CN105385983A - Hard coating preparation method with heat diffusion of carbon nanomaterials as pretreatment - Google Patents

Hard coating preparation method with heat diffusion of carbon nanomaterials as pretreatment Download PDF

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Publication number
CN105385983A
CN105385983A CN201510758066.1A CN201510758066A CN105385983A CN 105385983 A CN105385983 A CN 105385983A CN 201510758066 A CN201510758066 A CN 201510758066A CN 105385983 A CN105385983 A CN 105385983A
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hard coat
body material
preparation
carbon
heat diffusion
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CN105385983B (en
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陶庆
王健
赖伟
陈正
沈承金
刘建阳
刘伟
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China University of Mining and Technology CUMT
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China University of Mining and Technology CUMT
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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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/60—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using solids, e.g. powders, pastes
    • C23C8/62—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using solids, e.g. powders, pastes only one element being applied
    • C23C8/64—Carburising
    • C23C8/66—Carburising of ferrous surfaces
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C23C16/27—Diamond only
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C23C16/27—Diamond only
    • C23C16/276—Diamond only using plasma jets
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/513—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using plasma jets
    • 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
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

The invention discloses a hard coating preparation method with heat diffusion of carbon nanomaterials as pretreatment. The preparation method comprises the steps of solid heat diffusion treatment of carbon nanomaterials, cleaning and etching of pretreatment base materials and preparation of a hard coating. In the step of solid heat diffusion treatment of the carbon nanomaterials, nanoscale diamond, carbon nanotubes, graphene, graphite and carbon fiber are used as carbon sources, solid heat diffusion treatment is carried out at a certain temperature, and the concentration of the nano carbon sources is distributed in a graded manner in the depth direction of the base materials. In the step of the cleaning and etching of the pretreatment base materials, the decontamination treatment, polishing, cleaning, etching of corrosive liquid and drying are carried out to enable the surface of the base materials to be flat, smooth and clean, and the nanoscale second-phase particles are exposed on the surface of a base body through etching of the specific corrosive liquid. In the step of preparation of the hard coating, substances in gas, liquid and solid states are used as carbon sources, and the diamond/diamond-like hard coating is prepared through physical/chemical vapor deposition, solid heat diffusion and high-energy spraying technologies.

Description

A kind of is pretreated hard coat preparation method with the thermodiffusion of nano-carbon material
Technical field
The present invention relates to a kind of hard coat preparation method, particularly a kind of is pretreated hard coat preparation method with the thermodiffusion of nano-carbon material.
Background technology
Prepare hard coat at material surface, the surface strength hardness of material can be improved, the performances such as wear resistant corrosion resistant, can be applicable to the various fields such as lathe tool, drill bit, mould, precision instruments.The kind of current hard coat is varied, such as diamond like carbon film (DLC), diamond thin, TiC/TiN film, BN/CBN film etc.But, due to the existence of internal stress between body material and hard coat and interfacial energy, in acquisition excellent surface properties simultaneously, the bonding force problem of hard coat and body material becomes and generally believes insoluble technical bottleneck, limits the development and apply in hard coat field.
The method of existing several raising top coat bonding force mainly comprises following several mode:
(1) substrate material surface carries out physics or Chemical Pretreatment: prepare hard coat at metallic substance or non-metal material surface, and bonding force major surfaces is metal and intermetallic bonding or the mode for mechanical snap.The roughness of workpiece surface is also the key factor affecting bonding force, and workpiece surface is more coarse, and bonding interface just has more stress concentration, and bonding force is also poorer, but in order to increase necessary mechanical snap power, needs to ensure that surface has certain roughness.So, necessary clean, polishing and polished finish are carried out to workpiece surface, the bonding force of top coat can be strengthened.Adopt activating process, activation treatment is carried out to substrate material surface, the active center of surface adsorption, the preparation of follow-up coating can be brought out, also can strengthen the bonding force of surface hard coating.
(2) introduce transition layer: the character of coating internal stress and size are also the principal elements affecting coating binding force, internal stress is generally different by the thermal expansivity of coatings and substrate, and the difference of crystal interface lattice match produces.The surperficial tension stress caused thus can make top coat generation cracking, peeling even peels off.Introduce one or more layers transition layer at matrix surface, make by thermal expansivity, the internal stress that the difference of lattice match causes is cushioned, thus indirectly improves the bonding force of top coat and matrix.
(3) ion implantation technique introduces alloy element at matrix surface: before preparation coating, under action of high voltage, by ion implantation, the elements such as C, N, H are bombarded body material top layer, with body material generation alloying action.Prepare in coating process follow-up the metallurgical binding realizing interface, compared with mechanical treatment mode, the bonding force of coating and body material can be significantly improved.
Summary of the invention
The object of the invention is to provide a kind of and improve coating nucleation density, what strengthen hard coat and body material bonding force is pretreated hard coat preparation method with the thermodiffusion of nano-carbon material.
The object of the present invention is achieved like this: hard coat preparation method is the angle from solid state heat diffusion, second phase particles is introduced in interface, better surface nucleation condition is provided with the preparation that the surperficial valency that nanoparticle is active is good for and higher surface energy is ganoine thin film/coating, improve nucleation density, strengthen hard coat and body material bonding force simultaneously; Hard coat preparation method comprises the solid state heat DIFFUSION TREATMENT of nano-carbon material, the clean and etching of pre-treatment body material, the preparation of hard coat;
The solid state heat DIFFUSION TREATMENT of described nano-carbon material:
Metal or nonmetal block body material are done preliminary clean polished finish, surfacing, ensure without larger cut, without greasy dirt, without rusty stain; Adopt Nano diamond, carbon nanotube, carbon primitive fiber, Graphene, carbon ball, one or more combinations in nano-graphite, as the carbon source of solid state heat diffusion, add one or more combinations in sodium aluminum fluoride, rare earth, carbonate, nano-graphite, solution reunion dispersion agent, as penetration-assisting agent, at higher than metal austenitizing temperature 30 ~ 350 DEG C, carry out solid state heat DIFFUSION TREATMENT; Need isolated air in treating processes, carry out infiltrating and DIFFUSION TREATMENT in Ar, N2 rare gas element is as the furnace chamber of protective atmosphere; According to required depth of penetration, with reference to thickness direction rate of diffusion 0.1 ~ 0.5mm/ hour, select to add thermal diffusion time; After having processed, above-mentioned carbon source enters into body material, is present in body material top layer with the form of second phase particles, and distribution of successively decreasing in gradient from surface to body material heart portion; After vacuum/atmosphere heat treatment, from surface to body material heart portion, intensity hardness tapers off change, and what prevent from causing not because of body material intensity hardness comes off;
Clean and the etching of described pre-treatment body material:
Pretreated substrate material surface is at room temperature carried out decontamination, sanding and polishing, alcohol/washed with de-ionized water, ultrasonic cleaning, pickling/alkali cleaning, corrosive fluid etches, and desiccated surface process, make substrate material surface smooth, clean, and by the etching of the particular etch liquid such as 4% nitric acid alcohol by exposed for the second phase particles surface at body material; In order to the preparation of follow-up hard coat after cleaning-drying completes; Clean and the etching technics of pre-treatment body material make the surface nucleation of the easier second phase particles in the base of prepared hard coat, better surface nucleation condition is provided with the preparation that the surperficial valency that nanoparticle is active is good for and higher surface energy is ganoine thin film/coating, improve nucleation density, strengthen hard coat and body material bonding force simultaneously;
The preparation of described hard coat:
With gas, the material of solid or liquid different states as the raw material sources of hard coat, in 300 ~ 1100 DEG C of temperature ranges, low pressure, or under the pressure action of standard atmospheric pressure, pass into Ar, N 2deng protective atmosphere condition, the hard coat of the various materials prepared by physical/chemical vapour deposition, solid state heat diffusion, high energy spraying coating process, described low pressure is 30 ~ 500Pa.
Beneficial effect, owing to have employed such scheme, the angle that the method spreads from solid state heat, second phase particles is introduced in interface, better surface nucleation condition is provided with the preparation that the surperficial valency that nanoparticle is active is good for and higher surface energy is ganoine thin film/coating, improve nucleation density, improve the bonding force of coating and matrix.Its advantage has;
First, the present invention adopts the solid state heat of nano-carbon material to spread, in advance process is oozed to body material, the carbon source of the nanoscale that solid state heat is spread enters into body material, substrate material surface is present in the form of second phase particles, and distribution of successively decreasing in gradient from surface to body material heart portion.The surface energy higher due to nanoparticle and active surperficial valency are good for, and can provide higher Enhancing Nucleation Density for physical/chemical vapor deposition processes, and coupling that is particle reinforced with nanoscale carbon source and chemical bond strengthening improves the bonding force of coatings and substrate material.Simultaneously through vacuum/atmosphere heat treatment, from surface to body material heart portion, the graded of nano level second phase particles volumetric concentration makes the intensity hardness of integral material also change in gradient, prevents the hard coat caused because of body material and the intensity of top layer hard coat, the sudden change of hardness from coming off;
Second, the present invention carries out clean and etching processing to above-mentioned pre-treatment matrix, make the second phase particles that is pinned in body material exposed at matrix surface, and then make the surface nucleation of the follow-up prepared easier second phase particles exposed at matrix surface of hard coat, improve nucleation density, strengthen hard coat and body material bonding force simultaneously.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Fig. 2 is take nano-carbon material as the solid state heat diffusion process schematic diagram of carbon source.
Fig. 3 is that the present invention adopts chemical vapour deposition technique to prepare diamond/diamond like carbon film reaction process schematic diagram.
Fig. 4 is for adopting the diamond/diamond like carbon film structural representation prepared by present invention process.
In figure, a is nano-carbon material coat; B is the mixolimnion of nano-carbon material and penetration-assisting agent; C is body material; D is diamond/diamond like carbon film.
Embodiment
Below in conjunction with the embodiment in accompanying drawing, the present invention is further illustrated:
Hard coat preparation method of the present invention is the angle from solid state heat diffusion, second phase particles is introduced in interface, better surface nucleation condition is provided with the preparation that the surperficial valency that nanoparticle is active is good for and higher surface energy is ganoine thin film/coating, improve nucleation density, strengthen hard coat and body material bonding force simultaneously; Hard coat preparation method comprises the solid state heat DIFFUSION TREATMENT of nano-carbon material, the clean and etching of pre-treatment body material, the preparation of hard coat;
The solid state heat DIFFUSION TREATMENT of described nano-carbon material:
Metal or nonmetal block body material are done preliminary clean polished finish, surfacing, ensure without larger cut, without greasy dirt, without rusty stain; Adopt Nano diamond, carbon nanotube, carbon primitive fiber, Graphene, carbon ball, one or more combinations in nano-graphite, as the carbon source of solid state heat diffusion, add one or more combinations in sodium aluminum fluoride, rare earth, carbonate, nano-graphite, solution reunion dispersion agent, as penetration-assisting agent, at certain temperature is higher than metal austenitizing temperature 30 ~ 350 DEG C, carry out solid state heat DIFFUSION TREATMENT; Isolated air is needed, at Ar, N in treating processes 2rare gas element infiltrates and DIFFUSION TREATMENT as carrying out in the furnace chamber of protective atmosphere; According to required depth of penetration, with reference to thickness direction rate of diffusion 0.1 ~ 0.5mm/ hour, select to add thermal diffusion time; After having processed, above-mentioned carbon source enters into body material, is present in body material top layer with the form of second phase particles, and distribution of successively decreasing in gradient from surface to body material heart portion; After vacuum/atmosphere heat treatment, from surface to body material heart portion, intensity hardness tapers off change, and what prevent from causing not because of body material intensity hardness comes off;
Clean and the etching of described pre-treatment body material:
Pretreated substrate material surface is at room temperature carried out decontamination, sanding and polishing, alcohol/washed with de-ionized water, ultrasonic cleaning, pickling/alkali cleaning, corrosive fluid etches, and desiccated surface process, make substrate material surface smooth, clean, and by the etching of the particular etch liquid such as 4% nitric acid alcohol by exposed for the second phase particles surface at body material; In order to the preparation of follow-up hard coat after cleaning-drying completes; Clean and the etching technics of pre-treatment body material make the surface nucleation of the easier second phase particles in the base of prepared hard coat, better surface nucleation condition is provided with the preparation that the surperficial valency that nanoparticle is active is good for and higher surface energy is ganoine thin film/coating, improve nucleation density, strengthen hard coat and body material bonding force simultaneously;
The preparation of described hard coat:
With gas, solid, or the material of the different states such as liquid is as the raw material sources of hard coat, in 300 ~ 1100 DEG C of temperature ranges, and low pressure, or under the pressure action of standard atmospheric pressure, pass into Ar, N 2deng protective atmosphere condition, the hard coat of the various materials prepared by physical/chemical vapour deposition, solid state heat diffusion, high energy spraying coating process, described low pressure is 30 ~ 500Pa.
Embodiment 1:
With 20# steel for body material, carry out the solid state heat DIFFUSION TREATMENT of nano-carbon material using nano-diamond powder as carbon source, after clean polishing, adopt PECVD-plasma enhanced chemical vapor phase deposition technology to prepare diamond/diamond like carbon film at steel surface.Concrete method steps is as follows:
The first, carry out solid state heat diffusion using nano-diamond powder as carbon source at matrix surface.
To the surface finish process of body material 20# steel, remove the dirt on surface, burr and rusty stain, for ensureing homogeneity and the surface smoothness of solid state heat diffusion, before body material heat diffusion treatment, polished finish, deionized water/alcohol washes.The nano-diamond powder of 50 ~ 500nm granularity is placed in organic dispersing agent, solution reunion dispersion treatment is carried out under ultrasonic, centrifugal and other mechanical external force effects, scattered Nano diamond is removed partial solvent, adds the penetration-assisting agents such as appropriate other sodium aluminum fluorides, nano-graphite, rare earth, carbonate in addition and be modulated into paste penetration enhancer.By the paste penetration enhancer modulated, be coated in the surface of 20# steel as matrix material uniformly, thickness is 3 ~ 10mm, as shown in Fig. 2, b.Apply the nano-diamond powder of one deck after separating dispersion of reuniting uniformly on paste top layer after having applied, thickness is about 5mm, as shown in Fig. 2, a.The workpiece applied is placed in crucible, is then put in the lump in heat treatment furnace, heats.When heating less than 300 DEG C; with oil-sealed rotary pump, process is vacuumized to furnace chamber; eliminate the oxygen in furnace chamber; furnace chamber internal gas pressure can pass into argon gas/nitrogen as protective atmosphere when arriving 1 ~ 10Pa rank in furnace chamber; when stove internal gas pressure arrives normal atmosphere (An); open air outlet valve, prevent stove internal cause temperature boost air pressure excessive, damage or danger.Keep gas open, about continuing to be heated to 800 ~ 1200 DEG C of temperature ranges, be incubated 2 ~ 5 hours, carry out infiltration diffusion, after completing, furnace cooling.Take out after workpiece, workpiece be placed in heat treatment furnace and be heated to 900 ~ 950 DEG C, insulation 0.5h, after carry out quench treatment.
The second, after solid state heat diffusion pre-treatment, 20# steel as matrix material is cleaned and etching.
Take out pretreated workpiece in step one stove, remove surperficial penetration enhancer residue and greasy dirt, with deionized water/alcohol+ultrasonic cleaning process, if the inadequate flat smooth of workpiece surface, or there is the indenture of impurity or corrosion on surface, can suitably carry out polishing or polishing, obtain the fresh matrix surface of flat smooth.By volume fraction be 4% nital pretreated matrix surface is etched, at powerful microscope or observed under electron microscope, the second-phase of matrix surface is exposed on surface.With alcohol washes surface, workpiece is placed in vacuum drying oven, less than 100 DEG C dry about 20min.
3rd, the 20# steel top layer after above two-step pretreatment, adopts PECVD-plasma enhanced chemical vapor deposition technology to prepare diamond/diamond like carbon film.
Deposition reaction process as shown in Figure 3.Being taken out by workpiece in above-mentioned loft drier is placed in the reaction chamber of PECVD device, and after tightness system, carry out vacuumizing process with oil-sealed rotary pump and vacuum diffusion pump successively, vacuum reaches 10 -2after Pa rank, start to pass into hydrogen and methane, constantly regulate the flow of methane and hydrogen, ensure that hydrogen flowing quantity is at about 50 ~ 100sccm, methane flow is at about 30 ~ 50sccm.By controlling vacuum pump and charge flow rate, the pressure of the mixed gas in reaction chamber is made to remain at about 80 ~ 100Pa.Reacting by heating chamber, when temperature reaches about 400 DEG C, after insulation 10min, open RF plasma current, under the power of about 400W, reactant gases ionization, carries out build-up of luminance, and deposition starts.Off-response device after 2 ~ 5h, stops deposition reaction, and deposition terminates.Take out sample after being as cold as room temperature with stove, obtain the diamond/diamond like carbon film of 5 ~ 10 micron thickness on the top layer of 20# steel, as shown in Fig. 4, d.

Claims (1)

1. one kind is pretreated hard coat preparation method with the thermodiffusion of nano-carbon material, it is characterized in that: hard coat preparation method is the angle from solid state heat diffusion, second phase particles is introduced in interface, better surface nucleation condition is provided with the preparation that the surperficial valency that nanoparticle is active is good for and higher surface energy is ganoine thin film/coating, improve nucleation density, strengthen hard coat and body material bonding force simultaneously; Hard coat preparation method comprises the solid state heat DIFFUSION TREATMENT of nano-carbon material, the clean and etching of pre-treatment body material, the preparation of hard coat;
The solid state heat DIFFUSION TREATMENT of described nano-carbon material:
Metal or nonmetal block body material are done preliminary clean polished finish, surfacing, ensure without larger cut, without greasy dirt, without rusty stain; Adopt nano-diamond, carbon nanotube, carbon primitive fiber, Graphene, carbon ball, one or more combinations in nano-graphite, as the carbon source of solid state heat diffusion, add one or more combinations in sodium aluminum fluoride, rare earth, carbonate, nano-graphite, solution reunion dispersion agent, as penetration-assisting agent, at higher than metal austenitizing temperature 30 ~ 350 DEG C, carry out solid state heat DIFFUSION TREATMENT; Need isolated air in treating processes, carry out infiltrating and DIFFUSION TREATMENT in Ar, N2 rare gas element is as the furnace chamber of protective atmosphere; According to required depth of penetration, with reference to thickness direction rate of diffusion 0.1 ~ 0.5mm/ hour, select to add thermal diffusion time; After having processed, above-mentioned carbon source enters into body material, is present in body material top layer with the form of second phase particles, and distribution of successively decreasing in gradient from surface to body material heart portion; After vacuum/atmosphere heat treatment, from surface to body material heart portion, intensity hardness tapers off change, and what prevent from causing not because of body material intensity hardness comes off;
Clean and the etching of described pre-treatment body material:
Pretreated substrate material surface is at room temperature carried out decontamination, sanding and polishing, alcohol/washed with de-ionized water, ultrasonic cleaning, pickling/alkali cleaning, corrosive fluid etching and desiccated surface process, make substrate material surface smooth, clean, and the etching passing through the particular etch liquid such as 4% nitric acid alcohol is by exposed for the second phase particles surface at body material; In order to the preparation of follow-up hard coat after cleaning-drying completes; Clean and the etching technics of pre-treatment body material make the surface nucleation of the easier second phase particles in the base of prepared hard coat, better surface nucleation condition is provided with the preparation that the surperficial valency that nanoparticle is active is good for and higher surface energy is ganoine thin film/coating, improve nucleation density, strengthen hard coat and body material bonding force simultaneously;
The preparation of described hard coat:
With gas; solid; or the material of the different states such as liquid is as the raw material sources of hard coat; in 300 ~ 1100 DEG C of temperature ranges; low pressure, or under the pressure action of standard atmospheric pressure, pass into the protective atmosphere conditions such as Ar, N2; the hard coat of the various materials prepared by physical/chemical vapour deposition, solid state heat diffusion, high energy spraying coating process, described low pressure is 30 ~ 500Pa.
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PCT/CN2015/099330 WO2017080079A1 (en) 2015-11-09 2015-12-29 Hard coating preparation method using thermal diffusion of nanocarbon material as pretreatment

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CN106435460A (en) * 2016-10-18 2017-02-22 中国矿业大学 Niobium alloy surface high-temperature abrasion resisting coating and preparation method thereof
CN106676463A (en) * 2017-03-03 2017-05-17 中国矿业大学 Surface deep strengthening method with graphitizing micro-nano carbon material as diffusion source
CN109023360A (en) * 2018-06-29 2018-12-18 三联泵业股份有限公司 A kind of wear-resisting double-suction pump impeller process of surface treatment
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CN110983300A (en) * 2019-12-04 2020-04-10 江苏菲沃泰纳米科技有限公司 Coating equipment and application thereof
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CN106435460A (en) * 2016-10-18 2017-02-22 中国矿业大学 Niobium alloy surface high-temperature abrasion resisting coating and preparation method thereof
CN106676463A (en) * 2017-03-03 2017-05-17 中国矿业大学 Surface deep strengthening method with graphitizing micro-nano carbon material as diffusion source
CN110892009A (en) * 2017-03-17 2020-03-17 空中客车西班牙运营有限责任公司 Multifunctional diffusion barrier
CN110892009B (en) * 2017-03-17 2022-12-20 空中客车西班牙运营有限责任公司 Multifunctional diffusion barrier
CN109023360A (en) * 2018-06-29 2018-12-18 三联泵业股份有限公司 A kind of wear-resisting double-suction pump impeller process of surface treatment
CN110983300A (en) * 2019-12-04 2020-04-10 江苏菲沃泰纳米科技有限公司 Coating equipment and application thereof
CN110983300B (en) * 2019-12-04 2023-06-20 江苏菲沃泰纳米科技股份有限公司 Coating equipment and application thereof
CN112301324A (en) * 2020-09-21 2021-02-02 贾春德 Method for plating diamond film on steel substrate
CN112301324B (en) * 2020-09-21 2023-04-14 贾春德 Method for plating diamond film on steel substrate
CN114622201A (en) * 2020-12-10 2022-06-14 张国徽 Graphene nano composite metal section bar and preparation method thereof
CN114622201B (en) * 2020-12-10 2023-09-08 张国徽 Graphene nano composite metal section bar and preparation method thereof

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