WO2013044839A1 - Method for manufacturing medical implant material porous tantalum - Google Patents

Method for manufacturing medical implant material porous tantalum Download PDF

Info

Publication number
WO2013044839A1
WO2013044839A1 PCT/CN2012/082276 CN2012082276W WO2013044839A1 WO 2013044839 A1 WO2013044839 A1 WO 2013044839A1 CN 2012082276 W CN2012082276 W CN 2012082276W WO 2013044839 A1 WO2013044839 A1 WO 2013044839A1
Authority
WO
WIPO (PCT)
Prior art keywords
vacuum
temperature
cooled
rate
porous
Prior art date
Application number
PCT/CN2012/082276
Other languages
French (fr)
Chinese (zh)
Inventor
叶雷
Original Assignee
重庆润泽医药有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 重庆润泽医药有限公司 filed Critical 重庆润泽医药有限公司
Publication of WO2013044839A1 publication Critical patent/WO2013044839A1/en

Links

Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02Inorganic materials
    • A61L27/04Metals or alloys
    • A61L27/047Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/56Porous materials, e.g. foams or sponges
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10Sintering only
    • B22F3/11Making porous workpieces or articles
    • B22F3/1121Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers
    • B22F3/1137Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers by coating porous removable preforms
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C27/00Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/02Alloys based on vanadium, niobium, or tantalum

Definitions

  • the present invention relates to a method for preparing porous tantalum, and more particularly to a method for preparing a porous implant of medical implant material suitable for replacing weight-bearing bone tissue.
  • Porous medical metal implant materials have important and special applications for the treatment of bone tissue trauma and femoral tissue necrosis.
  • 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 the pores are connected and evenly distributed according to the need, so that The growth of the bone tissue of the human body is consistent, and the weight of the material itself is reduced to be suitable for human implantation.
  • the refractory metal ruthenium due to its excellent biocompatibility and mechanical properties, is expected to be used as a biomaterial for the treatment of bone tissue necrosis as a substitute for the traditional 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 implant metal crucible, if it has a high uniform distribution of connected pores and physical and mechanical properties compatible with the human body, it is an important connecting member constituting material for ensuring the normal growth of new bone tissue.
  • 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 materials with pore connectivity and uniform distribution obtained by powder sintering are generally not very good in metal mechanical properties. The main reason is how to arrange the support and elimination relationship of pore-forming medium and the collapse problem in the sintering process of metal powder. . However, there is no good solution in the known literature reports and it is natural.
  • 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.
  • 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.
  • the mechanical properties of the material such as ductility
  • the invention discloses a preparation method of a porous implant of a medical implant material, which is sintered by a foam impregnation method, and is characterized in that a solution prepared by using an organic binder and a dispersant and a tantalum powder are used to prepare a tantalum powder slurry, and poured into an organic foam.
  • the impregnation is performed until the pores of the organic foam are filled with the powder slurry, and then the dispersant in the organic foam in which the tantalum powder slurry is poured is dried, and degreased under an inert gas atmosphere to remove the organic binder and the organic
  • the foam body is sintered under vacuum to obtain a porous sintered body, cooled, and then annealed under vacuum and subjected to conventional post-treatment to obtain a porous crucible;
  • the sintering step is a vacuum degree of 10 - 4 Pa 10 10 - 3 Pa, 10 to 20 ° C/min is heated to 1500 ⁇ 1800 °C, kept for 120 ⁇ 240min, cooled to 200 ⁇ 300 °C with furnace, then heated to 1500 ⁇ 1800°C at 10 ⁇ 20°C/min, and kept at 180 ⁇ 240min, 5 ⁇ 10 ° C / min was heated to 2000 ⁇ 2200 ° C, incubated 120 ⁇ 360min; degree of vacuum of the heat treatment is 10- 4 Pa ⁇ 10-
  • the porous tantalum produced by the preparation method of the present invention is particularly suitable for use as a joint member for load-bearing bone tissue wounds or bone defects. Furthermore, the preparation method is simple and easy to control; the whole preparation process is harmless, non-polluting, non-toxic and dusty, and has no side effects on the human body. Moreover, in the preparation process, it is preferred to use all of the binders, dispersants, organic foams, etc. during the sintering process, which will ensure the biocompatibility and biosafety of the implant material.
  • the organic binder is preferably polyvinyl alcohol, and may also be a starch, ethyl cellulose or the like; the dispersing agent is usually water, anhydrous ethanol or the like, of which water is preferred.
  • the organic foam is preferably a polyurethane foam, and may also be a polyether ester foam or the like.
  • a further feature of the present invention is that a metal tantalum powder having an average particle diameter of less than 43 ⁇ m and an oxygen content of less than 0.1% is used, and a polyvinyl alcohol aqueous solution is used as a binder and water as a dispersing agent and the tantalum powder.
  • organic foam is poly The urethane foam is then removed by vacuum drying to form a porous crucible having a porosity of 50 to 70% and a pore diameter of 150 to 600 ⁇ M.
  • the polyvinyl alcohol is heated to dissolve with distilled water, and a bismuth powder slurry is prepared by using a polyvinyl alcohol aqueous solution and a metal cerium powder in a weight percentage of 2 to 8% (preferably 4 to 5%), wherein the weight is 6 to 9 parts.
  • the singularity of the material is 0. 48 ⁇ 0. 89mm, the density is selected to be 0. 48 ⁇ 0. 89mm, density 0. 025 g / cm 3 ⁇ 0. 035g / cm 3, hardness of more than 50 ° helps ensure that a polyurethane foam with a porosity of the porous tantalum pore diameter.
  • Such technical processing of the present invention optimizes process conditions and will ensure biocompatibility and biosafety of implanted porous tantalum materials.
  • a further feature of another aspect of the invention is: the degree of vacuum of the drying is maintained at a vacuum of 10 - 2 to 1 Pa, and then under a protective atmosphere, for example, a degree of vacuum of 10 - 4 to 10 - 3 Pa, and a temperature of 400 ° C to 80 (TC) Degreasing treatment for removing the organic binder and the organic foam;
  • the sintering step is a vacuum of 10 - 4 Pa to 10 - 3 Pa, and the temperature is raised to 1500 to 1800 ° C at 12 to 15 ° C / min, and the temperature is maintained at 180 ° ⁇ 200min, with the furnace cooled to 200 ⁇ 300 °C, then raise the temperature to 1500 ⁇ 1800 °C at 16 ⁇ 19 °C / min, keep warm for 220 ⁇ 240min, heat up to 2000 ⁇ 2200 °C at 5 ⁇ 8 °C/min Insulation for 250 ⁇ 300min, inert gas protection instead of vacuum protection during the sintering process; finally vacuum annealing treatment, wherein
  • the degreasing treatment conditions further include: gradually increasing the temperature to 400 ⁇ 800 ° C at a rate of 0.5 ° C / min ⁇ 5 ° C / min, argon gas into a protective atmosphere and holding for 30 min ⁇ 120 min;
  • the cooling conditions after vacuum sintering further include: the degree of vacuum is less than 10 - 3 P a , and the section of the sintered porous body is segmented at a temperature not lower than 25 ° C / min and not lower than 10 ° C / min. Cool down to 800 ° C, each holding period of 30 min ⁇ 90 min, and then cool to room temperature with the furnace.
  • the drying temperature of the vacuum drying is 60 to 100 ° C, and the drying time is 4 to 8 hours; the degreasing treatment conditions further include: gradually increasing the temperature to 600 to 800 ° C, to be pure 5 ⁇ 1. 5°C/min, the argon gas (99.999%) is used to form a protective atmosphere, and the temperature is raised from room temperature to 400 ° C at a rate of 1 to 5 ° C / min. The rate is increased from 400 ° C to 600 ⁇ 800 ° C, and the temperature is maintained for 60 to 120 min.
  • the vacuum sintering conditions are: vacuum degree is 10 - 4 Pa ⁇ 10 - 3 Pa, and the temperature is raised to 1800 ° C at 13 ° C / min.
  • the cooling conditions further include: a vacuum degree of 10 - 4 Pa to 10 - 3 P a; a cooling rate of 1500 to 1600 ° C at a rate of 10 to 20 ° C / m in, holding for 30 to 60 min; to 12 to 20 ° C/min rate is cooled to 1200 ⁇ 1250 °C, heat preservation 60 ⁇ 90min; cooled to 800 ° C at a rate of 10 ⁇ 20 ° C / min, and then cooled with the furnace; the vacuum annealing conditions also include: a vacuum of 10 - 4 Pa ⁇ 10 - 3 Pa, to 15 ° C/min was heated to 800-900 ° C, kept at 260-320 min, cooled to 400 ° C at 3 ° C
  • vacuum drying, degreasing treatment, etc. are helpful to reduce the content of impurities in porous tantalum, improve biocompatibility and biosafety and mechanical properties; optimize the organic foam material to solve the foam skeleton in the sintering process. Collapse problem; optimize the process conditions of the sintering and annealing steps to further improve the mechanical properties of the porous tantalum such as ductility and reduce the fracture rate of the sintered neck.
  • the porosity of the porous tantalum material prepared by the above method is less than 0.5%; the pores of the porous tantalum product are uniformly distributed and connected, and the density is 5 ⁇ 00 ⁇ 8 ⁇ 33g/cm 3 , and the porosity is 50 to 70%. 5% ⁇ 11. 7% ⁇ Having a pore diameter of 150 ⁇ 600 ⁇ m, an elastic modulus of 4. 5 ⁇ 6. OGPa, a bending strength of 130 ⁇ 150MPa, a compressive strength of 78 ⁇ 88MPa, an elongation of 10.5% ⁇ 11.7%.
  • the porous tantalum material of the invention not only has good biocompatibility and safety, but also has high mechanical strength and high strength, and is very suitable for replacing bone tissue of a human weight bearing part.
  • Fig. 1 is a scanning electron microscopic analysis chart (SEM image) of a porous tantalum structure prepared by the preparation method of the present invention; it can be observed from the drawing that: the porous tantalum of the present invention has high porosity and uniform pore distribution. It can be seen from the drawing that the porous ⁇ -connected pores of the present invention are beneficial to adhesion, differentiation and growth of osteoblasts, promote bone ingrowth, strengthen the connection between the implant and the bone, and facilitate bio-immobilization. . detailed description
  • Example 1 Weighing 12. 5 g of polyvinyl alcohol was placed in a vessel containing 240 ml of distilled water; it was placed on an electric furnace and heated and stirred to make an aqueous polyvinyl alcohol solution. 60 g of an anthracene powder having an average particle diameter of less than 43 ⁇ m and an oxygen content of less than 0.1% was weighed using a 200 g balance, and 50 ml of a cooled aqueous solution of polyvinyl alcohol was added thereto, and the mixture was stirred and mixed to obtain a tantalum powder slurry. Use 10 X 10 X 30mm porous polyurethane foam (average pore diameter of 0. 48mm, density 0.
  • Vacuum sintering the degree of vacuum is 10 - 4 Pa ⁇ 10 - 3 Pa, the temperature is raised to 1800 ° C at 13 ° C / min, the temperature is kept for 200 min, cooled to 200 ⁇ 300 ° C with the furnace, and then 17 ° C / min The temperature is raised to 1800 ° C, the temperature is kept for 230 min, the temperature is raised to 2000 ⁇ 2200 ° C at 7 ° C / min, the temperature is kept for 300 min, the argon gas is protected during the sintering process, the surface dust and dirt are removed after the product is taken out, and the sample is prepared after cooling.
  • the heat treatment and the conventional post-treatment are carried out to obtain a porous tantalum product;
  • the heat treatment is a vacuum degree of 10 - 4 Pa to 10 - 3 Pa, and the temperature is raised to 800 to 900 ° C at 15 ° C / min, and the temperature is maintained for 260 to 320 min. It was cooled to 400 ° C at 3 ° C / min, held for 120 min, and then cooled to room temperature at 18 ° C / min.
  • the 5% of the content of the porous material is less than 0.5%.
  • the inventor is tested according to the standard of GB/T5163_2006, GB/T5249_1985, GB/T6886-2001, etc., the porosity, porosity, pore size and various mechanical properties of the porous material: The finished product, the pores are evenly distributed and connected, the density is 7. 7 g / cm 3 , the porosity is 56%, the average pore diameter is 300 m, the elastic modulus is 5. 8 GPa, the bending strength is 150 MPa, the compressive strength is 83 MPa, and the elongation is 11.6. %.
  • Example 2 10 g of polyvinyl alcohol was weighed and placed in a vessel containing 200 ml of distilled water; it was placed on an electric furnace and heated and stirred to make an aqueous polyvinyl alcohol solution. 40 g of an anthracene powder having an average particle diameter of less than 43 ⁇ m and an oxygen content of less than 0.1% was weighed by a 200 g balance, and 32 ml of an aqueous polyvinyl alcohol solution was added thereto, and the mixture was stirred and mixed to make it into a tantalum powder slurry. 10 ⁇ 10 X 25mm porous polyurethane foam (average pore diameter of 0. 56mm, density 0.
  • Vacuum sintering The degree of vacuum is 10 - 4 Pa ⁇ 10 - 3 Pa, the temperature is raised to 1500 ° C at 10 ° C / min, the temperature is kept for 240 min, the furnace is cooled to 200 ⁇ 300 ° C, and then heated to 10 ° C / min to 1500 ° C, heat preservation for 180 min, heat up to 2000 ⁇ 2200 ° C at 5 ° C / min, heat preservation for 360 min, argon gas protection during the sintering process, remove the surface dust and dirt after removing the product, and then cool the sample after the preparation Heat treatment and conventional post-treatment to obtain a porous tantalum product; the heat treatment is a vacuum degree of 10 - 4 Pa to 10 - 3 Pa, and the temperature is raised to 800 to 900 ° C at lCTC / min, the temperature is maintained for 240 minutes, and then the temperature is 5 ° C / min. Cool to 400 ° C, hold for 300 min, then cool to room temperature at 23 ° C / min
  • the 5% of the content of the porous material is less than 0.5%.
  • the inventor is tested according to the standard of GB/T5163_2006, GB/T5249_1985, GB/T6886-2001, etc., the porosity, porosity, pore size and various mechanical properties of the porous material:
  • 87 g / cm 3 the porosity is 66%
  • the average pore diameter is 400 ⁇ ⁇
  • the elastic modulus is 4.
  • 8GPa the bending strength is 140MPa
  • the compressive strength is 80MPa
  • the elongation is 10. 6%.
  • Example 3 Polyvinyl alcohol l lg was weighed and placed in a vessel containing 220 ml of distilled water; it was placed on an electric furnace and heated and stirred to make an aqueous polyvinyl alcohol solution.
  • the granules having an average particle diameter of less than 43 ⁇ m and an oxygen content of less than 0.1% were weighed in an amount of 45 g, and 36 ml of an aqueous polyvinyl alcohol solution was added thereto, and the mixture was stirred and mixed to obtain a mash slurry.
  • 8 ⁇ 8 X 25mm porous polyurethane foam average pore diameter of 0. 70mm, density 0.
  • Vacuum sintering The degree of vacuum is 10 - 4 Pa ⁇ 10 - 3 Pa, the temperature is raised to 1800 ° C at 20 ° C / min, the temperature is kept for 120 min, the furnace is cooled to 200 ⁇ 300 ° C, and then heated to 20 ° C / min to 1800°C, heat preservation for 240min, heat up to 2000 ⁇ 2200°C at 10°C/min, heat preservation for 120min, argon gas protection during sintering, remove surface dust and dirt after removing the product, and then cool the sample after preparation.
  • Heat treatment and conventional post-treatment to obtain a porous tantalum product is a vacuum degree of 10 - 4 Pa to 10 - 3 Pa, and the temperature is raised to 800 to 900 ° C at 20 ° C / min, the temperature is maintained for 480 min, and then the temperature is 2 ° C. /min was cooled to 400 ° C, incubated for 120 min, and then cooled to room temperature at 18 ° C / min.
  • the 5% of the content of the porous material is less than 0.5%.
  • the inventor is tested according to the standard of GB/T5163_2006, GB/T5249_1985, GB/T6886-2001, etc., the porosity, porosity, pore size and various mechanical properties of the porous material:
  • the finished product, the pores are evenly distributed and connected, having a density of 5.0 g / cm 3 , a porosity of 70%, an average pore diameter of 450 m, an elastic modulus of 5. 2 GPa, a flexural strength of 130 MPa, a compressive strength of 79 MPa, an elongation of 10. 5 %.
  • Example 4 12 g of polyvinyl alcohol was weighed and placed in a vessel containing 230 ml of distilled water; it was placed on an electric furnace and heated and stirred to make an aqueous polyvinyl alcohol solution. 50 g of an anthracene powder having an average particle diameter of less than 43 ⁇ m and an oxygen content of less than 0.1% was weighed by a 200 g balance, and 40 ml of an aqueous polyvinyl alcohol solution was added thereto, and the mixture was stirred and mixed to obtain a tantalum powder slurry.
  • the 5% of the content of the porous material is less than 0.5%.
  • the inventor is tested according to the standard of GB/T5163_2006, GB/T5249_1985, GB/T6886-2001, etc., the porosity, porosity, pore size and various mechanical properties of the porous material:
  • Example 5 a porous crucible, which has a particle size of less than 43 m, an oxygen content of less than 0.1%, and a polyvinyl alcohol solution as a binder solution to prepare a tantalum powder slurry, and is poured. It is prepared in a polyurethane foam carrier; then vacuum drying, degreasing treatment, vacuum sintering, vacuum annealing and conventional post treatment.
  • the urethane foam having a pore size of 0. 72 ⁇ 0. 56 hidden, density 0. 025g/cm 3 , hardness 50. ⁇ 80 °; dried in vacuo: the degree of vacuum holding 10- 2 ⁇ lPa, to remove moisture tantalum slurry filled polyurethane foam; degreasing process: Under an inert gas atmosphere or a vacuum of 10-4 ⁇ 10- 3 Pa, temperature 400 ° C ⁇ 800 ° C, and Paul Heating time 30 ⁇ 120 minutes to remove the polyvinyl alcohol and polyurethane foam therein;
  • Vacuum sintering The degree of vacuum is 10 - 4 Pa ⁇ 10 - 3 Pa, the temperature is raised to 1500 ° C at 10 ° C / min, the temperature is kept for 240 min, the furnace is cooled to 200 ⁇ 300 ° C, and then heated to 10 ° C / min to 1500 ° C, holding 180min, heating at 5 ° C / min to 2000 ⁇ 2200 ° C for 360min;
  • Vacuum annealing a vacuum degree of 10- 4 Pa ⁇ 10- 3 Pa, at 10 ° C / min was heated to 800 ⁇ 900 ° C, insulation 240min, then cooled to 400 ° C at 5 ° C / min, incubated 300min, then Cool to room temperature at 23 ° C / min.
  • the 5% of the content of the porous material is less than 0.5%.
  • the inventor is tested according to the standard of GB/T5163_2006, GB/T5249_1985, GB/T6886-2001, etc., the porosity, porosity, pore size and various mechanical properties of the porous material: The finished product, the pores are evenly distributed and connected, the density is 7.83 g / cm 3 , the porosity is 62%, the average pore diameter is 220 m, the elastic modulus is 5. 3GPa, the bending strength is 136MPa, the compressive strength is 84MPa, and the elongation is 11.4. %.
  • °C / min vacuum 10 - 3 Pa, i rC / min heating vacuum of 10 - 4 Pa, to 1580 ° C, holding 200min, with the furnace to cool
  • the vacuum degree of 0.6 ° C / min is 10 4 Pa ⁇ 10 - 3 Pa; the temperature is cooled to 400 ° C at 12 ° C / min / min, the rate is from 400 ° C to 1530 ° C, and the temperature is maintained for 55 min; Then increase to 650 ° C, at a rate of 14 ° C / min) f3 ⁇ 4 to 1210 ° C, keep warm 20 ° C / min, cool to heat retention HOmin 85min;, ⁇ 14 at 14 ° C / min rate to 800 ° C And then with
  • the rate of °C/min is up to 1220°. , heat preservation 80min ;

Abstract

A method for manufacturing a medical implant material porous tantalum. A slurry is made from aqueous polyvinyl alcohol and tantalum powder, then poured into an organic foam, soaked until pores in the organic foam are filled with the tantalum powder slurry, and dried for dehydration, and then a degreasing treatment is conducted under the protection of an inert gas to remove polyvinyl alcohol and the organic foam. A porous sintered body is acquired by sintering in vacuum, cooled, annealed in vacuum, and subjected to a regular post-processing to acquire porous tantalum. The sintering has the steps of: at a degree of vacuum between 10-4 Pa and 10-3 Pa, heated to 1800°C at a rate of 10°C/min, kept warm for 240 min, cooled along with a furnace to 300°C, then heated to 1800°C at a rate of 10°C/min, kept warm for 180 min, heated to a temperature between 2000°C and 2200°C at a rate of 10°C/min, and kept warm for 360 min. A heat processing is done at a degree of vacuum between 10-4 Pa and 10-3 Pa, heated to 800°C at a rate of 20°C/min, kept warm for 240 min, cooled to 400°C at a rate of 2°C/min, kept warm for 300 min, and then cooled with the furnace to room temperature. The porous tantalum material manufactured has great biocompatibility and safety, greatly increased strength in mechanical property, and is highly applicable for use in substituting bone tissues of load-bearing parts of the human body.

