CN100560793C - A kind of method for preparing nano composite diamond coating - Google Patents
A kind of method for preparing nano composite diamond coating Download PDFInfo
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- CN100560793C CN100560793C CNB2007100530953A CN200710053095A CN100560793C CN 100560793 C CN100560793 C CN 100560793C CN B2007100530953 A CNB2007100530953 A CN B2007100530953A CN 200710053095 A CN200710053095 A CN 200710053095A CN 100560793 C CN100560793 C CN 100560793C
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Abstract
The invention discloses a kind of method for preparing nano composite diamond coating, utilize the cathode arc discharge of magnetic field control, feeding acetylene gas makes the preceding acetylene of metallic target excessive, target surface forms metal carbide layer, when arc motion, evaporate metallic carbide from target surface, electric arc target the place ahead utilizes the strong plasma body ionization acetylene gas that arc-over produces under the auxiliary magnetic field effect in addition, produce the carbon ion of height ionization, under the effect of bias voltage, form carbide dopen Nano composite diamond coating at workpiece surface from the metallic carbide of target surface evaporation and the carbon ion of acetylene generation.The present invention prepares characteristics such as diamond-like coating has coating hardness height, strong adhesion, the coating growth velocity is fast, production efficiency is high, production cost is low, coating apparatus is simple in structure, can carry out the preparation of different thickness diamond-like coating according to service requirements on all kinds of workpiece such as Wimet, rapid steel, stainless steel, carbon steel, die steel.
Description
Technical field
The present invention relates to a kind of method for preparing nano composite diamond coating, belong to the thin-film material field.
Background technology
Diamond-film-like is a kind of mainly by sp
2Key and sp
3The unordered metastable amorphous carbon-film of mixing that key is formed is divided into hydrogeneous amorphous carbon-film (a-C:H) and non-hydrogen amorphous film (a-C).Have low-friction coefficient, high rigidity, high elastic coefficient, high-wearing feature and thermal conductivity, a series of particular performances such as good chemical stability and resistance to corrosion.Since the eighties, be the focus of whole world research always.The DLC technology of preparing comprises two kinds of CVD (chemical vapour deposition) and PVD (physical vapor deposition), the CVD method as the treatment temp of plasma-assisted chemical deposition (PECVD), electron cyclotron resonace (ECR-CVD) more than 400 ℃, hydrogeneous in the coating simultaneously, coating stress is bigger, and growth velocity is lower, and body material is had relatively high expectations.Characteristics such as it is lower that PVD method such as magnetron sputtering, arc ion plating then have treatment temp, and preparation technology is flexible and changeable are adapted to the workpiece of various differing materials, have obtained application more and more widely at present, and the trend of further replacement CVD is arranged.
Among the diamond-like coating PVD preparation method, mainly comprise magnetron sputtering and arc-over at present.In magnetron sputtering, sputtering target material adopts graphite target, utilizing the Ar ion that carbon atom is sputtered out from target flies to workpiece and forms diamond-like coating, because the carbon ionization level low (less than 5%) of sputtering method, the hardness that causes coating generally below HV15GPa, coating growth velocity lower (less than 0.3 μ m/h) simultaneously.Because the sputter energy is lower, cause the sticking power of coating and matrix relatively poor in addition.Although technology such as gradient cladding, doping are widely used at present,, then cause disbonding at short notice because internal stress is excessive if surpass thickness 500 nanometers, effective coating film area of equipment is very little, the plated film homogeneity can not guarantee, can not mass industrialized production, and the coating cost is very high.Relative magnetron sputtering technique, the ionization level of arc discharge method very high (greater than 90%), but when using graphite as target, because the temperature factor that graphite is negative, cause arc spot speed when target surface moves very slow, the graphite of regional area is erupted in a large number, directly fly to film forming on the workpiece, cause the graphite that has particle bigger in the coating, cause particle contamination.In order to adopt the quasi-diamond of the no particle contamination of arc discharge method preparation, generally all adopt the filtering method of magnetic at present, that is to say a bend pipe is set before target surface, filter out bigger graphite granule.It is low that the use of bend pipe reduces the sedimentation rate of coating significantly, and device structure complexity, poor stability, maintenance difficult are unfavorable for industrial batch production.
It is a problem that needs are avoided as far as possible that target poisons that arc discharge method in routine prepares in the coating procedure, because target surface is poisoned, the material that evaporates from target surface reduces in a large number, and the sedimentation rate of coating is reduced significantly.And when it is used as the preparation diamond-like coating, owing to only need a spot of metallic carbide (less than 20at.%) in the coating, the shortcoming of target surface material slow evaporation becomes advantage, simultaneously owing to use acetylene gas not adopt graphite as target as carbon source, particle contamination problems when having overcome conventional electric arc graphite target, therefore it does not need complicated filter plant, causes device structure simple, easily operation.Because electric arc makes adhesive force of coatings good to the height ionization of acetylene gas, hardness is higher.
Because the high-performance that diamond-like coating has, make it in fields such as aerospace, machinery, biomedicine, computers, have a good application prospect, the target poisoned technique is because its technical superiority makes it not only can overcome particle issues for this reason, inherit simultaneously characteristics such as conventional cathode arc discharge method sedimentation rate is fast, ionization level height again, make the hardness, sticking power, homogeneity etc. of coating be better than conventional magnetron sputtering and arc discharge method, in the DLC coating preparation, have a good application prospect.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing nano composite diamond coating of novel suitable industrialized production, characteristics such as (greater than 1 μ m/h) that this method has the principle advanced person, coating apparatus is simple in structure, sedimentation rate is fast adopt the diamond-like coating of this method preparation to have higher hardness and good lubricating property; Can on all kinds of basic materials such as Wimet, rapid steel, stainless steel, carbon steel, die steel, carry out coating preparation.
For achieving the above object, technical scheme provided by the invention is a kind of method for preparing nano composite diamond coating, is positioned over workpiece in the vacuum chamber after glow discharge is cleaned, and utilizes the metallic target arc-over of magnetic field control to prepare intermediate metal; Feed acetylene gas then, acetylene and the metallic target surface formation metallic carbide that react, when electric arc when target surface moves, evaporate metallic carbide from target surface; Utilize the strong plasma body ionization acetylene gas of target surface arcing discharge generation, produce the carbon ion of height ionization; Under the effect of bias voltage, form carbide dopen Nano composite diamond coating at workpiece surface from the metallic carbide of target surface evaporation and the carbon ion of acetylene generation.
The magnetic field of above-mentioned control arc motion is produced by the coil electricity of the back that is placed on electric arc target, coil is by DC power supply, producing intensity at target surface is 30-50 Gauss's magnetic field, utilize magnetic field to drag electric arc and on target surface, move, improve electric arc in target surface incendiary homogeneity and electric Arc Motion speed.
Above-mentioned metallic target target is Ti target or Cr target, and the quantity of target is 1-2, target size be width at 140-200mm, length is at 500-1000mm, the acetylene flow range is at 300-600sccm; The electric current of metallic target is at the 120-200 ampere.
Above-mentioned glow discharge is cleaned at 150-200 ℃, carries out under the ar gas environment; After aura disappeared and washes end, the discharge of metallic target cathode arc was carried out under the 0.1-3Pa condition, and the deposit thickness of intermediate metal is the 100-200 nanometer; Feeding the acetylene gas flow is 80-600sccm, and metallic carbide content is controlled at 1-20at.%, and the carbide grain diameter is controlled at below 10 nanometers; Preparation temperature 100-200 ℃, bias voltage is-50~-150V.
It is the problem that a needs is avoided as far as possible that target poisons that arc discharge method in routine prepares in the coating procedure, because target surface is poisoned, the material that evaporates from target surface reduces in a large number, and the sedimentation rate of coating is reduced significantly.And when it is used as the preparation diamond-like coating, owing to only need a spot of metallic carbide (less than 20at.%) in the coating, the shortcoming of target surface material slow evaporation becomes advantage, simultaneously owing to use acetylene gas not adopt graphite as target as carbon source, particle contamination problems when having overcome conventional electric arc graphite target, therefore it does not need complicated filter plant, causes device structure simple, easily operation.Because electric arc makes adhesive force of coatings good to the height ionization of acetylene gas, hardness is higher.
Acetylene gas was excessive before preparation method provided by the invention mainly utilized the acetylene gas that feeds different flow in the cathode arc discharge process to make metallic target, target surface forms metal carbide layer poisons target surface, when arc motion, evaporate metallic carbide, utilize the high-melting-point characteristic of carbide to eliminate the metallic particles pollution that the conventional cathode arc-over causes from target surface.This external electric arc target the place ahead configuration auxiliary magnetic field, the strong plasma body ionization acetylene gas that utilizes magnetic focusing effect and arc-over to produce, produce the carbon ion of height ionization, under the effect of bias voltage, form carbide doped diamond coating from the metallic carbide of target surface evaporation and the carbon ion of acetylene ionization generation at workpiece surface, by adjusting the size and the content of carbide grain in the different acetylene flow control coatings.Because the carbon ionization level height that this method produces, the growth velocity of coating is higher, owing to the nanocrystalline and amorphous strengthening effect of carbide, is hanging down under the condition of coating stress simultaneously, also have higher hardness when keeping the good lubrication performance, its hardness can reach more than the 27Gpa.
Because the high-performance that diamond-like coating has, make it in fields such as aerospace, machinery, biomedicine, computers, have a good application prospect, the target poisoned technique is because its technical superiority makes it not only can overcome particle issues for this reason, inherit simultaneously characteristics such as conventional cathode arc discharge method sedimentation rate is fast, ionization level height again, make the hardness, sticking power, homogeneity etc. of coating be better than conventional magnetron sputtering and arc discharge method, in the DLC coating preparation, have a good application prospect.
Description of drawings
The coating system synoptic diagram of Fig. 1 for being adopted among the present invention
The surperficial SEM figure of coating layer of Nano composite diamond under the different acetylene flow conditions that Fig. 2 makes for the present invention;
Coating layer of Nano composite diamond surfaceness variation diagram during 480sccm that Fig. 3 makes for the present invention;
Coating layer of Nano composite diamond frictional coefficient figure under the different acetylene flow conditions that Fig. 4 makes for the present invention;
The Raman spectrogram of the coating layer of Nano composite diamond that Fig. 5 makes for the present invention;
Fig. 6 schemes for the XPS of the coating layer of Nano composite diamond that the present invention makes;
The transmission electron microscope image (a) of the coating layer of Nano composite diamond that Fig. 7 prepares during for different acetylene flow and (c) and (d) with selected area electron diffraction figure (b);
The nano hardness of the coating layer of Nano composite diamond that Fig. 8 makes for the present invention.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is described further:
Embodiment 1: utilize the Ti metallic target arc-over of magnetic field control to prepare the Ti intermediate metal under the condition of 2.5Pa, negative 100V bias voltage; Feed acetylene gas then, acetylene and the Ti metallic target surface formation titanium carbide that reacts utilizes magnetic field to drag electric arc and moves on target surface, when electric arc when target surface moves, evaporate metallic carbide from target surface; Utilize the strong plasma body ionization acetylene gas of target surface arcing discharge generation, produce the carbon ion of height ionization; Form carbide dopen Nano composite diamond coating from the metallic carbide titanium of target surface evaporation and the carbon ion of acetylene generation at workpiece surface.Wherein feeding the acetylene gas flow is 80-600sccm; The electric current of metallic target is at 180 amperes.
The magnetic field of above-mentioned control arc motion is produced by the coil electricity of the back that is placed on electric arc target, and coil is by DC power supply, and producing intensity at target surface is 50 Gausses' magnetic field.
Above-mentioned glow discharge is cleaned at 150-200 ℃, carries out under the ar gas environment; After aura cleaned and finishes, the discharge of metallic target cathode arc was carried out under the 2.5Pa condition, and the deposit thickness of intermediate metal is the 100-200 nanometer; Metallic carbide content is controlled at 1-20at.%, and the carbide grain diameter is controlled at below 10 nanometers; Feeding the acetylene gas flow is 300-600sccm, and preparation temperature 100-200 ℃, bias voltage is negative 100V.
Above-mentioned metallic target, target size be width at 140-200mm, length is at 500-1000mm.
Embodiment 2: utilize the Cr metallic target arc-over of magnetic field control to prepare the Cr intermediate metal under the condition of 0.1Pa, negative 80V bias voltage; Feed acetylene gas then, acetylene and the Cr metallic target surface formation chromium carbide that reacts utilizes magnetic field to drag electric arc and moves on target surface, when electric arc when target surface moves, evaporate chromium carbide from target surface; Utilize the strong plasma body ionization acetylene gas of target surface arcing discharge generation, produce the carbon ion of height ionization; Form chromium carbide dopen Nano composite diamond coating from the chromium carbide of target surface evaporation and the carbon ion of acetylene generation at workpiece surface.Wherein feeding the acetylene gas flow is 80-600sccm; The electric current of Cr target is at 130 amperes.
Above-mentioned glow discharge is cleaned at 150-200 ℃, carries out under the ar gas environment; After aura cleaned and finishes, the discharge of Cr metallic target cathode arc was carried out under the 0.1Pa condition, and the deposit thickness of Cr intermediate metal is 150 nanometers; Chromium carbide content is controlled at 1-20at.%, and crystal grain diameter is controlled at below 10 nanometers; Feeding the acetylene gas flow is 480sccm, 150 ℃ of preparation temperatures, and bias voltage is negative 80V.
The magnetic field of above-mentioned control arc motion is produced by the coil electricity of the back that is placed on electric arc target, coil is by DC power supply, producing intensity at target surface is 30 Gausses' magnetic field, utilizes magnetic field to drag electric arc and moves on target surface, improves electric arc in target surface incendiary homogeneity and electric Arc Motion speed.
The quantity of above-mentioned metallic target is 2, target size be width at 140-200mm, length is at 500-1000mm.
Fig. 1 is a coating system structural representation of the present invention, and this equipment is the opening door vacuum apparatus, and coating chamber door 4 is of a size of 500 * 1000mm
2, vacuum chamber 7 is of a size of Φ 1000 * 1500mm
2The unit of bleeding is bled by 1 pair of vacuum chamber of bleeding point.Be provided with metallic arc target 5 and work rest 6 in the vacuum chamber 7, the metallic arc target size is 1000 * 200mm
2, DC power supply produces magnetic field control arc motion by 3 energisings of coil behind the target.Coil 2 produces magnetic field article on plasma body and focuses on the raising plasma density before the target.Work rest is positioned at the middle part of vacuum chamber and carries out Three dimensional rotation, and well heater 8 is positioned at the inboard, furnace wall, is used for bake out and coating process and heats up.In vacuum chamber, one has two metallic arc targets, over against layout.The homogeneity of coating has obtained good assurance, has improved coating quality, has improved coating adhesion.
Fig. 2 feeds surface scan Electronic Speculum (SEM) figure that the acetylene gas flow is the TiC dopen Nano composite diamond coating that makes of 80sccm, 250sccm, 483sccm, 600sccm for the present invention, coatingsurface obvious defects without comparison as can be seen from SEM figure, very smooth.Along with the increase particle contamination disappearance of acetylene flow, illustrate that this method of employing has well solved particle contamination problems.
The surfaceness variation diagram of the TiC dopen Nano composite diamond coating that Fig. 3 makes for the present invention:
As can be seen from Figure 3, with the increase of acetylene flow, coating roughness progressively increases, but all is lower than 5nm.
The frictional coefficient curve of TiC dopen Nano composite diamond coating during different acetylene flow that Fig. 4 makes for the present invention:
As can be seen from Figure 4, with the variation of acetylene flow, apparent in view variation has taken place in the frictional coefficient of coating layer of Nano composite diamond.
The Raman spectrum of the coating layer of Nano composite diamond that Fig. 5 makes for the present invention:
Coating is based on TiC when 80sccm as can be seen for Fig. 5, and when the acetylene flow was increased to 250sccm, there was a small amount of change coating TiC vibration peak intensity and position, forms the TiC of distortion structure in the coating, at 1350~1580cm
-1Occur the signal of very little quasi-diamond in the scope, illustrate that DLC increases mutually in the coating.When flow is increased to 480sccm, at 1350~1580cm
-1The G peak and the D peak of typical diamond-like coating occur, illustrate that coating structure changes into based on quasi-diamond.When flow was increased to 600sccm, the TiC peak almost can't be observed, but nearly 3 times of the peak intensity increases of quasi-diamond, the D peak becomes more obvious simultaneously, illustrates that coating is based on DLC mutually.
The composition analysis figure of the coating layer of Nano composite diamond that Fig. 6 makes for the present invention:
Fig. 6 shows the increase with the acetylene flow, and the main peak of C1s does not have greatly changed, and just very big variation (shown in Fig. 4 .15) has taken place its intensity.The acromion of diamond phase is high-visible with TiC peak mutually in the C1s spectrum when 80sccm, and after acetylene content surpassed 80sccm, the C1s spectrum became mainly with sp
2Xiang Weizhu, TiC fades away mutually.
The structural analysis figure of the coating layer of Nano composite diamond that Fig. 7 makes for the present invention:
As can be seen from Figure 7, with the variation of acetylene flow, apparent in view variation has taken place in the coating microtexture, below the 10nm the when 50nm of TiC grain-size during from 80sccm is reduced to 250sccm.
The hardness of coating layer of Nano composite diamond during different acetylene flow that Fig. 8 makes for the present invention:
As can be seen from Figure 8 with the increase of acetylene flow, coating hardness progressively descends.
Claims (4)
1. nanometer
Close
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Be coated with
System
The side
Empty
Part
Light
0.1~3Pa ,-50~
150V is inclined to one side
Bar
Down
Magnetic field
The metallic target of system
Arc is put
Transition layer; So
Go into
Alkynes
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When arc moves at the metal target surface, evaporate metallic carbide from the metal target surface; Utilize the strong plasma body ionization acetylene gas of metallic target surface arcing discharge generation, produce the carbon ion of height ionization; Form metallic carbide dopen Nano composite diamond coating from the metallic carbide of metal target surface evaporation and the carbon ion of acetylene generation at workpiece surface; Wherein, the magnetic field of control arc motion is produced by the coil electricity of the back that is placed on metallic target, coil is by DC power supply, producing intensity at the metal target surface is 30~50 Gausses' magnetic field, utilize magnetic field to drag electric arc and on the metal target surface, move, improve electric arc in metal target surface incendiary homogeneity and electric Arc Motion speed; The acetylene gas flow that is fed is 80~600sccm.
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CN101550535B (en) * | 2009-05-07 | 2010-09-29 | 上海交通大学 | Method for preparing compound metal sulfide diamond composite membrane |
US8383200B2 (en) * | 2009-05-27 | 2013-02-26 | GM Global Technology Operations LLC | High hardness nanocomposite coatings on cemented carbide |
CN101701332B (en) * | 2009-11-17 | 2011-05-11 | 武汉大学 | Method for preparing compound diamond-like carbon coating by using medium-frequency magnetic-control glow discharge method |
JP5868017B2 (en) * | 2010-04-14 | 2016-02-24 | キヤノン株式会社 | Manufacturing method of optical element molding die and optical element molding die |
CN102261347A (en) * | 2010-05-25 | 2011-11-30 | 沈阳鼓风机集团股份有限公司 | Application of diamond-like film on impeller |
CN103160801B (en) * | 2011-12-16 | 2016-06-15 | 中国科学院兰州化学物理研究所 | In the method that metallic interior surface prepares diamond-like carbon film |
CN104141109B (en) * | 2014-06-19 | 2017-02-15 | 武汉大学 | Method for in-situ synthesis of composite TiC-DLC coating on surface of titanium |
CN107587115A (en) * | 2016-09-26 | 2018-01-16 | 上海紫日包装有限公司 | A kind of plastic bottle cap die of diamond-like composite coating on surface |
CN108374148A (en) * | 2017-01-04 | 2018-08-07 | 中国航空工业集团公司北京航空制造工程研究所 | A kind of diamond-like film preparation method based on arc target poison ing effect |
CN107400873B (en) * | 2017-07-26 | 2019-07-05 | 森科五金(深圳)有限公司 | A kind of DLC film and preparation method thereof |
CN110034281B (en) * | 2018-04-12 | 2021-06-15 | 南方科技大学 | Phosphorus/carbon composite material, preparation method thereof, lithium ion battery and sodium ion battery |
CN111304587B (en) * | 2018-12-12 | 2022-06-24 | 北京首量科技股份有限公司 | Preparation method of hydrogen-free amorphous carbon film |
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