CN1776027A - Diamond coating-like biological material and its preparing method - Google Patents
Diamond coating-like biological material and its preparing method Download PDFInfo
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- CN1776027A CN1776027A CN 200510122762 CN200510122762A CN1776027A CN 1776027 A CN1776027 A CN 1776027A CN 200510122762 CN200510122762 CN 200510122762 CN 200510122762 A CN200510122762 A CN 200510122762A CN 1776027 A CN1776027 A CN 1776027A
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Abstract
An eka-diamond coated biological material and preparation method. Titanium alloy (Ti6Al4V) is used as base unit, eka-diamond film as surface function layer, a silicon transition layer being between base unit and surface function layer for reinforcing joint strength. Said method adopts RF plasma for reinforcing CVD process, using Ar and organic silicon monomer vapor mixed gas as deposition gas, pre-depositing silicon transition layer on base unit surface, depositing eka-diamond film by liquid phase electric deposition using methanol as medium adopting high voltage dc power supply. The prepared film is amorphous structure with fine joint force between film and base unit and good blood compatibility.
Description
Technical field
The present invention relates to a kind of bio-medical material and preparation method thereof, particularly a kind of is the biomaterial and preparation method thereof of coating with the quasi-diamond.
Background technology
Quasi-diamond (diamond-like carbon, DLC) have a series of premium propertiess similar to diamond, as high strength and high rigidity, good thermal conductivity, light transmission, high abrasion, erosion resistance and excellent biological compatibility etc., therefore, obtained in fields such as machinery, electronics, biomedical engineerings using widely.
The common method of preparation DLC film has physical vapor deposition, as ion beam depositing, radio frequency sputtering method, vacuum cathode arc deposited method etc., and chemical Vapor deposition process, as direct current glow discharge plasma chemical vapor deposition, radio frequency glow discharge plasma activated chemical vapour deposition etc.But these methods have shortcomings such as depositing temperature height, apparatus expensive, vacuum requirement height, processing condition complexity.And the liquid phase rule has advantages such as depositing temperature is low, equipment is simple, processing condition are simple, has therefore caused the great interest of people.
From people (J.vac.Sci.Technol.A such as V.P.Novikov in 1997,10 (5), 1992:3368) utilize the liquid ammonia solution of acetylene as ionogen, successfully prepare after the diamond like carbon film, many investigators have carried out the research of depositing diamond-like film on different ionogen conditions and different matrix material.Wang etc. (Thin Solid Film, 293,1997:87-90) having studied with methyl alcohol is ionogen depositing diamond-like depositing of thin film technology on silicon substrate; (MaterialResearch Bulletin, 1999,30 (10): 1501-1506 such as Jiu and Cai; Surface and CoatungTechnology, 2000,130:266-273) having studied with methyl alcohol and DMF respectively is ionogen depositing diamond-like depositing of thin film technology on the conductive glass substrate; Guo etc. (Carbon, 2001,39:1395-1398) also among the DMF on aluminium substrate depositing diamond-like depositing of thin film technology study.
Though people have done many relevant work, and attempt theoretically this process to be analyzed, but present liquid phase method diamond-film-like deposition only limits to conductive glass, silicon and three kinds of matrixes of aluminium, research to depositing diamond-like film on other matrixes yet there are no report, and structure, the character of deposition rule that obtains on different matrixes and DLC film are not quite similar, this explanation character on matrix and surface thereof in electrolytic process is quite big to formation, structure and the property effect of film, is necessary further to expand different body materials.
Titanium alloy has obtained widely paying attention at biomedical sector as body implanting material, but because its wear resistance, blood compatibility are also not satisfactory, thereby limited its widespread use, can only be used for general surgery's embedded material at present.Therefore, be matrix with the titanium alloy, utilize that liquid phase method diamond-film-like deposition technology comes that the processing machinery performance is good, blood compatibility and the good composite biological material of histocompatibility have great significance at biomedical sector.
In addition in above-mentioned report, just reported on the different matrix material and prepared diamond like carbon film, but do not relate to the bonding strength between film and the matrix, and the power of the bonding strength between film and the matrix has directly determined the Practical Performance of deposition material.Because matrix especially metallic matrix and the crystalline structure of diamond like carbon film and the difference between the thermal expansivity, often can not get to satisfy the bonding strength between the film base of application request in direct deposition on the metallic matrix.
Because DLC has good wear resistance, blood compatibility and histocompatibility, and titanium alloy has favorable mechanical performance and better biocompatibility, is the common used material of surgery implant devices.Can prepare human body implant devices such as being applicable to heart valve prosthesis, joint prosthesis by depositing diamond-like film on titanium alloy substrate, and the bonding strength between the good film base is the precondition that guarantees practical application.Therefore, employing is that the bonding strength that the combination of appropriate means or several method obviously improves between the film composite material film base is the key that makes material practicability.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, a kind of good mechanical property is provided, and diamond-like coating biomaterial of favorable tissue consistency and blood compatibility and preparation method thereof is arranged with human body.
For achieving the above object, the technical solution used in the present invention is, a kind of diamond-like coating biomaterial is provided, and it is with Ti
6Al
4The V titanium alloy is a matrix, and diamond like carbon film is a surface functional layer, and a silicon transition layer is arranged between matrix and surface functional layer.
A kind of preparation method of diamond-like coating biomaterial is characterized in that preparation process is as follows:
(1) earlier to Ti
6Al
4The titanium alloy-based body and function radio-frequency plasma of V strengthens chemical Vapor deposition process to be handled, deposition gases is the mixed gas of Ar and organosilane monomer steam, its proportioning is 10～3: 1, and the plasma-treating technology condition is: radio frequency power 80～110W, bias voltage 300～400V, vacuum tightness 3～8Pa; Obtain the silicon transition layer that deposit thickness is 0.05～0.15 μ m at matrix surface;
(2) with high purity graphite as anode, the titanium alloy substrate of the above-mentioned transition layer of depositing silicon is a negative electrode, methyl alcohol is deposition medium, adopt liquid electrodeposition method depositing diamond-like film on the silicon transition layer, polar plate spacing is 6～12mm, and deposition voltage is 1650～1850V, and depositing temperature is 50～60 ℃; On the silicon transition layer, obtain the diamond like carbon film that deposit thickness is 0.1～0.5 μ m, make with Ti
6Al
4The V titanium alloy is a matrix, and diamond like carbon film is a surface functional layer, and the diamond-like coating biomaterial of a silicon transition layer is arranged between matrix and surface functional layer.
Described organosilane monomer is hexamethyldisilane, ethyl triethoxysilane, phenyl dimethyl methyl TMOS, tetramethoxy-silicane, hexamethyldisiloxane, octamethyltrisiloxane, octamethylcyclotetrasiloxane, 1,3,5-trimethylammonium-1,3, a kind of in 5-triphenyl cyclotrisiloxane, triethyl silicic acid, phenylbenzene silicon diacid, pentamethyl-hydroxyl sily oxide, vinyltrimethoxy silane, the vinyltriethoxysilane or their mixture.
Compared with prior art, characteristics of the present invention are: adopt titanium alloy (Ti
6Al
4V) as matrix, diamond like carbon film is as surface functional layer, it between matrix and surface functional layer the silicon transition layer, therefore, this film composite material not only possesses good mechanical property and abrasion resistance properties, and frictional coefficient is low, blood compatibility and histocompatibility is good, the bonding strength height between the film base, is the novel material of human body implant devices such as heart valve prosthesis, joint prosthesis; Preparation process has adopted radio-frequency plasma to strengthen chemical vapour deposition technique and liquid electrodeposition way of combining; two kinds of film preparing technologies are combined; the characteristics of various technologies of preparing have been made full use of; solved the contradiction of the bonding strength between surface functional layer performance and the film base preferably; by prefabricated intermediate layer; improve the bonding strength between the film base; therefore, the present invention has in preparation and has very positive meaning aspect the diamond-like coating biomaterial of actual application value.
Description of drawings
Accompanying drawing 1 is the Raman spectrogram by DLC film in the diamond-like coating biomaterial of embodiment of the invention preparation;
Accompanying drawing 2 is the XPS spectrum figure by DLC film in the diamond-like coating biomaterial of embodiment of the invention preparation;
Accompanying drawing 3 is the scanning electron microscope pictures by DLC film in the diamond-like coating biomaterial of embodiment of the invention preparation;
Accompanying drawing 4 is the cut graphic representations by DLC film in the diamond-like coating biomaterial of embodiment of the invention preparation.
Embodiment
Below in conjunction with drawings and Examples the present invention is further described:
Embodiment one:
Use Ti
6Al
4The V titanium alloy material cleans substrate earlier as substrate: after surface finish was handled, the dilute hydrochloric acid with about 10% soaked substrate 30 minutes, to remove the oxide compound on surface, in ethanolic soln, use ultrasonic cleaning 10 minutes again, to remove the residual of substrate surface, oven dry.
Depositing silicon transition layer: adopt radio-frequency plasma to strengthen chemical vapour deposition technique the substrate after the above-mentioned cleaning, mixed gas with Ar and organosilane monomer steam is a deposition gases, organosilane monomer can be a hexamethyldisilane, ethyl triethoxysilane, phenyl dimethyl methyl TMOS, tetramethoxy-silicane, hexamethyldisiloxane, octamethyltrisiloxane, octamethylcyclotetrasiloxane, 1,3,5-trimethylammonium-1,3,5-triphenyl cyclotrisiloxane, triethyl silicic acid, phenylbenzene silicon diacid, pentamethyl-hydroxyl sily oxide, vinyltrimethoxy silane, a kind of in the vinyltriethoxysilane or their mixture; The proportioning of Ar and organosilane monomer steam is 3～10: 1, is that 110W, bias voltage 400V, vacuum tightness are the condition deposit 15 minutes of 3Pa at radio frequency power, obtains the silicon coating that thickness is about 0.15 μ m at substrate surface.
Depositing diamond-like film: adopt the liquid electrodeposition method and apparatus, high purity graphite is as anode, and negative electrode is the titanium alloy substrate of depositing silicon transition layer in the above-mentioned steps, and polar plate spacing is 12mm, the employing high-voltage DC power supply is an external source, is deposition medium with methyl alcohol.Deposition voltage is 1650～1850V, depositing temperature is 50～60 ℃, about 24 hours of depositing time, being can obtain the diamond-like coating that thickness is about 0.5 μ m on the silicon coating of substrate at titanium alloy, is that excessively layer, surface were the biomaterial of diamond-like coating in the middle of substrate, silicon were thereby prepare with the titanium alloy.
By the diamond-like coating biomaterial of technical solution of the present invention preparation, be the diamond like carbon film of hydrogenous amorphous structure not at the deposited material of titanium alloy surface.Referring to accompanying drawing 1, it is Raman (Raman) spectrogram of present embodiment liquid electrodeposition DLC film under 1650V voltage, in the drawings, and 1350cm
-1And 1600cm
-1Two tangible Raman peaks appear in the place, these two peaks corresponding respectively D pattern and G pattern, this is the characteristic peak of quasi-diamond, shows that the film that electrolytic deposition with this understanding obtains is the DLC film.
Referring to accompanying drawing 2, it is XPS (x-ray photoelectron power spectrum) spectrogram of present embodiment liquid electrodeposition DLC film under 1650V voltage, as can be seen, at voltage is that the main component of the film that obtains of 1650V condition deposit is a carbon, result in conjunction with Raman spectrogram among Fig. 1 shows that it is diamond like carbon film that deposition obtains.
Referring to accompanying drawing 3, it is the scanning electron microscope picture of present embodiment liquid electrodeposition DLC under 1650V voltage, and the result shows that the film that deposition obtains when 1650V and 1850V is made up of homogeneous granules, and particle diameter is approximately about 400nm;
Referring to accompanying drawing 4, it is the cut graphic representation of present embodiment liquid deposition DLC film under 1650V voltage, the electrical signal of output when R1 is illustrated in delineation among the figure, and Fx is illustrated in frictional force in the delineation process, and Fz is illustrated in the load that puts on film in the delineation process.Along with the increase of load, frictional force also presents linear increasing, because diamond-film-like is an insulating, so provides tangible resistance value in the film.When load increased certain value, resistance went to zero, and sudden change also appears in frictional force simultaneously, and the load of this moment is the critical load value (Lc) that film begins to peel off.As seen from the figure, the critical load value of film is 90g, shows that film and matrix have bonding force preferably.
By the diamond-like coating biomaterial of embodiment of the invention preparation, it is good not only to have the favorable mechanical performance, and with human body favorable tissue consistency and blood compatibility is arranged.Table 1 is by blood compatibility index determining results such as several external dynamic clotting times that are used for the Artificial heart valve mould material at present of the diamond-like coating biomaterial of embodiment of the invention preparation and other, platelet consumption rate, hemolysis rates, from table 1 test data as can be seen, the blood compatibility of present embodiment sample and low temperature pyrogenation carbon are approaching, are better than TiAl
4The V titanium alloy.
Therefore, the quasi-diamond that the technology of the present invention provides is mechanical property and the biocompatibility requirement that the biomaterial of coating can satisfy body implanting material preferably, has broad application prospects.
Table 1:
| Material | Platelet consumption rate (%) | The external dynamic clotting time (min) | Hemolysis rate (%) |
| Low temperature pyrogenation carbon (LTIC) | 15.2 | 39.0 | 2.78 |
| Titanium alloy | 33.2 | 28.5 | 5.69 |
| Present embodiment (DLC) | 28.9 | 33.0 | 3.47 |
Claims (3)
1. diamond-like coating biomaterial, it is characterized in that: it is with Ti
6Al
4The V titanium alloy is a matrix, and diamond like carbon film is a surface functional layer, and a silicon transition layer is arranged between matrix and surface functional layer.
2. the preparation method of a diamond-like coating biomaterial is characterized in that preparation process is as follows:
(1) earlier to Ti
6Al
4The titanium alloy-based body and function radio-frequency plasma of V strengthens chemical Vapor deposition process to be handled, deposition gases is the mixed gas of Ar and organosilane monomer steam, its proportioning is 3～10: 1, and the plasma-treating technology condition is: radio frequency power 80～110W, bias voltage 300～400V, vacuum tightness 3～8Pa; Obtain the silicon transition layer that deposit thickness is 0.05～0.15 μ m at matrix surface;
(2) with high purity graphite as anode, the titanium alloy substrate of the above-mentioned transition layer of depositing silicon is a negative electrode, methyl alcohol is deposition medium, adopt liquid electrodeposition method depositing diamond-like film on the silicon transition layer, polar plate spacing is 6～12mm, and deposition voltage is 1650～1850V, and depositing temperature is 50～60 ℃; On the silicon transition layer, obtain the diamond like carbon film that deposit thickness is 0.1～0.5 μ m, making with the Ti6Al4V titanium alloy is matrix, diamond like carbon film is a surface functional layer, and the diamond-like coating biomaterial of a silicon transition layer is arranged between matrix and surface functional layer.
3. the preparation method of diamond-like coating biomaterial according to claim 2, it is characterized in that: described organosilane monomer is hexamethyldisilane, ethyl triethoxysilane, phenyl dimethyl methyl TMOS, tetramethoxy-silicane, hexamethyldisiloxane, octamethyltrisiloxane, octamethylcyclotetrasiloxane, 1,3,5-trimethylammonium-1,3, a kind of in 5-triphenyl cyclotrisiloxane, triethyl silicic acid, phenylbenzene silicon diacid, pentamethyl-hydroxyl sily oxide, vinyltrimethoxy silane, the vinyltriethoxysilane or their mixture.
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|---|---|---|---|
| CN 200510122762 CN1776027A (en) | 2005-12-01 | 2005-12-01 | Diamond coating-like biological material and its preparing method |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101451238B (en) * | 2007-11-30 | 2010-08-25 | 中芯国际集成电路制造(上海)有限公司 | Pre-deposition method for forming protection film in chamber |
| CN101671811B (en) * | 2009-10-16 | 2011-07-20 | 江苏大学 | Method for preparing high-load tribology DLC membrane on surface of titanium |
| CN102241827A (en) * | 2011-05-14 | 2011-11-16 | 中南林业科技大学 | Adjusting method of natural vegetable fiber and polylactic acid interface |
| CN102399092A (en) * | 2010-09-09 | 2012-04-04 | 西南科技大学 | Preparation method for nitrogen-doped nano-diamond thin film |
| CN105597149A (en) * | 2015-10-08 | 2016-05-25 | 西南交通大学 | Preparation method of carbon film biomaterial with wear self-repairing function in in-vivo environment |
| CN106037757A (en) * | 2016-07-13 | 2016-10-26 | 苏州大学 | In-vivo platelet instant label-free detection system and detection method |
| CN108950517A (en) * | 2018-07-10 | 2018-12-07 | 中国科学院宁波材料技术与工程研究所 | A kind of wear-resisting lubricant coating of aluminium alloy matrix surface and preparation method thereof |
| CN109023292A (en) * | 2018-09-26 | 2018-12-18 | 佳木斯大学 | A kind of Mg alloy surface DLC protective coating preparation method |
| CN111593298A (en) * | 2020-06-19 | 2020-08-28 | 长沙新材料产业研究院有限公司 | Surface-modified titanium alloy material and preparation method thereof |
| CN115233224A (en) * | 2022-06-30 | 2022-10-25 | 湖南碳康生物科技有限公司 | TC4 material with wear-resistant surface and low biotoxicity and preparation method thereof |
| CN115505907A (en) * | 2021-06-22 | 2022-12-23 | 江苏菲沃泰纳米科技股份有限公司 | Composite film applied to flexible substrate and preparation method and product thereof |
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2005
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101451238B (en) * | 2007-11-30 | 2010-08-25 | 中芯国际集成电路制造(上海)有限公司 | Pre-deposition method for forming protection film in chamber |
| CN101671811B (en) * | 2009-10-16 | 2011-07-20 | 江苏大学 | Method for preparing high-load tribology DLC membrane on surface of titanium |
| CN102399092A (en) * | 2010-09-09 | 2012-04-04 | 西南科技大学 | Preparation method for nitrogen-doped nano-diamond thin film |
| CN102399092B (en) * | 2010-09-09 | 2013-01-09 | 西南科技大学 | Preparation method for nitrogen-doped nano-diamond thin film |
| CN102241827A (en) * | 2011-05-14 | 2011-11-16 | 中南林业科技大学 | Adjusting method of natural vegetable fiber and polylactic acid interface |
| CN102241827B (en) * | 2011-05-14 | 2013-03-20 | 中南林业科技大学 | Adjusting method of natural vegetable fiber and polylactic acid interface |
| CN105597149A (en) * | 2015-10-08 | 2016-05-25 | 西南交通大学 | Preparation method of carbon film biomaterial with wear self-repairing function in in-vivo environment |
| CN106037757A (en) * | 2016-07-13 | 2016-10-26 | 苏州大学 | In-vivo platelet instant label-free detection system and detection method |
| CN106037757B (en) * | 2016-07-13 | 2023-10-17 | 心擎医疗（苏州）股份有限公司 | In-vivo platelet instant label-free detection system and detection method |
| CN108950517A (en) * | 2018-07-10 | 2018-12-07 | 中国科学院宁波材料技术与工程研究所 | A kind of wear-resisting lubricant coating of aluminium alloy matrix surface and preparation method thereof |
| CN109023292A (en) * | 2018-09-26 | 2018-12-18 | 佳木斯大学 | A kind of Mg alloy surface DLC protective coating preparation method |
| CN111593298A (en) * | 2020-06-19 | 2020-08-28 | 长沙新材料产业研究院有限公司 | Surface-modified titanium alloy material and preparation method thereof |
| CN115505907A (en) * | 2021-06-22 | 2022-12-23 | 江苏菲沃泰纳米科技股份有限公司 | Composite film applied to flexible substrate and preparation method and product thereof |
| CN115233224A (en) * | 2022-06-30 | 2022-10-25 | 湖南碳康生物科技有限公司 | TC4 material with wear-resistant surface and low biotoxicity and preparation method thereof |
| CN115233224B (en) * | 2022-06-30 | 2023-12-05 | 湖南碳康生物科技有限公司 | TC4 material with wear-resistant surface and low biotoxicity and preparation method thereof |
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