Description

一种医用植入材料多孔钽的制备方法 技术领域  Method for preparing porous implant of medical implant material
本发明涉及一种多孔钽的制备方法, 特别是涉及一种适于替代承重骨组织的医用植入 材料多孔钽的制备方法。  The present invention relates to a method for preparing porous tantalum, and more particularly to a method for preparing a porous implant of medical implant material suitable for replacing weight-bearing bone tissue.
背景技术 Background technique
多孔医用金属植入材料具有治疗骨组织创伤和股骨组织坏死等重要而特殊的用途, 现 常见的这类材料有多孔金属不锈钢、 多孔金属钛等。 作为骨组织创伤和股骨组织坏死治疗 使用的多孔植入材料, 其孔隙度应达 30〜80%, 而且孔隙最好全部连通与均匀分布, 或根 据需要孔隙部分连通与均匀分布, 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。  Porous medical metal implant materials have important and special applications for the treatment of bone tissue trauma and femoral tissue necrosis. Common materials such as porous metal stainless steel and porous metal titanium are common materials. As a porous implant material used for the treatment of bone tissue trauma and femoral tissue necrosis, the porosity should be 30~80%, and the pores are preferably all connected and evenly distributed, or the pores are connected and evenly distributed according to the need, so that The growth of the bone tissue of the human body is consistent, and the weight of the material itself is reduced to be suitable for human implantation.
而难熔金属钽, 由于它具有优秀的生物相容性和力学性能, 其多孔材料有望作为替代 前述等传统医用金属生物材料, 成为主要作为骨组织坏死治疗的生物材料。 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, 则是保证新生骨组织正常生长的重要连接件构成材料。  The refractory metal ruthenium, due to its excellent biocompatibility and mechanical properties, is expected to be used as a biomaterial for the treatment of bone tissue necrosis as a substitute for the traditional 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 implant metal crucible, if it has a high uniform distribution of connected pores and physical and mechanical properties compatible with the human body, it is an important connecting member constituting material for ensuring the normal growth of new bone tissue.
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 烧结所获得的孔隙连通与均匀分布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。  As a 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 materials with pore connectivity and uniform distribution obtained by powder sintering are generally not very good in metal mechanical properties. The main reason is how to arrange the support and elimination relationship of pore-forming medium and the collapse problem in the sintering process of metal powder. . However, there is no good solution in the known literature reports and it is natural.
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。  There have been few reports on the production of porous tantalum by metal powder sintering, and in particular, the porous tantalum powder sintering method for the purpose of obtaining medical implant materials has been reported in the literature. Reference may be made to the publication No. CN200510032174, entitled "Three-dimensional through-hole or partial-hole-connected porous metal foam and its preparation method" and CN200710152394, entitled "A novel porous foamed tungsten and its preparation method". However, 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.
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%。 但是将它作为医用植入材料的多孔钽,其材料的力学性能如延展性有明显不足之处, 会影响到后续的对多孔钽材料本身的加工, 例如成型件的切割等。 同样在前述的金属粉末 烧结法所获得的产品也均存在这样的不足。 再由于其制备方法的局限, 获得的成品纯度不 够, 有碳骨架残留物, 导致生物安全性降低。 With regard to 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, as a porous material for medical implant materials, the mechanical properties of the material, such as ductility, have obvious deficiencies, which will affect the subsequent processing of the porous tantalum material itself, such as the cutting of molded parts. Also in the products obtained by the aforementioned metal powder sintering method, there are such deficiencies. Due to the limitations of the preparation method, the purity of the obtained product is insufficient, and there is a carbon skeleton residue, resulting in a decrease in biosafety.
发明内容 Summary of the invention
本发明的目的在于提供一种生物相容性好、 力学强韧性均优异的医用植入材料多孔钽 的制备方法。  It is an object of the present invention to provide a method for preparing a porous implant of a medical implant material which is excellent in biocompatibility and excellent in mechanical strength and toughness.
本发明的目的是通过如下技术手段实现的:  The object of the present invention is achieved by the following technical means:
一种医用植入材料多孔钽的制备方法, 采用泡沫浸渍法烧结而成, 其特点在于用有机 粘结剂与分散剂配制成的溶液和钽粉制成钽粉浆料, 并浇注于有机泡沫体中, 浸渍直至有 机泡沫体孔隙注满钽粉浆料, 然后干燥除去浇注有钽粉浆料的有机泡沫体中的分散剂, 在 惰性气体保护气氛下脱脂处理以除去有机粘结剂和有机泡沫体, 真空下烧结制得多孔烧结 体、 冷却, 再真空下退火及常规后处理制得多孔钽; 所述烧结步骤是真空度为 10— 4Pa〜 10— 3Pa, 以 10〜20°C/min升温至 1500〜1800°C、 保温 120〜240min、 随炉冷至 200〜300 °C, 再以 10〜20°C/min升温至 1500〜1800°C、 保温 180〜240min, 以 5〜10°C/min升温 至 2000〜2200°C、 保温 120〜360min; 所述热处理是真空度为 10— 4Pa〜10— 3Pa, 以 10〜20 °C/min升温至 800〜900°C、 保温 240〜480min, 再以 2〜5°C/min冷至 400°C、 保温 120〜 300min, 然后随炉冷却至室温。 The invention discloses a preparation method of a porous implant of a medical implant material, which is sintered by a foam impregnation method, and is characterized in that a solution prepared by using an organic binder and a dispersant and a tantalum powder are used to prepare a tantalum powder slurry, and poured into an organic foam. In the body, the impregnation is performed until the pores of the organic foam are filled with the powder slurry, and then the dispersant in the organic foam in which the tantalum powder slurry is poured is dried, and degreased under an inert gas atmosphere to remove the organic binder and the organic The foam body is sintered under vacuum to obtain a porous sintered body, cooled, and then annealed under vacuum and subjected to conventional post-treatment to obtain a porous crucible; the sintering step is a vacuum degree of 10 - 4 Pa 10 10 - 3 Pa, 10 to 20 ° C/min is heated to 1500~1800 °C, kept for 120~240min, cooled to 200~300 °C with furnace, then heated to 1500~1800°C at 10~20°C/min, and kept at 180~240min, 5 ~10 ° C / min was heated to 2000~2200 ° C, incubated 120~360min; degree of vacuum of the heat treatment is 10- 4 Pa~10- 3 Pa, to 10~20 ° C / min was heated to 800~900 ° C, heat preservation 240~480min, then cool to 400 °C at 2~5 °C/min, keep warm 120~ 30 0 min, then cooled to room temperature with the furnace.
采用本发明所述制备方法制得的多孔钽特别适用于作为承重骨组织创伤或骨缺损处 的连结构件。 再者, 所述的制备方法工艺简单、 易控; 整个制备过程无害、 无污染、 无毒 害粉尘, 对人体无副作用。 而且在制备过程中优先采用在烧结过程中能够全部分解, 没有 残留的粘结剂、 分散剂、 有机泡沫体等, 将有利于保证植入材料的生物相容性和生物安全 性。  The porous tantalum produced by the preparation method of the present invention is particularly suitable for use as a joint member for load-bearing bone tissue wounds or bone defects. Furthermore, the preparation method is simple and easy to control; the whole preparation process is harmless, non-polluting, non-toxic and dusty, and has no side effects on the human body. Moreover, in the preparation process, it is preferred to use all of the binders, dispersants, organic foams, etc. during the sintering process, which will ensure the biocompatibility and biosafety of the implant material.
所述的有机粘结剂优选聚乙烯醇, 也可以采用淀粉、 乙基纤维素等类似物质; 所述的 分散剂通常采用水、 无水乙醇等, 其中优选水。 所述的有机泡沫体优选聚氨酯泡沫, 也可 以是聚醚酯泡沫等类似物质。  The organic binder is preferably polyvinyl alcohol, and may also be a starch, ethyl cellulose or the like; the dispersing agent is usually water, anhydrous ethanol or the like, of which water is preferred. The organic foam is preferably a polyurethane foam, and may also be a polyether ester foam or the like.
本发明的进一步的特点是:采用其平均粒径小于 43 μ m、氧含量小于 0. 1%的金属钽粉, 采用聚乙烯醇水溶液为粘结剂和水为分散剂与所述的钽粉制成钽粉浆料, 有机泡沫体为聚 氨酯泡沫, 然后真空干燥除去水, 形成的多孔钽的孔隙度介于 50〜70%, 孔隙直径 150〜 600 μ ΐΉ。 A further feature of the present invention is that a metal tantalum powder having an average particle diameter of less than 43 μm and an oxygen content of less than 0.1% is used, and a polyvinyl alcohol aqueous solution is used as a binder and water as a dispersing agent and the tantalum powder. Made of tantalum powder slurry, organic foam is poly The urethane foam is then removed by vacuum drying to form a porous crucible having a porosity of 50 to 70% and a pore diameter of 150 to 600 μM.
其中, 将聚乙烯醇用蒸馏水加热至溶解, 采用重量百分比 2〜8% (优选 4〜5%) 聚乙 烯醇水溶液与金属钽粉制成钽粉浆料, 其中, 将重量为 6〜9份 (优选 7份) 的金属钽粉 加入重量为 1份的所述聚乙烯醇水溶液中, 搅拌均匀制成浆糊状; 并浇注于孔径为 0. 48〜 0. 89mm, 密度 0. 015 g/cm3〜0. 035g/cm3, 硬度大于 50° (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。 Wherein, the polyvinyl alcohol is heated to dissolve with distilled water, and a bismuth powder slurry is prepared by using a polyvinyl alcohol aqueous solution and a metal cerium powder in a weight percentage of 2 to 8% (preferably 4 to 5%), wherein the weight is 6 to 9 parts. The singularity of 0. 00 g / 0. 89mm, density 0. 015 g / Cm 3 〜0. 035g/cm 3 , a polyurethane foam having a hardness of more than 50° (preferably a pore diameter of 0.56~0. 72mm, a density of 025g/cm 3 , a hardness of 50° to 80°).
优先选择平均粒径小于 43 μ m、 氧含量小于 0. 1%的金属钽粉有助于减少杂质的含量, 保证材料具有较好的力学性能;选择孔径为 0. 48〜0. 89mm,密度 0. 025 g/cm3〜0. 035g/cm3, 硬度大于 50°的聚氨酯泡沫有助于保证多孔钽的孔隙度与孔隙直径。 本发明这样的技术处 理优化了工艺条件, 将保证植入多孔钽材料的生物相容性和生物安全性。 The singularity of the material is 0. 48~0. 89mm, the density is selected to be 0. 48~0. 89mm, density 0. 025 g / cm 3 ~0. 035g / cm 3, hardness of more than 50 ° helps ensure that a polyurethane foam with a porosity of the porous tantalum pore diameter. Such technical processing of the present invention optimizes process conditions and will ensure biocompatibility and biosafety of implanted porous tantalum materials.
本发明另一方面的进一步的特点是: 干燥的真空度保持 10— 2〜lPa真空度, 然后在保 护气氛下, 例如真空度 10— 4〜10— 3Pa, 温度 400°C〜80(TC条件下进行除去有机粘结剂和有 机泡沫体的脱脂处理;烧结步骤是真空度为 10— 4Pa〜10— 3Pa,以 12〜15°C/min升温至 1500〜 1800°C、保温 180〜200min、随炉冷至 200〜300°C,再以 16〜19°C/min升温至 1500〜1800 °C、 保温 220〜240min, 以 5〜8°C/min升温至 2000〜2200°C、 保温 250〜300min, 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 (热处理) 是在真空度为 10— 4Pa〜10— 3Pa, 以 15°C/min 升温至 800〜900°C、 保温 260〜 320min, 再以 3°C/min冷至 400°C、 保温 120min, 然后随炉冷却至室温; A further feature of another aspect of the invention is: the degree of vacuum of the drying is maintained at a vacuum of 10 - 2 to 1 Pa, and then under a protective atmosphere, for example, a degree of vacuum of 10 - 4 to 10 - 3 Pa, and a temperature of 400 ° C to 80 (TC) Degreasing treatment for removing the organic binder and the organic foam; the sintering step is a vacuum of 10 - 4 Pa to 10 - 3 Pa, and the temperature is raised to 1500 to 1800 ° C at 12 to 15 ° C / min, and the temperature is maintained at 180 ° ~200min, with the furnace cooled to 200~300 °C, then raise the temperature to 1500~1800 °C at 16~19 °C / min, keep warm for 220~240min, heat up to 2000~2200 °C at 5~8 °C/min Insulation for 250~300min, inert gas protection instead of vacuum protection during the sintering process; finally vacuum annealing treatment, wherein the vacuum annealing treatment (heat treatment) is at a vacuum of 10 - 4 Pa~10 - 3 Pa, to 15 ° C / min heating to 800 ~ 900 ° C, holding 260 ~ 320min, then cooling to 400 ° C at 3 ° C / min, holding 120min, and then cooled to room temperature with the furnace;
上述脱脂处理条件还包括有: 以 0. 5°C/min〜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 30min〜120min;  The degreasing treatment conditions further include: gradually increasing the temperature to 400~800 ° C at a rate of 0.5 ° C / min ~ 5 ° C / min, argon gas into a protective atmosphere and holding for 30 min ~ 120 min;
真空烧结后的冷却条件还包括有: 真空度低于 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。 The cooling conditions after vacuum sintering further include: the degree of vacuum is less than 10 - 3 P a , and the section of the sintered porous body is segmented at a temperature not lower than 25 ° C / min and not lower than 10 ° C / min. Cool down to 800 ° C, each holding period of 30 min ~ 90 min, and then cool to room temperature with the furnace.
在此基础上更进一步的特点是: 所述真空干燥的干燥温度 60〜100°C, 干燥时间 4〜8 小时; 所述脱脂处理条件还包括有: 逐步升温至 600〜800°C, 以纯净氩气 (99. 9999%)通 入构成保护气氛, 以 l〜5°C/min 的速率从室温升至 400°C, 保温 30〜60min, 以 0. 5〜 1. 5°C/min的速率从 400°C升至 600〜800°C, 保温 60〜120min, 所述真空烧结条件为: 真 空度为 10— 4Pa〜10— 3Pa, 以 13°C/min升温至 1800°C、 保温 200min、 随炉冷至 200〜300°C, 再以 17°C/min升温至 1800°C、保温 230min,以 7°C/min升温至 2000〜2200°C、保温 300min; 真空烧结后的冷却条件还包括有: 真空度为 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: 真空度为 10— 4Pa〜10— 3Pa, 以 15°C/min升温至 800〜900°C、 保温 260〜320min, 再以 3°C/min冷至 400°C、 保温 120〜300min, 然后以 18〜23°C/min冷却至室温。 Further characterized on the basis of: the drying temperature of the vacuum drying is 60 to 100 ° C, and the drying time is 4 to 8 hours; the degreasing treatment conditions further include: gradually increasing the temperature to 600 to 800 ° C, to be pure 5〜 1. 5°C/min, the argon gas (99.999%) is used to form a protective atmosphere, and the temperature is raised from room temperature to 400 ° C at a rate of 1 to 5 ° C / min. The rate is increased from 400 ° C to 600 ~ 800 ° C, and the temperature is maintained for 60 to 120 min. The vacuum sintering conditions are: vacuum degree is 10 - 4 Pa ~ 10 - 3 Pa, and the temperature is raised to 1800 ° C at 13 ° C / min. , heat preservation for 200min, with the furnace cooled to 200~300 °C, then heat up to 1800 °C at 17 °C / min, heat for 230min, 7 °C / min to 2000~2200 °C, heat preservation for 300min; after vacuum sintering The cooling conditions further include: a vacuum degree of 10 - 4 Pa to 10 - 3 P a; a cooling rate of 1500 to 1600 ° C at a rate of 10 to 20 ° C / m in, holding for 30 to 60 min; to 12 to 20 ° C/min rate is cooled to 1200~1250 °C, heat preservation 60~90min; cooled to 800 ° C at a rate of 10~20 ° C / min, and then cooled with the furnace; the vacuum annealing conditions also include: a vacuum of 10 - 4 Pa ~ 10 - 3 Pa, to 15 ° C/min was heated to 800-900 ° C, kept at 260-320 min, cooled to 400 ° C at 3 ° C/min, held for 120-300 min, and then cooled to room temperature at 18-23 ° C/min.
其中对真空干燥、 脱脂处理等是有助于减少多孔钽中杂质的含量, 提高生物相容性和 生物安全性好及力学性能; 对有机泡沫体材料的优化以解决烧结过程中泡沫骨架的不易塌 陷问题; 对烧结及退火步骤的工艺条件优化, 进一步提高多孔钽的力学性能如延展性、 减 小烧结颈的断裂率。  Among them, vacuum drying, degreasing treatment, etc. are helpful to reduce the content of impurities in porous tantalum, improve biocompatibility and biosafety and mechanical properties; optimize the organic foam material to solve the foam skeleton in the sintering process. Collapse problem; optimize the process conditions of the sintering and annealing steps to further improve the mechanical properties of the porous tantalum such as ductility and reduce the fracture rate of the sintered neck.
上述方法制得的多孔钽材料, 经过测试其杂质含量低于 0. 5%; 该多孔钽成品孔隙分布 均匀且连通, 密度 5· 00〜8· 33g/cm3, 孔隙度 50〜70%, 孔隙直径 150〜600 μ m, 弹性模量 4. 5〜6. OGPa, 弯曲强度 130〜150MPa, 抗压强度 78〜88MPa, 延伸率 10. 5%〜11. 7%。 本发 明多孔钽材料不仅生物相容性、 安全性好, 而且力学性能特别强度高, 非常适合用于替代 人体承重部位的骨组织。 附图说明 The porosity of the porous tantalum material prepared by the above method is less than 0.5%; the pores of the porous tantalum product are uniformly distributed and connected, and the density is 5·00~8·33g/cm 3 , and the porosity is 50 to 70%. 5%〜11. 7%。 Having a pore diameter of 150~600 μ m, an elastic modulus of 4. 5~6. OGPa, a bending strength of 130~150MPa, a compressive strength of 78~88MPa, an elongation of 10.5%~11.7%. The porous tantalum material of the invention not only has good biocompatibility and safety, but also has high mechanical strength and high strength, and is very suitable for replacing bone tissue of a human weight bearing part. DRAWINGS
图 1是本发明所述制备方法制备的多孔钽结构的扫描电子显微镜分析图 (SEM图); 从附图可观察到: 本发明所述多孔钽高孔隙, 孔隙分布均匀连通。 从附图中可看出本 发明所述的多孔钽连通孔隙有利于成骨细胞粘附、 分化和生长, 促进骨的长入, 可加强植 入体与骨之间的连接, 利于实现生物固定。 具体实施方式  BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a scanning electron microscopic analysis chart (SEM image) of a porous tantalum structure prepared by the preparation method of the present invention; it can be observed from the drawing that: the porous tantalum of the present invention has high porosity and uniform pore distribution. It can be seen from the drawing that the porous 钽-connected pores of the present invention are beneficial to adhesion, differentiation and growth of osteoblasts, promote bone ingrowth, strengthen the connection between the implant and the bone, and facilitate bio-immobilization. . detailed description
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。  The present invention is specifically described by the following examples, and the following examples are intended to be illustrative of the present invention and are not to be construed as limiting the scope of the present invention. The content makes some non-essential improvements and adjustments to the invention.
实施例 1 : 称取聚乙烯醇 12. 5g, 放入装有 240ml蒸馏水的容器中; 将其放在电炉上 加温并搅拌使之成为聚乙烯醇水溶液。 用 200g天平称量平均粒径小于 43微米、 氧含量小 于 0. 1%的钽粉 60g, 加入 50ml冷却的聚乙烯醇水溶液, 搅拌混合均匀, 使之成为钽粉浆 料。选用 10 X 10 X 30mm多孔聚氨酯泡沫(平均孔径为 0. 48mm, 密度 0. 025g/cm3,硬度 50。) 放入其中浇注, 直至聚氨酯泡沫孔隙注满钽粉浆料, 用夹子夹出吸满钽粉浆料的聚氨酯泡 沫放入瓷盘中。在真空干燥箱中干燥, 干燥温度 60°C, 干燥时间 8小时, 真空度保持 lPa。 脱脂处理:真空度低于 10— 4Pa,温度 60CTC,保温时间 120分钟。真空烧结:真空度为 10— 4Pa〜 10— 3Pa, 以 13°C/min升温至 1800°C、 保温 200min、 随炉冷至 200〜300°C, 再以 17°C/min 升温至 1800°C、 保温 230min, 以 7°C/min升温至 2000〜2200°C、 保温 300min, 烧结过程 充氩气保护, 取出产品后去除表面灰尘及污物, 冷却后将制得的样品再进行热处理及常规 的后处理得多孔钽成品;所述热处理是真空度为 10— 4Pa〜10— 3Pa, 以 15°C/min升温至 800〜 900°C、 保温 260〜320min, 再以 3°C/min冷至 400°C、 保温 120min, 然后以 18°C/min冷 却至室温。 Example 1: Weighing 12. 5 g of polyvinyl alcohol was placed in a vessel containing 240 ml of distilled water; it was placed on an electric furnace and heated and stirred to make an aqueous polyvinyl alcohol solution. 60 g of an anthracene powder having an average particle diameter of less than 43 μm and an oxygen content of less than 0.1% was weighed using a 200 g balance, and 50 ml of a cooled aqueous solution of polyvinyl alcohol was added thereto, and the mixture was stirred and mixed to obtain a tantalum powder slurry. Use 10 X 10 X 30mm porous polyurethane foam (average pore diameter of 0. 48mm, density 0. 025g/cm 3 , hardness 50.) Put it into it, until the polyurethane foam pores are filled with the powder slurry, and clamp it with a clip. The polyurethane foam filled with the powder slurry is placed in a porcelain dish. It was dried in a vacuum oven, dried at 60 ° C, dried for 8 hours, and maintained at a vacuum of 1 Pa. Degreasing treatment: the vacuum is less than 10 - 4 Pa, the temperature is 60 CTC, and the holding time is 120 minutes. Vacuum sintering: the degree of vacuum is 10 - 4 Pa~ 10 - 3 Pa, the temperature is raised to 1800 ° C at 13 ° C / min, the temperature is kept for 200 min, cooled to 200 ~ 300 ° C with the furnace, and then 17 ° C / min The temperature is raised to 1800 ° C, the temperature is kept for 230 min, the temperature is raised to 2000~2200 ° C at 7 ° C / min, the temperature is kept for 300 min, the argon gas is protected during the sintering process, the surface dust and dirt are removed after the product is taken out, and the sample is prepared after cooling. The heat treatment and the conventional post-treatment are carried out to obtain a porous tantalum product; the heat treatment is a vacuum degree of 10 - 4 Pa to 10 - 3 Pa, and the temperature is raised to 800 to 900 ° C at 15 ° C / min, and the temperature is maintained for 260 to 320 min. It was cooled to 400 ° C at 3 ° C / min, held for 120 min, and then cooled to room temperature at 18 ° C / min.
