CN101912635A - Bio-medicinal porous titanium material and preparation method thereof - Google Patents
Bio-medicinal porous titanium material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a bio-medicinal porous titanium material. The porous titanium material comprises at least two layers, the porosity of the material is enlarged layer by layer from inside to outside, the porosity of the innermost layer is 0 to 50 percent, the porosity of the outermost layer is 30 to 90 percent, and the size of aperture is 50 to 500 microns. The porous titanium material has excellent corrosion resistance and biocompatibility, has the mechanical property matched with natural bones, meanwhile can provide a good transmission passage for growth of bone cells, and can solve the stress shielding phenomenon and the problems of loosening, breakage and the like.
Description
Technical field
The invention belongs to the bio-medical material technical field, particularly a kind of bio-medicinal porous titanium material and preparation method thereof.
Background technology
Being used for the surgical implant that human body hard tissue (as bone, joint, root of the tooth etc.) is repaired or replaced, is a kind of and human life and healthy closely-related specific function material, and demand clinically is widely used.At present, the surgery embedded material of clinical practice mainly is titanium or titanium alloy and hydroxyapatite (HA) ceramic material.
Hydroxyapatite (HA) pottery can make implant just can form coalition with tissue in early days, thereby be widely used bioactive materials owing to have superior bioactive.But, because inherent fragility of bioceramic material itself and fatiguability damage under physiological environment make it especially be restricted in the reparation of heavy burden bone section in application.
Titanium or titanium alloy has outstanding corrosion resistance, biocompatibility, low-density and high characteristics such as specific strength, particularly is used widely in bone reparation field at medical shaping material.(but the comprcssive strength of titanium alloy is about 750-1200MPa to its intensity, tensile strength is about 900MPa) and elastic modelling quantity (elastic modelling quantity of titanium alloy is about 110-120GPa) (comprcssive strength of natural bone is about 130-180MPa far above natural bone, tensile strength is about 50-170MPa, elastic modelling quantity is 3-20GPa), mechanical property (intensity and the elastic modelling quantity that mainly comprise the front) does not match with natural bone, load can not be delivered to adjacent bone tissue well by implant, be prone to the stress shielding phenomenon, cause implant surrounding bone stress absorption, finally cause the loosening or fracture of implant.
In order to increase the bond strength of titanium implants and osseous tissue, usually the implant titanium or titanium alloy is prepared into loose structure, area of new bone is grown into form biological fixation in the hole.The titanium or titanium alloy of loose structure can be regulated the intensity and the elastic modelling quantity of implant by the control porosity, reach the mechanical property that is complementary with osseous tissue, can alleviate the stress shielding problem effectively thereby receives much concern.Simultaneously, mutual pore structure that connects and suitably big or small hole help osteocyte well grows into, so that POROUS TITANIUM and natural bone formation favorable mechanical are sealed, avoids the loosening of implant, while also provides passage for the transmission of body fluid, is very ideal biological implantation piece.
Yet the porous titanium material of using titanium valve preparation at present is hole random distribution, almost uniform distribution from inside to outside.If adopt the high porosity POROUS TITANIUM, though hole number is more, the aperture helps area of new bone more greatly grows in the clinical practice, and its mechanical property is lower, is prone to the problem of undercapacity; If reduce the porosity of POROUS TITANIUM, then its mechanical property can be improved, but its hole number minimizing, the passage that provides for the body fluid transmission reduces, and is unfavorable for growing into of osteocyte again, and these have all limited the application of POROUS TITANIUM in medical field.
Summary of the invention
Main purpose of the present invention is not match with titanium or titanium alloy mechanical property and the natural bone that embedded material exists at bio-medical bone reparation in the above-mentioned prior art or replacement, be prone to the stress shielding phenomenon, cause implant surrounding bone stress absorption, finally cause the loosening or fracture of implant, reach problems such as high porosity POROUS TITANIUM undercapacity, a kind of new bio-medicinal porous titanium material is provided, with outstanding corrosion resistance, biocompatibility, has the mechanical property that is complementary with natural bone again, can be growing into of osteocyte simultaneously good transmission channel is provided, solve stress shielding phenomenon and loosening, problems such as fracture.
