CN105385983B - A kind of hard coat preparation method of thermal diffusion using nano-carbon material as pretreatment - Google Patents

A kind of hard coat preparation method of thermal diffusion using nano-carbon material as pretreatment Download PDF

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CN105385983B
CN105385983B CN201510758066.1A CN201510758066A CN105385983B CN 105385983 B CN105385983 B CN 105385983B CN 201510758066 A CN201510758066 A CN 201510758066A CN 105385983 B CN105385983 B CN 105385983B
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hard coat
nano
matrix material
preparation
solid
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CN105385983A (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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    • 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
    • C23C16/44—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

Abstract

The invention discloses a kind of thermal diffusion using nano-carbon material as the hard coat preparation method pre-processed, preparation method includes the solid-state heat diffusion treatment of nano-carbon material, pre-processes cleaning and the etching of matrix material, the preparation of hard coat.The solid-state thermal diffusion of nano-carbon material, as carbon source, is carried out solid-state heat diffusion treatment, makes nanometer carbon source concentration in the depth direction distribution gradient of matrix material at a certain temperature using nano-diamond, CNT, graphene, graphite, carbon fiber；The cleaning and etching for pre-processing matrix material include decontamination processing, sanding and polishing, cleaning, corrosive liquid etching, dry and make that substrate material surface is smooth, clean, and by the etching of particular etch liquid that nanoscale second phase particles are exposed in matrix surface；The preparation of hard coat include using the various forms of materials of gas liquid solid body as carbon source, be vapor-deposited by physical/chemical, solid-state thermal diffusion, high energy spraying coating process prepare diamond/DLC hard coat.

Description

A kind of hard coat preparation method of thermal diffusion using nano-carbon material as pretreatment
Technical field
The present invention relates to a kind of hard coat preparation method, particularly a kind of thermal diffusion using nano-carbon material is pretreatment Hard coat preparation method.
Background technology
Hard coat is prepared in material surface, the surface strength hardness of material can be improved, the performance such as wear resistant corrosion resistant can Apply in various fields such as lathe tool, drill bit, mould, precision instruments.The species of current hard coat is varied, such as diamond-like Stone film（DLC）, diamond thin, TiC/TiN films, BN/CBN films etc..However, due to matrix material and hard coat it Between internal stress and interface can presence, obtaining excellent surface properties simultaneously, the adhesion problem of hard coat and matrix material Become and generally believe insoluble technical bottleneck, limit the development and application in hard coat field.
Existing several methods for improving face coat adhesion mainly include following several ways：
（1）Substrate material surface is physically or chemically pre-processed：Hard coat, adhesion are prepared in metal material surface Major surfaces be metal and intermetallic bonding or be mechanical snap mode.The roughness of workpiece surface is also that influence is combined The key factor of power, workpiece surface is more coarse, and combination interface just has more stress concentrations, and adhesion is also poorer, still In order to increase necessary mechanical snap power, it is necessary to ensure that surface has certain roughness.So, workpiece surface is carried out necessary Cleaning, polishing and polishing, the adhesion of face coat can be strengthened.Using activating process, substrate material surface is entered Row activation process, the active centre of adsorption can induce the preparation of follow-up coating, can also strengthen surface hard coating Adhesion.
（2）Introduce transition zone：The property and size of coating internal stress are also to influence the principal element of coating binding force, planted agent Power be usually it is different with the thermal coefficient of expansion of matrix by coating, the difference of grain boundary lattice match and produce.Thus draw The surface tensile stress risen can make face coat produce cracking, peeling or even peel off.One or more layers mistake is introduced in matrix surface Layer is crossed, makes to be buffered by the internal stress caused by thermal coefficient of expansion, the difference of lattice match, so as to improve surface indirectly The adhesion of coating and matrix.
（3）Ion implantation technique introduces alloy element in matrix surface：Before prepares coating, in action of high voltage Under, by ion implanting, matrix material top layer is arrived into the bombardment of the elements such as C, N, H, occurs alloying action with matrix material.Rear The metallurgical binding at interface is realized in continuous prepares coating technique, compared with mechanical treatment mode, coating and matrix material can be significantly improved The adhesion of material.
The content of the invention
The invention aims to provide a kind of raising coating nucleation density, enhancing hard coat and matrix material adhesion The thermal diffusion using nano-carbon material as pretreatment hard coat preparation method.
The object of the present invention is achieved like this：Hard coat preparation method is the angle from solid-state thermal diffusion, at interface Place introduces second phase particles, with the strong and higher surface of the active surface valency of nano-particle can for ganoine thin film/coating preparation More preferable surface nucleation condition is provided, nucleation density is improved, while strengthening hard coat and matrix material adhesion；Hard coat Preparation method includes the solid-state heat diffusion treatment of nano-carbon material, pre-processes cleaning and the etching of matrix material, hard coat Prepare；
The solid-state heat diffusion treatment of described nano-carbon material：
Metallic monolith matrix material is done into preliminary cleaning polishing, surfacing, it is ensured that without larger cut, no greasy dirt, Without rusty stain；Using Nano diamond, CNT, carbon microfibre, graphene, carbon ball, one or more groups in nano-graphite Close, as the carbon source of solid-state thermal diffusion, the one kind added in ice crystal, rare earth, carbonate, nano-graphite, de-agglomerated dispersant Or multiple combinations, as penetration-assisting agent, higher than carrying out solid-state heat diffusion treatment at 30 ~ 350 DEG C of metal austenitizing temperature；Processing During need completely cut off air, in Ar, N2Inert gas in the furnace chamber of protective atmosphere as being penetrated into and DIFFUSION TREATMENT；According to institute The depth of penetration needed, reference thickness direction diffusion rate 0.1 ~ 0.5mm/ hours, selection heating diffusion time；After the completion of processing, Above-mentioned carbon source enters matrix material, and matrix material top layer is present in the form of second phase particles, and from surface to matrix Material center portion is successively decreased distribution in gradient；After vacuum/atmosphere heat treatment, from surface to matrix material center portion, intensity hardness is in Successively decrease change, prevent because matrix material intensity hardness not enough caused by come off；
The cleaning of described pretreatment matrix material and etching：
Pretreated substrate material surface is subjected to decontamination at room temperature, sanding and polishing, alcohol/deionized water is cleaned, Ultrasonic wave is cleaned, pickling/alkali cleaning, corrosive liquid etching, and dries surface treatment, makes that substrate material surface is smooth, cleaning, and is led to The etchings of the particular etch liquid such as 4% nitric acid alcohol is crossed by the exposed surface in matrix material of second phase particles；After the completion of cleaning-drying In case the preparation of follow-up hard coat；The cleaning of pretreatment matrix material is easier prepared hard coat with etching technics The surface nucleation of second phase particles in the base, can be thin for hard with the strong and higher surface of the active surface valency of nano-particle The preparation of film/coating provides more preferable surface nucleation condition, improves nucleation density, while strengthening hard coat and matrix material Adhesion；
The preparation of described hard coat：
With gas, the materials of solid or liquid different conditions as hard coat raw material sources, at 300 ~ 1100 DEG C In temperature range, under low pressure, or the pressure action of standard atmospheric pressure, Ar, N are passed through2Deng protective atmosphere condition, by physics/ The hard coat of various materials prepared by chemical vapor deposition, solid-state thermal diffusion, high energy spraying coating process, described low pressure for 30 ~ 500Pa。
Beneficial effect, as a result of such scheme, this method introduces second from the angle of solid-state thermal diffusion in interface Phase particle, is good for the active surface valency of nano-particle and higher surface can be provided preferably for the preparation of ganoine thin film/coating Surface nucleation condition, improves nucleation density, improves the adhesion of coating and matrix.Its advantage has；
First, the present invention is carried out oozing processing in advance to matrix material, is made solid state heat using the solid-state thermal diffusion of nano-carbon material The carbon source of the nanoscale of diffusion enters matrix material, and substrate material surface is present in the form of second phase particles, and Successively decrease in gradient from surface to matrix material center portion distribution.Because the higher surface of nano-particle can be good for active surface valency, Higher Enhancing Nucleation Density can be provided for physical/chemical vapor deposition processes, it is particle reinforced strong with chemical bond with nanoscale carbon source The coupling of change improves the adhesion of coating and matrix material.Pass through vacuum/atmosphere heat treatment simultaneously, from surface to matrix material Expect center portion, the graded of nanoscale second phase particles volumetric concentration makes the intensity hardness of integral material also change in gradient, prevent Hard coat caused by the mutation of intensity, hardness only because of matrix material and top layer hard coat comes off；
Second, the present invention is cleaned and etching processing to above-mentioned pretreatment matrix, makes to be pinned at the in matrix material Secondary phase particle is exposed in matrix surface, and then follow-up prepared hard coat is easier in the second exposed phase of matrix surface The surface nucleation of particle, improves nucleation density, while strengthening hard coat and matrix material adhesion.