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. 5%的成品, 其孔隙分布均匀且连通, 密度 7. 7g/cm3, 孔隙率 56%, 孔隙平均直径 300 m, 弹性模量 5. 8GPa, 弯曲强度 150MPa, 抗压强度 83MPa, 延伸率 11. 6%。 The 5% of the content of the porous material is less than 0.5%. The inventor is tested according to the standard of GB/T5163_2006, GB/T5249_1985, GB/T6886-2001, etc., the porosity, porosity, pore size and various mechanical properties of the porous material: The finished product, the pores are evenly distributed and connected, the density is 7. 7 g / cm 3 , the porosity is 56%, the average pore diameter is 300 m, the elastic modulus is 5. 8 GPa, the bending strength is 150 MPa, the compressive strength is 83 MPa, and the elongation is 11.6. %.
实施例 2: 称取聚乙烯醇 10g, 放入装有 200ml蒸馏水的容器中; 将其放在电炉上加 温并搅拌使之成为聚乙烯醇水溶液。 用 200g天平称量平均粒径小于 43微米、 氧含量小于 0. 1%的钽粉 40g, 加入 32ml 聚乙烯醇水溶液, 搅拌混合均匀, 使之成为钽粉浆料。 选用 10 X 10 X 25mm多孔聚氨酯泡沫 (平均孔径为 0. 56mm, 密度 0. 030g/cm3, 硬度 60°) 放入其 中浇注, 直至聚氨酯泡沫孔隙注满钽粉浆料, 用夹子夹出吸满钽粉浆料的聚氨酯泡沫放入 瓷盘中。 在真空干燥箱中干燥, 干燥温度 100°C, 干燥时间 4小时, 真空度保持 10— 2Pa。 脱脂处理: 真空度 10— 4Pa, 温度 800°C, 保温时间 120分钟。 真空烧结: 真空度为 10— 4Pa〜 10— 3Pa, 以 10°C/min升温至 1500°C、 保温 240min、 随炉冷至 200〜300°C, 再以 10°C/min 升温至 1500°C、 保温 180min, 以 5°C/min升温至 2000〜2200°C、 保温 360min, 烧结过程 充氩气保护, 取出产品后去除表面灰尘及污物, 冷却后将制得的样品再进行热处理及常规 的后处理得多孔钽成品;所述热处理是真空度为 10— 4Pa〜10— 3Pa, 以 lCTC/min升温至 800〜 900°C、 保温 240min, 再以 5°C/min冷至 400°C、 保温 300min, 然后以 23°C/min冷却至室 温。 Example 2: 10 g of polyvinyl alcohol was weighed and placed in a vessel containing 200 ml of distilled water; it was placed on an electric furnace and heated and stirred to make an aqueous polyvinyl alcohol solution. 40 g of an anthracene powder having an average particle diameter of less than 43 μm and an oxygen content of less than 0.1% was weighed by a 200 g balance, and 32 ml of an aqueous polyvinyl alcohol solution was added thereto, and the mixture was stirred and mixed to make it into a tantalum powder slurry. 10 × 10 X 25mm porous polyurethane foam (average pore diameter of 0. 56mm, density 0. 030g/cm 3 , hardness 60°) was used for casting, until the pores of the polyurethane foam were filled with the powder slurry, and the clamp was sucked out. The polyurethane foam filled with the powder slurry is placed in a porcelain dish. Dry in a vacuum oven, dry at 100 ° C, dry for 4 hours, and maintain a vacuum of 10 - 2 Pa. Degreasing treatment: vacuum degree 10 - 4 Pa, temperature 800 ° C, holding time 120 minutes. Vacuum sintering: The degree of vacuum is 10 - 4 Pa~ 10 - 3 Pa, the temperature is raised to 1500 ° C at 10 ° C / min, the temperature is kept for 240 min, the furnace is cooled to 200 ~ 300 ° C, and then heated to 10 ° C / min to 1500 ° C, heat preservation for 180 min, heat up to 2000~2200 ° C at 5 ° C / min, heat preservation for 360 min, argon gas protection during the sintering process, remove the surface dust and dirt after removing the product, and then cool the sample after the preparation Heat treatment and conventional post-treatment to obtain a porous tantalum product; the heat treatment is a vacuum degree of 10 - 4 Pa to 10 - 3 Pa, and the temperature is raised to 800 to 900 ° C at lCTC / min, the temperature is maintained for 240 minutes, and then the temperature is 5 ° C / min. Cool to 400 ° C, hold for 300 min, then cool to room temperature at 23 ° C / min.
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. 5%的成品, 其孔隙分布均匀且连通, 密度 5. 87g/cm3, 孔隙率 66%, 孔隙平均直径 400 μ πι, 弹性模量 4. 8GPa, 弯曲强度 140MPa, 抗压强度 80MPa, 延伸率 10. 6%。 The 5% of the content of the porous material is less than 0.5%. The inventor is tested according to the standard of GB/T5163_2006, GB/T5249_1985, GB/T6886-2001, etc., the porosity, porosity, pore size and various mechanical properties of the porous material: The finished product, the pore distribution is uniform and connected, the density is 5. 87 g / cm 3 , the porosity is 66%, the average pore diameter is 400 μ πι, the elastic modulus is 4. 8GPa, the bending strength is 140MPa, the compressive strength is 80MPa, and the elongation is 10. 6%.
实施例 3: 称取聚乙烯醇 l lg, 放入装有 220ml蒸馏水的容器中; 将其放在电炉上加 温并搅拌使之成为聚乙烯醇水溶液。 用 200g天平称量平均粒径小于 43微米、 氧含量小于 0. 1%的钽粉 45g, 加入 36ml 聚乙烯醇水溶液, 搅拌混合均匀, 使之成为钽粉浆料。 选用 8 X 8 X 25mm多孔聚氨酯泡沫 (平均孔径为 0. 70mm, 密度 0. 035g/cm3, 硬度 70°) 放入其中 浇注, 直至聚氨酯泡沫孔隙注满钽粉浆料, 用夹子夹出吸满钽粉浆料的聚氨酯泡沫放入瓷 盘中。 在真空干燥箱中干燥, 干燥温度 80°C, 干燥时间 6小时, 真空度保持 10— ^E 脱脂 处理: 真空度 10- 3Pa, 温度 700°C, 保温时间 90分钟。真空烧结: 真空度为 10— 4Pa〜10— 3Pa, 以 20°C/min升温至 1800°C、 保温 120min、 随炉冷至 200〜300°C, 再以 20°C/min升温至 1800°C、 保温 240min, 以 10°C/min升温至 2000〜2200°C、 保温 120min, 烧结过程充氩气 保护, 取出产品后去除表面灰尘及污物, 冷却后将制得的样品再进行热处理及常规的后处 理得多孔钽成品;所述热处理是真空度为 10— 4Pa〜10— 3Pa, 以 20°C/min升温至 800〜900°C、 保温 480min, 再以 2°C/min冷至 400°C、 保温 120min, 然后以 18°C/min冷却至室温。 Example 3: Polyvinyl alcohol l lg was weighed and placed in a vessel containing 220 ml of distilled water; it was placed on an electric furnace and heated and stirred to make an aqueous polyvinyl alcohol solution. The granules having an average particle diameter of less than 43 μm and an oxygen content of less than 0.1% were weighed in an amount of 45 g, and 36 ml of an aqueous polyvinyl alcohol solution was added thereto, and the mixture was stirred and mixed to obtain a mash slurry. 8× 8 X 25mm porous polyurethane foam (average pore diameter of 0. 70mm, density 0. 035g/cm 3 , hardness 70°) was used for casting, until the pores of the polyurethane foam were filled with the powder slurry, and the clamp was sucked out. The polyurethane foam filled with the powder slurry is placed in a porcelain dish. Dry in vacuum drying oven, drying temperature 80 ° C, drying time 6 hours, vacuum degree 10 - ^ E degreasing Treatment: Vacuum 10 - 3 Pa, temperature 700 ° C, holding time 90 minutes. Vacuum sintering: The degree of vacuum is 10 - 4 Pa~10 - 3 Pa, the temperature is raised to 1800 ° C at 20 ° C / min, the temperature is kept for 120 min, the furnace is cooled to 200 ~ 300 ° C, and then heated to 20 ° C / min to 1800°C, heat preservation for 240min, heat up to 2000~2200°C at 10°C/min, heat preservation for 120min, argon gas protection during sintering, remove surface dust and dirt after removing the product, and then cool the sample after preparation. Heat treatment and conventional post-treatment to obtain a porous tantalum product; the heat treatment is a vacuum degree of 10 - 4 Pa to 10 - 3 Pa, and the temperature is raised to 800 to 900 ° C at 20 ° C / min, the temperature is maintained for 480 min, and then the temperature is 2 ° C. /min was cooled to 400 ° C, incubated for 120 min, and then cooled to room temperature at 18 ° C / min.
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. 5%的成品, 其孔隙分布均匀且连通, 密度 5. 0g/cm3, 孔隙率 70%, 孔隙平均直径 450 m, 弹性模量 5. 2GPa, 弯曲强度 130MPa, 抗压强度 79MPa, 延伸率 10. 5%。 The 5% of the content of the porous material is less than 0.5%. The inventor is tested according to the standard of GB/T5163_2006, GB/T5249_1985, GB/T6886-2001, etc., the porosity, porosity, pore size and various mechanical properties of the porous material: The finished product, the pores are evenly distributed and connected, having a density of 5.0 g / cm 3 , a porosity of 70%, an average pore diameter of 450 m, an elastic modulus of 5. 2 GPa, a flexural strength of 130 MPa, a compressive strength of 79 MPa, an elongation of 10. 5 %.