Another object of the present invention provides a kind of preparation method of above-mentioned bio-medicinal porous titanium material.
In order to realize the foregoing invention purpose, the technical solution used in the present invention is as follows:
A kind of bio-medicinal porous titanium material, this porous titanium material comprises two-layerly at least (can be preferably the 2-10 layer, 3-5 layer more preferably), from the inside to the outside, its porosity successively increases, the porosity of innermost layer is 0-50%, and outermost porosity is 30%-90%, and pore size is 50 μ m-500 μ m.
The outermost layer of above-mentioned porous titanium material (also can be described as the top layer) also has the pore structure of three-dimensional communication (being interconnected between the Kong Yukong), can impel osteocyte and organize well and grow into.In fact, except the innermost layer porosity may not have the hole for 0 o'clock, all the other pore structures with position of certain porosity all have three-dimensional communication; But as the surgery embedded material, its outer with body fluid, organize directly and contact, this connectivity structure more helps the growing into of transmission, tissue of its body fluid.
Can be preferred, the porosity of porous titanium material innermost layer is 0-40%, outermost porosity is 50%-90%;
Further preferred, the porosity of porous titanium material innermost layer is 0-20%, and outermost porosity is 70%-90%;
In addition, the thickness of each level in the above-mentioned porous titanium material, can be identical also can be inequality.
Wherein, the porosity of porous titanium material is calculated according to formula 1-m/ (rV), and m is the quality of POROUS TITANIUM in the formula, and r is the density (4.5g/cm of pure titanium
3), V is the apparent volume of POROUS TITANIUM.
Bio-medicinal porous titanium material of the present invention can prepare by the method that comprises the steps:
(1), batch mixing:
(with bio-medical sized spherical titanium powder or titanium alloy powder is good to prepare the raw material titanium valve respectively according to the predefined porosity of each layer; The innermost layer porosity is 0% o'clock, can also be directly the titanium alloy plate of higher, the good biocompatibility of employing mechanical property as the raw material of innermost layer, as Ti
6Al
7Nb titanium alloy, Ti
5Al
2.5Fe alloy, Ti
13Nb
13The Zr alloy, Ti
12Mo
6Zr
2The Fe alloy, Ti
35Nb
5Ta
7Zr alloy etc.) and size be pore creating material (optional self-heating breakdown type pore creating material such as ammonium bicarbonate, carbamide, the TiH of 50 μ m-500 μ m
2Deng, also can be selected from water-soluble type pore creating material such as sodium carbonate, sodium chloride etc.), the usage ratio of pore creating material and raw material titanium valve calculates according to the porosity of each layer respectively that (as: certain layer porosity is 10%, the consumption volume ratio of pore creating material and raw material titanium valve then is 1:9 when preparing this layer so, and the rest may be inferred); With pore creating material and raw material titanium valve mix homogeneously, obtain pore creating material and raw material titanium valve composite;
(2), filling, pre-molding:
With the pore creating material behind step (1) batch mixing and raw material titanium valve composite from inside to outside successively layering be packed in the mould (according to requirement the concrete shape and the size of implant, can select the mould of the required forms such as cylindrical or rectangle of suitable size for use), pre-molding obtains base just;
The mould of using in this step can to prepare used mould identical with the prior art mesopore equally distributed porous titanium material of rate;
(3), sinter molding:
The first base that step (2) pre-molding is obtained carries out sintering in 500 ℃-1300 ℃ of temperature (can be preferably 800 ℃-1300 ℃), and insulation 5min-60min(can be preferably 10min-30min), obtain sintered body;
When the pore creating material that adopts is that thermal decomposition type pore creating material is (as ammonium bicarbonate, carbamide, TiH
2Deng) time, in this step sintering process, pore creating material decomposes and be removed (thereby staying the hole that the aperture is 50 μ m-500 μ m) at material internal, the sintered body that obtains behind the sintering is the porous titanium material that porosity from the inside to the outside successively increases.
When the pore creating material that adopts is non-thermal decomposition type, but during water-soluble type pore creating material (as sodium carbonate, sodium chloride etc.), in this step sintering process, pore creating material is heated and can decompose and still be retained in the sintered body that obtains behind the sintering, need carry out subsequent treatment, promptly the described removal pore creating material of following steps (4) is handled:
(4), remove pore creating material:
The sintered body that obtains behind the sintering in the step (3) is placed deionized water, water-soluble type pore creating material is wherein dissolved in water, removal is retained in the water-soluble type pore creating material (thereby staying the hole that the aperture is 50 μ m-500 μ m at material internal) in the sintered body, water solubility temperature is 20 ℃-100 ℃, water dissolution time 1h-2h, water dissolution finishes, and promptly obtains the porous titanium material that porosity from the inside to the outside successively increases.
Compared with prior art, the invention has the beneficial effects as follows:
Porous titanium material of the present invention from the inside to the outside, its porosity successively increases, regulate the intensity and the elastic modelling quantity of material by the distribution of control porosity, reach the mechanical property that is complementary with osseous tissue, the too high stress shielding problem that causes of mechanical property both can effectively alleviate fine and close titanium or titanium alloy owing to can effectively alleviate the undercapacity problem that the equally distributed POROUS TITANIUM mechanical properties decrease of present porosity too much causes again; And can regulate each porosity POROUS TITANIUM of control shared ratio in member according to the needs that the different parts bone is repaired mechanical property, prepare the gradient-structure porous titanium material that is complementary with natural bone, simultaneously, the pore structure of outer three-dimensional communication can impel osteocyte to grow into organizing well again, can be used as better bone reparation or replace and use embedded material, be applicable to embedded materials such as bone reparations such as preparing artificial bone, joint, root of the tooth, blade plate, screw or bone replacement.
Description of drawings
Fig. 1 is the sem photograph in the porous titanium material cross section of prior art (Comparative Examples) powder metallurgic method preparation.
Fig. 2 is the embodiment of the invention 4 Electronic Speculum figure of the porous titanium material partial cross section that successively increases of porosity from the inside to the outside; Labelling among Fig. 2: 1 is innermost layer, and 2 is outermost layer.
Fig. 3 is that POROUS TITANIUM body of the present invention is implanted into the grow into Electronic Speculum figure in cross section of test back bone; Labelling among Fig. 3: the 3rd, titanium granule, the 4th, osseous tissue.
The specific embodiment
Below in conjunction with the specific embodiment foregoing invention content of the present invention is described in further detail.
But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment.Not breaking away under the above-mentioned technological thought situation of the present invention, according to ordinary skill knowledge and customary means, make various replacements and change, all should comprise within the scope of the invention.
Embodiment 1
The present embodiment bio-medicinal porous titanium material comprises 15 layers, from the inside to the outside, its porosity successively increases, be followed successively by: (innermost layer) 0%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, (outermost layer) 70%, aperture are 100 μ m-300 μ m; The length that this material is is respectively the tabular of 30mm, 20mm, 10mm; Each layer thickness (in the same direction) is identical.
The method preparation of present embodiment bio-medicinal porous titanium material by comprising the steps:
(1), batch mixing:
The innermost layer porosity is that 0% part selects directly that mechanical property is higher, the Ti of good biocompatibility for use
6Al
7The Nb titanium alloy plate is a raw material; All the other each layers prepare raw material titanium valve (the atomizing sized spherical titanium powders of particle diameter 50 μ m) respectively according to above-mentioned porosity and particle diameter is the pore creating material (ammonium bicarbonate) of 100 μ m-300 μ m, and the usage ratio of pore creating material and raw material titanium valve is calculated according to the porosity of each layer respectively; With pore creating material and raw material titanium valve mix homogeneously, obtain pore creating material and raw material titanium valve composite;
(2), filling, pre-molding:
With the pore creating material behind step (1) batch mixing and raw material titanium valve composite from inside to outside successively layering be packed in the mould and (select for use length to be respectively 30mm, 20mm, 10mm tabular mould), each layer thickness (in the same direction) is identical, pre-molding obtains tabular base just;
(3), sinter molding:
The first base that step (2) pre-molding is obtained carries out vacuum high-temperature sintering in the vacuum-sintering system, about 1000 ℃ of sintering temperature, and insulation 30min obtains sintered body.
The pore creating material ammonium bicarbonate that adopts among this embodiment is a thermal decomposition type pore creating material, in the sinter molding process, pore creating material decomposes and being removed, the sintered body that obtains behind the sintering is the tabular porous titanium material that porosity from the inside to the outside successively increases, and its top layer has the three-dimensional communication pore structure.
By test, the comprcssive strength of this tabular porous titanium material reaches 160MPa, and elastic modelling quantity reaches 10GPa, is complementary with the compact bone mechanical property; Being implanted into test by body shows, the pore structure of top layer three-dimensional communication more help promoting osteoblast at the sticking of material surface, propagation, bone to differentiation function and final skeletonization effect, this material in vivo behind the Implantation Test bone grow into the cross section Electronic Speculum figure as shown in Figure 3.
The present embodiment bio-medicinal porous titanium material comprises 11 layers, from the inside to the outside, its porosity successively increases, and is followed successively by: (innermost layer) 0%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, (outermost layer) 50%, aperture are 50 μ m-200 μ m; The length that this material is is respectively the tabular of 30mm, 20mm, 10mm; Each layer thickness (in the same direction) is identical.
The method preparation of present embodiment bio-medicinal porous titanium material by comprising the steps:
(1), batch mixing:
Prepare raw material titanium valve (the spherical atomizing of the bio-medical of particle diameter 30 μ m titanium valves) respectively and particle diameter is the pore creating material (sodium chloride) of 50 μ m-200 μ m according to the different porosity of above-mentioned each layer, the usage ratio of pore creating material and raw material titanium valve is respectively according to the porosity calculating of each layer; With pore creating material and raw material titanium valve mix homogeneously, obtain pore creating material and raw material titanium valve composite;
(2), filling, pre-molding:
With the pore creating material behind step (1) batch mixing and raw material titanium valve composite from inside to outside successively layering be packed in the mould and (select for use length to be respectively 30mm, 20mm, 10mm tabular mould), each layer thickness (in the same direction) is identical, pre-molding obtains tabular base just;
(3), sinter molding:
The first base that step (2) pre-molding is obtained carries out sintering in the induction sintering system, about 800 ℃ of sintering temperature is incubated about 8min and obtains sintered body;
The pore creating material sodium chloride that adopts among this embodiment is water-soluble type pore creating material, in this step sintering process, pore creating material is heated and can decompose and still be retained in the sintered body that obtains behind the sintering, need carry out subsequent treatment, and promptly the described removal pore creating material of following steps (4) is handled:
(4), remove pore creating material:
Place 60 ℃ deionized water to dissolve 2h the sintered body that obtains behind the sintering in the step (3), wherein pore creating material sodium chloride is dissolved in water and be removed, water dissolution finishes, promptly obtain the tabular porous titanium material that porosity from the inside to the outside successively increases, and its top layer has the three-dimensional communication pore structure.
By test, the comprcssive strength of this tabular porous titanium material reaches 90MPa, and elastic modelling quantity reaches 1.3GPa, is complementary with the mechanical property of spongy bone, and the pore structure of top layer three-dimensional communication provides condition for the growing into of osteocyte of back that implant.
Embodiment 3
The present embodiment bio-medicinal porous titanium material comprises 10 layers, and from the inside to the outside, its porosity successively increases, and is followed successively by: (innermost layer) 0%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, (outermost layer) 90%, aperture are 200 μ m-400 μ m; This material is that diameter of section is the cylindric of 10mm, the high 20mm of being; Each layer thickness (in the same direction) is identical.
The method preparation of present embodiment bio-medicinal porous titanium material by comprising the steps:
(1), batch mixing:
Prepare raw material titanium valve (the atomizing sized spherical titanium powders of particle diameter 50 μ m) respectively and particle diameter is the pore creating material (carbamide) of 200 μ m-400 μ m according to the different porosity of above-mentioned each layer, the usage ratio of pore creating material and raw material titanium valve is calculated according to the porosity of each layer respectively; With pore creating material and raw material titanium valve mix homogeneously, obtain pore creating material and raw material titanium valve composite;
(2), filling, pre-molding:
With the pore creating material behind step (1) batch mixing and raw material titanium valve composite from inside to outside successively layering be packed in the mould (selecting for use the cross section internal diameter to be 10mm, highly to be the cylindrical mold of 20mm), each layer thickness (in the same direction) is identical, pre-molding obtains cylindric base just;
(3), sinter molding:
The first base that step (2) pre-molding is obtained carries out vacuum high-temperature sintering in the vacuum-sintering system, about 1300 ℃ of sintering temperature, and insulation 40min obtains sintered body.
The pore creating material carbamide that adopts among this embodiment is thermal decomposition type pore creating material, in the sinter molding process, pore creating material decomposes and being removed, the sintered body that obtains behind the sintering is the cylindric porous titanium material that porosity from the inside to the outside successively increases, and its top layer has the three-dimensional communication pore structure.
By test, the comprcssive strength of this cylindric porous titanium material reaches 150MPa, and elastic modelling quantity reaches 8GPa, is complementary with the natural bone mechanical property.
The present embodiment bio-medicinal porous titanium material comprises 5 layers, and from the inside to the outside, its porosity successively increases, and is followed successively by: (innermost layer) 0%, 10%, 30%, 50%, (outermost layer) 80%, aperture are 300 μ m-500 μ m; This material is that diameter of section is the cylindric of 10mm, the high 20mm of being; Each layer thickness (in the same direction) is identical.
The method preparation of present embodiment bio-medicinal porous titanium material by comprising the steps:
(1), batch mixing:
Prepare raw material titanium valve (the atomizing sized spherical titanium powders of particle diameter 50 μ m) respectively and particle diameter is the pore creating material (carbamide) of 300 μ m-500 μ m according to the different porosity of above-mentioned each layer, the usage ratio of pore creating material and raw material titanium valve is calculated according to the porosity of each layer respectively; With pore creating material and raw material titanium valve mix homogeneously, obtain pore creating material and raw material titanium valve composite;
(2), filling, pre-molding:
With the pore creating material behind step (1) batch mixing and raw material titanium valve composite from inside to outside successively layering be packed in the mould (selecting for use the cross section internal diameter to be 10mm, highly to be the cylindrical mold of 20mm), each layer thickness (in the same direction) is identical, pre-molding obtains cylindric base just;
(3), sinter molding:
The first base that step (2) pre-molding is obtained carries out vacuum high-temperature sintering in the vacuum-sintering system, about 1000 ℃ of sintering temperature, and insulation 60min obtains sintered body.
The pore creating material carbamide that adopts among this embodiment is thermal decomposition type pore creating material, in the sinter molding process, pore creating material decomposes and being removed, the sintered body that obtains behind the sintering is the cylindric porous titanium material that porosity from the inside to the outside successively increases, and its top layer has the three-dimensional communication pore structure.
By test, the comprcssive strength of this cylindric porous titanium material reaches 120MPa, and elastic modelling quantity reaches 5GPa, is complementary with the natural bone mechanical property.
Embodiment 5
The present embodiment bio-medicinal porous titanium material comprises 8 layers, and from the inside to the outside, its porosity successively increases, and is followed successively by: (innermost layer) 20%, 25%, 30%, 35%, 40%, 45%, 50%, (outermost layer) 55%, aperture are 200 μ m-400 μ m; This material is that diameter of section is the cylindric of 10mm, the high 20mm of being; Each layer thickness (in the same direction) is identical.
The method preparation of present embodiment bio-medicinal porous titanium material by comprising the steps:
(1), batch mixing:
Prepare raw material titanium valve (the atomizing sized spherical titanium powders of particle diameter 50 μ m) respectively and particle diameter is the pore creating material (TiH of 200 μ m-400 μ m according to the different porosity of above-mentioned each layer
2), the usage ratio of pore creating material and raw material titanium valve is calculated according to the porosity of each layer respectively; With pore creating material and raw material titanium valve mix homogeneously, obtain pore creating material and raw material titanium valve composite;
(2), filling, pre-molding:
With the pore creating material behind step (1) batch mixing and raw material titanium valve composite from inside to outside successively layering be packed in the mould (selecting for use the cross section internal diameter to be 10mm, highly to be the cylindrical mold of 20mm), each layer thickness (in the same direction) is identical, pre-molding obtains cylindric base just;
(3), sinter molding:
The first base that step (2) pre-molding is obtained carries out sintering in the induction sintering system, about 600 ℃ of sintering temperature, and insulation 10min obtains sintered body.
The pore creating material TiH that adopts among this embodiment
2For thermal decomposition type pore creating material, in the sinter molding process, pore creating material decomposes and being removed, the sintered body that obtains behind the sintering is the cylindric porous titanium material that porosity from the inside to the outside successively increases, and its top layer has the three-dimensional communication pore structure.
By test, the comprcssive strength of this cylindric porous titanium material reaches 160MPa, and elastic modelling quantity reaches 7GPa, is complementary with the natural bone mechanical property.
Embodiment 6
The present embodiment bio-medicinal porous titanium material comprises 2 layers, and from the inside to the outside, its porosity successively increases, and is followed successively by: (innermost layer) 10%, (outermost layer) 30%, aperture are 100 μ m-250 μ m; This material is that diameter of section is the cylindric of 10mm, the high 20mm of being; Each layer thickness (in the same direction) is identical.
The method preparation of present embodiment bio-medicinal porous titanium material by comprising the steps:
(1), batch mixing:
Prepare raw material titanium valve (the atomizing sized spherical titanium powders of particle diameter 50 μ m) respectively and particle diameter is the pore creating material (TiH of 100 μ m-250 μ m according to the different porosity of above-mentioned each layer
2), the usage ratio of pore creating material and raw material titanium valve is calculated according to the porosity of each layer respectively; With pore creating material and raw material titanium valve mix homogeneously, obtain pore creating material and raw material titanium valve composite;
(2), filling, pre-molding:
With the pore creating material behind step (1) batch mixing and raw material titanium valve composite from inside to outside successively layering be packed in the mould (selecting for use the cross section internal diameter to be 10mm, highly to be the cylindrical mold of 20mm), each layer thickness (in the same direction) is identical, pre-molding obtains cylindric base just;
(3), sinter molding:
The first base that step (2) pre-molding is obtained carries out sintering in the induction sintering system, about 1200 ℃ of sintering temperature, and insulation 5min obtains sintered body.
The pore creating material TiH that adopts among this embodiment
2For thermal decomposition type pore creating material, in the sinter molding process, pore creating material decomposes and being removed, the sintered body that obtains behind the sintering is the cylindric porous titanium material that porosity from the inside to the outside successively increases, and its top layer has the three-dimensional communication pore structure.
By test, the comprcssive strength of this cylindric porous titanium material reaches 150MPa, and elastic modelling quantity reaches 10GPa, is complementary with the natural bone mechanical property.
Embodiment 7
The present embodiment bio-medicinal porous titanium material comprises 4 layers, and from the inside to the outside, its porosity successively increases, and is followed successively by: (innermost layer) 40%, 50%, 60%, (outermost layer) 70%, aperture are 200 μ m-350 μ m; This material is that length is respectively 30mm, 20mm, 10mm tabular; Each layer thickness (in the same direction) is identical.
The method preparation of present embodiment bio-medicinal porous titanium material by comprising the steps:
(1), batch mixing:
Prepare raw material titanium valve (the atomizing sized spherical titanium powders of particle diameter 50 μ m) respectively and particle diameter is the pore creating material (sodium carbonate) of 200 μ m-350 μ m according to the different porosity of above-mentioned each layer, the usage ratio of pore creating material and raw material titanium valve is calculated according to the porosity of each layer respectively; With pore creating material and raw material titanium valve mix homogeneously, obtain pore creating material and raw material titanium valve composite;
(2), filling, pre-molding:
With the pore creating material behind step (1) batch mixing and raw material titanium valve composite from inside to outside successively layering be packed in the mould and (select for use length to be respectively 30mm, 20mm, 10mm tabular mould), each layer thickness (in the same direction) is identical, pre-molding obtains tabular base just;
(3), sinter molding:
The first base that step (2) pre-molding is obtained carries out vacuum high-temperature sintering in the vacuum-sintering system, about 800 ℃ of sintering temperature, and insulation 45min obtains sintered body.
The pore creating material sodium carbonate that adopts among this embodiment is water-soluble type pore creating material, in the sinter molding process, pore creating material is heated and can decompose and still be retained in the sintered body that obtains behind the sintering, need carry out subsequent treatment, and promptly the described removal pore creating material of following steps (4) is handled:
(4), remove pore creating material:
Place 100 ℃ deionized water to dissolve 1h the sintered body that obtains behind the sintering in the step (3), wherein pore creating material sodium carbonate is dissolved in water and be removed, water dissolution finishes, promptly obtain the tabular porous titanium material that porosity from the inside to the outside successively increases, and its top layer has the three-dimensional communication pore structure.
By test, the comprcssive strength of this tabular porous titanium material reaches 120MPa, and elastic modelling quantity reaches 6GPa, is complementary with the natural bone mechanical property.
Embodiment 8
The present embodiment bio-medicinal porous titanium material comprises 3 layers, and from the inside to the outside, its porosity successively increases, and is followed successively by: (innermost layer) 50%, 65%, (outermost layer) 80%, aperture are 250 μ m-400 μ m; This material is that length is respectively 30mm, 20mm, 10mm tabular; Each layer thickness (in the same direction) is identical.
The method preparation of present embodiment bio-medicinal porous titanium material by comprising the steps:
(1), batch mixing:
Prepare raw material titanium valve (the atomizing sized spherical titanium powders of particle diameter 50 μ m) respectively and particle diameter is the pore creating material (sodium carbonate) of 250 μ m-400 μ m according to the different porosity of above-mentioned each layer, the usage ratio of pore creating material and raw material titanium valve is calculated according to the porosity of each layer respectively; With pore creating material and raw material titanium valve mix homogeneously, obtain pore creating material and raw material titanium valve composite;
(2), filling, pre-molding:
With the pore creating material behind step (1) batch mixing and raw material titanium valve composite from inside to outside successively layering be packed in the mould and (select for use length to be respectively 30mm, 20mm, 10mm tabular mould), each layer thickness (in the same direction) is identical, pre-molding obtains cylindric base just;
(3), sinter molding:
The first base that step (2) pre-molding is obtained carries out sintering in the induction sintering system, about 700 ℃ of sintering temperature, and insulation 20min obtains sintered body.
The pore creating material sodium carbonate that adopts among this embodiment is water-soluble type pore creating material, in the sinter molding process, pore creating material is heated and can decompose and still be retained in the sintered body that obtains behind the sintering, need carry out subsequent treatment, and promptly the described removal pore creating material of following steps (4) is handled:
(4), remove pore creating material:
Place 20 ℃ deionized water to dissolve 2h the sintered body that obtains behind the sintering in the step (3), wherein pore creating material sodium carbonate is dissolved in water and be removed, water dissolution finishes, promptly obtain the tabular porous titanium material that porosity from the inside to the outside successively increases, and its top layer has the three-dimensional communication pore structure.
By test, the comprcssive strength of this flat board column porous titanium material reaches 130MPa, and elastic modelling quantity reaches 3GPa, is complementary with the natural bone mechanical property; The Electronic Speculum figure of its partial cross section as shown in Figure 2.
Comparative Examples
The porous titanium material (even pore distribution, its cross section Electronic Speculum figure as shown in Figure 1) that this Comparative Examples obtains for the powder metallurgic method preparation of adding pore creating material according to prior art, its concrete preparation method is: atomizing sized spherical titanium powder, particle diameter 30～50 μ m are adopted in experiment.Do pore creating material with ammonium bicarbonate, with titanium valve be the 1:1 mixing by volume, pre-molding obtains the cylindrical base substrate of Φ 10 * 10mm, adopts SPS-1050 type discharge plasma sintering system to carry out vacuum high-temperature sintering for 1200 ℃ then, insulation 20min obtains the POROUS TITANIUM sample.By test, the comprcssive strength 90MPa of this porous titanium material, the about 1.2GPa of elastic modelling quantity is lower than the natural bone mechanical property.
In the various embodiments described above, comprcssive strength and elastic modelling quantity data get by the test of INSTRON4034 type universal material experimental machine, and its assay method is with reference to the operation instruction of instrument.
Claims (10)
1. bio-medicinal porous titanium material, this porous titanium material comprises two-layer at least, and from the inside to the outside, its porosity successively increases, and the porosity of innermost layer is 0-50%, and outermost porosity is 30%-90%, pore size is 50 μ m-500 μ m.
2. bio-medicinal porous titanium material according to claim 1 is characterized in that:
Described porous titanium material comprises the 2-10 layer.
3. bio-medicinal porous titanium material according to claim 1 is characterized in that:
Described porous titanium material comprises the 3-5 layer.
4. according to each described bio-medicinal porous titanium material among the claim 1-3, it is characterized in that:
The outermost layer of described porous titanium material has the pore structure of three-dimensional communication.
5. according to each described bio-medicinal porous titanium material among the claim 1-4, it is characterized in that:
The innermost layer porosity of described porous titanium material is 0-40%; The outermost layer porosity is 50%-90%.
6. bio-medicinal porous titanium material according to claim 5 is characterized in that:
The innermost layer porosity of described porous titanium material is 0-20%; The outermost layer porosity is 70%-90%.
7. method for preparing the described bio-medicinal porous titanium material of claim 1 comprises following key step:
(1), batch mixing:
Prepare the raw material titanium valve respectively and size is the thermal decomposition type pore creating material of 50 μ m-, 500 μ m according to the predefined porosity of each layer, the usage ratio of pore creating material and raw material titanium valve is calculated according to the porosity of each layer respectively; With pore creating material and raw material titanium valve mix homogeneously, obtain pore creating material and raw material titanium valve composite;
(2), filling, pre-molding:
With the pore creating material behind step (1) batch mixing and raw material titanium valve composite from inside to outside successively layering be packed in the mould, pre-molding obtains base just;
(3), sinter molding:
The first base that step (2) pre-molding is obtained carries out sintering for 500 ℃-1300 ℃ in temperature, and insulation 5min-60min obtains sintered body and is the porous titanium material that porosity from the inside to the outside successively increases.
8. method for preparing the described bio-medicinal porous titanium material of claim 1 comprises following key step:
(1), batch mixing:
Prepare the raw material titanium valve respectively and size is the water-soluble type pore creating material of 50 μ m-500 μ m according to the predefined porosity of each layer, the usage ratio of pore creating material and raw material titanium valve is calculated according to the porosity of each layer respectively; With pore creating material and raw material titanium valve mix homogeneously, obtain pore creating material and raw material titanium valve composite;
(2), filling, pre-molding:
With the pore creating material behind step (1) batch mixing and raw material titanium valve composite from inside to outside successively layering be packed in the mould, pre-molding obtains base just;
(3), sinter molding:
The first base that step (2) pre-molding is obtained carries out sintering for 500 ℃-1300 ℃ in temperature, and insulation 5min-60min obtains sintered body;
(4), remove pore creating material:
The sintered body that obtains behind the sintering in the step (3) is placed deionized water, wherein water-soluble type pore creating material is dissolved in water and be removed, water solubility temperature is 20 ℃-100 ℃, water dissolution time 1h-2h, water dissolution finishes, and promptly obtains the porous titanium material that porosity from the inside to the outside successively increases.
9. according to claim 7 or 8 described methods, it is characterized in that:
Described porous titanium material innermost layer porosity is 0% o'clock, directly adopts the raw material of titanium alloy plate as innermost layer.
10. according to claim 7 or 8 described methods, it is characterized in that:
In the described step (3), sintering temperature is 800 ℃-1300 ℃, and temperature retention time is 10min-30min.
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