CN107115560A - Biomimetic porous titanium implantses of antibacterial and its preparation method and application - Google Patents
Biomimetic porous titanium implantses of antibacterial and its preparation method and application Download PDFInfo
- Publication number
- CN107115560A CN107115560A CN201710453072.5A CN201710453072A CN107115560A CN 107115560 A CN107115560 A CN 107115560A CN 201710453072 A CN201710453072 A CN 201710453072A CN 107115560 A CN107115560 A CN 107115560A
- Authority
- CN
- China
- Prior art keywords
- porous titanium
- antibacterial
- implantses
- biomimetic porous
- biomimetic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000010936 titanium Substances 0.000 title claims abstract description 94
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 93
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 70
- 230000003592 biomimetic effect Effects 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000007943 implant Substances 0.000 claims abstract description 32
- 238000005245 sintering Methods 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 22
- 238000009833 condensation Methods 0.000 claims abstract description 18
- 230000005494 condensation Effects 0.000 claims abstract description 18
- 239000002086 nanomaterial Substances 0.000 claims abstract description 18
- 239000002002 slurry Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 230000001174 ascending effect Effects 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 241000894006 Bacteria Species 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 13
- 239000011148 porous material Substances 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 11
- 230000001954 sterilising effect Effects 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000004659 sterilization and disinfection Methods 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 241000192125 Firmicutes Species 0.000 claims description 4
- 238000010010 raising Methods 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 239000008236 heating water Substances 0.000 claims description 2
- 230000002045 lasting effect Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 238000000935 solvent evaporation Methods 0.000 claims 1
- 238000004506 ultrasonic cleaning Methods 0.000 claims 1
- 238000009777 vacuum freeze-drying Methods 0.000 claims 1
- 238000010883 osseointegration Methods 0.000 abstract description 4
- 239000000523 sample Substances 0.000 description 36
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- 210000000988 bone and bone Anatomy 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 210000004027 cell Anatomy 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000012300 argon atmosphere Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000002513 implantation Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000000845 anti-microbial effect Effects 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 241000588724 Escherichia coli Species 0.000 description 4
- 241000191967 Staphylococcus aureus Species 0.000 description 4
- 230000002308 calcification Effects 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 230000004069 differentiation Effects 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910001069 Ti alloy Inorganic materials 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 239000011268 mixed slurry Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 238000009395 breeding Methods 0.000 description 2
- 230000001488 breeding effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013068 control sample Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000000338 in vitro Methods 0.000 description 2
- 210000004409 osteocyte Anatomy 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 210000001519 tissue Anatomy 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008512 biological response Effects 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 230000011712 cell development Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical class [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 230000011164 ossification Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical class [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 210000001082 somatic cell Anatomy 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- 108010046845 tryptones Proteins 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000012138 yeast extract Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
- B22F3/22—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
- B22F3/222—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip by freeze-casting or in a supercritical fluid
-
- 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
- B22F3/24—After-treatment of workpieces or articles
-
- 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
- A61L2400/18—Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment
-
- 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
-
- 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
- B22F3/24—After-treatment of workpieces or articles
- B22F2003/241—Chemical after-treatment on the surface
-
- 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
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Transplantation (AREA)
- Animal Behavior & Ethology (AREA)
- Manufacturing & Machinery (AREA)
- Dermatology (AREA)
- Medicinal Chemistry (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Engineering & Computer Science (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Mechanical Engineering (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Materials For Medical Uses (AREA)
- Prostheses (AREA)
Abstract
The invention discloses biomimetic porous titanium implant of a kind of antibacterial and its preparation method and application.The biomimetic porous titanium implantses of the antibacterial are in cylindrical structure, along cylinder outside the radial anisotropy loose structure in circumferential cylinder center and aperture be distributed in ascending gradient, hole surface has needle-like micro-nano structure.Preparation method includes (1) titanium powder and prepares slurry with dielectric solvent stirring under condition of water bath heating；(2) slurry condensation cured and drying, obtain drying base sample；(3) base sample sintering is dried, porous titanium implant sample is obtained；(4) porous titanium implant sample is sintered in the mixed atmosphere of inert gas and acetone, obtains the biomimetic porous titanium implantses of antibacterial.The biomimetic porous titanium implantses of antibacterial of the present invention have good antibacterial functions concurrently, excellent osseointegration character and mechanical property, can be widely applied to medical domain.
Description
Technical field
The invention belongs to orthopaedics implant preparing technical field, it is related to a kind of biomimetic porous titanium implantses of antibacterial and its preparation
Methods and applications, more particularly to a kind of method that freezing casting and thermal oxidation technique prepare the biomimetic porous titanium implantses of antibacterial.
Background technology
Titanium or titanium alloy has a many merits such as good biocompatibility and mechanical property as bone alternate material, but by
It is significantly larger than nature human body cortex of bone in the modulus of elasticity of titanium or titanium alloy implant, is implanted as carrying bone alternate material
Afterwards, only with mechanically integrated rather than firm biological combination, the especially growth when implant surfaces bacterium between bone tissue
With the severe complication such as implant loosening and bone tissue inflammatory reaction caused by breeding, it will fail after increase bone implant surgery
Risk so as to limiting its application clinically.
New bone implant needs to produce special response and interaction between bone tissue active somatic cell, so that in life
Manage under environment can induced osteogenesis cell development into vital freshman bone tissue or organ, i.e., good osseointegration character.Cause
This, obtain similar body bone tissue pore appearance and pore size has the biomimetic porous titanium implantses of excellent mechanical performances simultaneously
One of important research direction as bone implant.It is that planting body is planted successfully to form good bone implant-synosteosis interface
Key point, regulation and control Gegenbaur's cell sticks multiplication capacity in the behavior of material surface and Gegenbaur's cell, and suppresses bone and plant
How simultaneously the growth and breeding for entering body-synosteosis interface bacterium are most important for forming good synosteosis interface, so
Realize implant nanosizing surface be modified and it is possessed the research of anti-microbial property also to turn into research and development antibacterial of new generation bionical more
One of focus of hole titanium implantses.
The content of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art to have good antibacterial work(concurrently there is provided a kind of
Energy, the biomimetic porous titanium implantses of the antibacterial of excellent osseointegration character and mechanical property and its preparation method and application.
In order to solve the above technical problems, the present invention uses following technical scheme：
A kind of biomimetic porous titanium implantses of antibacterial, the biomimetic porous titanium implantses of antibacterial are in cylindrical structure, with edge
The radial anisotropic loose structure in circumferential cylinder center outside cylinder, the aperture of the loose structure is external along cylinder
Circumferential cylinder center is distributed in ascending gradient, and the hole substrate surface of the loose structure has needle-like micro-nano structure.
In the biomimetic porous titanium implantses of above-mentioned antibacterial, it is preferred that the porosity of the biomimetic porous titanium implantses of antibacterial
For 40%~70%, percent opening be 90%~99%, mean pore size be 80 μm~150 μm, compressive strength be 30MPa~
165MPa, modulus of elasticity is 1GPa~4GPa, and the biomimetic porous titanium implantses of antibacterial are big to the sterilization rate of Gram-negative bacteria
In 90%, 85% is more than to the sterilization rate of gram-positive bacteria.
As a total inventive concept, the present invention also provides a kind of preparation method of the biomimetic porous titanium implantses of antibacterial,
Comprise the following steps：
(1) prepared by slurry：By titanium powder, the lasting stirring under condition of water bath heating is mixed with dielectric solvent, obtains slurry,
The volume fraction of titanium valve is 10%~20% in slurry；
(2) condensation cured：Slurry obtained by step (1) is poured into the mould of precooling in carrying out cooling solidification at 20 DEG C~25 DEG C
Change, circular cylindrical cavity is provided with mould, mould keeps sealing heat-insulated, after condensation cured, is stripped drying, obtains drying base sample；
(3) sinter：Base sample will be dried obtained by step (2) first to heat with 1 DEG C/min~5 DEG C of speed/min under vacuum
400 DEG C~600 DEG C are warming up to, then 1200 DEG C~1300 are warming up under an inert atmosphere with 5 DEG C/min~10 DEG C of speed/min
DEG C it is sintered, sintering duration is 1h~4h, is subsequently cooled to room temperature, obtains porous titanium implant sample；
(4) surface micro-nano structure is handled：Imbedded body in porous titanium sample obtained by step (3) is cleaned by ultrasonic and dried,
Gained drying base sample is warming up to after 850 DEG C~900 DEG C with 10 DEG C/min~15 DEG C of speed/min under an inert atmosphere, in inertia
Acetone is continuously added into the air-flow of atmosphere, and controls the flow velocity of inert gas to be sintered for 50sccm~300sccm, sintering is held
Continue the time for 45min~60min, be cooled to room temperature after sintering, obtain the biomimetic porous titanium implantses of antibacterial.
In the preparation method of the biomimetic porous titanium implantses of above-mentioned antibacterial, it is preferred that in the step (1), the medium
Solvent is amphene, and the temperature of the heating water bath is 60 DEG C~65 DEG C.
In the preparation method of the biomimetic porous titanium implantses of above-mentioned antibacterial, it is preferred that in the step (1), the stirring
Time be 2h~4h, the speed of the stirring is 800r/min~1000r/min, and stirring is placed in stirring container simultaneously to be covered
Cover material is evaporated with reducing solvent.
In the preparation method of the biomimetic porous titanium implantses of above-mentioned antibacterial, it is preferred that in the step (2), the mould
Precooling temperature it is identical with condensation cured temperature, the pre-coo time of the mould is 30min~120min, the condensation cured
Time is 4h~6h.
In the preparation method of the biomimetic porous titanium implantses of above-mentioned antibacterial, it is preferred that in the step (2), in cooling solidification
Before being dried after change with the demoulding, in preserving 12h~24h under -18 DEG C~-20 DEG C low temperature, further solidify sample；The drying is true
Vacuum freecing-dry, the time of the drying is 24h~48h.
In the preparation method of the biomimetic porous titanium implantses of above-mentioned antibacterial, it is preferred that in the step (4), the ultrasound
Cleaning respectively cleans 15min~20min successively using acetone, absolute ethyl alcohol and distilled water as cleaning fluid；The temperature of the drying
For 60 DEG C~80 DEG C, the time of the drying is 4h~6h.
In the preparation method of the biomimetic porous titanium implantses of above-mentioned antibacterial, it is preferred that in the step (4), the acetone
For the acetone of liquid；After sintering stop add acetone, control inert gas flow velocity be 500sccm~600sccm under the conditions of oneself
So it is cooled to room temperature.
As a total inventive concept, the present invention also provide a kind of biomimetic porous titanium implantses of above-mentioned antibacterial or on
The application of the biomimetic porous titanium implantses of antibacterial made from the preparation method stated.
Compared with prior art, the advantage of the invention is that：
(1) present invention controls the side of medium condensation cured in mould by freezing casting method (i.e. step (1) to step (3))
To, that is, control condensation cured when medium along mould periphery to mould center the temperature difference (radial temperature difference of cylindrical cavity, such as outside
The temperature difference of 20 DEG C of the week extremely 60 DEG C of formation in center), it is in the central radial anisotropic of cylinder and hole to realize imbedded body in porous titanium
The pore appearance of footpath gradient distribution, its loose structure and native human skeletal tissue are closely similar.
(2) present invention includes titanium valve volume ratio, sintering temperature, the burning of mixed slurry by controlling and optimizing freezing casting
The technological parameter such as speed and sintering time is tied, realizes that the biomimetic porous titanium implantses of antibacterial prepared possess good porosity, hole
Footpath size and excellent mechanical property, effectively meet osteocyte and grow into the biological Integrated implant of formation in imbedded body in porous titanium
Condition.
(2) present invention realizes all three-dimensional pore space substrate tables in imbedded body in porous titanium by thermal oxidation method (i.e. step (1))
Face homoepitaxial goes out a nanometer acicular texture, and acicular texture is about 100~200nm.It is of the invention compared with conventional porous materials
Equally distributed needle-shaped nano-structure is by regulating and controlling absorption of the Gegenbaur's cell in material surface in biomimetic porous titanium implantses hole
Promote the propagation, differentiation performance and internal bon e formation, deposition and calcification of external Gegenbaur's cell in terms of effect, biological response,
With the extension of Implantation Time, Gegenbaur's cell breaks up more ripe in its hole, forms firm biological Integrated implant, has
Significant progress.Needle-shaped nano-structure effectively suppresses the growth of the bacterium around implant by physical effect simultaneously, is one
Plant the new surface for having antibacterial functions and good osseointegration character concurrently and there is good biocompatibility and be modified biomimetic porous titanium plant
Enter body.
Brief description of the drawings
Fig. 1 is the SEM figures in the biomimetic porous titanium implantses cross section of antibacterial prepared by the embodiment of the present invention 1.
Fig. 2 is the biomimetic porous titanium implantses hole substrate surface needle-like micro-nano structure of antibacterial prepared by the embodiment of the present invention 1
SEM schemes.
Embodiment
Below in conjunction with Figure of description and specific preferred embodiment, the invention will be further described, but not therefore and
Limit the scope of the invention.
Material and instrument employed in following examples are commercially available.
Embodiment 1：
A kind of preparation method of the biomimetic porous titanium implantses of antibacterial of the invention, comprises the following steps：
(1) prepared by slurry：By titanium powder and dielectric solvent amphene in 60 DEG C of water baths continuing magnetic force stirring to mix 2 small
When, mixing speed is 800r/min, and covering is placed in the top of stirring container, reduces the evaporation of solvent amphene.Gained slurry is mixed
The volume fraction of titanium valve accounts for 10% in compound.
(2) condensation cured：Cylindrical die is placed in precooling 30 minutes in water bath, precooling temperature is 20 DEG C, will be prepared
Good slurry is slowly poured into the mould of precooling, and dies cavity is cylinder, and the upper and lower side of mould keeps sealing heat-insulated, controlled cold
Cure temperature is at 20 DEG C, and the condensation cured time is 4 hours.After condensation cured, take out mould and be placed on preservation under -20 DEG C of low temperature
12h, further solidifies sample.Take out to be put into lyophilizer after the sample demoulding and dry 24h, obtain drying base sample.
(3) sinter：Base sample will be dried to be placed in sintering furnace, first under vacuum using speed as 1 DEG C/min heat temperature raisings
To 400 DEG C, then it is warming up to 1200 DEG C by 5 DEG C/min of speed under an argon atmosphere and is sintered, sintering duration is 1h,
Room temperature is naturally cooled to, porous titanium implant sample is obtained.
