CN1487117A - Method and product of sputtering and depositing bioactive gradient hydroxyapatite/Ti layer on Ti alloy surface - Google Patents
Method and product of sputtering and depositing bioactive gradient hydroxyapatite/Ti layer on Ti alloy surface Download PDFInfo
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- CN1487117A CN1487117A CNA021585598A CN02158559A CN1487117A CN 1487117 A CN1487117 A CN 1487117A CN A021585598 A CNA021585598 A CN A021585598A CN 02158559 A CN02158559 A CN 02158559A CN 1487117 A CN1487117 A CN 1487117A
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Abstract
The method of sputtering and depositing bioactive gradient hydroxyapatite/Ti layer on Ti alloy surface includes the following steps: mixing and ball milling material powder; hydrothermal reaction; stoving and grinding; mixing target material; cold pressing at 200-300 MPa to form; sintering; double-inclined target sputtering; and heat treatment of the sputtered film. The product has multilayer structure of Ti alloy matrix, compact transition TiO2 layer I with dispersed hydroxyapatite, TiO2 reinforced transition hydroxyapatite layer II, and porous hydroxyapatite layer. The present invention realizes the double gradient of both component and structure, and raises the interface binding strength effectively. The present invention has simple film preparing process and homogeneous film thickness, is suitable for surface activation of implant with complicated shape, and can prepare hard tissue for clinical need, especially as bearing bone repairing and substituting material.
Description
(1) technical field:
The invention belongs to metal and alloy surface and prepare the bioactive layer technology, the method and the goods thereof of particularly a kind of titanium alloy surface cosputtering deposited hydroxyl apatite (HA)/titanium (Ti) bioactive gradient layer.
(2) background technology:
The titanium or titanium alloy that has bioactive layer integrates the mechanical property and the HA excellent biological compatibility of metal excellence, is to be used for the reparation of human loaded bone tooth clinically to substitute institute's indispensable material.Coating combines with the interface of matrix and combines with the interface of body bone tissue is the key of this type of quality of materials of decision.At present, mainly to be many in its surface preparation hydroxyapatite (HA) coating or film, preparation technology commonly used comprises the surface bioactiveization of medical metal: methods such as plasma spraying, laser melting coating, so-gel, electrocrystallization, bionical solution growth, ion beam assisted depositing.Adopt aforesaid method, the greatest problem that the single coating for preparing on metallic matrix exists is an interface bond strength.Because matrix does not match with the coefficient of expansion that is coated with interlayer, will produce bigger unrelieved stress in heating or the process of cooling, makes the adhesion strength of coating be subjected to certain restriction.Therefore, improve Bond Strength of Coating, guarantee its stable existence in vivo, the demand that makes material can satisfy clinical application is a urgent problem.An effective means prepares gradient cladding in the metallic surface exactly, and the method for preparing the biological gradient coating at present has: detonation flame spraying, plasma spraying and powder coated sintering process.But still there are two-phase interface in the just compound coating or the double-deck ladder coating of these method preparations.Having only sol-gel method can make the coating of composition distribution gradient, is the media layer of calcium phosphate and titanium glue between coating and matrix, and the concentration of calcium phosphorus reduces from outside to inside gradually, and the content of titanium is just in time opposite.But also had to component gradient, still can't the implementation structure gradient.At present, the someone proposes to adopt radio frequency/direct magnetic control co-sputtering to prepare 316L stainless steel/SiO at monocrystalline silicon surface
2Laminated film.The method that is provided has been utilized in the sputter coating machine vacuum chamber a plurality of sputtering targets, and the characteristics of the different substances of sputter simultaneously make alloy and ceramic cosputtering, codeposition, and ceramic ion even dispersion distributes, and improves the wear resistance of material greatly.But utilize radio frequency/direct magnetic control co-sputtering technology still not to be reported at metallic surface prepared composition, structure double gradient bioactive layer.
(3) summary of the invention:
The object of the present invention is to provide the method and the goods thereof of a kind of titanium alloy surface cosputtering deposited hydroxyl apatite (HA)/titanium (Ti) bioactive gradient layer, it is from addressing the above problem, make matrix all be continuous variation to the component and the structure of coatingsurface, make coating and matrix not have sharp interface, be each other and combine closely, improved interface bond strength, simultaneously, the vesicular structure on microbial film top layer has guaranteed effective combination the between implant and osseous tissue again, thereby prepares a kind of human body hard tissue reparation, equivalent material that satisfies clinical demand.
Technical scheme of the present invention: the method for a kind of titanium alloy surface cosputtering deposited hydroxyl apatite (HA)/titanium (Ti) bioactive gradient layer is characterized in that it is realized by following steps: 1. raw material powder mixing and ball milling: with dicalcium phosphate dihydrate (CaHPO
42H
2O) and lime carbonate (CaCO
3) by 6: 4 mixed in molar ratio ball millings; 2. add hydro-thermal reaction: add enough deionized waters, temperature is 80-100 ℃; 3. dry, grind; 4. target mixes: hydroxyapatite (HA) powder mixes with 5-15% calcium oxide (CaO) powder; 5. coldmoulding: pressure is 200-300MPa; 6. sintering: temperature is 1100-1200 ℃; 7. double oblique target sputter: carry out the double oblique target sputter with the multi-target magnetic control sputtering instrument, argon flow amount 6-12cm
3/ min, pressure are 2-5Pa, sputtering voltage 100-500V, electric current 1-3A; 8. the thermal treatment of sputtered film.
The above-mentioned said raw material powder mixing and ball milling time can be 12-24 hour.
Above-mentionedly saidly add the hydro-thermal reaction time and can be 2-3 hour.
Temperature in above-mentioned said oven dry, the grinding can be 80-100 ℃, and the time can be 5-8 hour.
Time during above-mentioned said target mixes is 4-8 hour.
Above-mentioned said sintering can place air furnace 2-4 hour.
Magnetron sputtering target in the above-mentioned said double oblique target sputter is a commercial pure titanium, and the radio-frequency sputtering target is hydroxyapatite (HA), and sputtering chamber vacuum tightness is 1-9 * 10
-4
The thermal treatment of above-mentioned said sputtered film can adopt high-pressure steam to handle or Conventional Heat Treatment; The treatment temp that said high-pressure steam is handled is 100 ℃-200 ℃, pressure 0.1-1Mpa, time 3-8 hour; The treatment temp of said Conventional Heat Treatment is 500 ℃-800 ℃, and the time is 1-5 hour.
The goods of a kind of titanium alloy surface cosputtering deposited hydroxyl apatite (HA) that is made by above-mentioned said method/titanium (Ti) bioactive gradient layer is characterized in that it is titanium dioxide (TiO by titanium alloy substrate, disperse distribution hydroxyapatite (HA)
2) fine and close transition layer I, titanium dioxide (TiO
2) the hydroxyapatite transition layer II of dispersion-strengthened and the layer structure of porous hydroxyapatite layer constitute, and do not have sharp interface between above-mentioned layer structure, is continuous variation shape.
Superiority of the present invention is: 1, this method is by the control of sputtering power and gas flow, the interior concentration from matrix to surperficial titanium of film is reduced gradually, the concentration of HA increases (component gradient) gradually, and the quantity of hole increases gradually, making coating and matrix intersection is compact structure, the surface is vesicular structure (structure gradient), has both guaranteed that interface bond strength helped and the combining of osseous tissue; 2, reasonable component gradient design, the interface sudden change of weaken effectively matrix and film reaches thermal expansivity and gradually changes, and reduces unrelieved stress, and bonding strength is improved greatly; 3, rational porosity gradient design makes the porous HA on top layer, is beneficial to growing into of osseous tissue, has guaranteed that embedded material combines with the effective of tissue; 4, the titanium coating of film and the densification of matrix intersection is oxidized to TiO in heat treatment process subsequently
2, stop the stripping of harmful ions such as V, Al in the alloy substrate; 5, the titanium that is entrained in the transition layer among the HA is oxidized to TiO
2Play the effect of dispersion-strengthened, increase the stability of HA; 6, filming technology is simple, and thicknesses of layers is even, is applicable to the surface active of complex-shaped implant; 7, prepare a kind of reparation and equivalent material of the human body hard tissue that can satisfy clinical demand, particularly load bone.
(4) description of drawings:
Wherein: 1 is titanium alloy substrate, and 2 are the titanium dioxide (TiO of disperse distribution hydroxyapatite (HA)
2) fine and close transition layer I, 3 is titanium dioxide (TiO
2) the hydroxyapatite transition layer II of dispersion-strengthened, 4 is the porous hydroxyapatite layer.
(5) embodiment:
Embodiment: the method (see figure 1) of a kind of titanium alloy surface cosputtering deposited hydroxyl apatite (HA)/titanium (Ti) bioactive gradient layer is characterized in that it is realized by following steps:
1. raw material powder mixing and ball milling: with dicalcium phosphate dihydrate (CaHPO
42H
2O) and lime carbonate (CaCO
3) by 6: 4 mixed in molar ratio ball millings, the time was 16 hours;
2. add hydro-thermal reaction: add enough deionized waters, temperature is 90 ℃, and the reaction times is 2 hours;
3. dry, grind, bake out temperature is 80 ℃, and the time is 8 hours.；
4. target mixes: hydroxyapatite (HA) powder mixes with 10% calcium oxide (CaO) powder, and the time during target mixes is 8 hours;
5. coldmoulding: pressure is 200-300MPa;
6. sintering: temperature is 1150 ℃, places air furnace 3 hours;
7. double oblique target sputter: carry out the double oblique target sputter with the multi-target magnetic control sputtering instrument, argon flow amount 9cm
3/ min, pressure are 3Pa, sputtering voltage 300V, and electric current 2A, magnetron sputtering target are commercial pure titanium, and the radio-frequency sputtering target is hydroxyapatite (HA), and sputtering chamber vacuum tightness is 2 * 10
-4
8. the thermal treatment of sputtered film adopts high-pressure steam to handle and Conventional Heat Treatment; The treatment temp that said high-pressure steam is handled is 125 ℃, pressure 0.7Mpa, 3 hours time; The treatment temp of said Conventional Heat Treatment is 700 ℃, and the time is 2 hours.
The goods (see figure 2) of a kind of titanium alloy surface cosputtering deposited hydroxyl apatite (HA) that is made by above-mentioned said method/titanium (Ti) bioactive gradient layer is characterized in that it is titanium dioxide (TiO by titanium alloy substrate 1, disperse distribution hydroxyapatite (HA)
2) fine and close transition layer I 2, titanium dioxide (TiO
2) the hydroxyapatite transition layer II3 of dispersion-strengthened and the layer structure of porous hydroxyapatite layer 4 constitute, and do not have sharp interface between above-mentioned layer structure, is continuous variation shape (visible figure).
Claims (9)
1, the method for a kind of titanium alloy surface cosputtering deposited hydroxyl apatite (HA)/titanium (Ti) bioactive gradient layer is characterized in that it is realized by following steps: 1. raw material powder mixing and ball milling: with dicalcium phosphate dihydrate (CaHPO
42H
2O) and lime carbonate (CaCO
3) by 6: 4 mixed in molar ratio ball millings; 2. add hydro-thermal reaction: add enough deionized waters, temperature is 80-100 ℃; 3. dry, grind; 4. target mixes: hydroxyapatite (HA) powder mixes with 5-15% calcium oxide (CaO) powder; 5. coldmoulding: pressure is 200-300MPa; 6. sintering: temperature is 1100-1200 ℃; 7. double oblique target sputter: carry out the double oblique target sputter with the multi-target magnetic control sputtering instrument, argon flow amount 6-12cm
3/ min, pressure are 2-5Pa, sputtering voltage 100-500V, electric current 1-3A; 8. the thermal treatment of sputtered film.
2, according to the method for the said a kind of titanium alloy surface cosputtering deposited hydroxyl apatite of claim 1 (HA)/titanium (Ti) bioactive gradient layer, it is characterized in that the said raw material powder mixing and ball milling time can be 12-24 hour.
3,, it is characterized in that saidly adding the hydro-thermal reaction time and can be 2-3 hour according to the method for the said a kind of titanium alloy surface cosputtering deposited hydroxyl apatite of claim 1 (HA)/titanium (Ti) bioactive gradient layer.
4, according to the method for the said a kind of titanium alloy surface cosputtering deposited hydroxyl apatite of claim 1 (HA)/titanium (Ti) bioactive gradient layer, it is characterized in that the temperature in said oven dry, the grinding can be 80-100 ℃, the time can be 5-8 hour.
5,, it is characterized in that the time in the said target mixing is 4-8 hour according to the method for the said a kind of titanium alloy surface cosputtering deposited hydroxyl apatite of claim 1 (HA)/titanium (Ti) bioactive gradient layer.
6,, it is characterized in that said sintering can place air furnace 2-4 hour according to the method for the said a kind of titanium alloy surface cosputtering deposited hydroxyl apatite of claim 1 (HA)/titanium (Ti) bioactive gradient layer.
7, according to the method for the said a kind of titanium alloy surface cosputtering deposited hydroxyl apatite of claim 1 (HA)/titanium (Ti) bioactive gradient layer, it is characterized in that the magnetron sputtering target in the said double oblique target sputter is a commercial pure titanium, the radio-frequency sputtering target is hydroxyapatite (HA), and sputtering chamber vacuum tightness is 1-9 * 10
-4
8,, it is characterized in that the thermal treatment of said sputtered film can adopt high-pressure steam to handle or Conventional Heat Treatment according to the method for the said a kind of titanium alloy surface cosputtering deposited hydroxyl apatite of claim 1 (HA)/titanium (Ti) bioactive gradient layer; The treatment temp that said high-pressure steam is handled is 100 ℃-200 ℃, pressure 0.1-1Mpa, time 3-8 hour; The treatment temp of said Conventional Heat Treatment is 500 ℃-800 ℃, and the time is 1-5 hour.
9, the goods of a kind of titanium alloy surface cosputtering deposited hydroxyl apatite (HA) that is made by the said method of claim 1/titanium (Ti) bioactive gradient layer is characterized in that it is titanium dioxide (TiO by titanium alloy substrate, disperse distribution hydroxyapatite (HA)
2) fine and close transition layer I, titanium dioxide (TiO
2) the hydroxyapatite transition layer II of dispersion-strengthened and the layer structure of porous hydroxyapatite layer constitute, and do not have sharp interface between above-mentioned layer structure, is continuous variation shape.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1302820C (en) * | 2005-09-16 | 2007-03-07 | 哈尔滨工程大学 | Bone tissue rack of TiO2 reinforced polyhydroxyethyl methacrylate and its prepn process |
| CN100406611C (en) * | 2005-08-11 | 2008-07-30 | 上海交通大学 | Method of preparing nano-structure bioactive titanium metal film |
| CN101757689A (en) * | 2010-01-19 | 2010-06-30 | 上海理工大学 | Titanium or titanium alloy having TiO2-HA surface coating and preparation method thereof |
| CN101745148B (en) * | 2009-12-31 | 2013-04-10 | 四川大学 | Method for preparing plasma-sprayed three-dimensional porous titanium bioactive coating |
| CN104096264A (en) * | 2013-04-15 | 2014-10-15 | 长庚医疗科技(厦门)有限公司 | Surface-modified artificial bone material and surface modification method thereof |
| CN106109059A (en) * | 2016-08-05 | 2016-11-16 | 北京爱康宜诚医疗器材有限公司 | Borrowed structure |
| CN106264802A (en) * | 2016-08-05 | 2017-01-04 | 北京爱康宜诚医疗器材有限公司 | Knee-joint prosthesis |
| CN106673693A (en) * | 2016-12-23 | 2017-05-17 | 江南大学 | Preparation method of novel bioceramic porous material |
| RU2634394C1 (en) * | 2016-05-31 | 2017-10-26 | Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский Томский политехнический университет" | Method for manufacturing target from hydroxyapatite for ion-plasma coating deposition |
-
2002
- 2002-12-26 CN CN 02158559 patent/CN1221683C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100406611C (en) * | 2005-08-11 | 2008-07-30 | 上海交通大学 | Method of preparing nano-structure bioactive titanium metal film |
| CN1302820C (en) * | 2005-09-16 | 2007-03-07 | 哈尔滨工程大学 | Bone tissue rack of TiO2 reinforced polyhydroxyethyl methacrylate and its prepn process |
| CN101745148B (en) * | 2009-12-31 | 2013-04-10 | 四川大学 | Method for preparing plasma-sprayed three-dimensional porous titanium bioactive coating |
| CN101757689A (en) * | 2010-01-19 | 2010-06-30 | 上海理工大学 | Titanium or titanium alloy having TiO2-HA surface coating and preparation method thereof |
| CN104096264A (en) * | 2013-04-15 | 2014-10-15 | 长庚医疗科技(厦门)有限公司 | Surface-modified artificial bone material and surface modification method thereof |
| RU2634394C1 (en) * | 2016-05-31 | 2017-10-26 | Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский Томский политехнический университет" | Method for manufacturing target from hydroxyapatite for ion-plasma coating deposition |
| CN106109059A (en) * | 2016-08-05 | 2016-11-16 | 北京爱康宜诚医疗器材有限公司 | Borrowed structure |
| CN106264802A (en) * | 2016-08-05 | 2017-01-04 | 北京爱康宜诚医疗器材有限公司 | Knee-joint prosthesis |
| CN106673693A (en) * | 2016-12-23 | 2017-05-17 | 江南大学 | Preparation method of novel bioceramic porous material |
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|---|---|
| CN1221683C (en) | 2005-10-05 |
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