CN1492072A - Surface modifying technology of diamond-like film to titanium-nickel alloy - Google Patents
Surface modifying technology of diamond-like film to titanium-nickel alloy Download PDFInfo
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- CN1492072A CN1492072A CNA031342949A CN03134294A CN1492072A CN 1492072 A CN1492072 A CN 1492072A CN A031342949 A CNA031342949 A CN A031342949A CN 03134294 A CN03134294 A CN 03134294A CN 1492072 A CN1492072 A CN 1492072A
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Abstract
The present invention provides surface modifying technology of diamond-like film to Ti-Ni alloy. Ti-Ni alloy is better biological functional material for human body, and is used widely in dental surgery, plastic surgery and other field but results in ion release, contaminating tissue, negative reaction and other problems. The diamond-like film has excellent biocompatibility and wettability. The present invention plates the Ti-Ni alloy base sheet with diamond-like film with pulse vacuum electric arc source via the process including pre-treatment of the Ti-Ni alloy base sheet, high voltage heating of electric arc Ti ion source to plate Ti, and plating diamond-like film with high bonding strength to the base sheet, small friction coefficient, high wear resistance and high hardness. The diamond-like film has 1 micron over thickness. The present invention provides practical Ti-Ni alloy surface modifying technology.
Description
Technical field
The present invention relates to the film deposition techniques field, further relate to Ti-Ni alloy process for modifying surface field, specifically is the technology of a kind of diamond like carbon film to the surface modification of Ti-Ni alloy.
Background technology
Ti-Ni marmem have excellent mechanical property, in light weight, nonmagnetic, antifatigue, wear-resistant, anticorrosive, shape memory recovery rate is high, good biocompatibility, biological transformation are low, advantages such as high fatigue strength, breaking tenacity, impelling strength, bending strength, be at present unique shape memory alloy as biomedical material, also be study the most comprehensively in all shape memory alloys, alloy material that memory performance is the strongest.
Ti-Ni marmem has unique shape memory function, (0～5 ℃) freely deformable promptly at low temperatures, when temperature is increased to human body temperature (37 ℃), it just can return to the shape of setting voluntarily, produce a suitable shape restorer simultaneously, this provides good prospects for application just for all many-sides of medical field.Compare with traditional surgery embedded material (as stainless steel, cochrome, titanium or titanium alloy etc.), have good biocompatibility and low biological transformation, thereby implant into body safely, the Young's modulus of Ti-Ni marmem and people's bone are comparatively approaching, only are that 316L is stainless 1/4 in the time of 37 ℃, and this can further reduce its stress force shelter reaction, it is unusual ideal human-body biological functional materials, in dentistry, plastic surgery, aspects such as medical apparatus have broad application prospects.
International academic community begins to utilize Ti-Ni marmem memory function to its shape under design temperature (as human body temperature) through behind a large amount of biocompatibility experiments, is applied to the orthopedic fixation device tool.The orthopedic instrument that Ti-Ni marmem is made has the following advantages: artificially damage little, biocompatibility is good, low biological transformation, physicochemical property is good, simple to operate, healing cycle shortens, volume is little, the scope of application is big.
But as the main drawback of medical alloy is biologically active not, held by one deck packing fiber after implanting, be difficult to and organize form firm combination, simultaneously, its corrosion in physiological environment and the metal ion that causes therefrom and by product discharge, and can cause disadvantageous effect to body.In addition, in some clinical applications of hard tissue repair, the bad and hardness of its frictional coefficient is not good enough also to be weak point.Because these problems mainly concentrate on the surface.Therefore, except that the bulk property of further optimization material, can carry out surface modification by technology such as ion implantation, top coats.This is an important directions of present medical alloy research.On the other hand, oxidation easily takes place in the titanium or titanium alloy surface, generate oxide film TiO2, this film is not wear-resisting and peel off in friction contact, peel off the abrasive wear that the oxide compound that gets off quickens articular surface again, a large amount of metal ions accumulate in juxtra-articular and cause unusual biochemical reaction, cause the joint aseptic loosening and lost efficacy.As the necessary surface modification of the titanium alloy of joint material, improve its bio-tribology performance.
And the nickel ion in the Ti-Ni alloy is easily to the human carcinogen, so people hold prudent attitude to the Ni ion.The foreign scholar observes the Ti6Al4V biocompatibility not as diamond like carbon film in cell in vitro is cultivated, and suspection discharges relevant with the Ti ionic.Titanium is poisonous, can cause various neurologic disorder, and its a large amount of abrasive dusts can pollute surrounding tissue, cause bad biochemical reaction.These have all limited Ti-Ni alloy in application on medical field.Use for Ti-Ni alloy is had in medical field widely, will carry out surface modification Ti-Ni alloy.
As everyone knows, diamond has extremely excellent character, and the character of diamond like carbon film near or reach natural diamond, mainly show: diamond like carbon film has good mechanical character, the hardness height, near natural diamond, wear-resisting and frictional coefficient is low, have good wear-resistant grain polishing machine; The surface energy of diamond like carbon film is lower, has good wettability and diffusion impervious layer character preferably; The diamond like carbon film good corrosion resistance; Diamond like carbon film has good heat conductance, heat shock resistance; Diamond like carbon film has good chemical stability and biocompatibility, successfully as the blood capacitive protective layer in the artificial heart, has showed its application prospect aspect biotechnology abroad.In addition, diamond like carbon film preferably diffusion impervious layer character, preparation technology is simple, practicality good, and it is with a wide range of applications as planting material.If can improve its surface property at titanium and alloy surface depositing diamond-like film thereof.
The depositing diamond-like film is subjected to the reason that biomedical industries payes attention to gradually and is on the medical material surface: hard diamond like carbon film can be used as the protective membrane of surgery instrument, apparatus; The implant that can serve as contact part and immersion; Make the corrosive of anti-body fluid protective membrane; Improve wear resistance; The protective membrane of semipermanent part (as heart valve, joint, artificial lens, tooth etc.).
With coating technique Ti-Ni alloy being carried out surface modification, is an important directions of present medical alloy research." investigation of materials journal " calendar year 2001 No.4 have one piece and be entitled as the article of " Ti6Al4V/DLC is that the thermal stresses of heart valve prosthesis Functionally Graded Materials is calculated " and " the bio-tribology performance study of diamond-like carbon film/Ti6Al4V titanium alloy gradient material " on " aerospace medicine and engineering in medicine " calendar year 2001 No.4 literary composition disclosed all be to adopt diamond like carbon film to carry out the research of surface modification.These researchs all are effective research of depositing diamond-like film on the medical material surface, but all be on titanium and stainless steel, to adopt the rf (discharge) plasma chemical Vapor deposition process to prepare diamond like carbon film, because what they adopted is chemical Vapor deposition process, there is hydrocarbon gas to participate in during deposition, make and contain hydrogen in the film, and the content of hydrogen changes along with the variation of time, thereby makes the film performance instability.At present domestic this technology plating diamond film that also do not utilize carries out surface modification to titanium or titanium alloy.Abroad diamond-film-like, Ti-Ni marmem, the starting of filtered cathode vacuum arc Study on Technology are all compared early, obtained many achievements.At present,, also do not have the record of plating diamond film on Ti-Ni alloy, more do not utilize pulse vacuum arc ion deposition technology plating diamond film titanium or titanium alloy to be carried out the report of surface modification from consulting foreign patent.
In process for modifying surface, general metallic surface coating modification technology is after cleaning to substrate, adopt well heater that substrate is heated, Heating temperature not high enough (about 200 ℃), thereby be difficult in and form pseudo-diffusion layer and TiC transition layer between Ti-Ni alloy substrate and the diamond like carbon film, thereby make film base binding performance poor, and film surface appearance is poor.
Because the diamond-film-like internal stress that adopts the pulse vacuum arc ion deposition technology to be coated with is big; to on Ti-Ni alloy, be coated with very difficulty of the bigger diamond-film-like of thickness; and as the diamond-film-like thickness requirement of wear-resistant protection coating greater than 1 μ m; because thickness increases, thereby the firmness problem of deposit film has appearred.
The present inventor is engaged in recent years about with diamond like carbon film Ti-Ni alloy being carried out surface-treated research always, stability is good, hardness is high, frictional coefficient is little in order to obtain, anti abrasive diamond like carbon film, made a large amount of technical studies, finally adopt before pulsed vacuum arc ion source plating diamond film the Ti-Ni alloy substrate carried out special pre-treatment after, obtained success.
Summary of the invention
The objective of the invention is the technology that on Ti-Ni alloy plating diamond film carries out surface modification, provide a kind of diamond like carbon film thickness that makes to surpass 1 μ m, and good with the stability of substrate, frictional coefficient is little, wear-resistant, hardness is high.And make this process for modifying surface technology simple, easily row, be applicable to that the diamond like carbon film of needs of actual industrial production is to the process for modifying surface of Ti-Ni alloy.
Below in conjunction with accompanying drawing the present invention is elaborated.
Realization of the present invention is to adopt the pulsed vacuum arc ion source to the Ti-Ni alloy substrate, sees Fig. 1, plating diamond film, before plating diamond film to " substrate surface activation+plating transition layer " pre-treatment of Ti-Ni alloy substrate.
Adopt pulsed vacuum arc ion source plating diamond film, owing to do not need hydrogen and other hydrogen-containing compound, so can guarantee in the rete not hydrogeneous; The mortise of rete and substrate can be further guaranteed in " substrate surface activation+plating transition layer " pre-treatment before being coated with.The Ti-Ni alloy substrate can surpass 1 μ m through the diamond like carbon film thickness that is coated with after the pre-treatment, and stability is good, hardness is high, frictional coefficient is little, wear-resistant.
Realization of the present invention also is to adopt pulsed vacuum arc ion source plating diamond film on the Ti-Ni alloy substrate, and significant parameter has main circuit voltage 100～300V, pulse-repetition 1～3Hz, substrate apart from 4000～10000 of 240～300mm, sediment vein strokes per minute.By continuous test, draw the working parameter that is adapted at Ti-Ni alloy substrate surface plating diamond film.
Realization of the present invention also be the substrate pre-treatment comprise put vacuum chamber into before, clean substrate, ultrasonic cleaning substrate with mixed solution, clean substrate with argon ion source after putting vacuum chamber into, bombard, clean, make substrate surface obtain cleaning and activation with the argon ion irrigation source; Adopt high pressure heating of filtered arc titanium ion source and titanizing certain hour then.Can be controlled in 10～80s.
Owing to adopt filtered arc titanium ion source high pressure to substrate heating, titanizing, substrate temperature sharply risen.Make various ions and high energy neutral particle stream with higher-energy bombardment workpiece surface, can form pseudo-diffusion layer, improve the bonding force of rete and matrix, can also change rete weave construction and performance, further crystal grain thinning.But institute's biasing can not the ether height, otherwise can produce etching to matrix surface, makes film quality descend and sedimentation velocity also reduces.This moment is plating diamond film again, can under the pyritous situation, generate the TiC transition layer, thereby formed the Ti-TiC-DLC rete, can reach the effect that strengthens film-substrate cohesion, and the surface topography of film is improved, by before being coated be coated with after the flying-spot microscope photo contrast obviously as seen, as Fig. 1 and Fig. 2.General metallic surface coating modification technology is after cleaning to substrate, adopt well heater that substrate is heated, Heating temperature not high enough (about 200 ℃), thereby be difficult in and form pseudo-diffusion layer and TiC transition layer between Ti-Ni alloy substrate and the diamond like carbon film, thereby make film base binding performance poor, and film surface appearance is poor.
Realization of the present invention also is to adopt pulsed vacuum arc ion source plating diamond film preceding as follows to the specific practice and the step of Ti-Ni alloy substrate:
(1) before substrate is put vacuum chamber into, after earlier the Ti-Ni alloy substrate being cleaned with the mixed solution (volume ratio of ethanol and ether is 3: 1) of dehydrated alcohol and ether, use ultrasonic wave (power is 500W) to clean 15～30min again, clean the back and put into the vacuum chamber select location at once.
(2) when vacuum degree in vacuum chamber arrival 3～5 * 10
-3During Pa, charge into argon gas, make vacuum tightness reduce to 1.1～1.5 * 10
-1Pa opens the cleaning ion source, and institute's making alive is 4kv, and scavenging period is 20～40min, closes and cleans ion source and argon gas.
(3) open filtered arc titanium ion source, use high pressure 800v, electric current 75A, substrate rotation heating and titanizing time are 30～45s, close filtered arc titanium ion source.
(4) open the pulsed vacuum arc ion source, regulate parameters such as main circuit voltage, pulse-repetition, be coated with the diamond like carbon film of 5000～7000 pulses, keep taking out behind the 30min.Can obtain among the present invention the Ti-Ni alloy surface being carried out the diamond like carbon film of the excellent property of modification.This mainly be because adopt the present invention can make substrate surface bright and clean, strengthen the substrate surface activity, guarantee substrate temperature and guarantee depositing of thin film speed etc., thus make the tack of film good, hardness is high, wear-resistant.
This process for modifying surface technology is simple, easy row, and with low cost, be applicable to large-scale industrial production.
Test according to the diamond like carbon film that is coated with after the above substrate pre-treatment, concrete outcome is as follows:
Thicknesses of layers: greater than 1.12 μ m
Stability: dip in absorbent cotton that mixed solution is wiped examination and with Shanghai board friction-bar friction film, rete does not come off;
Diamond like carbon film composite hardness: surpass HV1200 (the hardness before the plating is not HV280～300);
Diamond like carbon film frictional coefficient: between 0.08～0.13 (the frictional coefficient before the plating is not 0.22);
Wearing test: adopt the load of 5N, the Ceramic Balls rotating speed is 120rpm, is not worn yet after 7000 commentaries on classics.Referring to Fig. 2.
Facts have proved, adopt the preceding substrate preconditioning technique of this plating, can be in the good diamond like carbon film of Ti-Ni alloy substrate surface obtained performance.
Sample such as Fig. 3 that the present invention provides some enterprises and producer have carried out the laboratory and have been coated with, and reflect fine.
As the human-body biological functional materials, the present invention has very wide application prospect.
The present invention is through a large amount of experimental study and theoretical analysis, studied scientific preparation process, adopt the pulsed vacuum arc ion source to Ti-Ni alloy substrate plating diamond film, can surpass 1 μ m thereby obtained thickness, and stability is good, hardness is high, frictional coefficient is little, anti abrasive diamond like carbon film.Integrate, the technology that plating diamond film carries out surface modification on Ti-Ni alloy provided by the present invention has the following advantages: the film base is in conjunction with firmly, and the surface topography of film is good; Film thickness can surpass 1 μ m, and stability is good, hardness is high, frictional coefficient is little, wear-resistant.Technology is simple, easy row, and with low cost, be applicable to large-scale industrial production.
Description of drawings
The SEM photo that Fig. 1 is untreated and carries out plating diamond film for Ti-Ni alloy of the present invention.
Fig. 2 plates the SEM photo of the diamond like carbon film that is coated with after the preceding pre-treatment for Ti-Ni alloy process of the present invention.
Fig. 3 is the photo of the diamond like carbon film that employing the present invention is coated with on the Ti-Ni alloy scalpel.
Embodiment
Embodiment:
The Ti-Ni alloy substrate of selecting for use is the square of length of side 10mm, and thickness is 1mm.
Concrete process for plating and step are as follows:
(1) before substrate is put vacuum chamber into, after earlier the Ti-Ni alloy substrate being cleaned with the mixed solution (volume ratio of ethanol and ether is 3: 1) of dehydrated alcohol and ether, use ultrasonic wave (power is 500W) to clean 20min again, clean the back and put into vacuum chamber, at once apart from cathode surface 270mm.
(2) when vacuum degree in vacuum chamber arrival 3～5 * 10
-3During Pa, charge into argon gas, make vacuum tightness reduce to 1.3 * 10
-1Pa opens the cleaning ion source, and institute's making alive is 4kv, and scavenging period is 20min, closes and cleans ion source and argon gas.
(3) open filtered arc titanium ion source, use high pressure 800v, electric current 75A, substrate rotation heating, titanizing time are 35s, close filtered arc titanium ion source.
(4) open the pulsed vacuum arc ion source, regulate parameters such as main circuit voltage 250v, pulse-repetition 1Hz, be coated with the diamond like carbon film of 6000 pulses, keep taking out behind the 30min.
Test result is:
Thicknesses of layers: 1.12 μ m
Stability: dip in absorbent cotton that mixed solution is wiped examination and with Shanghai board friction-bar friction film, rete does not come off;
Diamond like carbon film composite hardness: HV1356;
Diamond like carbon film frictional coefficient: 0.11;
Wearing test: adopt the load of 5N, the Ceramic Balls rotating speed is 120rpm, is not worn yet after 7000 commentaries on classics.
Claims (4)
1, a kind of diamond like carbon film is to the process for modifying surface of Ti-Ni alloy, it is characterized in that adopting the pulsed vacuum arc ion source to Ti-Ni alloy substrate plating diamond film, before plating diamond film to " substrate surface activation+plating transition layer " pre-treatment of Ti-Ni alloy substrate.
2, process for modifying surface according to claim 1, it is characterized in that adopting pulsed vacuum arc ion source plating diamond film on the Ti-Ni alloy substrate, significant parameter has main circuit voltage 100～300V, pulse-repetition 1～3Hz, substrate apart from 4000～10000 of 240～300mm, sediment vein strokes per minute.
3, process for modifying surface according to claim 1, it is characterized in that substrate " substrate surface activation+plating transition layer " pre-treatment comprise put vacuum chamber into before, clean substrate, ultrasonic cleaning substrate with mixed solution, clean substrate with argon ion source after putting vacuum chamber into, adopt high pressure heating of filtered arc titanium ion source and titanizing certain hour then.
4, according to claim 1 or 2 or 3 described process for modifying surface, it is characterized in that:
Specific practice and step are as follows:
(1) before substrate is put vacuum chamber into, after earlier the Ti-Ni alloy substrate being cleaned with the mixed solution (volume ratio of ethanol and ether is 3: 1) of dehydrated alcohol and ether, use ultrasonic wave (power is 500W) to clean 15～30min again, clean the back and put into the vacuum chamber select location at once.
(2) when vacuum degree in vacuum chamber arrival 3～5 * 10
-3During Pa, charge into argon gas, make vacuum tightness reduce to 1.1～1.5 * 10
-1Pa opens the cleaning ion source, and institute's making alive is 4kv, and scavenging period is 20～40min, closes and cleans ion source and argon gas.
(3) open filtered arc titanium ion source, use high pressure 800v, electric current 75A, substrate rotation heating and titanizing time are 30～45s, close filtered arc titanium ion source.
(4) open the pulsed vacuum arc ion source, regulate parameters such as main circuit voltage, pulse-repetition, be coated with the diamond like carbon film of 5000～7000 pulses, keep taking out behind the 30min.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008064517A1 (en) * | 2006-11-27 | 2008-06-05 | Lifetech Scientific (Shenzhen) Co., Ltd. | Method for preparing a coating on the surface of medical devices made of nickel-titanium alloy |
| CN101828044B (en) * | 2007-10-19 | 2013-04-10 | 株式会社iMott | Gap base material for reducing fretting wear, and fastening structure using gap base material |
| CN107604325A (en) * | 2017-09-04 | 2018-01-19 | 苏州云舒新材料科技有限公司 | A kind of preparation method for the DLC film material that radiates |
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2003
- 2003-06-13 CN CN 03134294 patent/CN1237201C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008064517A1 (en) * | 2006-11-27 | 2008-06-05 | Lifetech Scientific (Shenzhen) Co., Ltd. | Method for preparing a coating on the surface of medical devices made of nickel-titanium alloy |
| CN101828044B (en) * | 2007-10-19 | 2013-04-10 | 株式会社iMott | Gap base material for reducing fretting wear, and fastening structure using gap base material |
| US8481464B2 (en) | 2007-10-19 | 2013-07-09 | Imott Corporation | Spacer member reducing fretting wear and fastened structures using spacer member |
| CN107604325A (en) * | 2017-09-04 | 2018-01-19 | 苏州云舒新材料科技有限公司 | A kind of preparation method for the DLC film material that radiates |
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| CN1237201C (en) | 2006-01-18 |
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