(4) surface micro-nano structure is handled：By the imbedded body in porous titanium sample priority acetone, the absolute ethyl alcohol that are obtained after sintering
With distilled water as cleaning fluid, each cleaning 15min in supersonic wave cleaning machine, then 80 DEG C of dryings 4 are small in high temperature drying case
When.Base sample will be dried to be placed in sintering furnace, be warming up in 850 DEG C, argon gas stream and hold by 10 DEG C/min of speed under an argon atmosphere
It is continuous to add 25 DEG C of acetone, control argon gas flow velocity to be sintered for 50sccm, sintering duration is 45min, is then stopped
Logical acetone, controls argon gas flow velocity to naturally cool to room temperature under the conditions of 500sccm, obtains the biomimetic porous titanium implantation of antibacterial
Body, the biomimetic porous titanium implantses of the antibacterial have surface needle-like micro-nano structure.
As depicted in figs. 1 and 2, it is the biomimetic porous titanium implantses cross section of antibacterial manufactured in the present embodiment and pore surface
SEM schemes, and as seen from the figure, the implant has loose structure, along cylinder outside circumferential cylinder center it is radial it is each to
Different in nature and aperture is distributed in ascending gradient, and the loose structure and native human skeletal tissue are closely similar, porous implantation
The pore surface of body has a needle-like micro-nano structure, and acicular texture is about 100~200nm, and to illustrate the method for the present invention can make
It is standby go out the biomimetic porous titanium implantses of antibacterial that are modified of nanometer acicular surface.After tested, the hole of the imbedded body in porous titanium of the present embodiment
Porosity 58.32 ± 1.08%, percent opening 97.70%, 126.17 ± 18.64 μm of mean pore size, compressive strength 58.51 ±
1.70 ± 0.52GPa of 20.38MPa and modulus of elasticity.Implant biocompatibility reaches and clinical practice requirement.Implant hole
In needle-shaped nano-structure can promote the propagation of external Gegenbaur's cell, differentiation performance and internal bon e formation, deposition and calcification, with
The extension of Implantation Time, Gegenbaur's cell breaks up more ripe in its hole, forms firm biological Integrated implant.
The biomimetic porous titanium implantses of antibacterial manufactured in the present embodiment can be applied to orthopaedics implant field, apply also for it
Its related medical domain.
Embodiment 2：
A kind of preparation method of the biomimetic porous titanium implantses of antibacterial of the invention, this method comprises the following steps：
(1) prepared by slurry：By titanium powder and dielectric solvent amphene in 65 DEG C of water baths continuing magnetic force stirring to mix 4 small
When, mixing speed is 1000r/min, and covering is placed in the top of stirring container, reduces the evaporation of solvent amphene.Gained slurry is mixed
The volume fraction of titanium valve accounts for 20% in compound.
(2) condensation cured：Cylindrical die is placed in precooling 30 minutes in water bath, precooling temperature is 20 DEG C.It will prepare
Good mixed slurry is slowly poured into the mould of precooling, and horizontal tool inner chamber is cylinder, and the upper and lower side of mould keeps sealing heat-insulated.It is cold
Cure temperature control is at 20 DEG C, and hardening time is 4 hours.Taking-up mould, which is placed under -20 DEG C of low temperature, preserves 12h, further
Solidify sample.Take out to be put into lyophilizer after the sample demoulding and dry 24h.
(3) sinter：Base sample will be dried to be placed in sintering furnace, first under vacuum using speed as 5 DEG C/min heat temperature raisings
To 400 DEG C, then it is warming up to 1200 DEG C by 10 DEG C/min of speed under an argon atmosphere and is sintered, sintering duration is
4h, naturally cools to room temperature, obtains porous titanium implant sample.
(4) surface micro-nano structure is handled：Imbedded body in porous titanium sample after sintering is successively with acetone, absolute ethyl alcohol and double steamings
Water is as cleaning fluid, each cleaning 15min in supersonic wave cleaning machine, then 80 DEG C of dryings 4 hours in high temperature drying case.Will be dry
Dry base sample is placed in sintering furnace, is warming up under an argon atmosphere by 15 DEG C/min of speed in 850 DEG C, argon gas stream and is continuously added into 25
DEG C acetone, controls argon gas flow velocity to be sintered for 300sccm, sintering duration is 45min, then stops logical acetone,
Control argon gas flow velocity to naturally cool to room temperature under the conditions of 500sccm, obtain the biomimetic porous titanium implantses of antibacterial.
After tested, the biomimetic porous titanium of antibacterial for being prepared for the modification of nano whiskers surface using the method for above-mentioned the present embodiment is planted
Enter body, the biomimetic porous titanium implantses of the antibacterial are in cylindrical structure, with radial along circumferential cylinder center outside cylinder
Anisotropic loose structure, the aperture of loose structure is divided along circumferential cylinder center outside cylinder in ascending gradient
Cloth, the hole surface of loose structure has needle-like micro-nano structure.The porosity 45.99 ± 2.15% of the product of the present embodiment, perforate
Rate 92.50%, 94.35 ± 2.01 μm of mean pore size, 147.12 ± 15.53MPa of compressive strength and modulus of elasticity 2.99 ±
0.12GPa.Implant biocompatibility reaches clinical practice requirement.Needle-shaped nano-structure in implant hole can promote in vitro
The propagation of Gegenbaur's cell, differentiation performance and internal bon e formation, deposition and calcification, with the extension of Implantation Time, Gegenbaur's cell exists
Break up more ripe in its hole, form firm biological Integrated implant.
Embodiment 3：
A kind of preparation method of the biomimetic porous titanium implantses of antibacterial of the invention, this method comprises the following steps：
(1) prepared by slurry：By titanium powder and dielectric solvent amphene in 60 DEG C of water baths continuing magnetic force stirring to mix 4 small
When, mixing speed is 800r/min, and covering is placed in the top of stirring container, reduces the evaporation of solvent amphene.Gained slurry is mixed
The volume fraction of titanium valve accounts for 15% in compound.
(2) condensation cured：Cylindrical die is placed in precooling 30 minutes in water bath, precooling temperature is 25 DEG C.It will prepare
Good mixed slurry is slowly poured into the mould of precooling, and dies cavity is cylinder, and the upper and lower side of mould keeps sealing heat-insulated.It is cold
Cure temperature control is at 25 DEG C, and hardening time is 4 hours.Taking-up mould, which is placed under -20 DEG C of low temperature, preserves 12h, further
Solidify sample.Take out to be put into lyophilizer after the sample demoulding and dry 24h.
(3) sinter：Base sample will be dried to be placed in sintering furnace, first under vacuum using speed as 1 DEG C/min heat temperature raisings
To 400 DEG C, then it is warming up to 1300 DEG C by 10 DEG C/min of speed under an argon atmosphere and is sintered, sintering duration is
1h, naturally cools to room temperature, obtains porous titanium implant sample.
(4) surface micro-nano structure is handled：Imbedded body in porous titanium sample after sintering is successively with acetone, absolute ethyl alcohol and double steamings
Water is as cleaning fluid, each cleaning 15min in supersonic wave cleaning machine, then 80 DEG C of dryings 4 hours in high temperature drying case.By institute
Base sample must be dried to be placed in sintering furnace, be warming up in 850 DEG C, argon gas stream and persistently add by 10 DEG C/min of speed under an argon atmosphere
Enter 25 DEG C of acetone, control argon gas flow velocity to be sintered for 200sccm, sintering duration is 45min, then stop logical third
Ketone, controls argon gas flow velocity to naturally cool to room temperature under the conditions of 500sccm, obtains the biomimetic porous titanium implant of antibacterial.
After tested, the biomimetic porous titanium of antibacterial for being prepared for the modification of nano whiskers surface using the method for above-mentioned the present embodiment is planted
Enter body, the biomimetic porous titanium implantses of the antibacterial are in cylindrical structure, with radial along circumferential cylinder center outside cylinder
Anisotropic loose structure, the aperture of loose structure is divided along circumferential cylinder center outside cylinder in ascending gradient
Cloth, the hole surface of loose structure has needle-like micro-nano structure.The porosity 54.19 ± 2.01% of the implant of the present embodiment, open
Porosity 94.49%, 104.16 ± 16.05 μm of mean pore size, 113.37 ± 25.18MPa of compressive strength and modulus of elasticity
2.85±0.25GPa.Implant biocompatibility reaches and clinical practice requirement.Needle-shaped nano-structure energy in implant hole
Promote propagation, the differentiation performance and internal bon e formation, deposition and calcification of external Gegenbaur's cell, with the extension of Implantation Time, into
Osteocyte breaks up more ripe in its hole, forms firm biological Integrated implant.
Antimicrobial test：
The Antimicrobial test that the present invention is carried out proves that embodiment 1, embodiment 2 and the biomimetic porous titanium of 3 three kinds of embodiment are planted
Enter physical efficiency and substantially suppress staphylococcus aureus and Escherichia coli.
The example of the experiment in vitro carried out the following is the present invention, anti-microbial property detection method is as follows：(1) LB culture medium systems
Method：Weigh in the balance and take 10g tryptones, 5g yeast extracts, 10g sodium chloride, 20g agar, mentioned component is completely dissolved in
In 1000mL distilled water, the solution prepared is adjusted into pH to 7.0 with 0.1mol/L NaOH solution, high steam is placed in after packing
It is standby after the 20min that sterilized at 121 DEG C in autoclave.(2) PB (PBS) preparation method：By 2.84g disodium hydrogen phosphates
It is dissolved in 1.36g potassium dihydrogen phosphates in 1000mL distilled water, the solution prepared is adjusted into pH to 7.2~7.4, steam
121 DEG C sterilizing 30 minutes after it is standby.(3) sample is resisted for Gram-negative bacteria and gram-positive bacteria respectively in this experiment
Bacterium performance is detected.The representative strain that wherein Gram-negative bacteria is chosen is Escherichia coli, and gram-positive bacteria chooses generation
Table strain is staphylococcus aureus.The sample for carrying out antibacterial experiment is that fine and close titanium control sample and antibacterial of the invention are bionical more
Hole titanium sample, every kind of each 4 groups of sample.After sample is cleaned with acetone, absolute ethyl alcohol and distilled water, the autoclaving at 121 DEG C
30 minutes standby.Sample after sterilizing is placed in culture dish, and instills in culture dish 1000 μ L sterilizing PBSs.With
It is 1 × 10 that strain after inoculation is diluted to concentration by PBS liquid5Standard bacterium solution；Liquid-transfering gun draws 100 μ L bacterium solutions and drips to sample table
Face, it is uniform spreadable, and cultivate 24h in 37 DEG C of constant incubators.Liquid-transfering gun is drawn 80 μ L bacterium solutions from specimen surface and uniformly dripped
In the culture dish of LB culture mediums, bacterium solution is smeared uniform.The culture dish coated is placed in 37 DEG C of constant incubators and cultivated.Culture
Culture dish is taken out after 24h, the total plate count contained by each specimen surface is calculated.Antibiotic rate calculation formula is：
Wherein K is sample antibiotic rate, and A is the bacterium average that blank sample is on fine and close titanium, and B is the biomimetic porous titanium of antibacterial
Bacterium average in test sample.
