CN102864411A - CN-MCN superhard self-lubricating nano-composite coating and preparation method thereof - Google Patents
CN-MCN superhard self-lubricating nano-composite coating and preparation method thereof Download PDFInfo
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- CN102864411A CN102864411A CN2012103956925A CN201210395692A CN102864411A CN 102864411 A CN102864411 A CN 102864411A CN 2012103956925 A CN2012103956925 A CN 2012103956925A CN 201210395692 A CN201210395692 A CN 201210395692A CN 102864411 A CN102864411 A CN 102864411A
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- C—CHEMISTRY; METALLURGY
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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- C—CHEMISTRY; METALLURGY
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
- C23C14/325—Electric arc evaporation
Abstract
The invention discloses a CN-MCN superhard self-lubricating nano-composite coating and a preparation method thereof. An electric arc discharge method and a hollow cathode electric arc discharge carbon source combination method are adopted to generate a combination layer, a transition layer, a supporting layer and a lubricating layer to sequentially form the nano-composite coating. The preparation method has the advantages of being high in ionization rate, simple in coating device structure, high in deposition rate and the like. The prepared CN-MCN superhard self-lubricating nano-composite coating is high coating hardness, strong in adhesive power, good in self-lubricating property, high in coating growing speed and production efficiency, low in production cost and friction coefficient and good in coating toughness and can remarkably improve the abrasion-resisting and lubricating performance of processing cutters, dies and mechanical parts. In addition, the preparation method is simple, industrial production is easily achieved, and the CN-MCN superhard self-lubricating nano-composite coating has good application prospect.
Description
Technical field
The present invention relates to the thin-film material field, particularly a kind of CN-MCN super-hard self-lubricating nano-composite coating and preparation method thereof.
Background technology
The novel materials such as high strength and ultrastrength material, high tenacity, difficult cutting emerge in an endless stream, in the widespread use in the fields such as aerospace, shipbuilding, automobile, for cutting tool Secretary has been proposed such as various novel high-strength metal-base composites, fiber and particulate reinforced composite, non-ferrous metal and non-metallic material etc.: at a high speed, high precision, efficient, intelligence and environmental protection become pursuing a goal of machining.The superhard coating material is plated on the cutting tool surface, positive adaptation the hi-tech requirement of modern manufacturing industry to cutting tool, not only the cutting tool matrix has kept its higher intensity, the superhard compound coating that is plated on the surface can be brought into play again the advantage of " superhard, tough, wear-resisting, self-lubricating ", thereby greatly improves durability and the adaptability of cutting tool in the course of processing.
Since late 1960s first-generation chemical vapour deposition TiC carbide chip came out, coating technology was described as a revolution of speedy steel cutting-tool performance to successful Application on the cutter.From then on, coating technology has obtained development at full speed, and coating process is more and more ripe, and the coated cutting tool range of application is more and more extensive.The coated cutting tool that west industrially developed country uses account for indexable insert tip, throw away tip existing 1978 of ratio 26% rise to 2005 90%, about 80% is coated cutting tool in the used cutter of novel numerically-controlled machine.
The most frequently used polynary cutter coat is that TiCN is main coating.The TiCN coating has excellent toughness and the hardness of TiC and TiN coating concurrently, it can control by the composition that continuously changes C and N the character of TiCN in coating procedure, and can form the gradient-structure of different components, reduce the internal stress of coating, improve toughness, increase coat-thickness, Anticrack reduces tipping.Constantly in development, middle nineteen nineties, the appearance of middle temperature chemical vapour deposition (MT-CVD) new technology makes the CVD technology that revolutionary change occur to coating technology.The MT-CVD technology is as principal reaction gas, in the following generation of 700 degree TiCN coating with the organism acetonitrile.Very crisp G phase (Co has effectively been controlled in this TiCN coating process
3W
3C) generate, improved wear resistance, heat-shock resistance and the toughness of coating.Studies show that and when PVD depositing Ti CN coating, suitably increase hardness and the wear resistance that ion beam bombardment also can obviously improve coating.In recent years, the quaternary composition new coating material (such as TiZrCN, TiAlCN, TiSiCN etc.) take TiCN as base also occurs one after another.Along with metal cutting processing develops towards high cutting speed, high rate of feeding, high reliability, long lifetime, high precision and the good controlled aspect of cutting, the requirement of effects on surface coating is more and more higher.
Carbonitride (CN) film has the characteristics of high rigidity, low-friction coefficient and high thermal stability, is a kind of state-of-the art superhard material, and its theoretical hardness is expected to replacing diamond in some occasion near diamond.Studies show that carbonitride has obvious advantage when cutting high rigidity difficult-to-machine material.At present the CNx method for manufacturing thin film is a lot, and preparation method commonly used has wave of oscillation compression, high pressure pyrolysis, ion implantation, low energy ion radiation, ion beam depositing, reactive sputtering, chemical vapour deposition, laser ablation, pulse laser induced, electrochemical deposition and arc-over.Carbon nitride coatings is carried out large quantity research both at home and abroad at present, but because the CN coating stress is large, peeled off from matrix easily, do not obtained large-scale industrial application always.
Summary of the invention
The object of the invention is to overcome the deficiency that exists in the background, a kind of CN-MCN super-hard self-lubricating nano-composite coating and preparation method thereof is provided.
The technical scheme of product of the present invention is as follows:
At matrix surface the compound coating that is made of successively key coat, transition layer, supporting layer, lubricant film is from inside to outside arranged, wherein: the material of key coat is transition metal M, and wherein M is Ti, Cr, Zr or Mo; The material of transition layer is the nitride of M, i.e. MN; The material of supporting layer is the gradual change carbonitride of M, i.e. MCxN, wherein 0＜x≤1; The material of lubricant film is the compound coating that the carbonitride of carbonitride and M forms, i.e. CN-MCN.
For further improving the cost performance of product of the present invention:
1) joint thickness is the 10-100 nanometer; Transition region thickness is the 100-1000 nanometer; Supporting layer thickness is the 100-2000 nanometer; Lubricant film thickness is the 1-5 micron;
2) described matrix is Wimet, stainless steel, rapid steel, carbon steel or die steel;
3) MCN is nanocrystalline in the described lubricant film, and grain-size is 3-20nm; CN is amorphous phase, and CN content is 1-20at%.
Preparation method's of the present invention technical scheme is: it is characterized in that being formed successively by following step:
1) at matrix surface deposition key coat, the material of this key coat is the transition metal M layer; Wherein M is Ti, Cr, Zr or Mo;
2) key coat that obtained in the upper step deposits transition layer, and the material of this transition layer is the nitride of M, i.e. MN;
3) transition layer that obtained in the upper step deposits supporting layer, and the material of this supporting layer is the gradual change carbonitride of M, i.e. MCxN, wherein 0＜x≤1;
4) supporting layer that obtained in the upper step deposits lubricant film, and the material of this lubricant film is the compound coating that the carbonitride of carbonitride and M forms, i.e. CN-MCN; Naturally cooling, and get final product.
Be further to improve work efficiency and the quality of the inventive method, can be further the actual conditions of each step be chosen in:
1) mode of deposition of described key coat is: temperature is 50-500 ℃, air pressure 0.005-0.03Pa, and voltage-800V arrives-the 1000V bias voltage;
2) mode of deposition of described transition layer is: under the nitrogen environment, and air pressure 0.3-3Pa, voltage-100V arrives-the 200V bias voltage;
3) mode of deposition of described transition layer is: guaranteeing progressively to pass into acetylene under the nitrogen flow condition, the throughput ratio that progressively increases to acetylene and nitrogen of acetylene flow is 1:1, air pressure 0.1-2Pa, and voltage-50V arrives-the 200V bias voltage;
4) mode of deposition of described lubricant film is: under the environment of nitrogen and acetylene, voltage-50V is to-200V bias voltage, air pressure 0.5-2.5Pa.
As preference:
Described matrix is Wimet, stainless steel, rapid steel, carbon steel or die steel.
MCN is nanocrystalline in the described lubricant film, and grain-size is 3-20nm; CN is amorphous phase, and CN content is 1-20at%.
