WO2013044839A1

WO2013044839A1 - Method for manufacturing medical implant material porous tantalum

Info

Publication number: WO2013044839A1
Application number: PCT/CN2012/082276
Authority: WO
Inventors: 叶雷
Original assignee: 重庆润泽医药有限公司
Priority date: 2011-09-29
Filing date: 2012-09-28
Publication date: 2013-04-04
Also published as: CN102796897A; CN102796897B

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

Method for preparing porous implant of medical implant material

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.

Background technique

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.

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.

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.

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.

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.

Summary of the invention

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.

The object of the present invention is achieved by the following technical means:

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.

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 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.

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°).

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 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;

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.

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.

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.

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

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

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.

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.

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 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.

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%.

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.

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 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.

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 %.

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. %.

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.

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) /

(hours) (min) holding time (min)

61/65 / 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

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;

At a rate of 13 ° C / min to 800 ° C, and then

Furnace

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

Rate from room temperature to 12 ° C / min

200~300 °C, then raise the temperature to 16 °C/min to

Increased to 400 ° C, to 870 ° C, insulation

1700 ° C, insulation 220 min, 5 ° C / min liter

Insulation 58min / temperature to 2000~2200 °C, heat preservation 320min; 250min, then 5°C

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 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

Increased to 400 ° C, to 800 ° C, insulation

200~300 °C, then raise the temperature to 16 °C/min to

Insulation 56min / 270min, then 2 ° C

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, heat preservation 50min; to 15

The rate of °C/min is up to 1220°. , heat preservation 80min _;

At a rate of 15 ° C / min) f3⁄4 to 800 ° C, and then

Furnace The obtained porous tantalum product is inspected as described above

Claims

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. 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. 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. 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. 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. 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.

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.