Antibacterial tests result is shown：Fine and close titanium control sample and the biomimetic porous titanium sample of antibacterial are carried out using flat band method
Anti-microbial property is detected, and has obtained sterilization rate.Table 1 is the biomimetic porous titanium sample of antibacterial to Escherichia coli and staphylococcus aureus
Sterilization rate, as a result show the present invention antibacterial biomimetic porous titanium implantses staphylococcus aureus and Escherichia coli are all showed
Go out good antibacterial effect.
The anti-bacteria test result of the biomimetic porous titanium of the antibacterial of table 1
The above described is only a preferred embodiment of the present invention, not making any formal limitation to the present invention.Though
So the present invention is disclosed as above with preferred embodiment, but is not limited to the present invention.It is any to be familiar with those skilled in the art
Member, in the case where not departing from the Spirit Essence and technical scheme of the present invention, all using in the methods and techniques of the disclosure above
Appearance makes many possible variations and modification to technical solution of the present invention, or is revised as the equivalent embodiment of equivalent variations.Therefore,
Every content without departing from technical solution of the present invention, the technical spirit according to the present invention is to made for any of the above embodiments any simple
Modification, equivalent substitution, equivalence changes and modification, still fall within technical solution of the present invention protection in the range of.
Claims (10)
1. a kind of biomimetic porous titanium implantses of antibacterial, it is characterised in that the biomimetic porous titanium implantses of antibacterial are in cylinder knot
Structure, with along the radial anisotropic loose structure in circumferential cylinder center, the aperture of the loose structure outside cylinder
Circumferential cylinder center is distributed in ascending gradient outside along cylinder, and the hole substrate surface of the loose structure has needle-like
Micro-nano structure.
2. the biomimetic porous titanium implantses of antibacterial according to claim 1, it is characterised in that the biomimetic porous titanium of antibacterial is planted
The porosity for entering body is that 40%~70%, percent opening is that 90%~99%, mean pore size is 80 μm~150 μm, compresses strong
Spend for 30MPa~165MPa, modulus of elasticity is 1GPa~4GPa, and the biomimetic porous titanium implantses of antibacterial are to Gram-negative bacteria
Sterilization rate be more than 90%, 85% is more than to the sterilization rate of gram-positive bacteria.
3. a kind of preparation method of the biomimetic porous titanium implantses of antibacterial, comprises the following steps：
(1) prepared by slurry：By titanium powder, the lasting stirring under condition of water bath heating is mixed with dielectric solvent, obtains slurry, slurry
The volume fraction of middle titanium valve is 10%~20%；
(2) condensation cured：Slurry obtained by step (1) is poured into the mould of precooling in carrying out condensation cured at 20 DEG C~25 DEG C,
Circular cylindrical cavity is provided with mould, mould keeps sealing heat-insulated, after condensation cured, is stripped drying, obtains drying base sample；
(3) sinter：Base sample will be dried obtained by step (2) first under vacuum with 1 DEG C/min~5 DEG C of speed/min heat temperature raisings
To 400 DEG C~600 DEG C, then it is warming up to 1200 DEG C~1300 DEG C with 5 DEG C/min~10 DEG C of speed/min under an inert atmosphere and enters
Row sintering, sintering duration is 1h~4h, is subsequently cooled to room temperature, obtains porous titanium implant sample；
(4) surface micro-nano structure is handled：Imbedded body in porous titanium sample obtained by step (3) is cleaned by ultrasonic and dried, by institute
Base sample must be dried and be warming up under an inert atmosphere with 10 DEG C/min~15 DEG C of speed/min after 850 DEG C~900 DEG C, in inert atmosphere
Air-flow in be continuously added into acetone, and control the flow velocity of inert gas to be sintered for 50sccm~300sccm, when sintering continues
Between be 45min~60min, be cooled to room temperature after sintering, obtain the biomimetic porous titanium implantses of antibacterial.
4. the preparation method of the biomimetic porous titanium implantses of antibacterial according to claim 3, it is characterised in that the step
(1) in, the dielectric solvent is amphene, and the temperature of the heating water bath is 60 DEG C~65 DEG C.
5. the preparation method of the biomimetic porous titanium implantses of antibacterial according to claim 3, it is characterised in that the step
(1) in, the time of the stirring is 2h~4h, and the speed of the stirring is 800r/min~1000r/min, and stirring is being stirred simultaneously
Mix and place covering on container to reduce solvent evaporation.
6. the preparation method of the biomimetic porous titanium implantses of antibacterial according to claim 3, it is characterised in that the step
(2) in, the precooling temperature of the mould is identical with condensation cured temperature, and the pre-coo time of the mould is 30min~120min,
The time of the condensation cured is 4h~6h.
7. the preparation method of the biomimetic porous titanium implantses of antibacterial according to any one of claim 3~6, its feature exists
In, in the step (2), after condensation cured and the demoulding dry before, under -18 DEG C~-20 DEG C low temperature preserve 12h~24h, enter
One step solidifies sample；The drying is vacuum freeze drying, and the time of the drying is 24h~48h.
8. the preparation method of the biomimetic porous titanium implantses of antibacterial according to any one of claim 3~6, its feature exists
In in the step (4), the ultrasonic cleaning is successively using acetone, absolute ethyl alcohol and distilled water as cleaning fluid, each cleaning
15min~20min；The temperature of the drying is 60 DEG C~80 DEG C, and the time of the drying is 4h~6h.
9. the preparation method of the biomimetic porous titanium implantses of antibacterial according to any one of claim 3~6, its feature exists
In in the step (4), the acetone is the acetone of liquid；Stop adding acetone after sintering, the flow velocity for controlling inert gas is
Room temperature is naturally cooled under the conditions of 500sccm~600sccm.
10. a kind of biomimetic porous titanium implantses of antibacterial as claimed in claim 1 or 2 or such as any one of claim 3~9
The application of the biomimetic porous titanium implantses of antibacterial made from described preparation method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710453072.5A CN107115560B (en) | 2017-06-15 | 2017-06-15 | Antibacterial bionic porous titanium implant and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710453072.5A CN107115560B (en) | 2017-06-15 | 2017-06-15 | Antibacterial bionic porous titanium implant and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107115560A true CN107115560A (en) | 2017-09-01 |
| CN107115560B CN107115560B (en) | 2020-08-28 |
Family
ID=59719958
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710453072.5A Expired - Fee Related CN107115560B (en) | 2017-06-15 | 2017-06-15 | Antibacterial bionic porous titanium implant and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107115560B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109157677A (en) * | 2018-09-26 | 2019-01-08 | 中南大学湘雅三医院 | Personalized calcium phosphate bionic tone tissue bracket and its preparation method and application |
| CN109183023A (en) * | 2018-09-27 | 2019-01-11 | 长沙新材料产业研究院有限公司 | The preparation method and titanium exemplar of titanium surface porosity layer |
| CN110629072A (en) * | 2019-10-10 | 2019-12-31 | 太原理工大学 | Method for preparing porous titanium-aluminum alloy with lamellar structure based on freezing molding process |
| CN111482600A (en) * | 2020-03-13 | 2020-08-04 | 中南大学 | Method for constructing micro/nano structure on surface of pure titanium or titanium alloy based on additive manufacturing technology and application |
| CN112368092A (en) * | 2018-07-06 | 2021-02-12 | 赛莫必乐公司 | Magnesium-based alloy foam |
| CN114054772A (en) * | 2021-10-09 | 2022-02-18 | 季华实验室 | Metal part with micro-nano structure and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102285815A (en) * | 2011-06-07 | 2011-12-21 | 西安理工大学 | Method for preparing double-pore type porous ceramic |
| CN105816913A (en) * | 2010-07-02 | 2016-08-03 | 阿格诺沃医疗保健有限责任公司 | Composition comprising calcium phosphate and sulfate powders and tri-calcium phosphate particles used in the treatment of degenerative bone conditions |
| KR20170041302A (en) * | 2015-10-06 | 2017-04-17 | 한국생산기술연구원 | Method for manufacturing porous Titanium scaffolds by utilizing freeze casting |
-
2017
- 2017-06-15 CN CN201710453072.5A patent/CN107115560B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105816913A (en) * | 2010-07-02 | 2016-08-03 | 阿格诺沃医疗保健有限责任公司 | Composition comprising calcium phosphate and sulfate powders and tri-calcium phosphate particles used in the treatment of degenerative bone conditions |
| CN102285815A (en) * | 2011-06-07 | 2011-12-21 | 西安理工大学 | Method for preparing double-pore type porous ceramic |
| KR20170041302A (en) * | 2015-10-06 | 2017-04-17 | 한국생산기술연구원 | Method for manufacturing porous Titanium scaffolds by utilizing freeze casting |
Non-Patent Citations (3)
| Title |
|---|
| A. MACCHETTA等: "Fabrication of HA/TCP scaffolds with a graded and porous structure using a camphene-based freeze-casting method", 《ACTA BIOMATERIALIA》 * |