实施例 4: 称取聚乙烯醇 12g, 放入装有 230ml蒸馏水的容器中; 将其放在电炉上加 温并搅拌使之成为聚乙烯醇水溶液。 用 200g天平称量平均粒径小于 43微米、 氧含量小于 0. 1%的钽粉 50g, 加入 40ml 聚乙烯醇水溶液, 搅拌混合均匀, 使之成为钽粉浆料。 选用 12 X 12 X 30隱多孔聚氨酯泡沫 (孔径为 0. 60隱, 密度 0. 027g/cm3, 硬度 80。) 放入其中浇 注, 直至聚氨酯泡沫孔隙注满钽粉浆料, 用夹子夹出吸满钽粉浆料的聚氨酯泡沫放入瓷盘 中。 在真空干燥箱中干燥, 干燥温度 90°C, 干燥时间 5小时, 真空度保持 lPa。 脱脂处理: 真空度 10— 4〜10— 3Pa,温度 500 °C ,保温时间 120分钟。真空烧结:真空度为 10— 4Pa, 以 13. 5 °C/min升温至 1600°C、保温 155min、随炉冷至 200〜300°C,再以 17. 5°C/min升温至 1700 °C、 保温 190min, 以 6°C/min升温至 2000〜2200°C、 保温 300min, 烧结过程充氩气保护, 取出产品后去除表面灰尘及污物, 冷却后将制得的样品再进行热处理及常规的后处理得多 孔钽成品; 所述热处理是真空度为 10— 4Pa〜10— 3Pa, 以 12°C/min升温至 800〜900°C、 保温 240min, 再以 2. 5°C/min冷至 400°C、 保温 200min, 然后以 20°C/min冷却至室温。 Example 4: 12 g of polyvinyl alcohol was weighed and placed in a vessel containing 230 ml of distilled water; it was placed on an electric furnace and heated and stirred to make an aqueous polyvinyl alcohol solution. 50 g of an anthracene powder having an average particle diameter of less than 43 μm and an oxygen content of less than 0.1% was weighed by a 200 g balance, and 40 ml of an aqueous polyvinyl alcohol solution was added thereto, and the mixture was stirred and mixed to obtain a tantalum powder slurry. Use 12 X 12 X 30 hidden porous polyurethane foam (pore size is 0. 60 hidden, density 0. 027g/cm 3 , hardness 80.) Put it into it, until the polyurethane foam pores are filled with the powder slurry, clip it out with a clip The polyurethane foam filled with the powder slurry is placed in a porcelain dish. It was dried in a vacuum oven, dried at a temperature of 90 ° C, dried for 5 hours, and maintained at a vacuum of 1 Pa. Degreasing treatment: vacuum degree 10 - 4 ~ 10 - 3 Pa, temperature 500 ° C, holding time 120 minutes. Vacuum sintering: the degree of vacuum is 10 - 4 Pa, the temperature is raised to 1600 ° C at 13. 5 ° C / min, 155 min, chilled to 200 ~ 300 ° C, and then raised to 1700 at 17. 5 ° C / min. °C, heat preservation for 190min, heat up to 2000~2200°C at 6°C/min, heat preservation for 300min, argon gas protection during sintering, remove surface dust and dirt after removing the product, and heat the sample after heat treatment 5°。 The heat treatment is a vacuum of 10 - 4 Pa ~ 10 - 3 Pa, the temperature is raised to 800 ~ 900 ° C at 12 ° C / min, heat retention 240min, then 2. 5 ° C/min was cooled to 400 ° C, incubated for 200 min, and then cooled to room temperature at 20 ° C / min.
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. 5%的成品, 其孔隙分布均匀且连通, 密度 8. 21g/cm3, 孔隙率 50%, 孔隙平均直径 350 m, 弹性模量 4. 7GPa, 弯曲强度 142MPa, 抗压强度 81MPa, 延伸率 11. 5%。 The 5% of the content of the porous material is less than 0.5%. The inventor is tested according to the standard of GB/T5163_2006, GB/T5249_1985, GB/T6886-2001, etc., the porosity, porosity, pore size and various mechanical properties of the porous material: The finished product, the pore distribution is uniform and connected, the density is 8.21 g / cm 3 , the porosity is 50%, the average pore diameter is 350 m, the elastic modulus is 4. 7GPa, the bending strength is 142MPa, the compressive strength is 81MPa, the elongation is 11. 5 %.
实施例 5: —种多孔钽, 它以粒径小于 43 m、 氧含量小于 0. 1%的金属钽粉为原料, 以聚乙烯醇水溶液为粘结剂溶液制成钽粉浆料, 并浇注于聚氨酯泡沫载体中; 然后真空干 燥、 脱脂处理、 真空烧结、 真空退火及常规后处理制得。  Example 5: a porous crucible, which has a particle size of less than 43 m, an oxygen content of less than 0.1%, and a polyvinyl alcohol solution as a binder solution to prepare a tantalum powder slurry, and is poured. It is prepared in a polyurethane foam carrier; then vacuum drying, degreasing treatment, vacuum sintering, vacuum annealing and conventional post treatment.
其中, 选用的聚氨酯泡沫, 其孔径为 0. 72〜0. 56隱, 密度 0. 025g/cm3, 硬度 50。〜80°; 真空干燥: 真空度保持 10— 2〜lPa, 以除去注满钽粉浆料的聚氨酯泡沫中的水分; 脱脂处理: 在惰性气体保护气氛下或真空度 10— 4〜10— 3Pa, 温度 400°C〜800°C, 并保 温时间 30〜120分钟以除去其中的聚乙烯醇及聚氨酯泡沫; The urethane foam having a pore size of 0. 72~0. 56 hidden, density 0. 025g/cm 3 , hardness 50. ~80 °; dried in vacuo: the degree of vacuum holding 10- 2 ~lPa, to remove moisture tantalum slurry filled polyurethane foam; degreasing process: Under an inert gas atmosphere or a vacuum of 10-4 ~10- 3 Pa, temperature 400 ° C ~ 800 ° C, and Paul Heating time 30~120 minutes to remove the polyvinyl alcohol and polyurethane foam therein;
真空烧结: 真空度为 10— 4Pa〜10— 3Pa, 以 10°C/min升温至 1500°C、 保温 240min、 随炉 冷至 200〜300°C, 再以 10°C/min升温至 1500°C、保温 180min, 以 5°C/min升温至 2000〜 2200 °C 保温 360min; Vacuum sintering: The degree of vacuum is 10 - 4 Pa~10 - 3 Pa, the temperature is raised to 1500 ° C at 10 ° C / min, the temperature is kept for 240 min, the furnace is cooled to 200 ~ 300 ° C, and then heated to 10 ° C / min to 1500 ° C, holding 180min, heating at 5 ° C / min to 2000 ~ 2200 ° C for 360min;
真空退火: 真空度为 10— 4Pa〜10— 3Pa, 以 10°C/min升温至 800〜900°C、 保温 240min, 再以 5°C/min冷至 400°C、 保温 300min, 然后以 23°C/min冷却至室温。 Vacuum annealing: a vacuum degree of 10- 4 Pa~10- 3 Pa, at 10 ° C / min was heated to 800~900 ° C, insulation 240min, then cooled to 400 ° C at 5 ° C / min, incubated 300min, then Cool to room temperature at 23 ° C / min.
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. 5%的成品, 其孔隙分布均匀且连通, 密度 7. 83g/cm3, 孔隙率 62%, 孔隙平均直径 220 m, 弹性模量 5. 3GPa, 弯曲强度 136MPa, 抗压强度 84MPa, 延伸率 11. 4%。 The 5% of the content of the porous material is less than 0.5%. The inventor is tested according to the standard of GB/T5163_2006, GB/T5249_1985, GB/T6886-2001, etc., the porosity, porosity, pore size and various mechanical properties of the porous material: The finished product, the pores are evenly distributed and connected, the density is 7.83 g / cm 3 , the porosity is 62%, the average pore diameter is 220 m, the elastic modulus is 5. 3GPa, the bending strength is 136MPa, the compressive strength is 84MPa, and the elongation is 11.4. %.
在上述实施例 5给出的方法中, 我们还可以对其中的各种条件作其他选择同样能得到 本发明所述的多孔钽。  In the method given in the above embodiment 5, we can also obtain other options for various conditions among them to obtain the porous tantalum according to the present invention.
Figure imgf000009_0001
Figure imgf000009_0001
实 干燥真空度 脱脂气氛 烧结气氛(Pa) /温度 CC ) /时间 (min) 退火气氛(Pa) /升 施 (Pa) (Pa) /温度 温或降温速率 (°c 例 CO /时间 ( °C ) /时间 /min)温度 (°C ) /Real dry vacuum degreasing atmosphere sintering atmosphere (Pa) / temperature CC) / time (min) Annealing atmosphere (Pa) / liter (Pa) (Pa) / temperature temperature or cooling rate (°c example CO / time ( °C ) / time / min) temperature (°C) /
(小时) (min) 保温时间 (min)(hours) (min) holding time (min)
6 1/65/6.5 以 rC/min的 真空度为 10— 3Pa,以 i rC/min升温 真空度为 10— 4Pa, 速率从室温 至 1580°C、 保温 200min、 随炉冷至 以 20°C/min升温 升至 400°C, 200〜300°C, 再以 16°C/min 升温至 至 900 °C、 保温 保温 60min/ 1700°C、 保温 220min, 以 5°C/min升 290min, 再以 2. 561/65 / 6.5 at a degree of vacuum rC / min to 10- 3 Pa, to i rC / min heating degree of vacuum of 10- 4 Pa, a rate of from room temperature to 1580 ° C, holding 200min, cooled to 20 to the furnace °C/min heating Rise to 400 ° C, 200 ~ 300 ° C, then increase the temperature to 900 ° C at 16 ° C / min, insulation 60min / 1700 ° C, heat 220min, 290min at 5 ° C / min, then 2. 5
0.5°C/min的 温至 2000〜2200°C、 保温 320min; °C /min 冷至 400 速率从 400°C 真空度为 104Pa〜10- 3Pa; 以 ΐΓ。/ηώι °C、 保温 230min, 升至 600°C, 的速率 至 1520 °C, 保温 60min; 再以 18°C/min冷 保温 120min 以 13°C/min的速率) f¾至 1200 °C, 保温 却至室温 The temperature of 0.5 ° C / min to 2000 ~ 2200 ° C, heat 320min; ° C / min cold to 400 rate from 400 ° C vacuum 10 4 Pa ~ 10 - 3 Pa; /ηώι °C, heat for 230min, rise to 600 °C, the rate is to 1520 °C, keep warm for 60min; then heat at 18 °C / min for 120min at 13 °C / min) f3⁄4 to 1200 °C, keep warm But to room temperature
90min;  90min;
以 13°C/min的速率 至 800°C, 然后随  At a rate of 13 ° C / min to 800 ° C, and then
 Furnace
1/75/5.5 1.5°C/min的 真空度为 10— 3Pa, 以 i rC/min升温 真空度为 10— 4Pa, 至 1580°C、 保温 200min、 随炉冷至 1/75/5.5 1.5 °C / min vacuum is 10 - 3 Pa, i rC / min heating vacuum of 10 - 4 Pa, to 1580 ° C, holding 200min, with the furnace to cool
速率从室温 以 12°C/min升温  Rate from room temperature to 12 ° C / min
200〜300°C, 再以 16°C/min 升温至  200~300 °C, then raise the temperature to 16 °C/min to
升至 400°C, 至 870 °C、 保温  Increased to 400 ° C, to 870 ° C, insulation
1700°C、 保温 220min, 以 5°C/min升  1700 ° C, insulation 220 min, 5 ° C / min liter
保温 58min/ 温至 2000〜2200°C、 保温 320min; 250min, 再以 5°C Insulation 58min / temperature to 2000~2200 °C, heat preservation 320min; 250min, then 5°C
0.6°C/min的 真空度为 104Pa〜10— 3Pa; 以 12°C/min /min冷至 400 °C、 速率从 400°C 的速率 至 1530 °C, 保温 55min; 保温 250min,再以 升至 650°C, 以 14°C/min的速率) f¾至 1210°C, 保温 20°C/min 冷却至 保温 HOmin 85min; 、〉曰 以 14°C/min的速率 至 800°C, 然后随 The vacuum degree of 0.6 ° C / min is 10 4 Pa~10 - 3 Pa; the temperature is cooled to 400 ° C at 12 ° C / min / min, the rate is from 400 ° C to 1530 ° C, and the temperature is maintained for 55 min; Then increase to 650 ° C, at a rate of 14 ° C / min) f3⁄4 to 1210 ° C, keep warm 20 ° C / min, cool to heat retention HOmin 85min;, 曰 14 at 14 ° C / min rate to 800 ° C And then with
 Furnace
1/55/7 以 2°C/min的 真空度为 10— 3Pa,以 i rC/min升温 真空度为 10— 3Pa, 速率从室温 以 13°C/min升温 至 1580°C、 保温 200min、 随炉冷至 1/55/7 degree of vacuum of 2 ° C / min to 10- 3 Pa, to i rC / min heating a vacuum degree of 10- 3 Pa, at a rate of 13 ° C / min from room temperature to 1580 ° C, insulation 200min, cold with the furnace
升至 400°C, 至 800 °C、 保温  Increased to 400 ° C, to 800 ° C, insulation
200〜300°C, 再以 16°C/min 升温至  200~300 °C, then raise the temperature to 16 °C/min to
保温 56min/ 270min, 再以 2°C Insulation 56min / 270min, then 2 ° C
0.7°C/min的 1700°C、 保温 220min, 以 5°C/min升 /min冷至 400 °C、 速率从 400°C 温至 2000〜2200°C、 保温 320min; 保温 150min,再以 升至 680°C, 真 ¾S为 104Pa〜10— 3Pa; 以 13°C/min 20°C/min 冷却至 保温 lOOmin 的速率 至 、〉曰 1700 ° C at 0.7 ° C / min, heat for 220 min, cool to 400 ° C at 5 ° C / min liter / min, rate from 400 ° C temperature to 2000 ~ 2200 ° C, heat preservation 320 min; heat preservation 150 min, then liter to 680 ° C, is really ¾S 10 4 Pa~10- 3 Pa; to 13 ° C / min 20 ° C / min cooling rate to lOOmin to insulation,> said
1540 °C,保温 50min; 以 15  1540 °C, heat preservation 50min; to 15
°C/min的速率 至 1220°。,保温 80min; The rate of °C/min is up to 1220°. , heat preservation 80min ;
以 15°C/min的速率) f¾至 800°C, 然后随  At a rate of 15 ° C / min) f3⁄4 to 800 ° C, and then
炉 所得多孔钽成品按前述方法检 Furnace The obtained porous tantalum product is inspected as described above
Figure imgf000011_0001
Figure imgf000011_0001

Claims

1、 一种医用植入材料多孔钽的制备方法, 采用泡沫浸渍法烧结而成, 其特征在于: 用有机粘结剂与分散剂配制成的溶液和钽粉制成钽粉浆料, 并浇注于有机泡沫体中, 浸渍 直至有机泡沫体孔隙注满钽粉浆料, 然后干燥除去浇注有钽粉浆料的有机泡沫体中的分散 剂, 在惰性气体保护气氛下脱脂处理以除去有机粘结剂和有机泡沫体, 真空下烧结制得多 孔烧结体、 冷却, 再真空下退火及常规后处理制得多孔钽; 所述烧结步骤是真空度为 10— 4Pa 10— 3Pa,以 10 20°C/min升温至 1500 1800°C、保温 120 240min、随炉冷至 200 300 °C, 再以 10 20°C/min升温至 1500 1800°C、 保温 180 240min, 以 5 10°C/min升 温至 2000 2200°C、 保温 120 360min; 所述热处理是真空度为 10— 4Pa 10— 3Pa, 以 10 20°C/min升温至 800 900°C、保温 240 480min,再以 2 5°C/min冷至 400°C、保温 120 300min, 然后随炉冷却至室温。 1. A method for preparing a porous implant of a medical implant material, which is sintered by a foam impregnation method, characterized in that: a solution prepared by using an organic binder and a dispersant and a tantalum powder are used to prepare a tantalum powder slurry, and poured. In the organic foam, the liquid foam is impregnated until the pores of the organic foam are filled with the powder slurry, and then the dispersant in the organic foam in which the tantalum powder slurry is poured is removed, and degreased under an inert gas atmosphere to remove the organic binder. And the organic foam, sintered under vacuum to obtain a porous sintered body, cooling, annealing under vacuum and conventional post-treatment to obtain porous tantalum; the sintering step is a vacuum of 10 - 4 Pa 10 - 3 Pa, to 10 20 °C / min to 1500 1800 ° C, 120 240 min, with the furnace cooled to 200 300 ° C, then 10 20 ° C / min to 1500 1800 ° C, 180 240 min, 5 10 ° C / min The temperature is raised to 2000 2200 ° C, and the temperature is maintained for 120 360 min; the heat treatment is 10 - 4 Pa 10 - 3 Pa, the temperature is raised to 800 900 ° C at 10 20 ° C / min, the heat is 240 480 min, and then 2 5 ° C/min was cooled to 400 ° C, held for 120 300 min, and then cooled to room temperature with the furnace.
2、 如权利要求 1所述的方法, 其特征在于: 所述金属钽粉为平均粒径小于 43 μπκ 氧 含量小于 0.1%的金属钽粉; 所述有机粘结剂为聚乙烯醇, 分散剂为水, 配制成聚乙烯醇水 溶液与所述的钽粉制成钽粉浆料; 所述有机泡沫体为孔径 0.48 0.89 密度 0.015 g/cm3 0.035g/cm3, 硬度大于 50°的聚氨酯泡沫。 2. The method according to claim 1, wherein: the metal tantalum powder is a metal tantalum powder having an average particle diameter of less than 43 μπκ and an oxygen content of less than 0.1%; the organic binder is polyvinyl alcohol, a dispersant The water is formulated into a polyvinyl alcohol aqueous solution and the tantalum powder to form a tantalum powder slurry; the organic foam is a polyurethane foam having a pore diameter of 0.48 0.89 and a density of 0.015 g/cm 3 0.035 g/cm 3 and a hardness of more than 50°. .
3、 如权利要求 2 所述的方法, 其特征在于: 所述聚乙烯醇水溶液的重量百分比浓度 为 2 8%; 所述金属钽粉与聚乙烯醇水溶液得重量份比为 6 9份: 1份; 所述聚氨酯泡沫 孔径为 0.56 0.72 密度 0.025g/cm3, 硬度 50° 80° 3. The method according to claim 2, wherein: the weight percent concentration of the aqueous solution of polyvinyl alcohol is 2 8%; and the weight ratio of the metal cerium powder to the aqueous solution of polyvinyl alcohol is 6 9 parts: 1 The polyurethane foam has a pore size of 0.56 0.72 and a density of 0.025 g/cm 3 and a hardness of 50° 80°.
4、 如权利要求 2 所述的方法, 其特征在于: 所述聚乙烯醇水溶液的重量百分比浓度 为 4 5%; 所述金属钽粉与聚乙烯醇水溶液得重量份比为 7份: 1份; 所述聚氨酯泡沫孔 径为 0.56 0.72mm, 密度 0.025g/cm3, 硬度 50° 80° 4. The method according to claim 2, wherein: the polyvinyl alcohol aqueous solution has a concentration by weight of 45%; and the metal cerium powder and the polyvinyl alcohol aqueous solution have a weight ratio of 7 parts: 1 part The polyurethane foam has a pore size of 0.56 0.72 mm, a density of 0.025 g/cm 3 and a hardness of 50° 80°.
5、 如权利要求 1 2 3或 4所述的方法, 其特征在于: 干燥的真空度保持 10— 2 lPa 真空度, 然后在保护气氛下, 真空度 10— 4 10— 3Pa, 温度 400°C 80(TC条件下进行除去有 机粘结剂和有机泡沫体的脱脂处理;烧结步骤是真空度为 10— 4Pa 10— 3Pa, 以 12 15°C/min 升温至 1500 1800°C、 保温 180 200min、 随炉冷至 200 300°C, 再以 16 19°C/min升 温至 1500 1800°C、保温 220 240min, 以 5 8°C/min升温至 2000 2200°C、保温 250 300min, 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 中真空退火处理是在真空度为 10— 4Pa 10— 3Pa,以 15°C/min升温至 800 900°C、保温 260 320min, 再以 3°C/min冷至 400°C、 保温 120min, 然后随炉冷却至室温。 5. The method according to claim 1 2 or 3, wherein: the degree of vacuum of the drying is maintained at a vacuum of 10 - 2 lPa, and then under a protective atmosphere, the degree of vacuum is 10 - 4 10 - 3 Pa, and the temperature is 400 °. C 80 (de-fatting treatment for removing the organic binder and the organic foam under TC conditions; the sintering step is a vacuum of 10 - 4 Pa 10 - 3 P a , and the temperature is raised to 1500 1800 ° C at 12 15 ° C / min, Insulation 180 200min, with the furnace cooled to 200 300 ° C, then at 16 19 ° C / min to 1500 1800 ° C, insulation 220 240min, 5 8 ° C / min to 2000 2200 ° C, insulation 250 300min, During the sintering process, the inert gas protection may be used instead of the vacuum protection; finally, the vacuum annealing treatment is performed, wherein the vacuum annealing treatment is performed at a vacuum degree of 10 - 4 Pa 10 - 3 Pa, and the temperature is raised to 800 900 ° C at 15 ° C / min, The temperature was 260 320 min, then cooled to 400 ° C at 3 ° C / min, held for 120 min, and then cooled to room temperature with the furnace.
6、如权利要求 5所述的方法,其特征在于:所述脱脂处理条件还包括有:以 0.5°C/mir 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 30min 120min; 真空烧结后的冷却条件还包括有: 真空度低于 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。 6. The method according to claim 5, wherein the degreasing treatment condition further comprises: gradually increasing the temperature to 400 800 ° C at a rate of 0.5 ° C / mir 5 ° C / min, and introducing argon gas. Form a protective atmosphere and keep warm for 30min 120min; The cooling conditions after vacuum sintering further include: the degree of vacuum is less than 10 - 3 P a , and the section of the sintered porous body is segmented at a temperature not lower than 25 ° C / min and not lower than 10 ° C / min. Cool down to 800 ° C, each holding period of 30 min ~ 90 min, and then cool to room temperature with the furnace.
7、如权利要求 1、 2、 3或 4所述的方法, 其特征在于: 所述真空干燥的干燥温度 60〜 100°C, 干燥时间 4〜8小时; 所述脱脂处理条件还包括有: 逐步升温至 600〜800°C, 以纯 净氩气 (99. 9999%) 通入构成保护气氛, 以 l〜5°C/min 的速率从室温升至 400°C, 保温 30〜60min, 以 0. 5〜1. 5°C/min的速率从 400°C升至 600〜800°C, 保温 60〜120min, 所述 真空烧结条件为: 真空度为 10— 4Pa〜10— 3Pa, 以 13°C/min升温至 1800°C、 保温 200min、 随 炉冷至 200〜300°C,再以 17°C/min升温至 1800°C、保温 230min,以 7°C/min升温至 2000〜 2200°C、保温 300min; 真空烧结后的冷却条件还包括有: 真空度为 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: 真空度为 10— 4Pa〜10— 3Pa, 以 15°C/min升温至 800〜900°C、 保温 260〜320min, 再以 3°C/min冷至 400°C、 保温 120〜300min, 然后以 18〜23°C/min 冷却至室温。 The method according to claim 1, 2, 3 or 4, characterized in that: the drying temperature of the vacuum drying is 60 to 100 ° C, and the drying time is 4 to 8 hours; and the degreasing treatment conditions further include: Gradually heat up to 600~800 °C, pass pure argon (99.9999%) into the protective atmosphere, increase from room temperature to 400 °C at a rate of l~5 °C/min, keep warm for 30~60min, 0. 5~1. The rate of 5 ° C / min is increased from 400 ° C to 600 ~ 800 ° C, and the temperature is kept for 60 to 120 min. The vacuum sintering condition is: vacuum degree is 10 - 4 Pa ~ 10 - 3 Pa, Raise the temperature to 1800 ° C at 13 ° C / min, heat for 200 min, cool with the furnace to 200 ~ 300 ° C, then raise the temperature to 1800 ° C at 17 ° C / min, heat for 230 min, heat up to 2000 at 7 ° C / min ~ 2200 ° C, heat preservation 300 min; cooling conditions after vacuum sintering also include: vacuum degree of 10 - 4 Pa ~ 10 - 3 Pa; cooling at a rate of 10 ~ 20 ° C / min to 1500 ~ 1600 ° C, insulation 30~60min; cooled to 1200~1250°C at a rate of 12~20°C/min, kept at 60~90min; cooled to 800°C at a rate of 10~20°C/min, and then cooled with the furnace; Vacuum annealing conditions also include There are: The degree of vacuum is 10 - 4 Pa ~ 10 - 3 Pa, the temperature is raised to 800 ~ 900 ° C at 15 ° C / min, the temperature is 260 ~ 320min, and then cooled to 400 ° C at 3 ° C / min, insulation 120 ~ After 300 min, it was cooled to room temperature at 18 to 23 ° C/min.
PCT/CN2012/082276 2011-09-29 2012-09-28 Method for manufacturing medical implant material porous tantalum WO2013044839A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201110296565.5 2011-09-29
CN201110296565.5A CN102796897B (en) 2011-09-29 2011-09-29 Preparation method of medical implanting material porous tantalum

Publications (1)

Publication Number Publication Date
WO2013044839A1 true WO2013044839A1 (en) 2013-04-04

Family

ID=47196189

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2012/082276 WO2013044839A1 (en) 2011-09-29 2012-09-28 Method for manufacturing medical implant material porous tantalum

Country Status (2)

Country Link
CN (1) CN102796897B (en)
WO (1) WO2013044839A1 (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5282861A (en) * 1992-03-11 1994-02-01 Ultramet Open cell tantalum structures for cancellous bone implants and cell and tissue receptors
CN101405039A (en) * 2006-02-17 2009-04-08 拜欧麦特制造公司 Method and apparatus for forming porous metal implants
CN101660076A (en) * 2009-10-14 2010-03-03 北京师范大学 Macro mesh structural porous tantalum prepared by dipping and sintering organic foams

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101549175B (en) * 2009-05-15 2012-07-04 中南大学 Method for preparation of pore heterogeneous distribution bionic bone material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5282861A (en) * 1992-03-11 1994-02-01 Ultramet Open cell tantalum structures for cancellous bone implants and cell and tissue receptors
CN101405039A (en) * 2006-02-17 2009-04-08 拜欧麦特制造公司 Method and apparatus for forming porous metal implants
CN101660076A (en) * 2009-10-14 2010-03-03 北京师范大学 Macro mesh structural porous tantalum prepared by dipping and sintering organic foams

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JIE, YUNFENG ET AL.: "Fabrication of Porous Niobium-Based Biological Materials via Impregnation and Their Properties", RARE METAL MATERIALS AND ENGINEERING, vol. 39, no. 11, November 2010 (2010-11-01), pages 2015 - 2017, XP008173887 *

Also Published As

Publication number Publication date
CN102796897A (en) 2012-11-28
CN102796897B (en) 2014-08-20

Similar Documents

Publication Publication Date Title
EP2554187B1 (en) Metal porous tantalum used as medical implant material and preparation method thereof
CN103849792B (en) A kind of porous tantalum being applicable to alternative human dentale tissue
WO2013044773A1 (en) Preparation method for medical porous metal material for dental bone replacement
WO2013044832A1 (en) Preparation method for medical porous tantalum implant material
WO2013044780A1 (en) Medical porous metal material for weight-bearing bone tissue replacement and preparation method therefor
WO2013044852A1 (en) Preparation method for medical porous metal implant material
WO2013044767A1 (en) Medical porous tantalum material for dental bone replacement and preparation method therefor
CN103740962B (en) Preparation method of medical porous metal material substituting for dental bone
CN102796899A (en) Preparation method of medical porous metal implanting material
WO2013044835A1 (en) Preparation method for medical porous tantalum implant material
WO2013044834A1 (en) Preparation method for medical porous tantalum implant material
WO2013044779A1 (en) Method for manufacturing medical porous metal material
WO2013044778A1 (en) Medical porous metal material and preparation method therefor
WO2013044839A1 (en) Method for manufacturing medical implant material porous tantalum
WO2013044858A1 (en) Preparation method for medical porous metal implant material
WO2013044815A1 (en) Preparation method for medical porous tantalum material
CN103463674B (en) Method for preparing medical implant material multi-hole tantalum
WO2013044809A1 (en) Preparation method for medical porous metal material for weight-bearing bone tissue replacement
WO2013044781A1 (en) A method for manufacturing medical porous metal material for substituting load-bearing bone tissue
WO2013044833A1 (en) Preparation method for medical porous tantalum implant material
CN103740960B (en) Preparation method of medical porous tantalum implantation material
CN102796889B (en) Preparation method of medical porous tantalum material for replacing weight-bearing bone tissues of human body
CN102462862B (en) Preparation method for porous tantalum serving as medical metal implant material
WO2013044813A1 (en) Method for producing medical porous metallic material as alternative to load-bearing bone tissue
WO2013044777A1 (en) Medical porous metal material for replacing tooth bone, and preparation method thereof

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12836820

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12836820

Country of ref document: EP

Kind code of ref document: A1