The present invention utilizes arc discharge method and hollow cathode arc-over carbon source integrated process to prepare superhard CN-MCN compound coating as shown from the above technical solution.In the conventional MCN preparation process, the coated grains yardstick is generally micron order, and the hardness of coating is 25-30GPa, has larger technical difficulty if further improve coating hardness.The nano-structured coating technology is the coating new technology that develops rapidly in recent years, is divided into nano laminated coating and nanocrystalline and amorphous compound coating.The high rigidity of nano laminated coating mainly is because in the layer or due to the interlayer dislocation motion difficulty.Different from nano-multilayer film, in the nanocrystalline and amorphous composite superhard coating, the high rigidity of coating mainly has relation by the structure of the crystallization phases in the coating and amorphous phase, and the size of crystallization phases particle has directly determined the hardness of coating.The nanocomposite superhard material is with its excellent performance, such as ultrahigh hardness, high tenacity and low frictional coefficient etc., caused the very big interest of global researcher.Become the β-C that continues
3N
4, superhard coating investigation of materials after the superlattice coating another focus.
The present invention utilizes the high rigidity characteristic of CN, further improves the hardness of MCN coating; Utilize the internal stress of the dispersion effect reduction CN coating of MCN.Utilize the grain growing of CN coating amorphous characteristic restriction MCN coating, obtain the MCN of nanocrystalline state, make the MCN coating have good toughness, form the CN-MCN nanocrystalline composite coating, for the cutting of high rigidity difficult-to-machine material provides new selection.
Under the general condition, the MCN preparation mainly is prepared by metallic arc target arc-over in the environment of acetylene and nitrogen coexistence, but because ionization level is limited, and the MCN coating hardness of preparation is lower, sticking power is relatively poor, can not well satisfy industrial practical application.Arc-over utilizes the high ionization level of the hollow cathode ion source acetylene gas that dissociates to produce carbon source, and pass into nitrogen, produce carbon ion and the nitrogen ion of high density, nitrogen and carbon reaction form carbonitride at workpiece, utilize in addition the metallic arc target to produce high-concentration metallic ions, under metal ion and carbon ion and the common condition that exists of nitrogen ion, form MCN, utilize carbon source and the acting in conjunction of nitrogen ion to form CNx, regulate CN content, form the CN-MCN nano-composite coating of different CN content, utilize the high rigidity of CN to strengthen the MCN coating, utilize the rotation of work rest to prepare the CN-MCN compound coating.
In the present invention, the CN material forms amorphous phase easily, and it has very high hardness simultaneously.For this reason that it is mutually compound with the MCN coated material, it is nanocrystalline to utilize the restriction effect of CN that MCN is formed mutually, utilizes the complex effect of MCN to reduce the internal stress of CN coating.Utilize the hardness of the high rigidity raising MCN coating of CN, develop at last novel CN-MCN compound coating.In order to improve the bonding force between the coatings and substrate, what this patent at first utilized powerful circular arc source makes the ionization of M metal, add negative high voltage at workpiece, the M ion cleans the zone of oxidation of removing the surface to workpiece surface under the bias voltage bombardment, reduce subsequently workpiece bias, at the pure M key coat of workpiece deposition.Preparation through key coat, the body material composition has become single M material from complexity polynary, the hardness of M coating is 8-10GPa, progressively passes on this basis nitrogen, generates MN with the M reaction, MN is ceramic phase, comparatively approaching with the coefficient of expansion of steel, for the original position preparation, be metallurgical binding each other between MN and the M, MN hardness is 15-20GPa, and the hardness of steel matrix is 5-6GPa.In order further to improve