CN109666820A - A kind of porous orthopaedics of outer layer of radial structure-function integration is implanted into material and its preparation method and application firmly - Google Patents
A kind of porous orthopaedics of outer layer of radial structure-function integration is implanted into material and its preparation method and application firmly Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/06—Titanium or titanium alloys
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/12—Phosphorus-containing materials, e.g. apatite
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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
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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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
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/54—Biologically active materials, e.g. therapeutic substances
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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
- A61L27/50—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
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- 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
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/002—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of porous nature
- B22F7/004—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of porous nature comprising at least one non-porous part
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0089—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with other, not previously mentioned inorganic compounds as the main non-metallic constituent, e.g. sulfides, glass
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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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
- A61L2300/112—Phosphorus-containing compounds, e.g. phosphates, phosphonates
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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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/412—Tissue-regenerating or healing or proliferative agents
-
- 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
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
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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
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/12—Materials or treatment for tissue regeneration for dental implants or prostheses
-
- 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
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/24—Materials or treatment for tissue regeneration for joint reconstruction
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- 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
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
Abstract
The invention discloses a kind of porous orthopaedics of outer layer of radial structure-function integration to be implanted into material and its preparation method and application firmly.By titanium, niobium, zirconium powder, mechanical ball mill obtains Ti-Nb-Zr composite powder to the present invention according to the ratio, titanium, niobium, zirconium and HA powder mechanical ball mill are obtained into TiNbZr-HA powder, then it is mixed with pore creating material ammonium hydrogencarbonate powder and obtains composite powder B, Ti-Nb-Zr composite powder and composite powder B pre-molding obtain radial grading structure cylindrical body green compact, finally obtain the orthopaedics using the sintering of pulse plasma activated sintering furnace and are implanted into material firmly.Orthopaedics provided by the invention is implanted into material firmly not only due to outer layer is porous structure, and it is added to bioactive ceramics HA, make composite material that there is good synosteosis, osseointegration character and be suitble to and the matched low elastic modulus of bone, also as the fine and close structure of core makes it have excellent compressive property, good artifical bone's tissue alternate material can be used as.
Description
Technical field
The present invention relates to orthopaedics to be implanted into technical field of biological medical material preparation more particularly to a kind of radial structure-function firmly
The integrated porous orthopaedics of outer layer of energy is implanted into material and its preparation method and application firmly.
Background technique
Elasticity modulus is one of the important performance for evaluating orthopaedics implantation bio-medical material, the elastic mould value of biomaterial
It is excessively high compared with the value of natural bone that biomethanics to be presented incompatible.The elastic mould value of biomaterial is excessively high, answers when receiving is outer
The effect of power, the material to meet with stresses and natural bone tissue are being implanted into since the difference of elasticity modulus will generate different strains
There is opposite displacement at the contact interface of material and natural bone tissue, to cause the loosening at combination interface, active time
It even causes to fall off when longer, influences the function of being implanted into repair materials, cause " stress shielding ", cause natural bone function of organization
It degenerates or absorbs.The introducing of pore structure can reduce biomaterial elasticity modulus, so that the elasticity modulus of material be allowed to meet certainly
Right bone tissue requirement.However, the introducing of pore structure will cause the mechanical property of material, the sharply evil of corrosion resistance in material
Change.Secondly, especially having both high intensity, low-density, height as the widest biomedical metallic material of purposes in implantation material
Anti-corrosion biological medical titanium alloy is a kind of inert material, and surface inactive lacks active repair function.In implantation human body
Afterwards, it is only simply mutually locked, is only wrapped by one layer of packing fiber, it is difficult to base between titanium alloy surface and matrix
Body tissue forms strong chemical synostosis, and long-time service can generate loose phenomenon, lead to graft failure, cause to patient
Great pain.
Application No. is 201711110765.0 Chinese patent applications to be related to a kind of imitative cancellous bone structure and ultralow springform
The artificial bone and preparation method of amount, this artificial bone by β phase and α phase compound porous of titanium alloy and hydroxyapatite
Network nano structure sodium titanate superficial layer composition.Described has holey nanostructure metatitanic acid sodium superficial layer and metal surface
In conjunction with the holey surface generated by titanium or titanium alloy surface and sodium hydroxide solution hydro-thermal reaction.The hydroxy-apatite
Stone is compound, is obtained by being soaked in simulated body fluid.The preparation method comprises the following steps: selecting foam of polymers, titanium and other metals to add first
Exquisite close titanium alloy artificial bone；Then there is the sodium titanate layer of porous network structure with the synthesis of alkali liquor hydrothermal method；Then will
Obtained artificial bone, is soaked in simulated body fluid；Finally by after above-mentioned artificial bone alcohol and deionized water elution, do
Dry, Preservation in sterile condition after disinfection is spare.The material that this application obtains is that axial layer spreads reticular structure, and compression strength is lower, for a long time
Being easy to happen variation using mechanical property causes to loosen, fall off even failure；Since the skeletal shape of body support's class is mostly not
Rule is rodlike, will greatly increase following process and implantation difficulty, and the preparation process sintering temperature using layer structure material
Higher, sintering time is longer, increases material preparation cost.
Summary of the invention
In view of the deficiencies of the prior art, the present invention, which provides, a kind of prepares radial junction using pulse plasma activated sintering technology
The porous orthopaedics of structure-function integration outer layer is implanted into material and its preparation method and application firmly, and it is pure and without nocuousness to obtain ingredient
Impurity, interface cohesion are good, pore structure is controllable and have the function of the radial structure-of good synosteosis and Integrated implant ability
Integrated separated aggregate is implanted into material firmly, meets on Orthopedic Clinical to hard implantation or reconstructed tissue and the regeneration of alternate material
It is required that for realize its clinically application Research foundation is provided.
First aspect present invention, the porous orthopaedics of outer layer for providing a kind of radial structure-function integration are implanted into material firmly
Preparation method the described method comprises the following steps:
Step (1) will be put into ball grinder after the weighing mixing of titanium (Ti), niobium (Nb) and zirconium (Zr) metal powder, be added anhydrous
Ball grinder is put into progress ball milling mixing powder on mechanical ball grinding machine after ethyl alcohol sealing, obtains Ti-Nb-Zr composite metal powder；
The part Ti-Nb-Zr composite metal powder and nanometer hydroxyapatite (HA) powder that step (2) obtains step (1)
End obtains TiNbZr-HA composite powder through mechanical ball mill；
TiNbZr-HA composite powder and pore creating material ammonium hydrogen carbonate are mixed through V-type batch mixer and obtain composite powder by step (3)
B；
The Ti-Nb-Zr composite metal powder that step (4) obtains step (1) is packed into layering compacting hard alloy steel mold
In, guarantee that core Ti-Nb-Zr composite metal powder is located at mold center position using fixator, filling is multiple around core green compact
Powder B cold moudling under axial is closed, pressure maintaining completes retrogressing mould and obtains cylindrical body green compact；
Cylindrical body green compact is placed in the graphite jig of pulse plasma activation furnace by step (5), is then placed in furnace and is taken out
Vacuum-sintering is taken, is cooled to room temperature after ladder heat-agglomerating and is moved back mould to obtain radial structure-function integration outer layer porous
Orthopaedics is implanted into material firmly.
Further, niobium (Nb) mass percent is 6~20%, zirconium (Zr) matter in the Ti-Nb-Zr composite metal powder
Measure percentage be 6~20%, surplus Ti；
The mass percent of Ti-Nb-Zr composite metal powder is 80~95%, HA in the TiNbZr-HA composite powder
The mass percent of powder is 5~20%；
The mass percent of TiNbZr-HA composite powder is 70~90%, pore creating material ammonium hydrogen carbonate in the composite powder B
Mass percent be 10~30%.
Further, the titanium, niobium, zirconium metal powder purity >=99.9%, powder average particle size≤50 μm；Institute
State purity >=99.8% of hydroxyapatite, powder average particle size≤100nm；The purity of pore creating material ammonium hydrogen carbonate powder is analysis
Pure, powder average particle size is 100~500 μm.
Further, step (1) Mechanical Milling Process are as follows: titanium, niobium and zirconium metal powder are put into hard alloy ball mill
In tank, big ball is added: (additive amount of dehydrated alcohol floods the stainless steel ball and dehydrated alcohol of bead=1.5~2.5:1 (mass ratio)
Do not have powder and ball milling ball), material ball ratio is 4~6:1, and sealing is put into ball mill and carries out 5~20 hours mechanical ball mills, ball milling
Machine 200~600r/min of revolving speed, mixed slurry is dry in a vacuum drying oven after ball milling obtains Ti-Nb-Zr composite metal powder.
Further, step (2) Mechanical Milling Process are as follows: part Ti-Nb-Zr composite metal powder in step (1) exists
Hydroxyapatite bioactive ceramics are added after the completion of ball milling, sealing continues ball milling 2~5 hours in the ball mill, and ball mill turns
200~600r/min of speed, mixed slurry is dry in a vacuum drying oven after ball milling obtains TiNbZr-HA composite powder.
Further, step (3) mixing process are as follows: by the TiNbZr-HA composite powder being dried to obtain in step (2) with
Pore creating material ammonium hydrogen carbonate powder is put into 10~30min of mixing in V-type batch mixer after weighing by required porosity, V-type batch mixer
Revolving speed is 50~150r/min.
Further, step (4) cold moudling apply axial compressive force be 100~400MPa, the dwell time be 20~
40min。
Further, the ladder heat-agglomerating process are as follows: in pulse plasma activated sintering furnace after vacuum degree≤20Pa
Be heated to 150 DEG C with the rate of 50~100 DEG C/min, after heat preservation 3-10min makes pore creating material ammonium hydrogen carbonate sufficiently volatilize, continuation with
The rate of 60~250 DEG C/min is heated to 750~950 DEG C of sintered target temperature, and 3~15min is kept the temperature on target temperature,
Then it is cooled to room temperature with the cooling rate of 50~100 DEG C/min.
Second aspect of the present invention provides the porous orthopaedics that the preparation method obtains and is implanted into material firmly.
Third aspect present invention provides the application that the porous orthopaedics is implanted into material firmly.Using the method for the present invention preparation
The porous orthopaedics of radial structure-function integration outer layer is implanted into material firmly can be used as the artificial bone tissue implantation material of ideal bearing
Material is suitable for the materials such as preparation dental implant, joint prosthesis, bone wound product, and prepares work used by the method for the present invention
Skill is easy to operate, preparation of industrialization easy to accomplish.
The features of the present invention is as follows: the method for the invention prepares the porous bone of radial structure-function integration outer layer
Section is implanted into material firmly, and composite material core is in densifie state, keeps good mechanical property to provide necessary guarantee for material；It is compound
Material radial outer is porous TiNbZr-HA, and radial porous layer provides the association of high porosity and high bioactivity for implantation material
Same-action, wherein porous structure is the adherency of osteocyte, and new bone grows into offer space environment, and there are also be implanted into material internal structure
Capillary form vascularization and antimetabolic agent conveying, and form synosteosis and integration with bone tissue；Biology is living
Property ceramics HA addition reinforcing material bioactivity and Integrated implant ability, improve and improve implantation material and implantation body tissue it
Between synosteosis and Integrated implant, thus effectively repair, reconstruct bone tissue physiological function.Using pulse direct current activated sintering legal system
Standby artifical bone's organization material, sintering temperature is low, and sintering time is short, energy-efficient, does not need binder, environmentally protective.In addition, this
Invention by control Ti, Nb, Zr and HA proportion and sintering condition so that finally obtained bone material ectonexine faying face without
Apparent crack defect is presented metallurgy type and combines, to improve and improve material mechanical performance, low elastic modulus and bioactivity
Between Collaborative Control.
Compared with prior art, the invention has the following advantages:
(1) present invention is proposed using with good biocompatibility and high-intensitive, high-corrosion resistance Ti-Nb-Zr
Alloy is as core material, and radial outer Ti-Nb-Zr alloy introduces pore structure and bioactive ceramics HA, and preparation is radial
The porous orthopaedics of the integrated outer layer of structure-function is implanted into material firmly.Wherein, core Ti-Nb-Zr alloy provides necessity for material
Mechanical support, porous (the Ti-Nb-Zr)-HA of outer layer provides low elastic modulus and good synosteosis, Integrated implant for material
Energy.Meanwhile give full play to pulse plasma activated sintering technology prepare material heating speed it is fast, soaking time is short, prepared
Journey facilitates the advantages that cleaning, keeps the pore structure characteristic and bioactivity ability of material to greatest extent.
(2) the method for the invention prepares the porous orthopaedics of radial structure-function integration outer layer and is implanted into material system firmly
It is waved without addition powder adhesive or template, outer layer porous layer by the decomposition of nontoxic ammonium hydrogen carbonate during standby
It carrys out the coffin upon burial into pore structure, guarantees noresidue, the inorganization harmfulness of biomaterial.
(3) the method for the invention prepares the porous orthopaedics of radial structure-function integration outer layer and is implanted into material firmly
Compression strength is 163~481MPa, and the compression strength of bone is 100~230MPa, mechanical strength needed for meeting implantation material；Material
The elasticity modulus of material is 13~42GPa, and elasticity modulus≤30Gpa of bone, the two biomethanics matching is preferable, can effectively mitigate
" stress shielding " phenomenon caused by being mismatched because of biomethanics, implantation material is avoided to loosen under long-term stress service state,
It falls off and even fails.
(4) the method for the invention prepares the porous orthopaedics of radial structure-function integration outer layer and is implanted into material firmly
Basis material is Ti, Nb, Zr metal, this three kinds of metallic elements do not have cell and tissue poison to human body under long-term implanting state
Property effect.
Detailed description of the invention
Fig. 1 is titanium, niobium, zirconium metal powder scanning electron microscopy shape appearance figure and HA transmission electron microscopy shape appearance figure；
Fig. 2 is composite material in radial shape appearance figure after pulse plasma activated sintering；
Fig. 3 is composite material outside and core combination interface scanning electron microscopy pattern after pulse plasma activated sintering
Figure；
Fig. 4 is 7 days immersion rear surface shape appearance figures of composite material Artificial Bodys；
Fig. 5 is different HA content composite material combination interface shape appearance figures.
Specific embodiment
Technical solution of the present invention is described in further detail with reference to the accompanying drawings and detailed description, but the present invention
Protection scope be not limited to content as described below.
Embodiment 1
The present embodiment provides the preparation sides that a kind of porous orthopaedics of outer layer of radial structure-function integration is implanted into material firmly
Method, specifically includes the following steps:
(1) Ti:74% is pressed, the mass percent of Nb:20%, Zr:6%, weighing purity respectively in vacuum glove box is
99.9%, 50 μm of average grain diameter of Ti, Nb, Zr metal powder (titanium, niobium, zirconium metal powder scanning electron microscopy shape appearance figure and HA
Transmission electron microscopy shape appearance figure is as shown in Figure 1)；Ti, Nb, Zr metal powder of weighing are put into hard alloy steel ball grinder, are added
Enter ball milling dispersing agent dehydrated alcohol, stainless steel ball abrading-ball is added by ratio of grinding media to material 4:1 (mass ratio), wherein stainless steel ball abrading-ball is big
Bead ratio is 2:1 (mass ratio).Assembly finishes sealed shell of tank, which carries out operation completion in vacuum glove box；
(2) sealed shell of tank of step (1) is put into ball mill and carries out the mixed powder of ball milling, mechanical ball mill parameter are as follows: revolving speed:
300r/min, Ball-milling Time: 10 hours.Mixed slurry dry acquisition Ti- in a vacuum drying oven in part is taken out after ball milling
Nb-Zr composite metal powder；
It (3) is 99.99% by part mixed slurry in step (2) and purity, average grain diameter≤100nm HA powder warp
Mechanical ball mill obtains TiNbZr-HA composite powder, drum's speed of rotation 200r/min, and ball milling 5 hours, in TiNbZr-HA composite powder
In end, the mass percent of Ti-Nb-Zr composite metal powder is 90%, the mass percent of HA powder is 10%；
(4) the pore creating material ammonium hydrogen carbonate for being 100~500 μm by step (2) TiNbZr-HA composite powder and particle diameter distribution
(NH5CO3) through V-type batch mixer mixing acquisition composite powder B, the revolving speed of V-type batch mixer is 50r/min, mixing 30min, multiple
It closes in powder B, the mass percent of TiNbZr-HA composite powder is 90%, NH5CO3The mass percent of pore creating material is 10%；
(5) prepare radial structure-function integration composite material entirety green compact: the Ti-Nb-Zr that step (1) is obtained is multiple
It closes metal powder to be fitted into layering compacting hard alloy steel mold, guarantees core Ti-Nb-Zr composite metal powder using fixator
Last bit inserts composite powder B cold moudling 30min at axial compressive force 200MPa around mold center position, core green compact,
30min pressure maintaining completes retrogressing mould and obtains radial structure-function integration composite material entirety green compact；
(6) radial structure-function integration composite material entirety green compact that step (5) obtain pulse plasma is placed in live
In the graphite jig for changing furnace, be then placed in furnace and extract vacuum-sintering, in furnace vacuum degree≤20Pa continue to sintering to complete with
So that sintering process is since the gas that pore creating material ammonium bicarbonate breaks down generates quickly volatilizees, ladder heat-agglomerating process are as follows: with 50
DEG C/rate of min is heated to 150 DEG C, heat preservation 5min makes after pore creating material ammonium hydrogen carbonate sufficiently volatilize in material, continuation with 150 DEG C/
The rate of min is heated to 850 DEG C of target firing temperature, and 8min is kept the temperature on target temperature, then with 50 DEG C/min cooling
Speed is cooled to room temperature, and agglomerated material moves back mould from graphite jig and obtains the porous orthopaedics of radial structure-function integration outer layer
Hard implantation material.
Fig. 2 is implanted into material for the porous orthopaedics of radial structure-function integration outer layer after pulse plasma activated sintering firmly
Macro morphology figure, from figure 2 it can be seen that material shows apparent radially layered structure, wherein fine and close group is presented in core
Structure is knitted, porous structure is presented in radial outer.Fig. 3 is composite material outside boundary in conjunction with core after pulse plasma activated sintering
Surface scan electron microscopic shape appearance figure, as can be seen from Figure 3 metallurgy type combination is presented in combination interface between material ectonexine, to plant
Enter material and provides guarantee in stress load bearing process mechanics synergistic effect.Observe the pore character (as shown in Figure 2,3) of material, sample
Middle hole is uniformly distributed in the radially outer porous layer of material, and pore-size distribution meets pore creating material between 100~500 μ ms
The pore-size that volatilization leaves is decomposed in sintering process.This pore character is conducive to adherency growth and the tissue fluid of osteoblast
Flowing and transport.Using GB/T7314-2017 " metal material room temperature compression test method " to the mechanics of composite sample
Performance is tested.Mechanical test results show: prepared radial structure-function integration separated aggregate is implanted into material firmly
Compression strength is 386MPa, and the compression strength of natural bone tissue is 100~230MPa, mechanics needed for meeting implantation material
Intensity；The elasticity modulus that radial structure-function integration separated aggregate is implanted into material firmly is 27GPa, and natural bone tissue
Elasticity modulus≤30Gpa, the two biomethanics matching is preferable, caused by capable of effectively mitigating because biomethanics mismatches between the two
Primary bone tissue bone resorption, avoid " stress shielding " phenomenon.
Material is implanted into firmly to the integrated separated aggregate of radial structure-function using 7 days Soak Tests of Artificial Bodys
Rapid biological filter characterized, impregnate rear surface shape appearance figure it is as shown in Figure 4.From mineralising result it can be found that by
The introducing of bioactive ceramics HA in composite material in radial surface, one layer of mineralising white mine of radial porous layer surface deposition of material
Substance is osteoid apatite by EDS energy spectrum analysis；But composite material core tight section does not deposit osteoid apatite object
Matter.Contrast material core compacted zone is with external porous surface sediments the result shows that the addition of bioactive ceramics HA can effectively improve
Radial structure-function integration separated aggregate is implanted into bioactivity (biomineralization) ability of material firmly.
The above results show can be by introducing porous structure and HA active ceramic in radial surface in the way of this patent
The case where prepare have be suitble to the matched low elastic modulus of bone and good synosteosis, osseointegration character, also as core
The fine and close structure in portion makes it have excellent compressive property, can be used as good artifical bone's tissue alternate material.
Embodiment 2
The present embodiment provides a kind of radial ingredient is consistent, the porous orthopaedics of the outer layer of structure change is implanted into the preparation side of material firmly
Method, specifically includes the following steps:
(1) Ti:70% is pressed, the mass percent of Nb:17%, Zr:13%, weighing purity respectively in vacuum glove box is
99.9%, 50 μm of average grain diameter of Ti, Nb, Zr metal powder；Ti, Nb, Zr metal powder of weighing are put into hard alloy steel ball
In grinding jar, ball milling dispersing agent dehydrated alcohol is added, stainless steel ball abrading-ball is added by ratio of grinding media to material 4:1 (mass ratio), wherein stainless steel
The sizes of balls ratio of ball milling ball is 2:1 (mass ratio).Assembly finishes sealed shell of tank, which is grasped in vacuum glove box
It completes；
(2) sealed shell of tank of step (1) is put into ball mill and carries out the mixed powder of ball milling, mechanical ball mill parameter are as follows: revolving speed:
300r/min, Ball-milling Time: 10 hours.Mixed slurry dry acquisition Ti- in a vacuum drying oven in part is taken out after ball milling
Nb-Zr composite metal powder；
It (3) is 99.99% by part Ti-Nb-Zr composite metal powder in step (2) and purity, average grain diameter≤100nm
HA powder obtain TiNbZr-HA composite powder, drum's speed of rotation 400r/min, ball milling 3h, in composite powder through mechanical ball mill
In, the mass percent of Ti-Nb-Zr composite metal powder is 95%, the mass percent of HA powder is 5%；
(4) the pore creating material ammonium hydrogen carbonate for being 100~500 μm by step (2) TiNbZr-HA composite powder and particle diameter distribution
(NH5CO3) through V-type batch mixer mixing acquisition composite powder B, the revolving speed of V-type batch mixer is 100r/min, mixing 30min, multiple
It closes in powder B, the mass percent of TiNbZr-HA composite powder is 85%, NH5CO3The mass percent of pore creating material is 15%；
(5) prepare radial structure-function integration composite material entirety green compact: the Ti-Nb-Zr that step (1) is obtained is multiple
It closes metal powder to be fitted into layering compacting hard alloy steel mold, guarantees core Ti-Nb-Zr composite metal powder using fixator
Composite powder B cold moudling 60min at axial compressive force 350MPa is inserted around mold center position, core green compact, is protected
Pressure completes retrogressing mould and obtains radial structure-function integration composite material entirety green compact；
(6) radial structure-function integration composite material entirety green compact that step (5) obtain pulse plasma is placed in live
In the graphite jig for changing furnace, be then placed in furnace and extract vacuum-sintering, in furnace vacuum degree≤20Pa continue to sintering to complete with
So that sintering process is since the gas that pore creating material ammonium bicarbonate breaks down generates quickly volatilizees, ladder heat-agglomerating process are as follows: with 75
DEG C/rate of min is heated to 150 DEG C, heat preservation 5min makes after pore creating material ammonium hydrogen carbonate sufficiently volatilize in material, continuation with 100 DEG C/
The rate of min is heated to 950 DEG C of target firing temperature, and 5min is kept the temperature on target temperature, then cooling down to room temperature,
Agglomerated material moves back mould from graphite jig and obtains the porous orthopaedics of radial structure-function integration outer layer is implanted into material firmly.
By step in the present embodiment (1) and the identical process conditions of step (2), Ti-Nb-Zr composite metal powder is distinguished
The HA powder metallographic for being 10%, 15%, 20% with mass percent weighs and ball milling；Again by identical technique item in the present embodiment
Part sintering prepares the composite material of the porous difference HA content of radial surface.Using GB/T7314-2017, " metal material room temperature is compressed
Test method " material is implanted into firmly to radial structure-function integration separated aggregate under difference HA additive amount in embodiment
Mechanical property is detected, and the results are shown in Table 1 for the elasticity modulus and compression strength of material.
Table .1 difference HA content composite materials property test data
| HA content (wt.%) | Elasticity modulus (GPa) | Compression strength (MPa) | Porosity (%) |
| 5 | 23.2 | 348.5 | 39.6 |
| 10 | 22.9 | 333.2 | 41.2 |
| 15 | 21.7 | 318.8 | 42.6 |
| 20 | 21.4 | 312.6 | 42.9 |
Using GB/T7314-2017 " metal material room temperature compression test method " to integrated point of radial structure-function
The mechanical property that grade orthopaedics is implanted into material sample firmly is tested.Mechanical test results show: prepared radial structure-function
Integrated separated aggregate is implanted into material compression strength range between 312.6~348.5MPa firmly, and natural bone tissue is anti-
Compressive Strength is 100~230MPa, mechanical strength needed for compression strength meets implantation material；The composite wood of different HA additive amounts
The elasticity modulus range of material is 21.4~23.2GPa, and natural bone tissue elasticity modulus≤30Gpa, the matching of the two biomethanics
Property it is preferable, can effectively mitigate the bone resorption of primary bone tissue caused by mismatching because of biomethanics between the two, avoid " stress screen
Cover " phenomenon.From the results, it was seen that the elasticity modulus of composite material is on a declining curve, pressure resistance with the rising of HA additive amount
Degree is also on a declining curve, and porosity is in rising trend.
Using scanning electron microscope (SEM) to radial structure-function integration separated aggregate of different HA additive amounts
Hard implantation material transversal cross-section is observed (as shown in Figure 5).SEM the result shows that difference HA additive amount composite material core
All present higher consistency；The radial porous outer layer of composite material due to pore creating material ammonium hydrogen carbonate pyrolytic, volatilization
And it produces and is uniformly distributed, the pore structure characteristic that the internal macropore aperture being mutually communicated has both.Result can from Fig. 5
Out, different HA contents between the core compacted zone and outer layer porous layer of composite material without apparent combination interface or transition circle
The influence in face, and combine between the two without apparent crack defect, between ectonexine and metallurgy type is presented combines, it is composite material
Mechanics synergisticing performance provide sound assurance.Porous layer is presented macropore, aperture and deposits outside the composite material of different HA contents,
This pore structure characteristic is conducive to osteoblast adherency and increment.Moreover, perforation is presented between macropore aperture between macropore
The connected three-dimensional netted feature of biology, the connected reticular structure feature of this three-dimensional perforation on the one hand can for body fluid flowing,
It is the adherency of osteoblast and capillary and newborn；On the other hand work as implantation material during bearing stress deforms, three
Dimension perforation connected big fine-structure mesh shape structure feature energy buffer portion energy and cooperative transformation.
Claims (10)
1. a kind of porous orthopaedics of outer layer of radial structure-function integration is implanted into the preparation method of material firmly, it is characterised in that: institute
State method the following steps are included:
Step (1) will be put into ball grinder after the weighing mixing of titanium (Ti), niobium (Nb) and zirconium (Zr) metal powder, add dehydrated alcohol
Ball grinder is put into progress ball milling mixing powder on mechanical ball grinding machine after sealing, obtains Ti-Nb-Zr composite metal powder；
Part Ti-Nb-Zr composite metal powder and nanometer hydroxyapatite (HA) the powder warp that step (2) obtains step (1)
Mechanical ball mill obtains TiNbZr-HA composite powder；
TiNbZr-HA composite powder and pore creating material ammonium hydrogen carbonate are mixed through V-type batch mixer and obtain composite powder B by step (3)；
The Ti-Nb-Zr composite metal powder that step (1) obtains is fitted into layering compacting hard alloy steel mold by step (4), benefit
Guarantee that core Ti-Nb-Zr composite metal powder is located at mold center position with fixator, inserts composite powder around core green compact
B cold moudling under axial, pressure maintaining complete retrogressing mould and obtain cylindrical body green compact；
Cylindrical body green compact is placed in the graphite jig of pulse plasma activation furnace by step (5), is then placed in furnace and is extracted true
Sky sintering, is cooled to room temperature after ladder heat-agglomerating and moves back mould and obtain the porous orthopaedics of radial structure-function integration outer layer
Hard implantation material.