Brief description of the drawings
Fig. 1 is process chart of the invention.
Fig. 2 is the solid-state thermal diffusion process schematic diagram using nano-carbon material as carbon source.
Fig. 3 prepares diamond/DLC film course of reaction schematic diagram for the present invention using chemical vapour deposition technique.
Fig. 4 is using diamond/DLC film structural representation prepared by present invention process.
A is nano-carbon material coat in figure；B is the mixed layer of nano-carbon material and penetration-assisting agent；C is matrix material；D is Diamond/DLC film.
Embodiment
The present invention is further illustrated for embodiment in below in conjunction with the accompanying drawings：
The hard coat preparation method of the present invention is the angle from solid-state thermal diffusion, and second phase particles are introduced in interface, It is good for the active surface valency of nano-particle and higher surface can provides more preferable surface nucleation for the preparation of ganoine thin film/coating Condition, improves nucleation density, while strengthening hard coat and matrix material adhesion；Hard coat preparation method includes nano-sized carbon The solid-state heat diffusion treatment of material, pre-processes cleaning and the etching of matrix material, the preparation of hard coat；
The solid-state heat diffusion treatment of described nano-carbon material：
Metallic monolith matrix material is done into preliminary cleaning polishing, surfacing, it is ensured that without larger cut, no greasy dirt, Without rusty stain；Using Nano diamond, CNT, carbon microfibre, graphene, carbon ball, one or more groups in nano-graphite Close, as the carbon source of solid-state thermal diffusion, the one kind added in ice crystal, rare earth, carbonate, nano-graphite, de-agglomerated dispersant Or multiple combinations, as penetration-assisting agent, solid-state thermal diffusion is carried out in the case where certain temperature is higher than 30 ~ 350 DEG C of metal austenitizing temperature Processing；Need to completely cut off air in processing procedure, in Ar, N2Inert gas as penetrated into the furnace chamber of protective atmosphere and diffusion at Reason；According to required depth of penetration, reference thickness direction diffusion rate 0.1 ~ 0.5mm/ hours, selection heating diffusion time；Place After the completion of reason, above-mentioned carbon source enters matrix material, is present in matrix material top layer in the form of second phase particles, and from table Successively decrease in gradient distribution to matrix material center portion in face；After vacuum/atmosphere heat treatment, from surface to matrix material center portion, by force Degree hardness tapers off change, prevent because matrix material intensity hardness not enough caused by come off；
The cleaning of described pretreatment matrix material and etching：
Pretreated substrate material surface is subjected to decontamination at room temperature, sanding and polishing, alcohol/deionized water is cleaned, Ultrasonic wave is cleaned, pickling/alkali cleaning, corrosive liquid etching, and dries surface treatment, makes that substrate material surface is smooth, cleaning, and is led to The etchings of the particular etch liquid such as 4% nitric acid alcohol is crossed by the exposed surface in matrix material of second phase particles；After the completion of cleaning-drying In case the preparation of follow-up hard coat；The cleaning of pretreatment matrix material is easier prepared hard coat with etching technics The surface nucleation of second phase particles in the base, can be thin for hard with the strong and higher surface of the active surface valency of nano-particle The preparation of film/coating provides more preferable surface nucleation condition, improves nucleation density, while strengthening hard coat and matrix material Adhesion；
The preparation of described hard coat：
With gas, the materials of the different conditions such as solid, or liquid as hard coat raw material sources, 300 ~ 1100 In DEG C temperature range, under low pressure, or the pressure action of standard atmospheric pressure, Ar, N are passed through2Deng protective atmosphere condition, pass through thing The hard coat of various materials prepared by reason/chemical vapor deposition, solid-state thermal diffusion, high energy spraying coating process, described low pressure is 30~500Pa。
Embodiment 1：
Using 20# steel as matrix material, the solid-state thermal diffusion of nano-carbon material is carried out using nano-diamond powder as carbon source Processing, after cleaning polishing, diamond/class is prepared using PECVD- plasma enhanced chemical vapor phase deposition technologies in steel surface Diamond thin.Specific method and step is as follows：
First, carry out solid-state thermal diffusion in matrix surface using nano-diamond powder as carbon source.
To the surface grinding process of matrix material 20# steel, dirt, burr and the rusty stain on surface are removed, to ensure solid-state The uniformity and surface smoothness of thermal diffusion, before matrix material heat diffusion treatment, polishing, deionized water/alcohol washes. The nano-diamond powder of 50 ~ 500nm granularities is placed in organic dispersing agent, made in ultrasound, centrifugation and other mechanical external forces De-agglomerated decentralized processing is carried out under, scattered Nano diamond is removed into partial solvent, other appropriate ice crystals are it is possible to additionally incorporate The penetration-assisting agents such as stone, nano-graphite, rare earth, carbonate are modulated into paste penetration enhancer.By the paste penetration enhancer modulated, uniformly it is coated in The surface of 20# steel as matrix material, thickness is 3 ~ 10mm, such as Fig. 2, shown in b.After the completion of coating one is uniformly applied on paste top layer Nano-diamond powder of the layer after de-agglomerated is scattered, thickness is 5mm or so, such as Fig. 2, shown in a.The workpiece for coating completion is put Put in crucible, be then put into the lump in heat-treatment furnace, heated.When heating less than 300 DEG C, with oil-sealed rotary pump to stove Chamber vacuumize process, eliminate in the oxygen in furnace chamber, furnace chamber can be passed through when air pressure reaches 1 ~ 10Pa ranks into furnace chamber argon gas/ Nitrogen is as protective atmosphere, when air pressure reaches normal atmosphere (An) in stove, opens air outlet valve, prevents stove internal cause temperature boost air pressure mistake Greatly, damage or dangerous.Gas open is kept, continues to be heated to 800 ~ 1200 DEG C of temperature ranges or so, is incubated 2 ~ 5 hours, Infiltration diffusion is carried out, after the completion of, furnace cooling.Take out after workpiece, workpiece is placed into heat-treatment furnace and is heated to 900 ~ 950 DEG C, 0.5h is incubated, Quenching Treatment is carried out afterwards.
Second, 20# steel as matrix material is cleaned with etching after solid-state thermal diffusion pretreatment.
Take out pretreated workpiece in step one stove, remove surface penetration enhancer residue and greasy dirt, with deionized water/alcohol+ Ultrasonic cleaning is handled, if there are impurity or the indenture of corrosion in the inadequate flat smooth of workpiece surface, or surface, can suitably be polished Or polishing, obtain the fresh matrix surface of flat smooth.With the nital that volume fraction is 4% to pretreated base Body surface face is performed etching, and in high-power microscope or observed under electron microscope, the second of matrix surface is mutually exposed on surface. Alcohol washes surface is used, workpiece is placed in vacuum drying oven, less than 100 DEG C dry 20min or so.
3rd, the 20# steel top layer after above two-step pretreatment, using PECVD- plasma enhanced chemical vapor deposition skills Art prepares diamond/DLC film.
Deposition reaction process as shown in Figure 3.Workpiece in above-mentioned drying box is taken out to the reaction for being placed into PECVD devices In chamber, after sealing device, vacuumize process is carried out with oil-sealed rotary pump and diffusion vacuum pump successively, vacuum reaches 10-2Pa ranks Afterwards, start to be passed through the flow of hydrogen and methane, constantly regulate methane and hydrogen, it is ensured that hydrogen flowing quantity in 50 ~ 100sccm or so, Methane flow is in 30 ~ 50sccm or so.By controlling vavuum pump and charge flow rate, the pressure of the mixed gas in reaction chamber is set to begin 80 ~ 100Pa or so is maintained at eventually.Heating response chamber, when temperature reaches 400 DEG C or so, after insulation 10min, opens plasma and penetrates Frequency power, under 400W or so power, reacting gas ionization carries out build-up of luminance, deposition starts.Reaction dress is closed after 2 ~ 5h Put, terminate deposition reaction, deposition terminates.It is as cold as after room temperature taking out sample with stove, obtains 5 ~ 10 microns thick on the top layer of 20# steel Diamond/DLC film, such as Fig. 4, shown in d.

Claims (1)

1. a kind of thermal diffusion using nano-carbon material is the hard coat preparation method of pretreatment, it is characterized in that：Hard coat system Preparation Method is the angle from solid-state thermal diffusion, and second phase particles are introduced in interface, with the active surface valency of nano-particle it is strong and Higher surface can provide more preferable surface nucleation condition for the preparation of ganoine thin film/coating, improve nucleation density, strengthen simultaneously Hard coat and matrix material adhesion；Hard coat preparation method includes the solid-state heat diffusion treatment of nano-carbon material, pre- place Manage cleaning and the etching of matrix material, the preparation of hard coat；
The solid-state heat diffusion treatment of described nano-carbon material：
Metallic monolith matrix material is done into preliminary cleaning polishing, surfacing, it is ensured that without larger cut, no greasy dirt is rustless Mark；Using nano-diamond, CNT, carbon microfibre, graphene, carbon ball, one or more combinations in nano-graphite, As the carbon source of solid-state thermal diffusion, ice crystal, rare earth, carbonate, nano-graphite, one kind in de-agglomerated dispersant or many are added Kind of combination, as penetration-assisting agent, higher than carrying out solid-state heat diffusion treatment at 30 ~ 350 DEG C of metal austenitizing temperature；Processing procedure In need to completely cut off air, in Ar, N2Protective gas in the furnace chamber of protective atmosphere as being penetrated into and DIFFUSION TREATMENT；According to required Depth of penetration, with reference to thickness direction diffusion rate 0.1 ~ 0.5mm/ hour, diffusion time was heated in selection；After the completion of processing, on State carbon source and enter matrix material, matrix material top layer is present in the form of second phase particles, and from surface to matrix material Material center portion is successively decreased distribution in gradient；After vacuum/atmosphere heat treatment, from surface to matrix material center portion, intensity hardness is presented Subtract change, prevent because matrix material intensity hardness not enough caused by come off；
The cleaning of described pretreatment matrix material and etching：
Pretreated substrate material surface is subjected to decontamination, sanding and polishing, alcohol/deionized water cleaning, ultrasound at room temperature Ripple is cleaned, pickling/alkali cleaning, corrosive liquid etching and dries surface treatment, makes that substrate material surface is smooth, cleaning, and passes through 4% The etching of nitric acid alcohol particular etch liquid is by the exposed surface in matrix material of second phase particles；After the completion of cleaning-drying in case after The preparation of continuous hard coat；The cleaning and etching technics for pre-processing matrix material make prepared hard coat be easier in matrix In second phase particles surface nucleation, it is strong and higher surface can be ganoine thin film/painting with the active surface valency of nano-particle The preparation of layer provides more preferable surface nucleation condition, improves nucleation density, while strengthening hard coat and matrix material combination Power；
The preparation of described hard coat：
With gas, the materials of the different conditions such as solid, or liquid as hard coat raw material sources, in 300 ~ 1100 DEG C of temperature In the range of degree, under low pressure, or the pressure action of standard atmospheric pressure, Ar, N are passed through2Protective atmosphere condition, passes through physical/chemical The hard coat of various materials prepared by vapour deposition, solid-state thermal diffusion, high energy spraying coating process, described low pressure for 30 ~ 500Pa。
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