matrix hardness and to reduce stress, on the MN basis, progressively pass into acetylene, the MCxN that preparation hardness is higher supports coating, and the hardness of MCxN (0＜x≤1) coating is 25-30GPa.In the MCxN supporting layer, in order to reach composition gradual change and hardness gradual change, control acetylene and nitrogen flow, guaranteeing progressively to pass into acetylene under the nitrogen flow condition, progressively increasing of acetylene flow makes the MCN material that the gradual change on the composition occur, in the MCNx coating of low carbon content, the MN of its composition and bottom is more approaching, make its coefficient of expansion more approaching, hardness is also more approaching simultaneously, and this is conducive to reduce the internal stress of coating; Progressively increase subsequently the acetylene flow, last acetylene and nitrogen reach the ratio of 1:1, and the C:N ratio is 1:1 in the preparation MCN coating under this condition, reaches higher hardness value.On MCNx coating basis, open hollow cathode ion source, acetylene gas is passed into from the hollow cathode ion source afterbody, nitrogen enters vacuum chamber from other inlet mouth, when acetylene gas process hollow cathode ion source, become carbon ion by the arc discharge plasma ionization, because the pressure difference in hollow cathode ion source and the vacuum chamber, carbon ion sprays at a high speed hollow cathode ion source under pressure, when workpiece turned to the outlet position of hollow cathode ion source, the nitrogen ionic reaction in carbon ion and the vacuum chamber generated CN.Dispose the metallic arc target in the vacuum chamber simultaneously, when workpiece motion s arrived the metallic target front end, metal ion and carbon ion and nitrogen ionic reaction generated MCN, controlled the acetylene flow, then can control the content of CN.Then can prepare the CN-MCN compound coating by this process.
Therefore the present invention has following technological merit: the first, compare (25-30GPa) with conventional MCN coating, and the present invention adopts CN to strengthen MCN coating hardness higher (35-40GPa); The second, the use of hollow cathode carbon source has overcome the macrobead that produces when the filtering graphite target prepares carbonitride, has significantly simplified equipment; The 3rd, coating structure of the present invention is reasonable in design, until the superhard lubricant film in top not only has the composition gradual change, structural adjustment is arranged also from the bottom key coat, but the stress of decrease coating; The 4th, the present invention adopts amorphous CN to make MCN coating nanometer, make the CN-MCN compound coating have better toughness, this has improved reliability to the CN-MCN compound coating in the use of high abrasion occasion and heavily loaded occasion, has avoided relatively poor cause cracked of coating toughness under the large loading condiction; The 5th, Preparation equipment is close with existing coating apparatus, and coating apparatus is simple in structure simultaneously, is easy to control, and prospects for commercial application is good; According to requirements can carry out the preparation of different thickness CN-MCN compound coating at all kinds of workpiece such as Wimet, stainless steel, rapid steel, carbon steel, die steel.
In a word, preparation method of the present invention has the characteristics such as ionization level height, coating apparatus is simple in structure, sedimentation rate is fast.Prepared CN-MCN composite coating material has coating hardness height, strong adhesion, self-lubricating property is good, coatings growth speed is fast, production efficiency is high, production cost is low, frictional coefficient is low, the coating good toughness, can increase substantially the wear-resisting and lubricity of process tool, mould and component of machine, its preparation method is simple in addition, be easy to realize industrial production, have a good application prospect.
Description of drawings
Fig. 1. be the coating device synoptic diagram that adopts among the present invention;
Fig. 2. be the CN-MCN composite coating structure synoptic diagram of the present invention's preparation;
Fig. 3 is the CN-MoCN compound coating surface scan electromicroscopic photograph of embodiment 1 preparation; .