2. the porous orthopaedics of radial structure-function integration outer layer is implanted into the preparation method of material firmly according to claim 1,
It is characterized by: niobium (Nb) mass percent is 6~20%, zirconium (Zr) quality percentage in the Ti-Nb-Zr composite metal powder
Than for 6~20%, surplus Ti；
The mass percent of Ti-Nb-Zr composite metal powder is 80~95%, HA powder in the TiNbZr-HA composite powder
Mass percent be 5~20%；
The mass percent of TiNbZr-HA composite powder is the matter of 70~90%, pore creating material ammonium hydrogen carbonate in the composite powder B
Measuring percentage is 10~30%.
3. the porous orthopaedics of radial structure-function integration outer layer is implanted into the preparation method of material firmly according to claim 1,
It is characterized by: the titanium, niobium, zirconium metal powder purity >=99.9%, powder average particle size≤50 μm；The hydroxyl
Purity >=99.8% of apatite, powder average particle size≤100nm；The purity of pore creating material ammonium hydrogen carbonate powder is to analyze pure, powder
Last average grain diameter is 100~500 μm.
4. the porous orthopaedics of radial structure-function integration outer layer is implanted into the preparation method of material firmly according to claim 1,
It is characterized by: step (1) Mechanical Milling Process are as follows: titanium, niobium and zirconium metal powder are put into hard alloy steel ball grinder, added
Enter big ball: the stainless steel ball and dehydrated alcohol of bead=1.5~2.5:1 (mass ratio), 4~6:1 of material ball ratio, sealing is put into ball milling
Machine carries out 5~20 hours mechanical ball mills, 200~600r/min of drum's speed of rotation, and mixed slurry is in a vacuum drying oven after ball milling
It is dry to obtain Ti-Nb-Zr composite metal powder.
5. the porous orthopaedics of radial structure-function integration outer layer is implanted into the preparation method of material firmly according to claim 1,
It is characterized by: step (2) Mechanical Milling Process are as follows: part Ti-Nb-Zr composite metal powder in step (1) is complete in ball milling
At rear addition hydroxyapatite bioactive ceramics, seals and continue ball milling 2~5 hours in the ball mill, drum's speed of rotation 200~
600r/min, mixed slurry is dry in a vacuum drying oven after ball milling obtains TiNbZr-HA composite powder.
6. the porous orthopaedics of radial structure-function integration outer layer is implanted into the preparation method of material firmly according to claim 1,
It is characterized by: step (3) mixing process are as follows: by the TiNbZr-HA composite powder being dried to obtain in step (2) and pore creating material carbon
Sour hydrogen ammonium powder is put into 10~30min of mixing in V-type batch mixer after weighing by required porosity, the revolving speed of V-type batch mixer is 50
~150r/min.
7. the porous orthopaedics of radial structure-function integration outer layer is implanted into the preparation method of material firmly according to claim 1,
It is characterized by: it is 100~400MPa that step (4) cold moudling, which applies axial compressive force, the dwell time is 20~40min.
8. the porous orthopaedics of radial structure-function integration outer layer is implanted into the preparation method of material firmly according to claim 1,
It is characterized by: the ladder heat-agglomerating process are as follows: in pulse plasma activated sintering furnace after vacuum degree≤20Pa with 50~
The rate of 100 DEG C/min is heated to 150 DEG C, after heat preservation 3-10min makes pore creating material ammonium hydrogen carbonate sufficiently volatilize, continuation with 60~
The rate of 250 DEG C/min is heated to 750~950 DEG C of sintered target temperature, and 3~15min is kept the temperature on target temperature, then
It is cooled to room temperature with the cooling rate of 50~100 DEG C/min.
9. a kind of porous orthopaedics that the preparation method any according to claim 1~8 obtains is implanted into material firmly.
10. the application that a kind of porous orthopaedics according to claim 9 is implanted into material firmly.
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