| HYUN-DO JUNG等: "Dynamic freeze casting for the production of porous titanium (Ti) scaffolds", 《MATERIALS SCIENCE AND ENGINEERING C》 * |
| TERJE SJÖSTRÖM等: "Bactericidal nanospike surfaces via thermal oxidation of Ti alloy substrates", 《MATERIALS LETTERS》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112368092A (en) * | 2018-07-06 | 2021-02-12 | 赛莫必乐公司 | Magnesium-based alloy foam |
| US11913092B2 (en) * | 2018-07-06 | 2024-02-27 | Cellmo Materials Innovation, Inc. | Magnesium-based alloy foam |
| CN109157677A (en) * | 2018-09-26 | 2019-01-08 | 中南大学湘雅三医院 | Personalized calcium phosphate bionic tone tissue bracket and its preparation method and application |
| CN109157677B (en) * | 2018-09-26 | 2021-08-31 | 中南大学湘雅三医院 | Personalized calcium phosphate bionic bone tissue scaffold and preparation method and application thereof |
| CN109183023A (en) * | 2018-09-27 | 2019-01-11 | 长沙新材料产业研究院有限公司 | The preparation method and titanium exemplar of titanium surface porosity layer |
| CN110629072A (en) * | 2019-10-10 | 2019-12-31 | 太原理工大学 | Method for preparing porous titanium-aluminum alloy with lamellar structure based on freezing molding process |
| CN111482600A (en) * | 2020-03-13 | 2020-08-04 | 中南大学 | Method for constructing micro/nano structure on surface of pure titanium or titanium alloy based on additive manufacturing technology and application |
| CN111482600B (en) * | 2020-03-13 | 2022-09-20 | 中南大学 | Method for constructing micro/nano structure on surface of pure titanium or titanium alloy based on additive manufacturing technology and application |
| CN114054772A (en) * | 2021-10-09 | 2022-02-18 | 季华实验室 | Metal part with micro-nano structure and preparation method and application thereof |
| CN114054772B (en) * | 2021-10-09 | 2024-01-02 | 季华实验室 | Metal part with micro-nano structure and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107115560B (en) | 2020-08-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107115560A (en) | Biomimetic porous titanium implantses of antibacterial and its preparation method and application | |
| Tian et al. | Fabrication of silver nanoparticle-doped hydroxyapatite coatings with oriented block arrays for enhancing bactericidal effect and osteoinductivity | |
| CN100551450C (en) | A kind of preparation method of antiseptic biological active titanium coating | |
| Zhao et al. | Antibacterial and osteogenic activity of a multifunctional microporous coating codoped with Mg, Cu and F on titanium | |
| CN105903057B (en) | Preparation method of nano silver hydridization silk gum porous gel anti-biotic material and products thereof and application | |
| CN104645414B (en) | Titanium-based surface antibacterial and bone tissue regeneration inductivity functional coating and its preparation method and application | |
| JP2017127744A (en) | Biological implant | |
| CN102212717A (en) | Copper-bearing antibacterial titanium alloy and preparation method thereof | |
| JP2012040194A (en) | Biological implant | |
| CN107661544A (en) | Antibacterial facilitates porous orthopaedics implant of bone complex function and preparation method thereof | |
| EP3854423B1 (en) | Artificial dermis repair material and preparation method therefor | |
| CN107739886B (en) | A kind of titanium silver alloy and preparation method thereof for orthopaedics implant | |
| Bai et al. | Fabrication and characterization of suspension plasma-sprayed fluoridated hydroxyapatite coatings for biomedical applications | |
| KR102592558B1 (en) | Method for producing cellulose nonwovens synthesized by bacteria | |
| CN106637121B (en) | A kind of medical titanium metal alkyl materials and its manufacturing method | |
| Meng et al. | A wettability-transformable superhydrophobic composite coating of hydroxyapatite/bismuth sulfide/lauric acid on AZ31B Mg alloy with dual-function of antibacterial and osteogenic properties | |
| CN104784739A (en) | Preparation method of composite antibacterial dressing loaded with silver sulfadiazine | |
| CN103550254B (en) | Breathable itching-relieving antisepsis scar treating paster and preparation method thereof | |
| CN101862269A (en) | Preparation of nano-coating micropore surface implant having regeneration activity and antibacterial property | |
| CN110251722A (en) | Phosphoric acid magnesium-based bone renovating material, feedstock composition and preparation method thereof, application | |
| CN107648674A (en) | With antibacterial and the metal implant for promoting Integrated implant function and preparation method thereof | |
| Kumar et al. | 3D porous polyurethane (PU)/triethanolamine modified hydroxyapatite (TEA-HA) nano composite for enhanced bioactivity for biomedical applications | |
| Li et al. | Preparation and properties of a 3D printed nHA/PLA bone tissue engineering scaffold loaded with a β-CD–CHX combined dECM hydrogel | |
| CN107082907A (en) | Preparation method of porous silk gum/polyvinyl alcohol gel and products thereof and application | |
| CN203029680U (en) | Medical dressing |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200828 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |