CN1228098C - Composite metal-based porous metal oxide/hydroxyapatite artificial bone and its prepn process - Google Patents
Composite metal-based porous metal oxide/hydroxyapatite artificial bone and its prepn process Download PDFInfo
- Publication number
- CN1228098C CN1228098C CN 03142150 CN03142150A CN1228098C CN 1228098 C CN1228098 C CN 1228098C CN 03142150 CN03142150 CN 03142150 CN 03142150 A CN03142150 A CN 03142150A CN 1228098 C CN1228098 C CN 1228098C
- Authority
- CN
- China
- Prior art keywords
- metal
- hydroxyapatite
- artificial bone
- based porous
- metal oxide
- 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.)
- Expired - Fee Related
Links
Images
Landscapes
- Materials For Medical Uses (AREA)
Abstract
The present invention relates to a metal-based porous metal oxide/hydroxyapatite compound artificial bone which is prepared by orderly overlapping a metal base, a metal oxide ceramic layer and a hydroxyapatite layer. The preparation method orderly comprises the steps: cleaning the surface of the metal base, oxidizing the ceramic layer by micro-arcs and coating a hydroxyapatite film by a sol gel method. The metal-based porous metal oxide/hydroxyapatite compound artificial bone comprises the metal oxide ceramic layer and the hydroxyapatite layer on the metal base and has good biocompatibility and mechanical performance. The surface film layer is in a porous structure, and thereby, the metal-based porous metal oxide/hydroxyapatite compound artificial bone is beneficial to the combination of the surface film layer and tissues and can be effectively used as materials of a bone substitute in the position for bearing a large load, such as femur, hip joints, etc. The metal-based porous metal oxide/hydroxyapatite compound artificial bone has the advantages of simple preparation technology, convenient manufacture in laboratories and industrial production.
Description
Technical field
The present invention relates to a kind of metal-based porous metal-oxide/hydroxyapatite cmposite artificial bone and preparation method thereof, belong to biological composite medical investigation of materials field.
Background technology
Titanium, aluminum and alloy thereof have excellent mechanical property, and plantation has intensity and the elastic modelling quantity higher than skeleton when replacing skeleton in vivo.The good biocompatibility of titanium wherein, its corrosion-resistant and anti-fatigue performance all is better than rustless steel and cobalt-base alloys, and outstanding biocompatibility is because the oxide layer on surface: (1) TiO
2Has lower intrinsic toxicity; (2) TiO
2Dissolubility in water is very low; (3) the peroxide chemical phenomenon has the antiinflammatory action of meditation.
Hydroxyapatite (HA) is the main component that constitutes body bone tissue, and in natural bone, inorganic constituents is HA crystallization and other trace element, and the organic principle major part is the fibrin ossein.HA belongs to bioactive materials, and promptly area of new bone directly forms on its surface, the implantation body's internal skeleton bonding growth of directly growing into subsequently.Because its excellent biological compatibility and bone guided effect are used by clinical each section gradually.Single relation of growing into from material pore-size and human body soft tissue, porous HA pottery is better than the HA pottery in few hole.But artificial preparation HA pottery is than big many of the elastic modelling quantity of natural bone, and toughness is far below the natural bone at carrying position.
The bone that single HA, metal and alloy all are difficult to well finish at the carrying position is replaced, and the fragility of ceramic material has limited the application of biomaterial in carrying bone alternative aspect.Therefore, numerous bioactive ceramicses are used as the mechanical property of the coating material of metal surface with bond, thereby enlarge the application of bioceramic.The method that adopts has plasma spraying, chemical electro-deposition, laser cladding, ion beam assisted depositing etc. at present, but adopt these methods to be difficult to obtain the coating of multiple structure and porous surface pattern, equipment, technology and the complex process of preparation are difficult to realize commercial production.
Summary of the invention
The purpose of this invention is to provide a kind of metal-based porous metal-oxide/hydroxyapatite cmposite artificial bone and preparation method thereof, with the adhesion of further raising tissue and artificial bone with good biocompatibility.
Metal-based porous metal-oxide of the present invention/hydroxyapatite cmposite artificial bone is formed by stacking the putting of Metal Substrate, metal oxide ceramic layer and hydroxyapatite successively.
Above-mentioned Metal Substrate can be titanium, aluminium metal sheet or sheet, also can be the alloy sheets or the sheet of titanium, aluminum metal.
The preparation method of metal-based porous metal-oxide/hydroxyapatite cmposite artificial bone comprises that successively clean metal primary surface, arc differential oxide ceramic layer and sol-gal process apply the hydroxyapatite film, and concrete steps are as follows:
1), removes the greasy dirt on Metal Substrate surface, and clean with clear water with alkali cleaning or pickling clean metal primary surface;
2) in the electrolyte of acidity or basic salt, be negative electrode with the corrosion resistant plate, be anode with the Metal Substrate that cleaned, under 0～70 ℃ temperature, at 1000～6000A/m
2Current density range carries out differential arc oxidation to be handled 5～20 minutes, cleaned, dried;
3) will contain Ca alcoholic solution and P
2O
5Alcoholic solution is to be mixed with uniform solution in 3: 1～1: 1 by the Ca/P mol ratio;
4) will be through step 2) handle Metal Substrate place solution, lift thin film with the speed dipping of 4.4～8.6cm/min;
5) thin film is handled 5～20min at 150～200 ℃ and form colloidal sol, handle 5～30min at 500～700 ℃ again and form the apatite phase, promptly get product.
Above-mentioned Ca alcoholic solution can adopt Ca (NO
3)
2, Ca (HCO
3)
2Or CaCl
2Alcoholic solution.
Among the present invention, the thickness of metal oxide ceramic layer can be controlled by the time of regulating differential arc oxidation.The thickness of apatite phase rete can be by repeating step 4 successively) and the number of times of step 5) decide.
Metal-based porous metal-oxide of the present invention/hydroxyapatite cmposite artificial bone has metal oxide ceramic layer and hydroxyapatite double-layer structure on Metal Substrate, have good biocompatibility and mechanical property, and superficial film has porous structure, help being in the same place with tissue bond, can effectively be used as the material of the bone substitute that bears big load position, for example femur, hip joint etc.Preparation technology of the present invention is simple, promptly is convenient to making in laboratory, can be used for commercial production again.
Description of drawings
Fig. 1 is metal-based porous metal-oxide/hydroxyapatite cmposite artificial bone schematic cross-section.
Fig. 2 is the microscopic appearance figure of embodiment 1.
Fig. 3 is the microscopic appearance figure of embodiment 2.
The specific embodiment
With reference to Fig. 1, metal-based porous metal-oxide of the present invention/hydroxyapatite cmposite artificial bone is repeatedly put by Metal Substrate 1, metal oxide ceramic layer 2 and hydroxyapatite layer 3 successively and is formed.
Further specify preparation method below in conjunction with embodiment.
Embodiment 1
Depletion belongs to pure titanium sheet, removes behind the surface and oil contaminant with 10% NaOH solution and cleans with clear water, at 10g/lNa
2SiO
3And 0.2M/lH
2SO
4Electrolyte in, electric current density keeps 2000A/m
2, electrolyte temperature is no more than 70 ℃, 15 minutes afterwash of differential arc oxidation, oven dry.Sol-gal process applies hydroxyapatite films, with Ca (NO
3)
2And P
2O
5Be mixed with alcoholic solution, press Ca/P mol ratio preparation in 5: 3 apatite precursor.Lift thin film with the speed of 4.4～8.6cm/min dipping, handle 20min for 150 ℃ and form colloidal sols, handle 30min for 600 ℃ and form the apatite phases, the above-mentioned repeatedly thin film that lifts is handled and is formed colloidal sol, apatite is operated 5 times mutually and obtained certain thickness apatite film.The products obtained therefrom surface has loose structure, sees Fig. 2.
Embodiment 2
Get aluminium alloy LY12, remove behind the surface and oil contaminant with 10% NaOH solution and clean, at 10g/lH with clear water
3BO
3, 2g/lKOH and 2g/lNa
2WO
4In the electrolyte, keep electric current density 1500A/m
2, electrolyte temperature is no more than 70 ℃, 30 minutes afterwash of differential arc oxidation, oven dry.Sol-gal process applies hydroxyapatite films, with Ca (NO
3)
2And P
2O
5Be mixed with alcoholic solution, according to stoichiometry mol ratio preparation in 5: 3 apatite precursor.Lift thin film with the speed of 4.4～8.6cm/min dipping, handle 15min for 150 ℃ and form colloidal sols, handle 15min for 500 ℃ and form the apatite phases, repeat the above-mentioned thin film that lifts, handle and form colloidal sol, apatite is operated mutually and obtained the certain thickness apatite film for twice.The surface topography of products obtained therefrom is seen Fig. 3, and its surface has loose structure.
Claims (2)
1. the preparation method of metal-based porous metal-oxide/hydroxyapatite cmposite artificial bone is characterized in that may further comprise the steps:
1) with alkali cleaning or pickling clean metal surface;
2) in the electrolyte of acidity or basic salt, be negative electrode with the corrosion resistant plate, be anode with the Metal Substrate that cleaned, under 0～70 ℃ temperature, at 1000～6000A/m
2Current density range carries out differential arc oxidation to be handled 5～20 minutes, cleaned, dried;
3) will contain Ca alcoholic solution and P
2O
5Alcoholic solution is to be mixed with uniform solution in 3: 1～1: 1 by the Ca/P mol ratio;
4) will be through step 2) Metal Substrate handled places solution, lifts thin film with the speed dipping of 4.4～8.6cm/min;
5) thin film is formed colloidal sol at 150～200 ℃ of heat treatment 5～20min, form the apatite phase at 500～700 ℃ of heat treatment 5～30min again, promptly get product.
2. the preparation method of metal-based porous metal-oxide according to claim 1/hydroxyapatite cmposite artificial bone is characterized in that said Ca alcoholic solution is Ca (NO
3)
2, Ca (HCO
3)
2Or CaCl
2Alcoholic solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03142150 CN1228098C (en) | 2003-08-06 | 2003-08-06 | Composite metal-based porous metal oxide/hydroxyapatite artificial bone and its prepn process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03142150 CN1228098C (en) | 2003-08-06 | 2003-08-06 | Composite metal-based porous metal oxide/hydroxyapatite artificial bone and its prepn process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1486752A CN1486752A (en) | 2004-04-07 |
| CN1228098C true CN1228098C (en) | 2005-11-23 |
Family
ID=34155626
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03142150 Expired - Fee Related CN1228098C (en) | 2003-08-06 | 2003-08-06 | Composite metal-based porous metal oxide/hydroxyapatite artificial bone and its prepn process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1228098C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101091589B1 (en) * | 2009-06-18 | 2011-12-13 | 오스템임플란트 주식회사 | Implants coated with low crystalline hydroxyapatite in form of a network or an island and a method for coating the same |
| CN101766843B (en) * | 2010-02-05 | 2013-06-19 | 清华大学 | Artificial bone with porous laminated structure and passages and preparation method thereof |
| CN102614545A (en) * | 2012-03-15 | 2012-08-01 | 河南师范大学 | Metal-based implant ternary compound coating material and preparation method thereof |
| CN108103551B (en) * | 2017-11-23 | 2019-07-16 | 昆明理工大学 | A kind of method of hydroxylapatite crystal in promotion differential arc oxidation film layer |
| CN110560695B (en) * | 2019-09-03 | 2021-10-22 | 西安建筑科技大学 | Titanium-based functional gradient material with porous surface and preparation method thereof |
| CN111554948B (en) * | 2020-05-19 | 2021-10-22 | 湖南金天铝业高科技股份有限公司 | Bipolar plate, preparation method and application thereof |
-
2003
- 2003-08-06 CN CN 03142150 patent/CN1228098C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1486752A (en) | 2004-04-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU2013217081B2 (en) | Products of manufacture having tantalum coated nanostructures, and methods of making and using them | |
| CN102146577B (en) | Pure-titanium metal surface micro-arc oxidation treatment electrolyte and antimicrobial bioactive coating preparation method thereof | |
| AU2008315782B2 (en) | Method of forming a bioactive coating | |
| CN1974876B (en) | Bioactive film on titanium metal surface and its sand blasting-micro arc oxidizing compounding process | |
| CN1115170A (en) | Bone substitute material and process for producing the same | |
| CN101575726B (en) | Method for preparing bioactive gradient film of fluor-hydroxyapatite | |
| Durgalakshmi et al. | Stacked Bioglass/TiO2 nanocoatings on titanium substrate for enhanced osseointegration and its electrochemical corrosion studies | |
| Xuhui et al. | Hydroxyapatite coatings on titanium prepared by electrodeposition in a modified simulated body fluid | |
| Saharudin et al. | Surface modification and bioactivity of anodic Ti6Al4V alloy | |
| CN109680266A (en) | A kind of bioactive ceramic coating and preparation method thereof preparing tantalum atom doping in titanium alloy surface | |
| Wang et al. | Apatite-inducing ability of titanium oxide layer on titanium surface: the effect of surface energy | |
| CN102409382A (en) | Bioactive coating of metal implant and preparation method thereof | |
| CN1228098C (en) | Composite metal-based porous metal oxide/hydroxyapatite artificial bone and its prepn process | |
| Zhang et al. | Preparation and bioactivity of apatite coating on Ti6Al4V alloy by microwave assisted aqueous chemical method | |
| Hsu et al. | Fabrication of nanotube arrays on commercially pure titanium and their apatite-forming ability in a simulated body fluid | |
| CN101491692A (en) | Preparation method of calcium titanate nano-tube array biological coatings | |
| CN100341587C (en) | Biomedicine material of titanium or titanium alloy in use for artificial bones, and preparation method | |
| CN105420786A (en) | Preparation method for nano-sodium silicotitanate/titanium dioxide bio-coatings on titanium surfaces | |
| CN101153409A (en) | Method for producing TiO*/Na*Ti*O* biological ceramic film by differential arc oxidization | |
| Zaniolo et al. | Physical characterization and biological tests of bioactive titanium surfaces prepared by short-time micro-arc oxidation in green electrolyte | |
| CN100557087C (en) | Differential arc oxidation prepares K 2Ti 6O 13Coating and K 2Ti 6O 13The method of/HAp bioceramic film | |
| Gautam et al. | Implant surface modification as a basis of osseointegration: A narrative review | |
| JP2775523B2 (en) | Bone substitute material and its manufacturing method | |
| Jiman et al. | Surface characterization and cytotoxicity analysis of the titanium alloys for dentistry | |
| Tsai et al. | Synthesis of the mesoporous TiO2 array for hydroxyapatite precipitation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |