小于 35/0.1% 68.5 硬脂酸锌； 9.5 尿素； 22 9 铌粉小于 42/0.1% 66 石蜡； 8 氯化钠、 甲基纤维 素，其中氯化钠与甲 基纤维素质量比为 1： 4； 26
10 钽粉小于 41/0.1% 69 丁苯橡胶； 7 甲基纤维素； 24
11 铌粉小于 39/0.1% 64.5 异戊橡胶； 6.5 乙基纤维素； 29
12 钽粉小于 42/0.1% 62.5 硬脂酸、石蜡， 其中 尿素、氯化钠，其中 其中石蜡与硬脂酸 尿素与氯化钠质量 质量比为 1 : 1. 7； 7.5 比为 1 : 1； 30
13 钽粉小于 40/0.1% 62 硬脂酸； 10 甲基纤维素； 28
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)
7 66Mpa 以 1.0°C/min 10°C/min的速率 至 1200°C，保温 10 Pa/
的速率从室 60min, 真 为 104Pa; 15 °C/min的速率升 温升至 400 以 irC/min的速率升至 1250 °C， 保温 至 1030 °C， 保温
。C ， 保温 60min; 480min/
lOOmin; 以 6 °C/min 的速率升至 2030 °C， 保温 5°C/min的速率
2.2°C/min的 240min, 真空度为 10- 3Pa; 至 1000 °C， 保温 速率从 400°C 真空度为 104Pa〜10— 3Pa;以 irC/min的速 180min/
升至 600°C， 率 至 1520 °C， 保温 60min; 以 irC/min的速率 保温 210min 以 13°C/min的速率) f¾至 1200 °C， 保温 至 800°C，保温
90min; 108min/
以 13°C/min的速率 至 800°C， 然后随 21 °C/min的速率冷 炉 却至室温
8 60Mpa 2.0°C/min的 irC/min的速率 至 1210°。，保温 10"3Pa/17 °C /min 的 速率从室温 58min, 真空度为 104Pa; 速率升至 1050 °C， 升至 400°C， 以 12°C/min的速率升至 1270 °C， 保温 保温 450min/ 保温 120min/ 55min; 6°C/min的速率
3.0°C/min的 以 8 °C/min 的速率升至 2050°C， 保温 至 1000 °c， 保温 速率从 400°C 220min, 真空度为 10- 3Pa; 150min/ 升至 700°C， 真空度为 104Pa〜10— 3Pa;以 12°C/min的速 以 12°C/min的速率 保温 240min 率 至 1530 °C， 保温 55min; 至 800°C，保温 以 14°C/min的速率) f¾至 1210°C， 保温 102min/
85min; 22°C/min的速率冷 以 14°C/min的速率 至 800°C， 然后随 却至室温 炉
50Mpa 以 1.5 °C/min 12°C/min的速率 至 1220°。，保温 10"3Pa/20 °C /min 的 的速率从室 55min, 真 为 104Pa; 速率升至 1励。 C， 温升至 400 以 13 °C/min的速率升至 1300 °C， 保温 保温 420min/
。C ， 保温 50min; 7°C/min的速率
112min/ 以 10°C/min的速率升至 2100 °C， 保温 至 1000 °C， 保温
2.0°C/min的 200min, 真空度为 10- 3Pa; 130min/ 速率从 400°C 真空度为 104Pa〜10— 3Pa;以 13°C/min的速 以 13°C/min的速率 升至 780°C， 率 至 1540 °C， 保温 50min; Ρ 800 °C,保温 保温 225min 以 15°C/min的速率) f¾至 1220 °C， 保温 96min/
80min; 23 °C/min的速率冷 以 15°C/min的速率 至 800°C， 然后随 却至室温 炉
lOOMpa 1.2°C/min的 13°C/min的速率 至 1230°。，保温 10 Pa/22 °C /min 的 速率从室温 50min, 真 为 104Pa; 速率升至 1150°C， 升至 400°C， 以 14°C/min的速率升至 1350 °C， 保温 保温 360min/ 保温 106min/ 45min; 8°C/min的速率
2.8°C/min的 以 12°C/min的速率升至 2150 °C， 保温 至 1000 °C， 保温 速率从 400°C 180min, 真空度为 10—3Pa; 120min/ 升至 780°C， 真空度为 104Pa〜10— 3Pa;以 14°C/min的速 以 14°C/min的速率 保温 235min 率 至 1550 °C， 保温 45min; Ρ 800 °C,保温 以 16°C/min的速率) f¾至 1230 °C， 保温 90min/
75min; 24°C/min的速率冷 以 16°C/min的速率冷却至 800°C， 然后随 却至室温 炉 63Mpa 1.8°C/min的 14°C/min的速率 至 1240°C，保温 10"3Pa/25 °C /min 的 速率从室温 40min, 真 ¾g为 104Pa; 速率升至 1200 °C， 升至 400°C， 以 15 °C/min的速率升至 1400 °C， 保温 保温 300min/ 保温 117min/ 40min; 9°C/min的速率
2.5°C/min的 以 14°C/min的速率升至 2160 °C， 保温 至 1000 °c， 保温 速率从 400°C 160min, 真空度为 10- 3Pa; lOOmin/ 升至 600°C， 真空度为 104Pa〜10— 3Pa;以 15°C/min的速 以 15°C/min的速率 保温 220min 率 至 1560 °C， 保温 40min; 至 800°C，保温 以 17°C/min的速率) f¾至 1240 °C， 保温 84min/
70min; 26°C/min的速率冷 以 17°C/min的速率 至 800°C， 然后随 却至室温 炉
55Mpa 1.6°C/min的 15°C/min的速率 至 1250°。，保温 10 Pa/27 °C /min 的 速率从室温 30min, 真 为 104Pa; 速率升至 1230 °C, 升至 400°C， 以 16°C/min的速率升至 1450 °C， 保温 保温 270min/ 保温 104min/ 35min; 10°C/min的速率冷
2.6°C/min的 以 16°C/min的速率升至 2170 °C， 保温 却至 1000 °c， 保温 速率从 400°C 140min, 真空度为 10- 3Pa; 90min/ 升至 600°C， 真空度为 104Pa〜10— 3Pa;以 16°C/min的速 以 16°C/min的速率 保温 215min 率 至 1570 °C， 保温 35min; Ρ 800 °C,保温 以 18°C/min的速率) f¾至 1245°C， 保温 78min/
65min; 27°C/min的速率冷 以 18°C/min的速率冷却至 800°C， 然后随 却至室温 炉
78Mpa 2°C/min的速 13°C/min的速率 至 1225°。，保温 10 Pa/30 °C /min 的 率从室温升 45min, 真 为 104Pa; 速率升至 1250 °C， 至 400°C，保 以 17°C/min的速率升至 1500 °C， 保温 保温 240min/ 温 102min/ 30min; 5.5°C/min的速率冷
2.7°C/min的 以 18 °C/min的速率升至 2180°C， 保温 却至誦 0°C， 保温 速率从 400°C 120min, 真空度为 10- 3Pa; 170min/ 升至 600°C， 真空度为 104Pa〜10— 3Pa;以 18°C/min的速 以 17°C/min的速率 保温 236min 率 至 1580 °C， 保温 30min; Ρ 800 °C,保温 以 19°C/min的速率) f¾至 1250 °C， 保温 72min/
60min; 29°C/min的速率冷 以 19°C/min的速率 至 800°C， 然后随 却至室温 炉
所得多孔钽或多孔铌成品按前述方法检
实施例 7 8 9 10 11 12 13 密度 （g/cm3) 12.00 11.67 6.86 13.00 6.43 12.67 12.17 孔隙率 （％) 28 30 20 22 25 24 27 孔径 （μηι) 19 15 8 11 27 23 25 弹性模量 (GPa) 4.5 5.0 2.6 4.8 1.5 5.0 5.7 弯曲强度 (MPa) 120 115 76 130 82 122 117 抗压强度 (MPa) 118 100 55 127 67 123 107

Claims

权 利 要 求 书
1、 一种替代牙骨的医用多孔金属材料的制备方法， 其特征在于： 以钽粉与造孔剂、 成型剂混合成混合粉末， 再将所述混合粉末压制到有机泡沫体中成型、 脱脂、 烧结、 冷却 和热处理制得多孔钽材料； 所述压制成型采用的压力为 50〜100Mpa， 所述造孔剂为尿素、 氯化钠、 乙基纤维素、 甲基纤维素中的一种或多种任意组合， 所述成型剂为硬脂酸、 硬脂 酸锌、 石蜡、 合成橡胶中的一种或多种任意组合。
2、 如权利要求 1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%、 上述的造孔剂用量为 20〜30%、 余量为钽粉， 以体积百分含量计； 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 1或 2所述的制备方法， 其特征在于： 所述的成型剂占 5〜6. 5%、 所述 的造孔剂占 21〜24%、余量为钽粉，以体积百分含量计；所述压制成型过程中的压力为 55〜 65Mpa。
4、 如权利要求 3所述的制备方法， 其特征在于： 所述的成型剂占 6%、 所述的造孔剂 占 23%、 余量为钽粉， 以体积百分含量计。
5、 如权利要求 1或 2所述的制备方法， 其特征在于： 所述脱脂过程是以 2°C/mir！〜 3. 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 100min〜 240min。
6、如权利要求 3所述的制备方法，其特征在于：所述脱脂过程是以 2°C/mir！〜 3. 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 100min〜240min。
7、 如权利要求 6所述的制备方法， 其特征在于： 所述脱脂过程是以 3〜3. 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 150min〜200min。
8、 如权利要求 6 所述的制备方法， 其特征在于： 所述烧结是在真空度不低于 10— 4〜 10— 3Pa， 温度 2000〜2200°C， 保温时间 1〜5小时； 最后进行真空退火处理， 其中真空退火 处理是指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 不低于 10— 4〜10— 3Pa。
9、 如权利要求 8 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;
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 lCTC/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；
所述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。
10、 如权利要求 9所述的制备方法， 其特征在于： 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〜2°C/min 的速率从室温升至 400°C， 保温 100〜120min， 以 2〜3°C/min的速率从 400°C升至 600〜 800°C， 保温 200〜240min; 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； 所述真空退火条件还包括有： 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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