CN106421892A - Titanium-based tantalum coating bio-scaffold material and preparation method thereof - Google Patents
Titanium-based tantalum coating bio-scaffold material and preparation method thereof Download PDFInfo
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- CN106421892A CN106421892A CN201610877672.XA CN201610877672A CN106421892A CN 106421892 A CN106421892 A CN 106421892A CN 201610877672 A CN201610877672 A CN 201610877672A CN 106421892 A CN106421892 A CN 106421892A
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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
- A61L27/28—Materials for coating prostheses
- A61L27/30—Inorganic materials
- A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
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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
- A61L27/56—Porous materials, e.g. foams or sponges
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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
- A61L2430/02—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
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Abstract
The invention provides a titanium-based tantalum coating bio-scaffold material. The titanium-based tantalum coating bio-scaffold material comprises a titanium alloy matrix; a tantalum coating is attached to the surface of the titanium alloy matrix, the thickness of the tantalum coating is controlled to range from 3 micrometers to 150 micrometers, and the elasticity modulus of the titanium-based tantalum coating scaffold is controlled to range from 10 GPa to 30 GPa. A preparation method includes the steps that the form and structure of the titanium alloy matrix are determined according to a three-dimensional result established with the digital scanning and three-dimensional reconstruction technology, metal 3D printing rapid prototyping manufacturing is carried out, tantalum powder is subjected to ball milling and melting, the titanium alloy matrix is subjected to plasma spraying treatment, and then the titanium-based tantalum coating bio-scaffold material is obtained. The titanium-based tantalum coating scaffold solves the problem of stress shielding of artificial scaffold materials fundamentally, the personalized artificial scaffold material matched with a defect in form and structure is prepared through 3D printing rapid prototyping, and the good biocompatibility of tantalum is utilized.
Description
Technical field
The present invention relates to medical metal material process for modifying surface field, in particular to a kind of life of titanio tantalum coating
Thing timbering material and preparation method thereof.
Background technology
The man-made support matrix material clinically commonly used is mainly titanium alloy support, and its intensity and processing characteristics are superior to
Pure titanium, but long-term clinical practice proves, and titanium is had big difference with the elastic modelling quantity of osseous tissue, and " stress shielding " will be caused to imitate
Should, Artificial Intervention material, with the prolongation of use time, leads to implant to loosen or ruptures, cause repairing failure.So-called stress
Screen effect refer to the different material of two elastic modelling quantity simultaneously stress when, the high material of elastic modelling quantity can bear more should
Power, for example, the elastic modelling quantity of titanium plate is compared with the big several times of skeleton, therefore skeleton hardly undertakes stress, leads to postoperative skeleton can not obtain
Take exercise and gradually atrophy, embedded material and osseous tissue can not combine together well, the long-term effect that final impact is repaired.
In prior art, the man-made support making band coating is usually to utilize plasma spraying skill in titanium alloy-based basal surface
Art prepares titanium coating, carries out pretreatment to titanium alloy substrate:Using SIC sand papering, Al2O3Sandblasting, prepares coarse substrate
Face, medical titanium valve is sprayed into titanium alloy-based basal surface after air plasma spraying machine fully melts, thus preparing titanium coating
Man-made support material, but the simple beam material of planar structure can only be sprayed using plasma spraying technology, for complicated
There is spraying non-uniform phenomenon in concrete dynamic modulus bulk timbering material, some positions are limited not by spraying technology and timbering material structure
Energy direct spraying, thus cause substrate to expose.Also the decay resistance of titanium alloy itself is not good, and perishable service life is short.
In addition titanium alloy itself also there are metal toxicity, because titanium alloy timbering material is generally Ti6Al4V, vanadium is poisonous, and human body is had
Potentially hazardous, aluminium element also can cause osteomalacia, the symptom such as neurological disorders.
In view of this, the special proposition present invention.
Content of the invention
The first object of the present invention is to provide a kind of titanio tantalum coating biology bracket material, and this support passes through to close using titanium
Auri body is coordinated with the coating of tantalum material, so because the finished product porous tantalum prepared and flexible bone modulus are close, and applies
The micro-nano structure of layer surface can obtain the elasticity similar with human Cortex's bone close to the micro-nano structure on surface, titanio tantalum coating bracket
Modulus, thus fundamentally solving the problems, such as that man-made support material stress shields, in addition fine and close tantalum coating has ensured support
The good biocompatibility of material, solves titanium alloy timbering material metal toxicity itself and corrosion-prone problem, fully ensures that
The safety in utilization of timbering material, also more conducively wide popularization and application.Also have tantalum coating preparation be also not limited to etc. from
Sub- spraying technology, can select different technology according to actual needs, solve plasma spraying technology intermediate ion linear motion institute
The structure brought limits.
The second object of the present invention is to provide the preparation method of above-mentioned titanio tantalum coating bracket, and this preparation method is simply easy
In operation, closely, operating condition is gentle, by using plasma spraying technology and chemical vapour deposition technique for step linking in front and back
Combine, flexibly can be selected according to practical situation, to different shape needed for clinic timbering material and prepare phase
The tantalum coating answered.
In order to realize the above-mentioned purpose of the present invention, spy employs the following technical solutions:
Embodiments provide a kind of titanio tantalum coating biology bracket material, including:Titanium alloy substrate;Described titanium closes
The surface of auri body have tantalum coating, the THICKNESS CONTROL of described tantalum coating between 3-150 μm, described titanio tantalum coating bracket
Elastic modelling quantity controls between 10-30GPa.
In prior art, the man-made support material making band coating is usually to utilize plasma spray in titanium alloy-based basal surface
Painting technology prepares titanium coating, carries out pretreatment to titanium alloy substrate:Using SIC sand papering, Al2O3Sandblasting, prepares coarse base
Bottom surface, medical titanium valve is sprayed into titanium alloy-based basal surface after air plasma spraying machine fully melts, thus prepare titanium applying
Layer man-made support material, but the simple beam material of planar structure can only be sprayed using plasma spraying technology, for complexity
Concrete dynamic modulus bulk timbering material exist spraying non-uniform phenomenon, some positions are limited by spraying technology and timbering material structure
Can not direct spraying, thus cause substrate expose.Also have the decay resistance of titanium alloy itself not good, perishable service life
Short.In addition titanium alloy itself also there are metal toxicity, and titanium alloy timbering material is generally Ti6Al4V, vanadium is poisonous, and human body is had
Potentially hazardous, aluminium element also can cause osteomalacia, the symptom such as neurological disorders.
In order to solve many technical problems present in prior art, the invention provides a kind of new titanio tantalum coating
Biologic bracket material, the coating material being attached to titanium alloy substrate surface is tantalum coating, and the titanium alloy substrate adopting is to it
Elastic modelling quantity has certain requirement, and it needs with human Cortex's bone relatively, because porous tantalum and flexible bone modulus are close, titanium
Base tantalum coating bracket can obtain the elastic modelling quantity similar with human Cortex's bone, thus fundamentally solve man-made support material should
The problem of power shielding, in addition fine and close tantalum coating ensured the good biocompatibility of timbering material, solve titanium alloy support
Material metal toxicity itself and corrosion-prone problem.The attachment preparation also having tantalum coating is also not limited to plasma spraying skill
Art, can select different technology according to actual needs, solve the brought knot of plasma spraying technology intermediate ion linear motion
Structure limits.And tantalum coating is due to itself having splendid biocompatibility, beneficial to the expansion of bone marrow stroma stem cell pseudopodium,
Increased the ability of bone marrow stroma stem cell adhesion, propagation and differentiation, have bone conduction, self-bone grafting and osteogenesis effect concurrently, favorably
Fusion in man-made support material and osseous tissue.
Tantalum metal has splendid biocompatibility and corrosion resistance in itself, have the title of " parent biological metal ", porous tantalum
Show wide application prospect in osteoarthrosis surgical field, be considered the medical metal material of new generation of alternative titanium, but
High cost, the drawback such as process technology difficulty is big, limit its extensive clinical practice.With deepening continuously of research, tantalum conduct
The coating material of implant is gradually widely applied, the surface topography of metal implant material and the decision of chemical composition
Its biological activity, thus affect the clinical success rate of implant.Coating modifying by improving the physicochemical property of implant surfaces, with
The biological behaviours such as the adhesion of regulating cell, migration, propagation and Osteoblast Differentiation, thus promote implant fast with surrounding bone formation
The firm synosteosis of speed.The present invention exactly make use of the premium properties of tantalum, and support is done in common to itself and titanium alloy substrate cooperation
Material, still belongs to pioneering in this connected applications of medical metal material field of surface modification, has ground-breaking meaning.
Wherein, tantalum coating can be by being attached to using any one in chemical vapour deposition technique, plasma spraying technology
The surface of titanium alloy substrate.At present, the technology that the preparation of tantalum coating is commonly used at present has two kinds:One kind is plasma spraying technology,
One kind is chemical gaseous phase depositing process, is limited by know-why, plasma spraying technology be only suitable for with two dimension and simple
The surface treatment of three-dimensional artificial embedded material (such as implantation body), and chemical vapor deposition applies also for complex three-dimensional loose structure
Surface treatment, but the tantalum coating of plasma spraying technology preparation is fine and close, and the coating layer thickness of chemical gaseous phase depositing process preparation
Not high, coating layer thickness is relatively thin, but bond strength is high.
Plasma spraying technology and chemical vapour deposition technique are combined and can tackle different shape needed for clinic
Timbering material and prepare corresponding tantalum coating, solve plasma spraying technology intermediate ion linear motion brought structure limit
System.Chemical vapour deposition technique can prepare tantalum coating on the timbering material surface of block multi-pore structure.Can be according to reality
Need to carry out unrestricted choice, and avoid the limitation only with plasma spraying technology in prior art.
Additionally, the thickness of tantalum coating needs to control between 3-150 μm, if not reaching the possible material of certain thickness originally
The aspects such as the biocompatibility of body, corrosion resistance can be affected accordingly.
Further, using plasma spraying technology tantalum coating THICKNESS CONTROL between 80-150 μm, preferably 90-
Between 120 μm, using chemical vapour deposition technique tantalum coating THICKNESS CONTROL between 3-7 μm, between preferably 4-6 μm.
Its thickness requirement of different technologies according to adopting also has corresponding difference.
Further, controlled in 30MPa using the tantalum coating of plasma spraying technology and the bond strength of titanium alloy substrate
More than, controlled in more than 30MPa using the tantalum coating of chemical vapour deposition technique and the bond strength of titanium alloy substrate.
Further, the tantalum coating surface using plasma spraying technology is in many micro-nano porous structures, and pore diameter controls
Between 50-350nm, the tantalum coating surface using chemical vapour deposition technique is in nanoparticle structure, and grain diameter controls
Between 50-200nm.
Further, the elastic modelling quantity of described titanio tantalum coating bracket controls between 11-13GPa.Such springform
Amount is generally 10-30GPa closer to the elastic modelling quantity of human Cortex's bone, the elastic modelling quantity of human Cortex's bone.
Further, the comprcssive strength of described titanio tantalum coating bracket controls between 80-90MPa, and yield strength controls
Between 70-80MPa.
Further, described titanio tantalum coating bracket is in netted pore structure, and porosity is more than 70%.
It can be seen that, the titanio tantalum coating bracket of the present invention is in performances such as comprcssive strength, elastic modelling quantity, yield strength, porositys
The lifting of matter is all had on index, improves and in prior art, adopt that titanium alloy support porosity itself is low, perishable, metallic poison
Property big, the problems such as being hazardous to the human body.
The embodiment of the present invention, except providing a kind of titanio tantalum coating biology bracket material, additionally provides the more excellent of this support
A kind of preparation method, comprise the steps:
The form of titanium alloy substrate, knot needed for being determined using the three-dimensional result that digital scanning and three-dimensional reconstruction are set up
Structure, using this technology, scans local Cranial defect shape, builds the three-dimensional rack similar to defect by three-dimensional reconstruction, repair
Multiple Cranial defect, and carry out 3D printing quick forming fabri-cation, tantalum powder is heated under argon protective condition, switches to hydrogen and enter
Row chemical vapor deposition, finally leads to argon cooling, you can.
Preferably, after the temperature of heating reaches more than 950 DEG C, switch to hydrogen and carry out chemical vapor deposition;
Preferably, the time control of chemical vapor deposition is in more than 30min;
Preferably, finally it is cooled to less than 200 DEG C.
In addition, this titanio tantalum coating bracket also has a kind of ratio more preferably preparation method, comprise the steps:
The form of titanium alloy substrate, knot needed for being determined using the three-dimensional result that digital scanning and three-dimensional reconstruction are set up
Structure, and carry out 3D printing and quick forming fabri-cation, by tantalum powder ball milling, melting, carries out plasma spraying process to titanium alloy substrate,
Obtain final product.
Preferably, in more than 4h, the rotating speed of ball milling controls in 200-300rad/min the time control of ball milling;
Preferably, in 30-40kw, powder feeding rate controls between 14-16g/min the Power Control of spraying, and argon is supplied gas
Between 47-49L/min, helium supplies gas rate controlled between 12-15L/min to rate controlled.
In above two preparation method, it is all to prepare cancellated titanium alloy support first with 3D printing technique,
By pore structure characteristic, realize mating of timbering material elastic modelling quantity and human Cortex's bone, thus improve porous titanium alloy
The deficiency of timbering material high elastic modulus, and adopt the titanium alloy substrate that such method prepares to reach and Human Cortex
Flexible bone modulus is close, effectively solves " stress shielding " this problem, then coordinates follow-up plasma spraying technology again
Or the application of chemical gaseous phase depositing process, contribute to preparing the et al. Ke timbering material of various complex shapes needed for clinic, shape
One-tenth adhesion is strong, uniform tantalum coating, you can to solve the problems, such as elastic modelling quantity, significantly improve biocompatibility, and then solves
The difficult problem that clinical different parts Cranial defect plasticity is repaired.
In a word, there is controlled pore or the manufacture of cancellated titanium alloy support can pass through direct metal 3D printing technique
Realize, this technology is a kind of new forming technique shaping thought based on discrete dynamics models, and it adopts the manufacturing theory of material addition,
By computer disposal CAD data model, and produce Three-dimensional Entity Components under the control of the computer.Therefore, using this technology
The pore structure of support can be pre-designed, by pore structure characteristic, realize timbering material elastic modelling quantity and human Cortex's bone
Coupling, to improve the deficiency of titanium alloy timbering material high elastic modulus, additionally, using plasma spraying technology or chemical gas
Phase deposition technique coats tantalum metal in titanium alloy surface, so that implant is provided simultaneously with excellent mechanical property and the tantalum of titanium alloy
The excellent biology performance of metal.In a word, 3D printing technique combines plasma spraying technology or chemical vapour deposition technique system
Wide application prospect shown in terms of the reparation of peri-implant, periodontal and jaw defect by standby titanio tantalum coating bracket material.
Certainly, above two preparation method is ratio more preferably two methods, does not represent and does not have other preparation sides
Method, as long as enable the preparation method of the titanio tantalum coating that titanium alloy substrate is combined with tantalum coating, all in the protection model of the present invention
In enclosing.
Compared with prior art, beneficial effects of the present invention are:
(1) the titanio tantalum coating biology bracket material of the present invention, by being entered using the coating of titanium alloy substrate and tantalum material
Row cooperation, the rack elasticity modulus of preparation is close with human Cortex's bone, and builds form and the knot of support by titanium alloy substrate
Structure, by tantalum coating good biological, biocompatibility, mechanical property as both combined branches realizations and bone photo;By 3D
Printing technique prepares support examination and three-dimensional reconstruction mechanism accurately mate, and the personalized support of preparation, thus fundamentally solve
The problem of man-made support material stress shielding, in addition fine and close tantalum coating ensured the good biocompatibility of timbering material, solution
Determine titanium alloy timbering material metal toxicity itself and corrosion-prone problem, fully ensured that the safety in utilization of timbering material,
Also it is more conducive to wide popularization and application;
(2) preparation method of the titanio tantalum coating biology bracket material of the present invention, simply easily operated, in front and back step linking
Closely, operating condition is gentle, by being combined using plasma spraying technology and chemical vapour deposition technique, can be according to reality
Border situation is flexibly selected, to different shape needed for clinic timbering material and prepare corresponding tantalum coating;
(3), in the preparation method of the present invention, first swept according to defective region digitized according to the size of frame material, shape, structure
The three-dimensional reconstruction result retouching foundation determines, prepares the personalized support of mesh, multi-pore structure by 3D printing technique, and according to
Its own shape of support, by the tantalum coating that plasma spraying technology or chemical vapour deposition technique preparation are fine and close, thus
So that the titanio tantalum coating bracket prepared can go out different personalized supports according to the different designs of individual variation, faced with meeting
The changeable demand of bed situation, the various aspects of performance of support itself there has also been the lifting of matter.
Specific embodiment
Below in conjunction with embodiment, embodiment of the present invention is described in detail, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and be not construed as limiting the scope of the present invention.Unreceipted concrete in embodiment
Condition person, the condition according to normal condition or manufacturer's suggestion is carried out.Agents useful for same or the unreceipted production firm person of instrument, are
Can be by the commercially available conventional products bought and obtain.
Embodiment 1
The preparation method of titanio tantalum coating biology bracket material is following (plasma spraying technology):
1) carry out loose structure design first with UnigraphixNX software, and design data is deposited with stl file form
Storage, after hierarchy slicing is processed, is input to EBM device systems and carries out Direct Metal Rapid Prototyping manufacture.Taking-up has manufactured
Test specimen, removes the powder body remaining in test specimen hole, is dried after ultrasound wave cleaning;
2) pretreatment medical titanium alloy matrix, using SIC sand papering, Al2O3Sandblasting 5S (0.8MPa), ultrasonic vibration is clear
Wash;
3) Medical tantalum powder (35-75 μm of particle diameter) is placed in drying and screening after ball mill ball milling 4h, rotating speed is 200rad/min,
By the mixed powder of described ball milling after air plasma spraying machine fully melts, it is sprayed into the titanium at 110mm and closes
Golden matrix surface;
4) after parameter optimization, spray power is 30kw, and powder feeding rate is 14g/min, and argon supplies gas speed for 47L/
Min, helium supplies gas speed for 12L/min, after plasma spray is processed, forms thickness in netted titanium alloy rack surface homogeneous
Tantalum metal layer, thickness be about 150 μm, its mean compressive strength be more than 80MPa, yield strength be more than 70MPa, in conjunction with strong
Spend for more than 30MPa, elastic modelling quantity is 11GPa, with sclerotin closer to porosity is more than 70%.
Embodiment 2
The preparation method of titanio tantalum coating biology bracket material is following (plasma spraying technology):
1) carry out loose structure design first with UnigraphixNX software, and design data is deposited with stl file form
Storage, after hierarchy slicing is processed, is input to EBM device systems and carries out Direct Metal Rapid Prototyping manufacture.Taking-up has manufactured
Test specimen, removes the powder body remaining in test specimen hole, is dried after ultrasound wave cleaning;
2) pretreatment medical titanium alloy matrix, using SIC sand papering, Al2O3Sandblasting 5S (0.8MPa), ultrasonic vibration is clear
Wash;
3) Medical tantalum powder (35-75 μm of particle diameter) is placed in drying and screening after ball mill ball milling 5h, rotating speed is 300rad/min,
By the mixed powder of described ball milling after air plasma spraying machine fully melts, it is sprayed into the titanium at 110mm and closes
Golden matrix surface;
4) after parameter optimization, spray power is 40kw, and powder feeding rate is 16g/min, and argon supplies gas speed for 49L/
Min, helium supplies gas speed for 15L/min, after plasma spray is processed, forms thickness in netted titanium alloy rack surface homogeneous
Tantalum metal layer, thickness be about 80 μm, its mean compressive strength be more than 90MPa, yield strength be more than 80MPa, in conjunction with strong
Spend for more than 32MPa, elastic modelling quantity is 12GPa, with sclerotin closer to more than 70%, pore diameter controls in 50- porosity
Between 350nm or between 5-45 μm.
Embodiment 3
The preparation method of titanio tantalum coating biology bracket material is following (chemical vapour deposition technique):
1) carry out loose structure design first with UnigraphixNX software, and design data is deposited with stl file form
Storage, after hierarchy slicing is processed, is input to EBM device systems and carries out Direct Metal Rapid Prototyping manufacture.Taking-up has manufactured
Test specimen, removes the powder body remaining in test specimen hole, is dried after ultrasound wave cleaning;
2) first by the dilute hydrochloric acid etch of porous titanium alloy sample, wash, after ethanol purge, dried up with drying nitrogen, insert
In reactor;
3) connect import/exhaust pipeline, and check sealing condition, heated under argon atmosphere;
4), when the temperature of pure tantalum powder rises to 120 DEG C, after depositing temperature rises to 950 DEG C, close argon, sequentially adjust hydrogen
Gas, starts to deposit, and after deposition 30min, closes hydrogen, logical argon protection cooling, when temperature is down to 200 DEG C, opens reactor and take
Sample, surface tantalum metal layer thickness is about 3 μm, and its mean compressive strength is more than 85MPa, and yield strength is more than 75MPa, in conjunction with
Intensity is more than 30MPa, and elastic modelling quantity is 30GPa, with sclerotin closer to, more than 75%, particle diameter is in 50-200nm for porosity
Between.
Embodiment 4
The preparation method of titanio tantalum coating biology bracket material is following (chemical vapour deposition technique):
1) carry out loose structure design first with UnigraphixNX software, and design data is deposited with stl file form
Storage, after hierarchy slicing is processed, is input to EBM device systems and carries out Direct Metal Rapid Prototyping manufacture.Taking-up has manufactured
Test specimen, removes the powder body remaining in test specimen hole, is dried after ultrasound wave cleaning;
2) first by the dilute hydrochloric acid etch of porous titanium alloy sample, wash, after ethanol purge, dried up with drying nitrogen, insert
In reactor;
3) connect import/exhaust pipeline, and check sealing condition, heated under argon atmosphere;
4), when the temperature of pure tantalum powder rises to 120 DEG C, after depositing temperature rises to 960 DEG C, close argon, sequentially adjust hydrogen
Gas, starts to deposit, and after deposition 40min, closes hydrogen, logical argon protection cooling, when temperature is down to 150 DEG C, opens reactor and take
Sample, surface tantalum metal layer thickness is about 7 μm, and its mean compressive strength is more than 85MPa, and yield strength is more than 75MPa, in conjunction with
Intensity is more than 30MPa, and elastic modelling quantity is 13GPa, with sclerotin closer to, more than 75%, particle diameter is in 50-200nm for porosity
Between.
Comparative example 1
Using SIC sand papering, Al2O3Sandblasting, prepares coarse basal surface, by medical titanium valve in air plasma spraying
Machine is sprayed into titanium alloy-based basal surface after fully melting, thus preparing titanium coating man-made support material, this timbering material average
Comprcssive strength is 50MPa, and yield strength is 50MPa, and bond strength is 30MPa, and elastic modelling quantity is 50GPa.
Although illustrate and describing the present invention with specific embodiment, but it will be appreciated that without departing substantially from the present invention's
Many other changes can be made in the case of spirit and scope and change.It is, therefore, intended that in the following claims
Including all such changes and modifications belonging in the scope of the invention.
Claims (10)
1. a kind of titanio tantalum coating biology bracket material is it is characterised in that include titanium alloy substrate;The table of described titanium alloy substrate
Face have tantalum coating, the THICKNESS CONTROL of described tantalum coating between 3-150 μm, the elastic modelling quantity control of described titanio tantalum coating bracket
System is between 10-30GPa.
2. a kind of titanio tantalum coating biology bracket material according to claim 1 is it is characterised in that described tantalum coating is passed through
It is attached to the surface of titanium alloy substrate using any one in chemical vapour deposition technique, plasma spraying technology.
3. a kind of titanio tantalum coating biology bracket material according to claim 2 is it is characterised in that adopt plasma spraying
The THICKNESS CONTROL of the tantalum coating of technology between 80-150 μm, between preferably 90-120 μm;
Using chemical vapour deposition technique tantalum coating THICKNESS CONTROL between 3-7 μm, between preferably 4-6 μm.
4. a kind of titanio tantalum coating biology bracket material according to claim 2 is it is characterised in that adopt plasma spraying
The tantalum coating of technology and the bond strength of titanium alloy substrate control in more than 30MPa, and the tantalum using chemical vapour deposition technique applies
Layer is controlled in more than 30MPa with the bond strength of titanium alloy substrate.
5. a kind of titanio tantalum coating biology bracket material according to claim 2 is it is characterised in that adopt plasma spraying
The tantalum coating surface of technology is in micro-nano porous structure, and pore diameter controls between 50-350nm;
Using chemical vapour deposition technique tantalum coating surface be in nanoparticle structure, grain diameter control 50-200nm it
Between.
6. a kind of titanio tantalum coating biology bracket material according to any one of claim 1-6 is it is characterised in that described titanium
The elastic modelling quantity of base tantalum coating bracket controls between 11-13GPa.
7. a kind of titanio tantalum coating biology bracket material according to any one of claim 1-6 is it is characterised in that described titanium
The comprcssive strength of base tantalum coating bracket controls between 80-90MPa, and yield strength controls between 70-80MPa.
8. a kind of titanio tantalum coating biology bracket material according to any one of claim 1-6 is it is characterised in that described titanium
Base tantalum coating bracket is in netted pore structure, and porosity is more than 70%.
9. a kind of titanio tantalum coating biology bracket material described in any one of claim 1-7 preparation method it is characterised in that
Mainly comprise the steps:
The form of titanium alloy substrate, structure needed for being determined using the three-dimensional result that digital scanning and three-dimensional reconstruction are set up,
And carry out 3D printing quick forming fabri-cation, by tantalum powder ball milling, melting, plasma spraying process is carried out to titanium alloy substrate, obtain final product;
Preferably, in more than 4h, the rotating speed of ball milling controls in 200-300rad/min the time control of ball milling;
Preferably, in 30-40kw, powder feeding rate controls between 14-16g/min the Power Control of spraying, and argon is supplied gas speed
Control between 47-49L/min, helium supplies gas rate controlled between 12-15L/min.
10. the preparation method of a kind of titanio tantalum coating biology bracket material described in any one of claim 1-7, its feature exists
In mainly comprising the steps:
The form of titanium alloy substrate, structure needed for being determined using the three-dimensional result that digital scanning and three-dimensional reconstruction are set up,
And carry out 3D printing quick forming fabri-cation, tantalum powder is heated under argon protective condition, switches to hydrogen and carry out chemical gas
Mutually deposit, finally lead to argon cooling, you can;
Preferably, after the temperature of heating reaches more than 950 DEG C, switch to hydrogen and carry out chemical vapor deposition;
Preferably, the time control of chemical vapor deposition is in more than 30min;
Preferably, finally it is cooled to less than 200 DEG C.
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