CN106868500B - A kind of surface alloying coating, preparation method and mold electron beam alloyage method - Google Patents
A kind of surface alloying coating, preparation method and mold electron beam alloyage method Download PDFInfo
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- CN106868500B CN106868500B CN201710120483.2A CN201710120483A CN106868500B CN 106868500 B CN106868500 B CN 106868500B CN 201710120483 A CN201710120483 A CN 201710120483A CN 106868500 B CN106868500 B CN 106868500B
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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
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
- C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
Abstract
The invention discloses a kind of surface alloying coating, preparation method and mold electron beam alloyage methods.The surface alloying coating includes the raw material of following mass parts: SiO220 ~ 30 parts, 20 ~ 25 parts of SiC, 20 ~ 25 parts of Nb, 20 ~ 25 parts of W, 20-25 parts of Hf, 20 ~ 25 parts of Al, 20 ~ 25 parts of Si, 20 ~ 25 parts of Be, 15 ~ 25 parts of bentonite, 6 ~ 10 parts of shellac, 300 ~ 400 parts of dehydrated alcohol.Can effectively avoid stomata, be mingled with, crackle the defects of generation.Preparation method is by SiO2, SiC, Nb, W, Hf, