CN104138616A - Medicinal titanium and titanium alloy surface oxidation-carbon plated-diamond-like composite film and manufacturing method thereof - Google Patents
Medicinal titanium and titanium alloy surface oxidation-carbon plated-diamond-like composite film and manufacturing method thereof Download PDFInfo
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 61
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000010936 titanium Substances 0.000 title claims abstract description 41
- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 40
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title abstract 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 20
- 230000003647 oxidation Effects 0.000 claims abstract description 17
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 32
- 229910003460 diamond Inorganic materials 0.000 claims description 28
- 239000010432 diamond Substances 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 25
- 239000012528 membrane Substances 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 17
- 239000011248 coating agent Substances 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 16
- 238000007747 plating Methods 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000002347 injection Methods 0.000 claims description 10
- 239000007924 injection Substances 0.000 claims description 10
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 7
- 238000005498 polishing Methods 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 7
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 5
- 238000002513 implantation Methods 0.000 claims description 5
- 238000005468 ion implantation Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 239000007921 spray Substances 0.000 claims description 5
- 230000003746 surface roughness Effects 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 29
- 239000010408 film Substances 0.000 description 24
- 239000010409 thin film Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 6
- 230000007812 deficiency Effects 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010849 ion bombardment Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 206010060872 Transplant failure Diseases 0.000 description 1
- 238000006701 autoxidation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- Materials For Medical Uses (AREA)
- Prostheses (AREA)
Abstract
The invention discloses a medicinal titanium and titanium alloy surface oxidation-carbon plated-diamond-like composite film and a manufacturing method of the medicinal titanium and titanium alloy surface oxidation-carbon plated-diamond-like composite film. According to the composite film, an oxidation layer, a carbon/titanium carbide carbon plated layer and a diamond-like layer are sequentially manufactured on the medicinal titanium and titanium alloy surface. The invention further discloses the manufacturing method of the composite film. Based on in-situ growth, the manufactured composite film is large in film base binding strength and thickness and excellent in comprehensive performance, the technology is simple, the cost performance is high, and production in batches can be achieved.
Description
Technical field
The invention belongs to medical metal material field of surface treatment, be specifically related to a kind of medical titanium and titanium alloy surface and be oxidized-plate carbon-diamond like carbon (TiO
2-C/TiC-DLC) composite membrane and preparation method thereof.
Background technology
Titanium or titanium alloy, because having the performances such as excellent specific strength, elastic modelling quantity, biocompatibility in biomedical sector extensive application, is especially used as hard tissue substituting material, as is used as structural material of the prostheses such as artificial joint, artificial intervertebral disk etc.But titanium or titanium alloy has the abrasion resistance properties of extreme difference, after titanium prosthesis implant into body, under human body complex physiologic and mechanical environment effect, the wear-resistant life-span is significantly not enough, even can cause bone dissolving to cause graft failure because producing a large amount of wear particles.Wearability is not enough, and the earth to the utmost has limited the extensive use of titanium or titanium alloy at biomedical sector, and along with the rise of surface engineering technology, therefore, recent domestic is all in active development titanium or titanium alloy surface abrasion resistance modified technique technology.
For improving the surface modifying treatment of titanium or titanium alloy abrasion resistance properties, mainly contain at present:
(1) ion injection method is mainly to adopt high energy ion bombardment material surface to obtain thin film, good bonding strength, there will not be and the phenomenon such as peel off, but that maximum deficiency is implanted layer is very thin, be conventionally no more than 1 μ m, once after implanted layer is destroyed, matrix will directly expose and participate in friction.And this technique cost is huge, and cost performance is lower.
(2) coating diamond-like film process, DLC has extreme hardness and anti-wear performance, but DLC is a kind of fragile material, in growth course, do not mate with substrate material physical property, produce larger internal stress, thereby thin film and substrate combinating strength are poor, limited being connected and film thickness of film and matrix.
(3) laser modifying method, it between coating and matrix, is the metallurgical binding that bond strength is very high, coating layer thickness is larger, there is the excellent properties such as hardness is high, coefficient of friction is little, wear-resisting, anti-corrosion and high temperature resistant, but because the quick cooling meeting in molten bath makes crisp generation mutually and surface generation higher residual stresses in thin film, can crack.In addition, in the molten bath in superheat state, bubble be may form, micropore and hole in melting coating, occurred sometimes.
(4) oxidation treatment method, have that technique is simple, cost performance is high, the advantage such as growth in situ, film thickness are larger, but thin film Growing Process of Crystal Particles is wayward, conventional method for oxidation is prone to the phenomenons such as inhomogeneous and undue growth of growing, and reduces thin film combination property.
At present, single wear-resisting modified film generally all can not meet the requirement of the complicated mechanics of human body and physiological environment preferably, and future developing trend is to prepare laminated film, solves the problems such as single thin film adhesion is not enough, film thickness is not enough.
Summary of the invention
The object of the invention is to the deficiency for above-mentioned various existing method of modifying, propose a kind ofly based on growth in situ, there is larger film-substrate cohesion, larger film thickness, thin film excellent combination property and technique is simple, cost performance is high, can be mass-produced, applied range, can process the wear-resisting modification preparation technology of labyrinth.
The invention discloses a kind of medical titanium and titanium alloy surface and be oxidized-plate carbon-diamond like carbon (TiO
2-C/TiC-DLC) composite membrane, described composite membrane is to be prepared with successively in order layer of oxide layer, one deck carbon/titanium carbide plating carbon-coating and one deck diamond like carbon layer in medical titanium and titanium alloy surface.
Described composite membrane gross thickness is 1.8～3.6 μ m.
Described oxide layer main component is rutile titanium dioxide, and its thickness is 1～2 μ m.
In described carbon/titanium carbide plating carbon-coating, sp in C-C structure
2linkage content 50%～66%, sp
3linkage content 34%～50%, plating carbon-coating thickness is 300～600nm.
In described diamond like carbon layer, sp in C-C structure
2linkage content 40%～50%, sp
3linkage content 50%～60%, diamond like carbon layer thickness is 500～1000nm.
The invention also discloses the preparation method that above-mentioned medical titanium and titanium alloy surface were oxidized-plated carbon-diamond like carbon composite membrane, comprise the steps:
(1) pretreatment: medical titanium or titanium alloy specimen surface are carried out to grinding and polishing, ultrasonic cleaning, dry successively;
(2) thermal oxidation: will put into tube furnace through pretreated titanium or titanium alloy sample and carry out thermal oxidation;
(3) carbon ion injects and processes: the titanium after thermal oxidation or titanium alloy sample are carried out to carbon ion injection processing;
(4) sample after carbon ion injects being sprayed to diamond-film-like processes.
In step (1), sample is after grinding and polishing, and surface roughness is 0.05～0.1 μ m, then ultrasonic cleaning 20-30 minute in dehydrated alcohol or acetone soln, in deionized water for ultrasonic, clean 20-30 minute again, be finally placed in vacuum drying oven dry 20-30 hour stand-by.
In step (2), thermal oxidation temperature is 600～700 ℃, the thermal oxide time is 2～4 hours, in thermal oxidation process, constantly pass into nitrogen oxygen mixed gas, nitrogen and oxygen proportion are controlled at 3:1-4:1, the type of cooling adopts natural cooling, is cooled to room temperature, still has the nitrogen oxygen mixed gas of same ratio constantly to pass in cooling procedure.
In step (3), carbon ion injects to process and refers to carbon ion Implantation Energy 60keV, and implantation dosage is (1～50) * 10
15individual/cm
2.
In step (4), described spraying diamond-film-like is processed and is referred to, using plasma vapour deposition spraying, and gases used is CH
4or C
2h
2and H
2, CH wherein
4or C
2h
2gas flow is 30-60 standard ml/min, H
2gas flow is 30-90 standard ml/min, and air pressure used is 1～5Pa, and base reservoir temperature is 60～200 ℃, and power is 200～300W, and spray time is 0.5～4 hour.
Beneficial effect of the present invention is:
(1), because titanium or titanium alloy are under natural laying state, can there is autoxidation in surface, form one deck Natural Oxide Film, but this layer of oxide thickness only has several nanometers, and enough adhesion and wear-resistant decay resistances can not be provided.The present invention is based on growth in situ thought, first at titanium or titanium alloy surface, prepared the titanium deoxid film of growth in situ, its main component is hardness and the fabulous rutile titanium dioxide of wearability, by reasonable adjustment oxidizing temperature, time, the growth of the controlled oxygenerating film of the parameter such as atmosphere and type of cooling crystal grain, guarantee that oxide-film distributes from the teeth outwards densely, and there is not the situations such as inhomogeneous or undue growth of growing, its thickness can reach 1～2 μ m, greatly guaranteed the gross thickness of composite membrane, in addition, this layer of oxide-film is based on growth in situ, itself has high adhesion with substrate.Therefore, the final effect of oxide-film is to improve composite membrane gross thickness and enhancing and titanium or titanium alloy substrate caking power.
(2) adopt the carbon ion bombardment oxide-film of high-energy and high dose, prepare a layer thickness be again about 300～600nm carbon ion implanted layer on the surface of oxide-film, this carbon ion implanted layer, because adopting ion injection method, has higher adhesion with oxide-film.In addition, can be in oxide-film fully the titanium elements of reaction be combined and form TiC, because plating carbon-coating main chemical elements is the same with outer field DLC layer, be also carbon, can further strengthen and the adhesion of DLC layer.Therefore, the final effect of this carbon/titanium carbide plating carbon-coating be as transition zone improve and the oxide-film of internal layer and and outer field DLC layer between adhesion, and then improved the problem of DLC binding force of membrane deficiency.
(3) using plasma chemical gaseous phase depositing process, on plating carbon-coating basis, prepare again the diamond like carbon layer that a layer thickness is about 500～1000nm, because diamond like carbon self has high case hardness and the wear-resistant performance such as corrosion-resistant, and this DLC film thickness surpasses 0.5 μ m, the outermost layer using it as composite membrane has greatly improved the performance such as wear-resistant corrosion-resistant of titanium or titanium alloy.
To sum up, the present invention has solved titanium or the conventional wear-resistant coating adhesion deficiency of titanium alloy surface and the too little problem of thickness effectively, because rutile titanium dioxide, titanium carbide and diamond like carbon are all the high materials of wearability, and three's hardness presents graded trend, guaranteed that preferably the existing high adhesion of this composite membrane can significantly improve the wear-resistant decay resistance of substrate again.
Accompanying drawing explanation
Fig. 1 is that the present invention is oxidized-plates carbon-diamond like carbon (TiO
2-C/TiC-DLC) complex thin film structure schematic diagram, wherein 1 represents base material, and 2 represent oxidation film layer, 3 representative plating carbon-coatings, and 4 represent diamond like carbon layer.
The specific embodiment
Below by specific embodiment, the present invention is further elaborated by reference to the accompanying drawings.
Embodiment 1:
The present embodiment adopts medical titanium dish as sample, prepares laminated film thickness and is approximately 2 μ m, and nano-hardness improvement is about 10.5GPa, C-C structure sp in carbon/titanium carbide plating carbon-coating
2linkage content 66%, sp
3linkage content 34%, thickness is about 300nm, C-C structure sp in diamond like carbon layer
2linkage content 50%, sp
3linkage content 50%, thickness is about 600nm.Concrete steps are as follows:
(1) sample is after grinding and polishing, surface roughness 0.05～0.1 μ m, then ultrasonic cleaning 20 minutes in dehydrated alcohol or acetone soln, then clean 30 minutes in deionized water for ultrasonic, be finally placed in vacuum drying oven dry 24 hours stand-by.
(2) pending sample is put into tube furnace and carry out thermal oxidation.Oxidate temperature is 600 ℃, oxidization time is 2 hours, constantly passes into nitrogen oxygen mixed gas in oxidizing process, and nitrogen and oxygen proportion are controlled at 3:1, the type of cooling adopts and naturally cools to room temperature, but in cooling procedure, still has the nitrogen oxygen mixed gas of same ratio constantly to pass into.
(3) the titanium sample after processing is carried out to carbon ion injection, ion implantation energy 60keV, implantation dosage is 5 * 10
15individual/square centimeter.
(4) sample after carbon ion injection is sprayed to diamond-film-like and process, using plasma vapour deposition spraying, gases used is CH
4and H
2, CH wherein
4gas flow is 30 standard ml/min (sccm), H
2gas flow is 60 standard ml/min (sccm), and air pressure used is 1Pa, and base reservoir temperature is 100 ℃, and power is 200W, and spray time is 1 hour.
Embodiment 2:
The present embodiment adopts medical titanium alloy dish (Ti6Al4V) as sample, and preparing laminated film thickness is 3.6 μ m, and nano-hardness improvement is about 12GPa, C-C structure sp in carbon/titanium carbide plating carbon-coating
2linkage content 50%, sp
3linkage content 50%, this layer thickness is about 600nm, C-C structure sp in diamond like carbon layer
2linkage content 40%, sp
3linkage content 60%, this layer thickness is about 900nm.Concrete steps are as follows:
(1) sample is after grinding and polishing, surface roughness 0.05～0.1 μ m, then ultrasonic cleaning 30 minutes in dehydrated alcohol or acetone soln, then clean 25 minutes in deionized water for ultrasonic, be finally placed in vacuum drying oven dry 30 hours stand-by.
(2) pending sample is put into tube furnace and carry out thermal oxidation.Oxidate temperature is 700 ℃, oxidization time is 3 hours, constantly passes into nitrogen oxygen mixed gas in oxidizing process, and nitrogen and oxygen proportion are controlled at 4:1, the type of cooling adopts natural cooling, but in cooling procedure, still has the nitrogen oxygen mixed gas of same ratio constantly to pass into.
(3) the titanium alloy sample after processing is carried out to carbon ion injection, ion implantation energy 60keV, implantation dosage is 5 * 10
16individual/square centimeter.
(4) sample after carbon ion injection is sprayed to diamond-film-like and process, using plasma vapour deposition spraying, gases used is C
2h
2and H
2, C wherein
2h
2gas flow is 60 standard ml/min, H
2gas flow is 30 standard ml/min, and air pressure used is 3Pa, and base reservoir temperature is 200 ℃, and power is 200W, and spray time is 3 hours.
Embodiment 3:
The present embodiment adopts soleplate articular prosthesis on medical titanium alloy (Ti6Al4V) cervical artificial disc as sample, to prepare laminated film thickness and be approximately 3 μ m, and nano-hardness improvement is about 11GPa, C-C structure sp in carbon/titanium carbide plating carbon-coating
2linkage content 60%, sp
3linkage content 40%, this layer thickness is about 500nm, C-C structure sp in diamond like carbon layer
2linkage content 40%, sp
3linkage content 60%, this layer thickness is about 800nm.Concrete steps are as follows:
(1) sample articular surface is after professional grinding and polishing, surface roughness 0.08～0.1 μ m, then ultrasonic cleaning 25 minutes in dehydrated alcohol or acetone soln, then clean 20 minutes in deionized water for ultrasonic, be finally placed in vacuum drying oven dry 20 hours stand-by.
(2) pending sample is put into tube furnace and carry out thermal oxidation.Oxidate temperature is 600 ℃, oxidization time is 4 hours, constantly passes into nitrogen oxygen mixed gas in oxidizing process, and nitrogen and oxygen proportion are controlled at 3.5:1, the type of cooling adopts natural cooling, but in cooling procedure, still has the nitrogen oxygen mixed gas of same ratio constantly to pass into.
(3) the upper soleplate prosthetic joint face after processing is carried out to carbon ion injection, ion implantation energy 60keV, implantation dosage is 1 * 10
16individual/square centimeter.
(4) the sample articular surface after carbon ion injection is sprayed to diamond-film-like and process, using plasma vapour deposition spraying, gases used is C
2h
2and H
2, C wherein
2h
2gas flow is 60 standard ml/min, H
2gas flow is 30 standard ml/min, and air pressure used is 3Pa, and base reservoir temperature is 200 ℃, and power is 200W, and spray time is 3 hours.
In sum; although the specific embodiment of the present invention have been described in detail the present invention; but persons skilled in the art should be understood that; above-described embodiment is only the description to the preferred embodiments of the present invention; but not limiting the scope of the invention; persons skilled in the art are in the disclosed technical scope of the present invention, and the variation that can expect easily, all within protection scope of the present invention.
Claims (10)
1. medical titanium and titanium alloy surface are oxidized-plate carbon-diamond like carbon composite membrane, it is characterized in that: described composite membrane is to be prepared with successively in order layer of oxide layer, one deck carbon/titanium carbide plating carbon-coating and one deck diamond like carbon layer in medical titanium and titanium alloy surface.
2. medical titanium as claimed in claim 1 and titanium alloy surface are oxidized-plate carbon-diamond like carbon composite membrane, it is characterized in that: described composite membrane gross thickness is 1.8～3.6 μ m.
3. medical titanium as claimed in claim 1 and titanium alloy surface are oxidized-plate carbon-diamond like carbon composite membrane, it is characterized in that: described oxide layer main component is rutile titanium dioxide, and its thickness is 1～2 μ m.
4. medical titanium as claimed in claim 1 and titanium alloy surface are oxidized-plate carbon-diamond like carbon composite membrane, it is characterized in that: in described carbon/titanium carbide plating carbon-coating, and sp in C-C structure
2linkage content 50%～66%, sp
3linkage content 34%～50%, plating carbon-coating thickness is 300～600nm.
5. medical titanium as claimed in claim 1 and titanium alloy surface are oxidized-plate carbon-diamond like carbon composite membrane, it is characterized in that: in described diamond like carbon layer, and sp in C-C structure
2linkage content 40%～50%, sp
3linkage content 50%～60%, diamond like carbon layer thickness is 500～1000nm.
6. medical titanium as claimed in claim 1 and titanium alloy surface are oxidized-plate the preparation method of carbon-diamond like carbon composite membrane, it is characterized in that comprising the steps:
(1) pretreatment: medical titanium or titanium alloy specimen surface are carried out to grinding and polishing, ultrasonic cleaning, dry successively;
(2) thermal oxidation: will put into tube furnace through pretreated titanium or titanium alloy sample and carry out thermal oxidation;
(3) carbon ion injects and processes: the titanium after thermal oxidation or titanium alloy sample are carried out to carbon ion injection processing;
(4) sample after carbon ion injects being sprayed to diamond-film-like processes.
7. medical titanium as claimed in claim 1 and titanium alloy surface are oxidized-plate the preparation method of carbon-diamond like carbon composite membrane, it is characterized in that: in step (1), sample is after grinding and polishing, surface roughness is 0.05～0.1 μ m, then ultrasonic cleaning 20-30 minute in dehydrated alcohol or acetone soln, in deionized water for ultrasonic, clean 20-30 minute again, be finally placed in vacuum drying oven dry 20-30 hour stand-by.
8. medical titanium as claimed in claim 1 and titanium alloy surface are oxidized-plate the preparation method of carbon-diamond like carbon composite membrane, it is characterized in that: in step (2), thermal oxidation temperature is 600～700 ℃, the thermal oxide time is 2～4 hours, in thermal oxidation process, constantly pass into nitrogen oxygen mixed gas, nitrogen and oxygen proportion are controlled at 3:1-4:1, and the type of cooling adopts natural cooling, be cooled to room temperature, in cooling procedure, still have the nitrogen oxygen mixed gas of same ratio constantly to pass into.
9. medical titanium as claimed in claim 1 and titanium alloy surface are oxidized-plate the preparation method of carbon-diamond like carbon composite membrane, it is characterized in that: in step (3), carbon ion injects to process and refers to carbon ion Implantation Energy 60keV, and implantation dosage is (1～50) * 10
15individual/cm
2.
10. medical titanium as claimed in claim 1 and titanium alloy surface are oxidized-plate the preparation method of carbon-diamond like carbon composite membrane, it is characterized in that: in step (4), described spraying diamond-film-like is processed and is referred to, using plasma vapour deposition spraying, and gases used is CH
4or C
2h
2and H
2, CH wherein
4or C
2h
2gas flow is 30-60 standard ml/min, H
2gas flow is 30-90 standard ml/min, and air pressure used is 1～5Pa, and base reservoir temperature is 60～200 ℃, and power is 200～300W, and spray time is 0.5～4 hour.
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|---|---|---|---|
| CN201410352632.4A CN104138616B (en) | 2014-07-23 | 2014-07-23 | A kind of medical titanium and titanium alloy surface aoxidize-plate carbon-diamond like carbon composite membrane and preparation method thereof |
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Cited By (8)
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| CN105648417A (en) * | 2016-03-14 | 2016-06-08 | 三峡大学 | Method for utilizing low-temperature chemical vapor deposition technology to prepare amorphous carbon film |
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| CN110257756A (en) * | 2019-07-23 | 2019-09-20 | 海南中航特玻科技有限公司 | A kind of preparation method of surface carbonation titanium metal products |
| CN111908935A (en) * | 2020-01-19 | 2020-11-10 | 湖南碳康生物科技有限公司 | Carbon-based composite material bone screw and preparation method thereof |
| CN113355644A (en) * | 2020-03-05 | 2021-09-07 | 四川大学 | Modification process method for immersed injection in-situ surface gradient reconstruction wear-resistant diamond-like coating |
| CN114922809A (en) * | 2022-06-06 | 2022-08-19 | 大庆市聚通祥机械设备有限公司 | High-abrasion-resistance hydraulic end plunger |
| CN117462745A (en) * | 2023-11-01 | 2024-01-30 | 浙江扶康生物科技有限公司 | Super wear-resistant titanium alloy femoral condyle prosthesis, preparation method thereof and artificial knee joint |
| CN118326325A (en) * | 2024-04-17 | 2024-07-12 | 哈尔滨工业大学 | Composite carburization method for preparing high-bearing antifriction self-lubricating functional layer |
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