Fig. 4. be the CN-TiCN compound coating Cross Section Morphology figure of embodiment 3 preparations;
Among Fig. 1:
1. bleeding point; 2. furnace wall; 3.1#M metallic arc target; 4. fire door; 5. hollow cathode arc-over carbon source; 6. central heater; 7.2#M metallic arc target; 8. work rest;
Among Fig. 2:
1. matrix; 2. key coat M; 3. transition layer MN; 4. supporting layer MCxN; 5. lubricant film CN-MCN; 6.MCN nanocrystalline
Embodiment
Implement the device of the inventive method as shown in Figure 1, the vacuum chamber of device is surrounded by the furnace wall, and the vacuum chamber height is 50cm, and volume is 50x50x50cm
3The vacuum chamber side is provided with fire door, to make things convenient for the loading and unloading of workpiece.Vacuum chamber is provided with vacuum orifice, vacuumizes unit and by vacuum orifice vacuum chamber is vacuumized, and vacuumizes unit and is comprised of mechanical pump and molecular pump, and highest attainable vacuum can reach 10
-4Pa.Hollow cathode ion source is installed on the fire door, and in order to improve the ionization level of acetylene gas, two electric arc Ti targets are installed respectively in the vacuum chamber both sides, and the diameter of circular electric arc target is 100mm, and the shape that epistasis magnet is used for constraint target arc is housed on the electric arc target.Well heater is installed in the burner hearth, can regulates easily the temperature in the vacuum chamber.Specimen holder is positioned at the central position of burner hearth, and sample hangs on the specimen holder, can revolve round the sun and rotation, and the specimen holder rotating speed is adjustable.Layout can make vacuum chamber ionic medium volume density increase considerably like this, and workpiece is immersed in the plasma body fully.Coating sedimentation rate, hardness, sticking power are greatly improved.Because target structure is optimized, Distribution of Magnetic Field is more even, makes electric arc evenly burning on target surface, has improved the homogeneity and the consumption that has reduced target of coating.
Below in conjunction with specific embodiment technical scheme of the present invention is described further.This embodiment is not the restriction to its protection domain.
Embodiment 1: at 50 ℃, and at 0.005Pa, the transition metal Ti layer of-800V condition deposit 10 nanometer thickness; Under the nitrogen environment, at 0.3Pa ,-100V condition deposits the transition layer TiN of 100 nanometer thickness; Then at 0.1Pa, under-50V the condition, guarantee progressively to pass into acetylene under the nitrogen flow condition, the acetylene flow progressively increase to acetylene and nitrogen ratios is 1:1, deposit the supporting layer TiCxN of 100 nanometer thickness; Then under nitrogen and acetylene environment ,-50V bias voltage, 1 micron CN-TiCN super-hard self-lubricating of 0.5Pa air pressure conditions deposit coating; Coating hardness is controlled at 35GPa, and frictional coefficient is lower than 0.20, and total coating thickness is 1.21 microns.Naturally cooling after preparation finishes obtains CN-TiCN super-hard self-lubricating nano-composite coating.TiCN crystal grain is nanocrystalline in the lubricant film, and grain-size is 3nm, and CN is amorphous phase, and the CN phase content is 20at.%.
Embodiment 2: at 100 ℃, at 0.1Pa ,-900V condition deposits the transition metal Cr layer of 20 nanometer thickness; Under the nitrogen environment, at 0.4Pa ,-150V condition deposits the transition layer CrN of 200 nanometer thickness; Then at 0.2Pa, under-60V the condition, guarantee progressively to pass into acetylene under the nitrogen flow condition, the acetylene flow progressively increase to acetylene and nitrogen ratios is 1:1, deposit the supporting layer CrCxN of 200 nanometer thickness; Then under nitrogen and acetylene environment ,-60V bias voltage, 2 microns CN-CrCN super-hard self-lubricatings of 0.6Pa air pressure conditions deposit coating; Coating hardness is controlled at 35-40GPa, and frictional coefficient is lower than 0.20, and total coating thickness is 2.42 microns.Naturally cooling after preparation finishes obtains CN-CrCN super-hard self-lubricating nano-composite coating.CrCN crystal grain is nanocrystalline in the lubricant film, and grain-size is 5nm, and CN is amorphous phase, and the CN phase content is 15at.%.
Embodiment 3: at 250 ℃, at 0.02Pa ,-900V condition deposits the transition metal M o layer of 80 nanometer thickness; Under the nitrogen environment, at 1Pa ,-150V condition deposits the transition layer MoN of 800 nanometer thickness; Then at 1Pa, under-150V the condition, guarantee progressively to pass into acetylene under the nitrogen flow condition, the acetylene flow progressively increase to acetylene and nitrogen ratios is 1:1, deposit the supporting layer MoCxN of 1500 nanometer thickness; Then under nitrogen and acetylene environment ,-150V bias voltage, 1.5 microns CN-MoCN super-hard self-lubricatings of 1.5Pa air pressure conditions deposit coating; Coating hardness is controlled at 35-40GPa, and frictional coefficient is lower than 0.20, and total coating thickness is at 3.88 microns.Naturally cooling after preparation finishes obtains CN-MoCN super-hard self-lubricating nano-composite coating.MoCN crystal grain is nanocrystalline in the lubricant film, and grain-size is 10nm, and CN is amorphous phase, and the CN phase content is 10at%.
