CN113355644A - Modification process method for immersed injection in-situ surface gradient reconstruction wear-resistant diamond-like coating - Google Patents
Modification process method for immersed injection in-situ surface gradient reconstruction wear-resistant diamond-like coating Download PDFInfo
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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Abstract
The invention discloses a modification process method for reconstructing a wear-resistant diamond-like coating based on immersion injection in-situ surface gradient, which comprises the steps of cleaning the surface of the diamond-like coating, immersion injection of inert gas ions, stress removal treatment and the like, wherein the inert gas ions are He+、Ne+、Ar+. In-situ defects are introduced by inert gas ion immersion implantation of diamond-like coating to enable part of carbon atoms in the coating to be hybridized by diamond (sp)3) Structural transformation to graphite (sp)2) The structure further enhances the lubricating property of the coating on the premise of ensuring the strength and toughness of the coating by micro-regulating and controlling the gradient distribution of graphite components in the coating thickness direction. The surface roughness of the modified coating is reduced, and the dry friction coefficient is as low as 0.1-0.2. The modification tool is adoptedThe process method can further improve the wear resistance and service life of the diamond-like coating and the integral mechanical equipment part, can be used for surface modification of a workpiece with a complex appearance structure, and has the outstanding characteristics of high efficiency, low cost, no pollution and the like.
Description
Technical Field
The invention belongs to the technical field of diamond-like carbon coating surface modification, and particularly relates to a process method for modifying an immersed injection in-situ surface gradient reconstruction wear-resistant diamond-like carbon coating.
Background
In the industrial manufacturing field with a large amount of mechanical contact in the automobile industry, aerospace, die processing and the like, the surfaces of mechanical equipment parts are subjected to long-term friction and wear, so that the parts are easy to lose effectiveness, the normal operation of the equipment is further influenced, and the production efficiency and the service life of the equipment are even greatly reduced. According to statistics, 1/3 energy is consumed on friction in various forms, about 80% of mechanical equipment parts are damaged due to continuous friction, and economic loss accounts for 5% -7% of GDP in industrialized countries, see documents [ Zhengquan, Ouyang, Maring, Zhangzhuang, Zhao Hua, Donghua, Lin Li. science and technology guide 34 (2016) 12-26 ]. In view of this, various techniques for strengthening the surface of parts have been developed, wherein the surface coating technique is one of the most widely used and rapidly developed techniques [ liu yi. Among the hard coating materials, diamond-like carbon is a high mechanical property material with characteristics of high hardness, low friction, wear resistance and the like, and is suitable for many harsh working environments, so diamond-like carbon is a preferred material for modifying the surface coating of parts and components, as shown in the literature [ Liu Yi Qi, Korea, Ling Guo Qiang, Shi Chang Lun, Lu Chi Ying, Li Xiao Yong, vacuum science and technology bulletin 37 (2017) 100-.
Diamondoids are a class mainly composed of sp3Hybridization and sp2Metastable amorphous material formed by hybridized carbon atoms, sp3、sp2The coexistence of the structures determines that the diamond-like carbon has the excellent properties of diamond and graphite at the same time. In the face of rapid development of scientific and technological society and actual industrial requirements, particularly, parts which need to work under severe conditions of high speed, high temperature, high pressure, heavy load and the like, higher requirements are put forward on the performance of diamond-like carbon. Therefore, the surface of the diamond-like carbon is strengthened, the wear resistance of the diamond-like carbon is improved, the service life of the diamond-like carbon is prolonged, and the diamond-like carbon has high social value and economic value in the aspects of reducing labor and material cost, saving energy and the like. In this context, diamond-like surface modification technology is becoming an increasingly interesting technology. The friction properties of diamond-like carbon are influenced by a number of factors, e.g. sp3/sp2Bond ratio, surface roughness, etc. Modification of diamond-like sp3/sp2The bond ratio can adjust the bond angle and bond length distortion to promote the amorphous carbon network structure reforming; the change of the surface roughness can influence the resistance of the friction pair to relative movement, thereby changing the friction coefficient. Thus through a series ofMethod for regulating diamond-like carbon surface roughness and sp by using technology3/sp2The bond ratio may improve the diamond-like frictional wear performance to some extent. At present, the diamond-like modification Technology mainly focuses on two aspects of adjusting and controlling preparation process parameters and element doping, for example, Kumar et al, adopting a plasma assisted chemical vapor deposition method to prepare a diamond-like thin film to study the friction and wear performance of the diamond-like thin film, find that the friction coefficient is reduced along with the reduction of the Surface roughness of the diamond-like thin film as the substrate bias voltage is increased, and can realize low friction and low wear at a bias voltage of-300V [ H.A. Esquirt-places, T.S. Fisher, G.Capote, J.J.Olaya. Surface and Coatings Technology 350 (2018) -](ii) a Han et al discovered CH by ion beam enhanced deposition technique for preparing diamond-like thin film4/H2The gas flow is reduced from 9 sccm to 3 sccm, and the D, G peak intensity ratio I of Raman spectrum testD/IGIncrease or sp2/sp3Increased ratio and sp in the film2The increased structural content is the main cause of the decrease in the friction coefficient of diamond-like carbon [ B.B Han, D.Y. Ju, S. SATO, H.J. ZHao. Sci China Tech Sci 62 (2019) 1939-]. Although the friction performance of the diamond-like material can be improved to a certain extent by regulating and controlling the preparation process, the implementation process of regulating and controlling the process parameters is complex and tedious, and the cost of large-scale industrial production is not reduced. In addition, researchers have also made more intensive researches on the aspect of element doping regulation of diamond-like carbon performance, such as preparation of a chromium transition layer/diamond-like carbon composite structure by Miao et al and chromium doping, and the synergistic effect of the transition layer and the doping layer effectively reduces the Surface roughness of the film, so that the wear resistance of diamond-like carbon is remarkably improved [ Y.P. Miao, X.H. Jiang, D.G. Piliptsou, Y.Z. ZHuang, A.V. Rogachev, A.S. Rudenkov, A.Balmakou. Applied Surface Science 379 (2016) 424-]. Zhangjiaojiao et al find that the carbon-philic non-metal Si and the weak carbon metal Ag co-doped diamond-like carbon has a special double-nano structure, thereby promoting sp2The structure is increased to improve the wear resistance and the structural toughness of the coating, but Si-C bonds form a rigid layer which weakens the carbon network and reduces the mechanical property of the diamond-like coating (Zhangshujiao, Wu Yanxia, Julie, Tangbin, Liu Ying. surface technology 47（2018）193-198]. Luo et al found that Cu-doped diamond-like thin film has low internal stress and good friction performance, but interface slippage between the nano-crystalline Cu metal cluster and the amorphous carbon matrix is easy to occur, and excessive doping reduces the mechanical strength of the thin film [ J.Y. Luo, D.E.SUN, S.Zhang. Nanoscience and Nanotechnology Letters 9 (2017) -]. Although element doping can effectively improve the film-substrate bonding strength and toughness, the properties and performances of the material can be influenced while external impurities are introduced. The low-energy inert gas ion injection technology can not only avoid the bonding reaction between ions and materials, but also effectively improve the comprehensive properties of the materials, such as mechanics, friction, abrasion and the like, and has the advantages of low cost, large-area controllable operation and the like [ R, Hobbs, C.S. KIM, A, Agarwal, Y, Yang, nanotechnology 31 (2019) 4]。
Therefore, the invention adopts the inert gas ions to evenly immerse and inject the diamond-like coating, and the sp is micro-regulated and controlled on the premise of ensuring the strength and the toughness of the coating3/sp2The proportion of the structure is used for further enhancing the surface lubricating property of the coating; meanwhile, the energy-carrying ions effectively collide and sputter the surface of the coating, the nano-scale protrusions on the surface are sputtered and removed, and the roughness of the surface of the coating is reduced. Both together result in a reduction of the friction coefficient of the diamond-like coating, thereby improving the frictional wear resistance of the coating. Because the damage degree inside the coating tends to be normally distributed along with the change of the injection depth due to a series of cascade collisions between ions with certain energy and carbon atoms, the coating structure with gradient change of graphite components is formed to improve the toughness and the interface bonding force of the coating structure. Compared with the traditional surface treatment technology, the immersion ion implantation technology can overcome the sight effect and can effectively treat workpieces with complex appearance structures; and has a series of advantages of high efficiency, low cost, no pollution and the like, thereby having wide application prospect in the aspect of improving the wear resistance of the diamond-like carbon coating.
Disclosure of Invention
Based on the requirement on high wear resistance of the diamond-like carbon coating, the invention aims to provide a modification process method for reconstructing the wear-resistant diamond-like carbon coating based on immersion injection in-situ surface gradient, wherein inert gas is adopted at room temperatureObliquely injecting gas ions into the coating sample, wherein the inert gas ions are He+、Ne+、Ar+Is mixed with one or two of them, the ion inclined implantation angle is 30-90 deg., and the ion beam dose is 1X 1016 cm-2 - 1×1017 cm-2The energy is 60 keV to 80 keV. The method can meet higher performance requirements of mechanical equipment parts, can process and modify workpieces with complex appearance structures, and has the advantages of low cost, no pollution and obvious wear resistance improvement effect.
The technical scheme provided by the invention comprises the following steps:
a. cleaning the surface of the sample:
cleaning the diamond-like coating sample in an ultrasonic instrument by using acetone and absolute ethyl alcohol in sequence to remove surface impurities, then cleaning with deionized water, taking out, drying in a vacuum drier under vacuum degree< 10-2Pa, temperature 100 ℃; drying, placing the sample in a vacuum chamber of an immersed ion implantation device, and vacuumizing< 6×10-3Pa; cleaning the sample by adopting bias reverse sputtering for 10min, wherein the reverse sputtering bias voltage is-500V, the working atmosphere is Ar, and the air pressure in the vacuum chamber is 3.0 Pa;
b. and (3) immersion ion implantation:
closing Ar, vacuumizing again to< 6×10-3Pa; introducing inert gas into the vacuum chamber, wherein the flow rate of the inert gas is 20-25 sccm; when the vacuum degree is 2 x 10-2When Pa is needed, the filament current is adjusted to 12A, the arc voltage is adjusted to 120V, and the lead-out voltage is added to 0.5-0.8 kV after the arc current is shown and stabilized; alternately adjusting the suppression voltage to 1-4 kV and the acceleration voltage to 60-80kV, so that the difference between the acceleration current and the suppression current is 1-4 mA; the inert gas ions are obliquely injected into the surface layer of the sample, the injection angle is 30-90 degrees, the injection dosage is controlled according to the injection time of the immersed ions, and the injection time is 3-30 min;
c. stress relief treatment:
and placing the sample after ion implantation in a vacuum chamber of an annealing furnace, vacuumizing to 10 Pa, keeping the temperature at 200-300 ℃ for 10min, naturally cooling along with the furnace, and then taking out.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention adopts the immersion ion implantation technology, the dosage and the depth of implanted ions are controllable, and the automatic production is easy to realize; the sample is immersed in the diffused ions, and the uniformity of the implanted surface ions is good, and the purity is high;
2. the invention adopts an immersion ion implantation technology which can modify the surface of a workpiece with a complex appearance structure without being limited by a sight effect;
3. the method adopts the inert gas ion injection, ions do not generate bonding reaction with materials, and in-situ defects are only introduced into the coating;
4. according to the invention, the diamond-like carbon coating is implanted by adopting immersion ions, so that the graphite component in the coating is changed in a gradient manner, thereby being beneficial to releasing the internal stress of the coating, enhancing the interface binding force and improving the toughness;
5. the invention obviously improves the wear resistance of the diamond-like carbon coating, and the friction performance can be controllably adjusted according to the requirement.
Drawings
FIG. 1 is a Raman test spectrum of the diamond-like coating of examples 1 and 2.
FIG. 2 is an atomic force microscope test surface topography of the diamond-like coating of examples 1 and 2.
FIG. 3 is a scanning electron microscope image of the wear profile of the diamond-like coating of example 1.
FIG. 4 is a scanning electron microscope image of the wear profile of the diamond-like coating of example 2.
Detailed Description
The present invention is described in detail below with reference to the drawings and examples, but the present invention is not limited thereto.
The invention provides a modification process method for reconstructing a wear-resistant diamond-like coating based on immersion injection in-situ surface gradient, which comprises the following steps: introducing inert gas into the vacuum chamber, wherein the gas is one or mixture of He, Ne and Ar, the flow rate is 20-25 sccm, and the vacuum degree is 2 × 10-2When Pa is needed, the filament current is adjusted to 12A, the arc voltage is adjusted to 120V, the lead-out voltage is adjusted to 0.5-0.8 kV, and the suppression is alternately adjustedThe voltage is controlled and accelerated to 1-4 kV of inhibiting voltage and 60-80kV of accelerating voltage. The difference value between the accelerating current and the inhibiting current is 1-4 mA, the ion inclined injection angle is 30-90 degrees, and the injection time is 3-30 min.
Example 1
a. Cleaning the surface of the sample:
cleaning the diamond-like coating sample in an ultrasonic instrument by using acetone and absolute ethyl alcohol in sequence to remove surface impurities, then cleaning with deionized water, taking out and putting into a vacuum drier for drying, wherein the vacuum degree is less than 10-2Pa, temperature 100 ℃; drying, placing the sample in a vacuum chamber of an immersed ion implantation device, and vacuumizing<6×10-3Pa; cleaning the sample by adopting bias reverse sputtering for 10min, wherein the reverse sputtering bias voltage is-500V, the working atmosphere is Ar, and the air pressure in the vacuum chamber is 3.0 Pa;
b. and (3) immersion ion implantation:
closing Ar, vacuumizing again to<6×10-3Pa; introducing inert gas into the vacuum chamber, wherein the flow rate of the inert gas is 25 sccm; when the vacuum degree is 2 x 10-2When Pa is needed, the filament current is adjusted to 12A, the arc voltage is adjusted to 120V, and the lead-out voltage is added to 0.5 kV after the arc current is displayed and stabilized; alternately adjusting the suppression voltage to 1 kV and the acceleration voltage to 60 kV to make the difference between the acceleration current and the suppression current be 2 mA; implanting ions perpendicular to the surface of the sample at an implantation angle of 90 deg. for 3 min with an implantation dose of 1 × 1016 cm-2；
c. Stress relief treatment:
and placing the sample after ion implantation in a vacuum chamber of an annealing furnace, vacuumizing to 10 Pa, keeping the temperature at 200 ℃ for 10min, naturally cooling along with the furnace, and then taking out.
FIG. 1 shows the D, G peak-to-peak intensity ratio I of the Raman spectroscopy test of diamond-like coatings described in example 1 aboveD/IGAt 1.63, FIG. 2 shows that the surface average roughness Ra of the diamond-like coating of example 1 was 2.7 nm as measured by atomic force microscopy. The frictional wear performance of the coating is tested by adopting a frictional wear testing machine, the normal load is 5N, the frequency is 5 Hz, and a GCr15 steel ball friction pair with the diameter of 6 mm and the diamond-like carbon coating are continuously usedFor 66 min. The average dry coefficient of friction of the coating was detected to be 0.2 and the depth of the wear scar was greater with some abrasive particles present at the edge of the wear scar as shown in figure 3.
Example 2
a. Cleaning the surface of the sample:
cleaning the diamond-like coating sample in an ultrasonic instrument by using acetone and absolute ethyl alcohol in sequence to remove surface impurities, then cleaning with deionized water, taking out and putting into a vacuum drier for drying, wherein the vacuum degree is less than 10-2Pa, temperature 100 ℃; drying, placing the sample in a vacuum chamber of an immersed ion implantation device, and vacuumizing<6×10-3Pa; cleaning the sample by adopting bias reverse sputtering for 10min, wherein the reverse sputtering bias voltage is-500V, the working atmosphere is Ar, and the air pressure in the vacuum chamber is 3.0 Pa;
b. and (3) immersion ion implantation:
closing Ar, vacuumizing again to<6×10-3Pa; introducing inert gas into the vacuum chamber, wherein the flow rate of the inert gas is 25 sccm; when the vacuum degree is 2 x 10-2When Pa is needed, the filament current is adjusted to 12A, the arc voltage is adjusted to 120V, and the lead-out voltage is added to 0.5 kV after the arc current is displayed and stabilized; alternately adjusting the suppression voltage to 1 kV and the acceleration voltage to 60 kV to make the difference between the acceleration current and the suppression current be 2 mA; implanting ions perpendicular to the surface of the sample at an implantation angle of 90 deg. for 9 min with a corresponding implantation dose of 3 × 1016 cm-2；
c. Stress relief treatment:
and placing the sample after ion implantation in a vacuum chamber of an annealing furnace, vacuumizing to 10 Pa, keeping the temperature at 200 ℃ for 10min, naturally cooling along with the furnace, and then taking out.
FIG. 1 shows the D, G peak-to-peak intensity ratio I of the Raman spectroscopy test of the diamond-like coating described in example 2 aboveD/IGThe value was 2.36 higher than example 1, indicating sp2The bond content increases, that is, the graphite component excellent in lubricating property increases. Figure 2 shows that the surface average roughness Ra of the diamond-like coating of example 2 as measured by atomic force microscopy is lower than 2.3 nm for example 1, indicating a reduction in surface roughness with increasing implant dose. Method for testing frictional wear of coating by adopting frictional wear testing machineThe normal load is 5N, the frequency is 5 Hz, the GCr15 steel ball friction pair with the diameter of 6 mm and the diamond-like carbon coating are continuously rubbed for 66 min, and the average dry friction coefficient of the coating is detected to be 0.184. Compared to example 1, example 2 had insignificant depth of wear scar, no significant abrasive dust was observed at the edges of the wear scar, and the center of the wear scar track was smoother, showing mild wear, as shown in fig. 4. The implantation dosage is regulated and controlled by changing the immersion ion implantation time, the implantation angle is changed, and the ion implantation depth is regulated and controlled by changing the ion energy, so that the wear resistance of the coating is improved. The structure and performance of the prepared diamond-like coating can be regulated and controlled, so that the use requirement of product application can be met.
Claims (5)
1. A modification process method for an immersion injection in-situ surface gradient reconstruction wear-resistant diamond-like coating is characterized by comprising the following process steps:
a. cleaning the surface of the sample:
cleaning the diamond-like coating sample in an ultrasonic instrument by using acetone and absolute ethyl alcohol in sequence to remove surface impurities, cleaning with deionized water, and drying in a vacuum drier under vacuum degree< 10-2 Pa, temperature 100 ℃; drying, placing the sample in a vacuum chamber of an immersed ion implantation device, and vacuumizing< 6×10-3Pa; cleaning the sample by reverse sputtering under bias voltage of-500V in Ar working atmosphere for 10min under pressure of 3.0 Pa;
b. and (3) immersion ion implantation:
closing Ar, vacuumizing again to< 6×10-3Pa; introducing inert gas into the vacuum chamber, wherein the flow rate of the inert gas is 20-25 sccm; when the vacuum degree is 2 x 10-2When Pa is needed, the filament current is adjusted to 12A, the arc voltage is adjusted to 120V, and the lead-out voltage is added to 0.5-0.8 kV after the arc current is shown and stabilized; alternately adjusting the suppression voltage to 1-4 kV and the acceleration voltage to 60-80kV, so that the difference between the acceleration current and the suppression current is 1-4 mA; obliquely injecting inert gas ions into the surface layer of the sample, and controlling the injection dosage according to the injection time of the immersed ions, wherein the injection time is 3-30 min;
c. stress relief treatment:
and placing the sample after ion implantation in a vacuum chamber of an annealing furnace, vacuumizing to 10 Pa, keeping the temperature at 200-300 ℃ for 10min, naturally cooling along with the furnace, and then taking out.
2. The process of modifying an immersion implantation in situ surface gradient reconstruction abrasion resistant diamond-like coating as claimed in claim 1, wherein: selecting inert gas ion as He+、Ne+、Ar+Either one or two of them are mixed, and the purity of the inert gas is 99.99%.
3. The process of modifying an immersion implantation in situ surface gradient reconstruction abrasion resistant diamond-like coating as claimed in claim 1, wherein: the pressure of the vacuum chamber is maintained at 2 × 10 during ion implantation-2 Pa。
4. The process of modifying an immersion implantation in situ surface gradient reconstruction abrasion resistant diamond-like coating as claimed in claim 1, wherein: the inclined implantation angle of the inert gas ions is 30-90 degrees, the acceleration voltage of 60-80kV corresponds to the ion beam energy of 60 keV-80 keV, and the ion implantation depth is 500-900 nm.
5. The process of modifying an immersion implantation in situ surface gradient reconstruction abrasion resistant diamond-like coating as claimed in claim 1, wherein: the implantation time is 3-30 min, and the corresponding ion beam dose is 1 × 1016 cm-2 - 1×1017cm-2。
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH059725A (en) * | 1991-07-04 | 1993-01-19 | Sumitomo Electric Ind Ltd | Method for coating hard carbon film |
| WO2001059172A1 (en) * | 2000-02-08 | 2001-08-16 | Epion Corporation | Diamond-like carbon film with enhanced adhesion |
| CN1363715A (en) * | 2001-12-17 | 2002-08-14 | 中国科学院兰州化学物理研究所 | Process for preparing modified non-crystal carbon film by metal iron implantation |
| JP2006249539A (en) * | 2005-03-11 | 2006-09-21 | Plus:Kk | Compound surface reforming treatment method and apparatus, and surface reforming treated material |
| US20070082129A1 (en) * | 2005-10-06 | 2007-04-12 | Toyota Jidosha Kabushiki Kaisha | Metal composite diamond-like carbon (DLC) film, method and apparatus for forming the same, and slide member |
| KR20070056580A (en) * | 2005-11-30 | 2007-06-04 | 주식회사 진우엔지니어링 | Method and facility for coating the 3-dimensional member with diamond-like carbon film by plasma cvd combined with plasma ion implantation |
| EP1884978A1 (en) * | 2006-08-03 | 2008-02-06 | Creepservice S.à.r.l. | Process and apparatus for the coating of substrates with diamond-like carbon layers |
| CN104138616A (en) * | 2014-07-23 | 2014-11-12 | 深圳清华大学研究院 | Medicinal titanium and titanium alloy surface oxidation-carbon plated-diamond-like composite film and manufacturing method thereof |
| CN105331945A (en) * | 2014-08-12 | 2016-02-17 | 上海航天设备制造总厂 | Preparing method for diamond-like carbon base solid-liquid composite lubricating film under high vacuum |
| CN106244986A (en) * | 2016-08-08 | 2016-12-21 | 珠海罗西尼表业有限公司 | Diamond-like carbon film of functionally gradient and preparation method thereof and goods |
| CN106702341A (en) * | 2016-11-24 | 2017-05-24 | 中国科学院深圳先进技术研究院 | Polyether-ether-ketone material and modification method based on plasma immersion ion implantation and application |
| CN107641788A (en) * | 2016-07-22 | 2018-01-30 | 北京华石联合能源科技发展有限公司 | A kind of preparation method of the diamond-film-like of anti-coking |
-
2020
- 2020-03-05 CN CN202010145330.5A patent/CN113355644B/en not_active Expired - Fee Related
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH059725A (en) * | 1991-07-04 | 1993-01-19 | Sumitomo Electric Ind Ltd | Method for coating hard carbon film |
| WO2001059172A1 (en) * | 2000-02-08 | 2001-08-16 | Epion Corporation | Diamond-like carbon film with enhanced adhesion |
| CN1363715A (en) * | 2001-12-17 | 2002-08-14 | 中国科学院兰州化学物理研究所 | Process for preparing modified non-crystal carbon film by metal iron implantation |
| JP2006249539A (en) * | 2005-03-11 | 2006-09-21 | Plus:Kk | Compound surface reforming treatment method and apparatus, and surface reforming treated material |
| US20070082129A1 (en) * | 2005-10-06 | 2007-04-12 | Toyota Jidosha Kabushiki Kaisha | Metal composite diamond-like carbon (DLC) film, method and apparatus for forming the same, and slide member |
| KR20070056580A (en) * | 2005-11-30 | 2007-06-04 | 주식회사 진우엔지니어링 | Method and facility for coating the 3-dimensional member with diamond-like carbon film by plasma cvd combined with plasma ion implantation |
| EP1884978A1 (en) * | 2006-08-03 | 2008-02-06 | Creepservice S.à.r.l. | Process and apparatus for the coating of substrates with diamond-like carbon layers |
| CN101501813A (en) * | 2006-08-03 | 2009-08-05 | 科里普瑟维斯赛尔公司 | Process and apparatus for the modification of surfaces |
| CN104138616A (en) * | 2014-07-23 | 2014-11-12 | 深圳清华大学研究院 | Medicinal titanium and titanium alloy surface oxidation-carbon plated-diamond-like composite film and manufacturing method thereof |
| CN105331945A (en) * | 2014-08-12 | 2016-02-17 | 上海航天设备制造总厂 | Preparing method for diamond-like carbon base solid-liquid composite lubricating film under high vacuum |
| CN107641788A (en) * | 2016-07-22 | 2018-01-30 | 北京华石联合能源科技发展有限公司 | A kind of preparation method of the diamond-film-like of anti-coking |
| CN106244986A (en) * | 2016-08-08 | 2016-12-21 | 珠海罗西尼表业有限公司 | Diamond-like carbon film of functionally gradient and preparation method thereof and goods |
| CN106702341A (en) * | 2016-11-24 | 2017-05-24 | 中国科学院深圳先进技术研究院 | Polyether-ether-ketone material and modification method based on plasma immersion ion implantation and application |
Non-Patent Citations (3)
| Title |
|---|
| NA ZHANG等: "tribological properties improvement of H-DLC films through reconstruction of microstructure and surface morphology by low-energy helium ion irradiation", 《DIAMOND & RELATED MATERIALS》 * |
| Y.OKA等: "effects of consecutive processing between cleaning and deposition on adhesion of diamond-like carbon prepared by plasma-based ion implantation and deposition", 《NUCLEAR INST. AND METHODS IN PHYSICS RESEARCH B》 * |
| 柳翠等: "钛离子注入类金刚石碳膜的结构与性能的研究", 《功能材料》 * |
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