CN102051569B - Method for preparing titanium/hydroxyapatite composite coating - Google Patents
Method for preparing titanium/hydroxyapatite composite coating Download PDFInfo
- Publication number
- CN102051569B CN102051569B CN 201110027453 CN201110027453A CN102051569B CN 102051569 B CN102051569 B CN 102051569B CN 201110027453 CN201110027453 CN 201110027453 CN 201110027453 A CN201110027453 A CN 201110027453A CN 102051569 B CN102051569 B CN 102051569B
- Authority
- CN
- China
- Prior art keywords
- spray
- titanium
- composite coating
- spraying
- hydroxyapatite powder
- 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 invention relates to a method for preparing a titanium/hydroxyapatite composite coating, which is characterized by comprising the following steps of: cladding hydroxyapatite powder serving as a spraying material by pure titanium; operating in a spraying cabin of which the atmosphere is controllable by an electric-arc spraying method; and preparing the titanium/hydroxyapatite composite coating by sedimenting on the surfaces of various metal substrates. In the invention, two biological materials which have widest prospects are blended so as to not only keep the strength and the toughness of the metal material, but also keep the bioactivity of hydroxyapatite and realize high biocompatibility.
Description
Technical field
The invention belongs to bio-medical material manufacturing technology field, refer in particular to a kind of method for preparing titanium/carboxy apatite composite coating.
Background technology
Titanium has high breaking tenacity and corrosion resisting property and excellent biological compatibility as the biomaterial that is widely used in plastic sugery and dentistry.But the biological activity of titanium is relatively poor, is difficult for forming biological the combination with natural bone.The chemical ingredients of Win 40350 is similar with the calcium phosphate inorganics in the biological osseous tissue, can with the firm Chemical bond of bone forming, impel new bone in its surperficial growth, help implant and produce bone property bonding, and can shorten healing time with new bone.The generally acknowledged artificial skelecton equivalent material of medical circle is the alloy material and the hydroxyapatite material of metal titanium at present.Metal titanium has intensity and good toughness, the requirement of very approaching biological bone, but behind implant into body or the organism; Often be difficult to produce the ideal biocompatibility; Lacking biological activity, is that simple mechanical-physical combines, and makes the application of this material receive very big restriction.Win 40350 is the stupalith the same with the bone composition; After making artificial skelecton; Test shows that though have good biocompatibility behind the implantable bioartificial body, intensity and toughness are very low; All the time can not become the ideal substitute of bone, also limit its application greatly at medical field.Present many research work concentrate on the surface-active improvement of titanium or titanium alloy, prepare hydroxyapatite coating layer or preparation titanium/carboxy apatite composite coating method at titanium alloy surface, improve the biological activity of implant.Preparation hydroxyapatite coating layer technology has many kinds at present, for example: plasma spraying method, ion beam depositing method and electrochemical deposition method etc.
In the above-mentioned method for preparing joint prosthesis, spraying method is that technology is the simplest, a kind of method that cost is also minimum.In recent years, some have been arranged about prepare the research of HA coating with plasma spraying abroad, for example the spray power of employing 30kW such as K.de Groot of Holland has successfully prepared the HA coating that thickness is about 50 μ m; The Lv Yu of Harbin Institute of Technology roc etc. has been studied with low power air plasma spraying method and has prepared hydroxyapatite coating layer and thermal treatment crystallization process thereof; The He Ding of Beijing University of Technology bravely waits and has studied the technology of utilizing the microplasma spraying hydroxyapatite coating layer.But this kind process method existing questions is the resolution problem of Win 40350 under spraying high temperature at present; In addition, plasma spraying is owing to be difficult to the structure and the chemical constitution of accurate control coating, and bonding strength also is difficult to reach people's expected value.In order to overcome these problems, some research both at home and abroad adopts the vacuum spraying technology to combine with the accurate control of spraying standard, prepares the HA coating of articular surface.The vacuum spraying method is a kind of new technology that is proposed by people such as German Steffens.H.D nineteen ninety, and the L.Zhao of Aachen, Germany polytechnical university and E. Lugscheider are used for this technology the preparation of titanium compound coating again.
But in these research work in the past; Still there is following problem still not have good solution: the 1. bonding strength problem of spraying particle: for the metal spraying particle; If adopt the atmosphere spraying; Particle surface is certain to form zone of oxidation, and this oxidation interface in advance can't be eliminated by aftertreatment, makes Bond Strength of Coating can only reach 1/5～1/10 of its tensile strength usually.And for Ti, can't spray by atmosphere at all and obtain the qualified coating of composition.2. adopt the vacuum plasma spray coating technology that the problem of surface oxidation is improved; But since particle when arriving coating layer temperature usually all below 200 ℃; Even its flattening can accumulate certain resilient energy; But, also can't improve bonding strength by recrystallize because this moment, temperature was low excessively.3. when adopting Ti/Win 40350 powder mix to spray, the temperature of rifle body is difficult to be provided with.If spraying temperature is low, then Ti powder lack of fusion causes a large amount of holes and is mingled with.And if with the spraying temperature raising, then decomposition failure can take place again in Win 40350, loses its characteristic of biological activity.
Summary of the invention
Technical scheme according to the invention had both kept the intensity and the toughness of metallic substance, had kept the biological activity of Win 40350 again.
Technical scheme of the present invention is:
A kind of method for preparing titanium/carboxy apatite composite coating; It is characterized in that: coat hydroxyapatite powder as spray material with the pure titanium metal crust; Through the spray booth operation of arc spray process at controlled atmosphere; At multiple metallic substrate surface deposition, preparation titanium/carboxy apatite composite coating.
Distance between spray gun and the metal base is 100-150mm.
When in the spray booth of controlled atmosphere, adopting arc spray process to operate, protection gas is argon gas with the spraying atomizing gas in the cabin.
The WV of spray gun is 30-32V, and electric current 120-180A, the argon pressure of injection are 0.5-0.8Mpa.
The parallel connection of 2-3 bottle argon gas is used together.
When making spray material, use pure titanium band, coat hydroxyapatite powder, be specially: at first pure titanium band is shaped and be U-shaped, and fill hydroxyapatite powder therein, be shaped as the seam tubulose as spray material as crust; Final drawing patent medicine core Spray Wire.
The thickness of pure titanium band is between 0.2-0.4mm.
The granularity of hydroxyapatite powder is 50-100 μ m.
The diameter of medicine core Spray Wire is 2.0mm.
The invention provides a kind of titanium/carboxy apatite composite coating method that is used to prepare, two kinds of biomaterials that have future most are blended together.The intensity and the toughness that have promptly kept metallic substance have kept the biological activity of Win 40350 again, have realized excellent biological compatibility.
Description of drawings:
Fig. 1 is the microtexture pattern of electric arc spraying titanium/carboxy apatite composite coating;
Fig. 2 is titanium/carboxy apatite composite coating composition energy spectrum analysis position view;
Fig. 3 is the composition analysis result at Fig. 2 mid point 2 places;
Fig. 4 is the composition analysis result at Fig. 2 mid point 1 place;
Embodiment:
Below in conjunction with accompanying drawing and specific embodiment the present invention is elaborated.
1. the preparation of special-purpose electric arc spraying medicine core Spray Wire:
Adopting full tandem rolling method, is that the thick pure titanium band of 0.3mm is configured as U-shaped with thickness earlier, and the filling granularity is the high purity hydroxyapatite powder of 50-100 μ m in the titanium band, is shaped as the seam tubulose; Rolling through several roads, finally being drawn into diameter is the medicine core Spray Wire of 2.0mm.
Wherein the high purity hydroxyapatite powder adopts following method to make: claim to take out respectively 59.036g, 30.47g, 2.01g with nitrocalcite (CaNO3-4H2O), phosphoric acid ammonia ((NH4) 3PO4-3H2O) and sodium hydroxide (NaOH) with electronic balance; Put into the beaker of three 500ml then respectively; Pour 82ml respectively successively into, 92ml, the deionized water of 50ml; Stir with whisking appliance, wait to be stirred to the three and all dissolve.Let ℃ insulation of water bath with thermostatic control heater heats to 85.The beaker of nitrocalcite is put into water-bath.Pour into phosphoric acid ammonia in the beaker of nitrocalcite again and begin slowly to pour into sodium hydroxide and stir with glass stick simultaneously, fully react.At this moment occur in the beaker white flocks by rare to thick., reaction to test when carrying out with the qualitative test paper of pH.The test paper reflection should be to drop to pH7 gradually by pH9-10.By the time reaction finishes, and beaker is put well, leaves standstill 12 hours.Utilize 300 order filter clothes to filter away the aqueous solution then, keep deposition, refilter all over the white precipitate that is generated with deionized water wash is several then, add absolute ethanol washing twice at last, to guarantee that big agglomeration does not appear in powder.Place loft drier with filtering good deposition, oven dry is 20 hours under 60 ℃ of conditions.After dry the completion, the grinding of agglomerative powder is obtained superfine powder, sieving for standby gets final product.
2. electric arc spraying titanium/carboxy apatite composite coating in the controlled atmosphere spray booth:
Before the spraying, need sandblast alligatoring pre-treatment is carried out on the surface of metal base, the sandblast quality reaches the Sa3 level.Select for use argon gas as the spraying atomizing gas during electric arc spraying, in order to guarantee gas flow, need be with use of 2-3 bottle argon gas parallel connection.
Earlier the test specimen base material is placed on the clamping device of controlled atmosphere spray booth, fixing, then, distance is 120mm. between adjustment spray gun and the matrix.Seal hatch door more successively, vacuumize injecting inert gas.When adopting electric arc spraying titanium/Win 40350 medicine core Spray Wire to spray, WV is 31V, and electric current 150A, the argon pressure of injection are 0.7Mpa.Open vent valve during spraying, guarantee in spray booth, to form enough pressure reduction.Coat-thickness 150 μ m.Spraying is opened hatch door after accomplishing, and can take out test specimen.
Accompanying drawing 1 is exactly the microtexture pattern of prepared titanium/carboxy apatite composite coating.Accompanying drawing 2-4 is the result who compound coating is carried out the composition energy spectrum analysis.By visible among the figure, white is the Win 40350 phase mutually, and black matrix is organized as metal titanium.
The composition analysis table at point 2 places is as shown in table 1:
Table 1
The composition analysis table at point 1 place is as shown in table 2:
Table 2.
Claims (1)
1. method for preparing titanium/carboxy apatite composite coating; It is characterized in that: coat hydroxyapatite powder as spray material with the pure titanium metal crust; Through the spray booth operation of arc spray process at controlled atmosphere; At multiple metallic substrate surface deposition, preparation titanium/carboxy apatite composite coating; Distance between spray gun and the metal base is 100-150mm; The WV of spray gun is 30-32V, and electric current 120-180A, the argon pressure of injection are 0.5-0.8Mpa;
When making spray material, use pure titanium band, coat hydroxyapatite powder, be specially: at first pure titanium band is shaped and be U-shaped, and fill hydroxyapatite powder therein, be shaped as the seam tubulose as spray material as crust; Final drawing patent medicine core Spray Wire;
The thickness of pure titanium band is between 0.2-0.4mm;
The granularity of hydroxyapatite powder is 50-100 μ m;
The diameter of medicine core Spray Wire is 2.0mm.
2. according to the said method for preparing titanium/carboxy apatite composite coating of claim 1, it is characterized in that: when in the spray booth of controlled atmosphere, adopting arc spray process to operate, protection gas is argon gas with the spraying atomizing gas in the cabin.
3. according to the said method for preparing titanium/carboxy apatite composite coating of claim 1, it is characterized in that: the parallel connection of 2-3 bottle argon gas is used together.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110027453 CN102051569B (en) | 2011-01-26 | 2011-01-26 | Method for preparing titanium/hydroxyapatite composite coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110027453 CN102051569B (en) | 2011-01-26 | 2011-01-26 | Method for preparing titanium/hydroxyapatite composite coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102051569A CN102051569A (en) | 2011-05-11 |
| CN102051569B true CN102051569B (en) | 2012-12-19 |
Family
ID=43956361
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110027453 Expired - Fee Related CN102051569B (en) | 2011-01-26 | 2011-01-26 | Method for preparing titanium/hydroxyapatite composite coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102051569B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105018924B (en) * | 2014-11-14 | 2017-12-26 | 中国兵器工业第五二研究所 | A kind of preparation method of titanium alloy substrate hydroxyapatite coating on surface |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1908231A (en) * | 2006-08-23 | 2007-02-07 | 天津理工大学 | Method of fast growing HA biologically active layer from oxidation film on titanium alloy surface by ultraviolet excitation |
| CN101011599A (en) * | 2007-02-01 | 2007-08-08 | 厦门大学 | Process for preparing composite coat of hydroxy apatite and aluminum oxide |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE527610C2 (en) * | 2004-06-15 | 2006-04-25 | Promimic Ab | Process for the preparation of synthetic crystalline calcium phosphate in nano size |
-
2011
- 2011-01-26 CN CN 201110027453 patent/CN102051569B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1908231A (en) * | 2006-08-23 | 2007-02-07 | 天津理工大学 | Method of fast growing HA biologically active layer from oxidation film on titanium alloy surface by ultraviolet excitation |
| CN101011599A (en) * | 2007-02-01 | 2007-08-08 | 厦门大学 | Process for preparing composite coat of hydroxy apatite and aluminum oxide |
Non-Patent Citations (2)
| Title |
|---|
| 李德元等.可控气氛喷涂钛涂层及涂层电化学性能.《沈阳工业大学学报》.2010,第32卷(第1期),第37页左栏第19行至右栏第2行. * |
| 郑学斌等.等离子喷涂HA/Ti复合涂层研究Ⅰ.结构、组成和力学性能.《无机材料学报》.2000,第15卷(第5期),第897页倒数第4-1行. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102051569A (en) | 2011-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102268711B (en) | Method for preparing biological composite coating on surface of magnesium-based material | |
| CA2351009C (en) | Coating for metallic implant materials | |
| CA2150036C (en) | A material for a bone substitute and the manufacturing method thereof | |
| CN110152056B (en) | Method for rapidly introducing functional ions into surface of titanium alloy | |
| CN103751840B (en) | A kind of have bone defect repair support of the controlled low modulus of porous and preparation method thereof | |
| CN101461964B (en) | Bioactivity surface modification method of biological medical degradable magnesium alloy | |
| CN101249279B (en) | Method for using laser quick forming for producing HA/Ti gradient biological activity material | |
| CN103933611B (en) | The preparation method of medical magnesium alloy surface hydroxyapatite/polylactic acid composite coating | |
| CN101984144B (en) | Surface mount method of mineralized collagen gradient coating for medical titanium implant | |
| CN101643929A (en) | Pulse electrodeposition preparation method of hydroxyapatite coating on surface of pure magnesium or magnesium alloy | |
| CN104947097B (en) | A kind of preparation method of pure titanium surface phosphoric acid hydrogen calcium micro nanometer fiber conversion film | |
| WO2010130109A1 (en) | Method for preparing porous hydroxyapatite coatings by suspension plasma spraying | |
| CN104888271A (en) | Method for preparing strontium-containing hydroxyapatite coating on surface of biodegradable magnesium alloy | |
| CN104436301A (en) | Preparation method of phytic acid/hydroxyapatite hybrid coating on magnesium alloy | |
| CN101991879A (en) | Preparation method of carbon-carbon composite material/hydroxyapatite/polylactic acid biological material | |
| CN102330086A (en) | Titanium dioxide-hydroxyapatite gradient coating of medical titanium or titanium alloy surface and preparation method | |
| Liu et al. | Micro-arc oxidation-assisted sol-gel preparation of calcium metaphosphate coatings on magnesium alloys for bone repair | |
| WO2004098436A2 (en) | Method for producing adherent coatings | |
| CN107761148A (en) | A kind of method that fibroin albumen hydroxyapatite coating layer is prepared in metal surface | |
| CN105497990B (en) | A kind of three-dimensional porous titanium-based magnesium doping coating and preparation method thereof | |
| CN102051569B (en) | Method for preparing titanium/hydroxyapatite composite coating | |
| CN103785066B (en) | Type I collagen modified porous titanium coat and making method thereof | |
| CA2757157A1 (en) | A method of surface treatment of an implant, an implant treated by said method and an electrolyte solution for use in said method | |
| CN107338425A (en) | A kind of preparation method of the titanium surface bioactivity conversion film of phosphate containing strontium | |
| CN1128251C (en) | Bioactive composite Ca-P ceramics/chitosan film on metal surface and electrochemical co-deposition process for preparing it |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121219 Termination date: 20150126 |
|
| EXPY | Termination of patent right or utility model |