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 PDFInfo
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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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- 238000009792 diffusion process Methods 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 18
- 229910021392 nanocarbon Inorganic materials 0.000 title claims abstract description 18
- 239000011159 matrix material Substances 0.000 claims abstract description 66
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000004140 cleaning Methods 0.000 claims abstract description 24
- 238000000576 coating method Methods 0.000 claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- 238000005530 etching Methods 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 238000005498 polishing Methods 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 239000002113 nanodiamond Substances 0.000 claims abstract description 9
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 8
- 239000010439 graphite Substances 0.000 claims abstract description 8
- 238000009826 distribution Methods 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 5
- 238000005202 decontamination Methods 0.000 claims abstract description 4
- 230000003588 decontaminative effect Effects 0.000 claims abstract description 4
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 4
- 238000005507 spraying Methods 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000007781 pre-processing Methods 0.000 claims abstract 2
- 230000006911 nucleation Effects 0.000 claims description 21
- 238000010899 nucleation Methods 0.000 claims description 21
- 239000011248 coating agent Substances 0.000 claims description 20
- 239000012298 atmosphere Substances 0.000 claims description 12
- QFUKUPZJJSMEGE-UHFFFAOYSA-N 5-(hydroxymethyl)-1-(3-methylbutyl)pyrrole-2-carbaldehyde Chemical compound CC(C)CCN1C(CO)=CC=C1C=O QFUKUPZJJSMEGE-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000002105 nanoparticle Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 238000005728 strengthening Methods 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000010409 thin film Substances 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 150000002910 rare earth metals Chemical class 0.000 claims description 4
- 229920001410 Microfiber Polymers 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 239000003658 microfiber Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 230000035515 penetration Effects 0.000 claims description 3
- 238000005554 pickling Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000004381 surface treatment Methods 0.000 claims description 3
- 230000003247 decreasing effect Effects 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 238000010422 painting Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 10
- 229910003460 diamond Inorganic materials 0.000 abstract description 9
- 239000010432 diamond Substances 0.000 abstract description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 7
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 abstract 1
- 229920000049 Carbon (fiber) Polymers 0.000 abstract 1
- 239000004917 carbon fiber Substances 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 13
- 239000010408 film Substances 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- 229910000831 Steel Inorganic materials 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000003961 penetration enhancing agent Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 235000019580 granularity Nutrition 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
Classifications
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Plasma & Fusion (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Chemical Vapour Deposition (AREA)
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
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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| 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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| CN106435460B (en) * | 2016-10-18 | 2018-10-12 | 中国矿业大学 | A kind of niobium alloy surface high-temp wear-resistant coating and preparation method thereof |
| CN106676463B (en) * | 2017-03-03 | 2020-03-31 | 中国矿业大学 | Surface deep layer strengthening method using graphitized micro-nano carbon material as diffusion source |
| EP3375811A1 (en) * | 2017-03-17 | 2018-09-19 | Airbus Operations S.L. | Multifunctional diffusion barrier |
| CN109023360B (en) * | 2018-06-29 | 2020-07-28 | 三联泵业股份有限公司 | Wear-resistant double-suction pump impeller surface treatment process |
| 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 |
| CN111058011A (en) * | 2019-12-25 | 2020-04-24 | 浙江工业大学 | Nano-diamond-graphene composite film electrode and preparation method thereof |
| CN111777335B (en) * | 2020-05-22 | 2022-11-11 | 碳中(广东)科技有限公司 | Heating coating material for glass substrate and preparation method thereof |
| CN112301324B (en) * | 2020-09-21 | 2023-04-14 | 贾春德 | Method for plating diamond film on steel substrate |
| CN114622201B (en) * | 2020-12-10 | 2023-09-08 | 张国徽 | Graphene nano composite metal section bar and preparation method thereof |
| CN113755815A (en) * | 2021-09-10 | 2021-12-07 | 安徽光智科技有限公司 | Substrate pretreatment method and preparation method of diamond film |
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