CN1486752A - 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
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- CN1486752A CN1486752A CNA031421504A CN03142150A CN1486752A CN 1486752 A CN1486752 A CN 1486752A CN A031421504 A CNA031421504 A CN A031421504A CN 03142150 A CN03142150 A CN 03142150A CN 1486752 A CN1486752 A CN 1486752A
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- Prior art keywords
- metal
- hydroxyapatite
- artificial bone
- based porous
- oxide
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 35
- 239000002184 metal Substances 0.000 title claims abstract description 35
- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 32
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 title claims abstract description 32
- 210000000988 bone and bone Anatomy 0.000 title claims abstract description 25
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 21
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 21
- 239000002131 composite material Substances 0.000 title abstract description 3
- 238000000034 method Methods 0.000 title description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 239000011224 oxide ceramic Substances 0.000 claims abstract description 8
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 229910052586 apatite Inorganic materials 0.000 claims description 11
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- 239000010409 thin film Substances 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 230000001476 alcoholic effect Effects 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 150000001447 alkali salts Chemical class 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims description 2
- 210000001519 tissue Anatomy 0.000 abstract description 3
- 239000000316 bone substitute Substances 0.000 abstract description 2
- 210000004394 hip joint Anatomy 0.000 abstract description 2
- 239000000919 ceramic Substances 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000010422 painting Methods 0.000 abstract 1
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 abstract 1
- 210000001694 thigh bone Anatomy 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 230000000975 bioactive effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 102000009123 Fibrin Human genes 0.000 description 1
- 108010073385 Fibrin Proteins 0.000 description 1
- BWGVNKXGVNDBDI-UHFFFAOYSA-N Fibrin monomer Chemical compound CNC(=O)CNC(=O)CN BWGVNKXGVNDBDI-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002929 anti-fatigue Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003462 bioceramic Substances 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 229950003499 fibrin Drugs 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 238000004372 laser cladding Methods 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 210000004872 soft tissue Anatomy 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 210000000689 upper leg Anatomy 0.000 description 1
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Abstract
The composite metal-based porous metal oxide/hydroxyapatite artificial bone consists of metal base, metal oxide ceramic layer and hydroxyapatite layer superposed together. The preparation process includes successively cleaning the surface of the metal base, micro arc oxidation to form the ceramic layer and sol-gel painting to form the hydroxyapatite film. The artificial bone with two-layer structure of metal oxide ceramic layer and hydroxyapatite layer on the metal base has excellent biocompatibility and mechanical performance. The porous structure of surface film is favorable to combination with tissue, and the artificial bone may be used as bone substitute with great load, such as for thighbone and hip joint. The simple preparation process is suitable for both lab making 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/1Na
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 (4)
1. metal-based porous metal-oxide/hydroxyapatite cmposite artificial bone is characterized in that repeatedly being put by Metal Substrate (1), metal oxide ceramic layer (2) and hydroxyapatite layer (3) successively forming.
2. metal-based porous metal-oxide according to claim 1/hydroxyapatite cmposite artificial bone is characterized in that said Metal Substrate is titanium, aluminium metal sheet or sheet, or the alloy sheets or the sheet of titanium, aluminum metal.
3. the preparation method of metal-based porous metal-oxide according to claim 1/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 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.
4. the preparation method of metal-based porous metal-oxide according to claim 3/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 true CN1486752A (en) | 2004-04-07 |
| CN1228098C 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 |
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| Country | Link |
|---|---|
| CN (1) | CN1228098C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102802557A (en) * | 2009-06-18 | 2012-11-28 | 奥齿泰种植体股份有限公司 | Implant coated with net-shaped or island-shaped low-crystallized hydroxyapatite and method for coating 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 |
| CN108103551A (en) * | 2017-11-23 | 2018-06-01 | 昆明理工大学 | A kind of method of hydroxylapatite crystal in promotion differential arc oxidation film layer |
| CN110560695A (en) * | 2019-09-03 | 2019-12-13 | 西安建筑科技大学 | Titanium-based functional gradient material with porous surface and preparation method thereof |
| CN111554948A (en) * | 2020-05-19 | 2020-08-18 | 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
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102802557A (en) * | 2009-06-18 | 2012-11-28 | 奥齿泰种植体股份有限公司 | Implant coated with net-shaped or island-shaped low-crystallized hydroxyapatite and method for coating same |
| US9517187B2 (en) | 2009-06-18 | 2016-12-13 | Osstemimplant Co., Ltd. | Implant coated with net-shaped or island-shaped low-crystallized hydroxyapatite and method for coating 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 |
| CN108103551A (en) * | 2017-11-23 | 2018-06-01 | 昆明理工大学 | A kind of method of hydroxylapatite crystal in promotion differential arc oxidation film layer |
| 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 |
| CN110560695A (en) * | 2019-09-03 | 2019-12-13 | 西安建筑科技大学 | Titanium-based functional gradient material with porous surface and preparation method thereof |
| 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 |
| CN111554948A (en) * | 2020-05-19 | 2020-08-18 | 湖南金天铝业高科技股份有限公司 | Bipolar plate, preparation method and application 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 |
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| Publication number | Publication date |
|---|---|
| CN1228098C (en) | 2005-11-23 |
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