Embodiment 4: at 500 ℃, at 0.03Pa ,-1000V condition deposits the transition metal Zr layer of 100 nanometer thickness; Under the nitrogen environment, at 3Pa ,-200V condition deposits the transition layer ZrN of 1000 nanometer thickness; Then at 2Pa, under-200V the condition, guarantee progressively to pass into acetylene under the nitrogen flow condition, the acetylene flow progressively increase to acetylene and nitrogen ratios is 1:1, deposit the supporting layer ZrCxN of 2000 nanometer thickness; Then under nitrogen and acetylene environment ,-200V bias voltage, 5 microns CN-ZrCN super-hard self-lubricatings of 2.5Pa air pressure conditions deposit coating; Coating hardness is controlled at 35-40GPa, and frictional coefficient is lower than 0.20, and total coating thickness is at 8.1 microns.Naturally cooling after preparation finishes obtains CN-ZrCN super-hard self-lubricating nano-composite coating.ZrCN crystal grain is nanocrystalline in the lubricant film, and grain-size is 20nm, and CN is amorphous phase, and the CN phase content is 1at%.
Fig. 2 is the designed CN-MCN composite coating structure synoptic diagram of the present invention, coating is transitioned into the MN layer from pure metal M layer, crossfade into subsequently the MCxN layer, arrive at last the CN-MCN compound coating, gradual change is arranged on the coated component, on the hardness gradual change is arranged also simultaneously, reasonably design makes the internal stress of coating little, strong adhesion.
Fig. 3 be the CN-TiCN compound coating that makes of embodiment 1 surface topography map, as can be seen from the figure, coatingsurface has a small amount of small-particle, this is a small amount of pollution that causes in the arc discharge process, mainly is the molten drop of titanium.
Fig. 4 be the CN-MoCN compound coating that makes of embodiment 3 Cross Section Morphology figure, as can be seen from the figure coating structure is fine and close, between the coatings and substrate without obvious slit, in conjunction with well.The columnar growth of coating is blocked by multilayered structure, can not form the space of penetrance, and coating has preferably corrosion resistance.
Claims (8)
1. CN-MCN super-hard self-lubricating nano-composite coating is characterized in that: at matrix surface the compound coating that is made of successively key coat, transition layer, supporting layer, lubricant film is from inside to outside arranged, and:
1) material of key coat is transition metal M, and wherein M is Ti, Cr, Zr or Mo;
2) material of transition layer is the nitride of M, i.e. MN;
3) material of supporting layer is the gradual change carbonitride of M, i.e. MCxN, wherein 0＜x≤1;
4) material of lubricant film is the compound coating of the carbonitride formation of carbonitride and M, i.e. CN-MCN.
2. CN-MCN super-hard self-lubricating nano-composite coating as claimed in claim 1 is characterized in that: described checking in the coating:
1) joint thickness is the 10-100 nanometer;
2) transition region thickness is the 100-1000 nanometer;
3) supporting layer thickness is the 100-2000 nanometer;
4) lubricant film thickness is the 1-5 micron.
3. CN-MCN super-hard self-lubricating nano-composite coating as claimed in claim 1 or 2, it is characterized in that: described matrix is Wimet, stainless steel, rapid steel, carbon steel or die steel.
4. CN-MCN super-hard self-lubricating nano-composite coating as claimed in claim 1 or 2, it is characterized in that: MCN is nanocrystalline in the described lubricant film, grain-size is 3-20nm; CN is amorphous phase, and CN content is 1-20 at%.
5. the preparation method of a CN-MCN super-hard self-lubricating nano-composite coating as claimed in claim 1 is characterized in that: formed successively by following step:
1) at matrix surface deposition key coat, the material of this key coat is the transition metal M layer, and wherein M is Ti, Cr, Zr or Mo;
2) key coat that obtained in the upper step deposits transition layer, and the material of this transition layer is the nitride of M, i.e. MN;
3) transition layer that obtained in the upper step deposits supporting layer, and the material of this supporting layer is the gradual change carbonitride of M, i.e. MCxN, wherein 0＜x≤1;
4) supporting layer that obtained in the upper step deposits lubricant film, and the material of this lubricant film is the compound coating that the carbonitride of carbonitride and M forms, i.e. CN-MCN; Naturally cooling, and get final product.
6. such as the preparation method of the arbitrary described CN-MCN super-hard self-lubricating nano-composite coating of claim 5, it is characterized in that:
1) mode of deposition of described key coat is: temperature is 50-500 ℃, air pressure 0.005-0.03Pa, and voltage-800V arrives-the 1000V bias voltage;
2) mode of deposition of described transition layer is: under the nitrogen environment, and air pressure 0.3-3Pa, voltage-100V arrives-the 200V bias voltage;
3) mode of deposition of described transition layer is: guaranteeing progressively to pass into acetylene under the nitrogen flow condition, the throughput ratio that progressively increases to acetylene and nitrogen of acetylene flow is 1:1, air pressure 0.1-2Pa, and voltage-50V arrives-the 200V bias voltage;
4) mode of deposition of described lubricant film is: under the environment of nitrogen and acetylene, voltage-50V is to-200V bias voltage, air pressure 0.5-2.5Pa.
7. such as the preparation method of claim 5 or 6 described CN-MCN super-hard self-lubricating nano-composite coatings, it is characterized in that: described matrix is Wimet, stainless steel, rapid steel, carbon steel or die steel.
8. such as the preparation method of claim 5 or 6 described CN-MCN super-hard self-lubricating nano-composite coatings, it is characterized in that: MCN is nanocrystalline in the described lubricant film, and grain-size is 3-20nm; CN is amorphous phase, and CN content is 1-20 at%.
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| CN111778485A (en) * | 2020-06-16 | 2020-10-16 | 广东正德材料表面科技有限公司 | Coating and preparation method thereof |
| CN112030121A (en) * | 2019-06-03 | 2020-12-04 | 中国科学院宁波材料技术与工程研究所 | Wide-temperature-range antifriction and wear-resistant MoCN composite film, and preparation method and application thereof |
| CN112725792A (en) * | 2020-12-28 | 2021-04-30 | 成都美奢锐新材料有限公司 | Preparation method of chromium nitride-titanium carbonitride base metal ceramic composite coating |
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| CN103143761A (en) * | 2013-03-22 | 2013-06-12 | 武汉大学 | AlTiN-MoN nano multi-layer composite coating milling cutter and preparation method thereof |
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| CN112030121A (en) * | 2019-06-03 | 2020-12-04 | 中国科学院宁波材料技术与工程研究所 | Wide-temperature-range antifriction and wear-resistant MoCN composite film, and preparation method and application thereof |
| CN112030121B (en) * | 2019-06-03 | 2023-06-02 | 中国科学院宁波材料技术与工程研究所 | Wide-temperature-range antifriction wear-resistant MoCN composite film, and preparation method and application thereof |
| CN111778485A (en) * | 2020-06-16 | 2020-10-16 | 广东正德材料表面科技有限公司 | Coating and preparation method thereof |
| CN111778485B (en) * | 2020-06-16 | 2023-03-10 | 广东正德材料表面科技有限公司 | Coating and preparation method thereof |
| CN112725792A (en) * | 2020-12-28 | 2021-04-30 | 成都美奢锐新材料有限公司 | Preparation method of chromium nitride-titanium carbonitride base metal ceramic composite coating |
| RU2767970C1 (en) * | 2021-10-29 | 2022-03-22 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Казанский национальный исследовательский технический университет им. А.Н. Туполева - КАИ" | Method for applying a protective coating to a metal mold for casting copper alloys |
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