CN106421904A - Method for preparing porous implant through gelcasting 3D printing and electroreduction - Google Patents

Method for preparing porous implant through gelcasting 3D printing and electroreduction Download PDF

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CN106421904A
CN106421904A CN201610831706.1A CN201610831706A CN106421904A CN 106421904 A CN106421904 A CN 106421904A CN 201610831706 A CN201610831706 A CN 201610831706A CN 106421904 A CN106421904 A CN 106421904A
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porous
electroreduction
implant
support
moulding
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CN106421904B (en
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刘亚雄
伍言龙
赵广宾
陈旭
黄亚江
安超
李涤尘
贺健康
王玲
连芩
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Xian Jiaotong University
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Xian Jiaotong University
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
    • A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/10—Ceramics or glasses
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/56—Porous materials, e.g. foams or sponges
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/11—Making porous workpieces or articles
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/495—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
    • C04B38/063—Preparing or treating the raw materials individually or as batches
    • C04B38/0635—Compounding ingredients
    • C04B38/0645—Burnable, meltable, sublimable materials
    • C04B38/067—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
    • C04B41/5133—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal with a composition mainly composed of one or more of the refractory metals
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/88—Metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
    • C25C5/04—Electrolytic production, recovery or refining of metal powders or porous metal masses from melts
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/12—Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3251—Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof

Abstract

The invention discloses a method for preparing a porous implant through gelcasting 3D printing and electroreduction. The preparation method comprises steps as follows: according to the human body features of a to-be-implanted part, a personalized gradient porous implant negative-type mold adopting a microstructure is designed by the aid of a medical image data reverse solution model; a gradient porous implant negative-type resin mold is prepared through photo-curing forming equipment; metal oxide ceramic slurry is injected into the negative-type resin mold through a gel injection mold and sintered at the high temperature, and a metal oxide ceramic porous scaffold is obtained; a primary porous metal implant is produced through molten salt in-situ reduction; a metal coating is deposited on the surface of the primary porous metal implant with a chemical vapor deposition method. The defects that implants with complex shapes, precise sizes and uncontrollable microstructures cannot be produced with a traditional porous implant preparation method are overcome, structure nanosizing can be realized, and a new way for preparing the porous implant is expected to be developed.

Description

A kind of method that gel injection-moulding 3D printing and electroreduction prepare porous implant
Technical field
The present invention relates to a kind of method that gel injection-moulding 3D printing and electroreduction prepare porous implant, the method belongs to Biological increasing material manufacturing (3d printing) field, can be applicable to biologic medical field.
Background technology
Increasing material manufacturing has important application in medical domain, has incomparable particularly with the personalized implant of manufacture Advantage, future there are tens billion of potential markets.At present, rustless steel, titanium alloy and cobalt-base alloyss various metals material are entered The implant of row metal direct forming manufacture have been widely used for heart valve bracket, intravascular stent, alimentary stent and Bone Defect Repari and replacement support and other supports clinic, achieve preferable therapeutic effect.But the human internal environment of complexity can draw Play material corrosion and lead to the release of toxic element, thus leading to the biocompatibility of metal material and mechanical property to reduce.This Outward, current porous implant does not have controlled grand microcosmic integrated structure and nanorize structure：Rational design is macroscopical and micro- The integral structure seen can reduce the stress problem of porous implant, strengthens its mechanical property；Nanostructured not only contributes to Adhesion, the regeneration that can also promote osteocyte and the differentiation of internal osteocyte, improves the biocompatibility of implant.Increasing material manufacturing skill Art is capable of the control manufacture of the microcosmic gradient-structure of porous implant, and electrolytic reduction technology can form nanostructured.Cause How this, solve the problems, such as that porous implant microcosmic bionic gradient structure is uncontrollable and no nanostructured, prepare bio-compatible Property and all good porous implant of mechanical property be that it is applied to one of key issue of clinic.
The manufacture method of traditional porous metal implants mainly includes：Polymeric sponge method, pore creating material-powder sintered Method, vapour deposition process.But these process controllability differences are it is difficult to realize the personalization to implant macrostructure and the bionical ladder of microcosmic The active control of degree pore structure, and cannot shape nanostructured, and technique preparation flow is complicated in addition, investment is big, produce into This height.
Content of the invention
In order to overcome porous implant support microcosmic gradient-structure uncontrollable and the deficiencies such as nanostructured can not be formed, this Bright purpose is to provide a kind of method that gel injection-moulding 3D printing and electroreduction prepare porous implant, and the method is solid by light Chemical conversion shape, gel casting, reduction of fused salts technology and chemical vapour deposition technique combine, achievable microcosmic gradient knot The controlled shaping of structure, and shape nanostructured beneficial to cellular activity, improve the biocompatibility of porous implant, be expected to open up porous The new way of support preparation, significant for the clinical practice promoting porous implant.
For reaching above-mentioned purpose, present invention employs technical scheme below：
A kind of gel injection-moulding 3D printing and electroreduction prepare the method for porous implant it is characterised in that including as follows Step：
1) according to actual requirement, in three-dimensional software, then model is imported by the threedimensional model of construction coupling macrostructure Complete the threedimensional model design with gradient porous structure support minus mould in reverse software, there is inside it connecting pipe and bear Type structure；
2) use optical soliton interaction equipment preparation process 1) the middle gradient porous structure support negative resin mould designing；
3) prepare slurry, by mass ratio：Metal oxide ceramic spherical powder 40%～80%, solvent 5%～60%, have Machine monomer 5%～60%, cross-linking agent 0.005%～5%, dispersant 0.005%～5%, then add 0.0003%～0.1% and draw Send out agent and catalyst, mix homogeneously obtains slurry；
4) by step 3) be obtained slurry injection porous support negative resin mould in, be dried at room temperature for 24-48 hour；
5) by step 4) in dried slurry insert in high temperature sintering furnace together with porous support negative resin mould, Remove organic monomer and resin, obtain metal oxide ceramic porous support；
6) by step 5) be obtained metal oxide ceramic porous support insert in electrolysis of fused chloride salt reduction apparatus, enter The reduction of row in-situ electrolysis obtains primary porous metals support；
7) by step 6) be obtained primary porous metals support insert in vacuum high temperature furnace, high temperature burning is carried out to porous support Knot, finally utilizes the method for vapour deposition in porous scaffold surface deposited metal coating, obtains porous metals support.
The present invention is further improved by, step 1) in, using the many planes of CT or MRI of clinical patients pathological tissues Reconstruction image reconstruction group organization model in 3 d modeling software, designs the minus structure of gradient porous microstructure support, micro- See physical dimension and be 30-1000 μm.
The present invention is further improved by, step 3) in, metal oxide ceramic is refractory metals tantalum, titanium, niobium, beryllium Oxide ceramics, the sphere diameter of its spherical powder is 10-200 μm.Solvent is in deionized water, glycerol, dehydrated alcohol and acetone At least one；Monomer is at least one in acrylic, methacrylic acid group, acrylamido and ethyleneamino；Crosslinked Agent is N, N- dimethylene diacrylamine, N, in N- bis- acetonyl acrylamide and dibenzalacetone base acrylamide extremely Few one kind；Dispersant is sodium hexameta phosphate, Polyvinylpyrrolidone, sodium polyacrylate, Polyethylene Glycol and ammonium polyacrylate and lemon At least one in lemon acid ammonium；Initiator is many sodium sulfate, at least one in many potassium sulfate and many ammonium sulfate；Catalyst is N, N, N ' N '-tetramethylethylenediamine, N, N- dimethyl cyclohexyl amine and N, N, N ', N ", N " in-pentamethyl-diethylenetriamine at least one Kind.
The present invention is further improved by, step 5) in, described sintering process parameter is：First make 2 DEG C of intensification～ 30 DEG C/h, rise to 150 DEG C～400 DEG C from room temperature, be then incubated 0.5～5 hour；Again with 2 DEG C～30 DEG C/h rise to 500 DEG C～ 800 DEG C, it is incubated 0.5～5 hour；Finally rise to 1100 DEG C～1600 DEG C with 40 DEG C～200 DEG C/h, be incubated 2～5 hours；Insulation Close furnace power afterwards, be naturally down to room temperature and take out.
The present invention is further improved by, step 6) in, in-situ electrolysis reduction is prepared 5 during porous support) middle system Obtain metal oxide ceramic porous support molybdenum filament to pass through as cathod system；Carbon saturation copper in yttria-stabilized zirconia pipe Liquid is as anode system；In the graphite crucible equipped with fused salt mixt MgF2-GaF2 for the negative electrode insertion, protective gas is argon or helium Gas, electroreduction temperature is 500-1500 DEG C, and electrolysis time is 0.5-5h.
The present invention is further improved by, step 7) in, the temperature of sintered porous support is 1150-2500 DEG C, profit With the method for vapour deposition in porous scaffold surface deposited metal coating, reaction temperature is 500-2000 DEG C, and coating layer thickness is 10- 500 μm, reaction atmosphere is hydrogen.
The present invention is further improved by, step 7) in, obtaining final porous metal implants can be used as the artificial heart Dirty valve bracket, intravascular stent, alimentary stent and Bone Defect Repari and replacement support and other supports use.
The present invention compared with prior art has the advantage that：
1. this technology is by optical soliton interaction, gel casting, reduction of fused salts technology and chemical vapour deposition technique Combine, be capable of the shaping gradient pore structured to porous implant microcosmic and control.
2. the porous implant of preparation has macrostructure and the gradient micropore structure of personalization, and personalized customization is more Plus beneficial to patient's treatment.
3. the porous implant of preparation has nanostructured, beneficial to cellular activity, improves the biocompatibility of implant.
Specific embodiment
The method that a kind of gel injection-moulding 3D printing of the present invention and electroreduction prepare porous implant, including bionical ladder Degree loose structure design, optical soliton interaction, gel casting, reduction of fused salts and chemical vapor deposition four processes：
Described preparation method constructs the threedimensional model of coupling macrostructure in three-dimensional software, then model is imported reverse In software
Complete the threedimensional model design with gradient porous structure support minus mould, there is inside it connecting pipe minus Structure.
The minus structure design with gradient porous structure support is to be put down using CT or MRI of clinical patients pathological tissues more Face reconstruction image reconstruction group organization model in 3 d modeling software, designs the minus structure of gradient porous microstructure support, Microstructure sizes are 30-1000 μm.
Described preparation method uses the gradient porous structure support negative resin mould of optical soliton interaction equipment preparation design.
Described preparation method need to prepare slurry, by mass ratio：Metal oxide ceramic spherical powder 40%～80%, solvent 5%～60%, organic monomer 5%～60%, cross-linking agent 0.005%～5%, dispersant 0.005%～5%, then add 0.0003%～0.1% initiator and catalyst, mix homogeneously obtains slurry.
Preparing slurry and using metal oxide ceramic is refractory metals tantalum, the oxide ceramics of titanium, niobium or beryllium, its metal oxygen The sphere diameter of compound spherical powder is 10-200 μm, and solvent is at least one in deionized water, glycerol, dehydrated alcohol and acetone；Single Body is at least one in acrylic, methacrylic acid group, acrylamido and ethyleneamino；Cross-linking agent is N, and N- bis- is sub- Methyl diacrylamine, N, at least one in N- bis- acetonyl acrylamide and dibenzalacetone base acrylamide；Dispersion Agent is sodium hexameta phosphate, Polyvinylpyrrolidone, sodium polyacrylate, Polyethylene Glycol, in ammonium polyacrylate and ammonium citrate extremely Few one kind；Initiator is many sodium sulfate, at least one in many potassium sulfate and many ammonium sulfate；Catalyst is N, N, N ' N '-tetramethyl Base ethylenediamine, N, N- dimethyl cyclohexyl amine and N, N, N ', N ", N " and at least one in-pentamethyl-diethylenetriamine.
Described preparation method, by the slurry being obtained injection porous support negative resin mould, is dried at room temperature for 24-48 Hour.
Dried slurry is inserted high temperature sintering furnace together with porous support negative resin mould by described preparation method In, remove organic monomer and resin, obtain metal oxide ceramic porous support.
Sintering process parameter is：First make 2 DEG C of intensification～30 DEG C/h, rise to 150 DEG C～400 DEG C from room temperature, be then incubated 0.5 ～5 hours；Rise to 500 DEG C～800 DEG C with 2 DEG C～30 DEG C/h again, be incubated 0.5～5 hour；Finally with 40 DEG C～200 DEG C/h liter To 1100 DEG C～1600 DEG C, it is incubated 2～5 hours；Close furnace power after insulation, be naturally down to room temperature and take out.
The metal oxide ceramic porous support being obtained is inserted electrolysis of fused chloride salt reduction apparatus by described preparation method In, carry out in-situ electrolysis reduction and obtain primary porous metals support.
During in-situ electrolysis reduction preparation primary porous metals support, metal oxide ceramic porous support molybdenum filament is passed through As cathod system；Carbon saturation copper liquid in yttria-stabilized zirconia pipe is as anode system；Negative electrode insertion is molten equipped with mixing In the graphite crucible of salt MgF2-GaF2, protective gas is argon or helium, and electroreduction temperature is 500-1500 DEG C, electrolysis Time is 0.5-5h.
Primary porous metals support is inserted in vacuum high temperature furnace by described preparation method, high temperature sintering porous support, finally Using vapour deposition method in porous scaffold surface deposited metal coating, obtain porous metals support.
The temperature of sintered porous tantalum support is 1150-2500 DEG C, and the method using vapour deposition is sunk in porous scaffold surface Long-pending metal coating, reaction temperature is 500-2000 DEG C, and coating layer thickness is 10-500 μm, and reaction atmosphere is hydrogen.
Described obtain final porous support can be used as prosthetic heart valve holder, intravascular stent, alimentary stent and bone Repair and substitute support and other supports use.
Embodiment
A kind of method that gel injection-moulding 3D printing and electroreduction prepare porous implant, including bionic gradient loose structure Design, optical soliton interaction, gel casting, reduction of fused salts and chemical vapor deposition four processes：
With Ta2O5By the personalized porous tantalum implant that optical soliton interaction and electroreduction preparation have micro-nano structure it is Example.First in three-dimensional software, then model is imported and completes tool in reverse software by the threedimensional model of construction coupling macrostructure The threedimensional model having gradient porous structure support minus mould designs, and has connecting pipe minus structure inside it.Then use The gradient porous structure support negative resin mould of optical soliton interaction equipment preparation design.Prepare Ta2O5Spherical powder and solvent, have Machine monomer, cross-linking agent, the mixed slurry of dispersant.The slurry being obtained is injected in porous support negative resin mould, in room temperature Lower drying.Again dried slurry is inserted in high temperature sintering furnace together with porous support negative resin mould, remove organic Monomer and resin, obtain Ta2O5Porous support.The Ta that will be obtained2O5Porous support is inserted in molten chloride, carries out electricity in situ Solution reduction obtains primary porous tantalum support.Finally primary porous tantalum support is inserted in vacuum high temperature furnace, porous tantalum support is entered Row high temperature sintering, finally utilizes the method for vapour deposition in porous tantalum rack surface deposition of tantalum coating, obtains porous tantalum support.System Standby porous tantalum support has the macrostructure of personalization and controlled microstructure, inserts beneficial to personalization.
The minus structure design of gradient porous structure support, is put down using CT or MRI using clinical patients pathological tissues more Face reconstruction image reconstruction group organization model in 3 d modeling software, designs the minus structure of gradient porous microstructure support, Determine the minus physical dimension of gradient porous microstructure.Gradient porous microstructure negative is obtained using optical soliton interaction equipment Type resin scaffold.In mass ratio by Ta2O5Spherical powder, solvent, organic monomer, dispersant, cross-linking agent mix homogeneously obtain slurry. In the slurry cast negative resin support that will be obtained, it is dried, inserts in vacuum high temperature furnace, carry out heating up, protect according to sintering process Gentle cooling removes Ta2O5Impurity in porous support, obtains Ta2O5Porous support.Porous tantalum implantation is prepared in in-situ electrolysis reduction By Ta during thing2O5Porous implant is passed through as cathod system with molybdenum filament；Carbon saturation copper liquid in yttria-stabilized zirconia pipe is made For anode system；Negative electrode inserts equipped with fused salt mixt MgF2-GaF2Graphite crucible in, control electroreduction temperature, electrolysis time And protective gas.The porous tantalum implant that high temperature sintering electroreduction obtains, finally utilizes the method for vapour deposition in porous tantalum Implant surface deposition of tantalum coating, controlling reaction temperature, tantalum coating layer thickness and reaction atmosphere.Obtaining final porous tantalum implant can Use in the tissue to be implanted.

Claims (10)

1. a kind of gel injection-moulding 3D printing and electroreduction prepare the method for porous implant it is characterised in that including following Step：
1) medical image data of the physiology size, interior environmental characteristic and pathological changes situation according to diseased region to be implanted tissue, The threedimensional model of construction coupling macrostructure in three-dimensional software is then many with gradient by completing in model importing reverse software The threedimensional model design of pore structure support minus mould, has connecting pipe minus structure inside it；
2) use optical soliton interaction equipment preparation process 1) the middle gradient porous structure support negative resin mould designing；
3) prepare slurry, by mass ratio：Metal oxide ceramic spherical powder 40%～80%, solvent 5%～60%, You Jidan Body 5%～60%, cross-linking agent 0.005%～5%, dispersant 0.005%～5%, then add 0.0003%～0.1% initiator With catalyst, mix homogeneously obtains slurry；
4) by step 3) be obtained slurry injection porous support negative resin mould in, be dried at room temperature for 24-48 hour；
5) by step 4) in dried slurry insert in high temperature sintering furnace together with porous support negative resin mould, remove Organic monomer and resin, obtain metal oxide ceramic porous support；
6) by step 5) be obtained metal oxide ceramic porous support insert in electrolysis of fused chloride salt reduction apparatus, carry out former Position electroreduction obtains primary porous metals support；
7) by step 6) be obtained primary porous metals support insert in vacuum high temperature furnace, high temperature sintering is carried out to porous support, Finally utilize the method for vapour deposition in porous scaffold surface deposited metal coating, obtain porous metals support.
2. the method that a kind of gel injection-moulding 3D printing according to claim 1 and electroreduction prepare porous implant, its It is characterised by：Step 1) in, using clinical patients pathological tissues CT or MRI multiplanar reconstruction image in 3 d modeling software Reconstruction group organization model, designs the minus structure of gradient porous microstructure support, and microstructure sizes are 30-1000 μm.
3. the method that a kind of gel injection-moulding 3D printing according to claim 1 and electroreduction prepare porous implant, its It is characterised by：Step 3) in, metal oxide ceramic is refractory metals tantalum, the oxide ceramics of titanium, niobium or beryllium, its spherical flour gold The sphere diameter belonging to oxide is 10-200 μm.
4. the method that a kind of gel injection-moulding 3D printing according to claim 1 and electroreduction prepare porous implant, its It is characterised by, described solvent is at least one in deionized water, glycerol, dehydrated alcohol and acetone.
5. the method that a kind of gel injection-moulding 3D printing according to claim 1 and electroreduction prepare porous implant, its It is characterised by, organic monomer is at least one in acrylic, methacrylic acid group, acrylamido and ethyleneamino； Cross-linking agent is N, and N- dimethylene diacrylamine, N, in N- bis- acetonyl acrylamide and dibenzalacetone base acrylamide At least one.
6. the method that a kind of gel injection-moulding 3D printing according to claim 1 and electroreduction prepare porous implant, its Be characterised by, dispersant is sodium hexameta phosphate, Polyvinylpyrrolidone, sodium polyacrylate, Polyethylene Glycol or ammonium polyacrylate and At least one in ammonium citrate；Initiator is many sodium sulfate, at least one in many potassium sulfate and many ammonium sulfate.
7. the method that a kind of gel injection-moulding 3D printing according to claim 1 and electroreduction prepare porous implant, its It is characterised by, catalyst is N, N, N ' N '-tetramethylethylenediamine, N, N- dimethyl cyclohexyl amine and N, N, N ', N ", N " and-pentamethyl At least one in diethylenetriamine.
8. the method that a kind of gel injection-moulding 3D printing according to claim 1 and electroreduction prepare porous implant, its It is characterised by：Step 5) in, described sintering process parameter is：First make 2 DEG C of intensification～30 DEG C/h, from room temperature rise to 150 DEG C～ 400 DEG C, then it is incubated 0.5～5 hour；Rise to 500 DEG C～800 DEG C with 2 DEG C～30 DEG C/h again, be incubated 0.5～5 hour；Finally Rise to 1100 DEG C～1600 DEG C with 40 DEG C～200 DEG C/h, be incubated 2～5 hours；Close furnace power after insulation, be naturally down to room Temperature is taken out.
9. the method that a kind of gel injection-moulding 3D printing according to claim 1 and electroreduction prepare porous implant, its It is characterised by：Step 6) in, in-situ electrolysis reduction is prepared 5 during porous metals support) in be obtained metal oxide ceramic porous Support is passed through as cathod system with molybdenum filament；Carbon saturation copper liquid in yttria-stabilized zirconia pipe is as anode system；Negative electrode In the graphite crucible equipped with fused salt mixt MgF2-GaF2 for the insertion, protective gas is argon or helium, and electroreduction temperature is 500-1500 DEG C, electrolysis time is 0.5-5h.
10. the method that a kind of gel injection-moulding 3D printing according to claim 1 and electroreduction prepare porous implant, its It is characterised by：Step 7) in, the temperature of sintered porous support is 1150-2500 DEG C, and the method using vapour deposition is propped up in porous Frame surface deposited metal coating, reaction temperature is 500-2000 DEG C, and coating layer thickness is 10-500 μm, and reaction atmosphere is hydrogen.
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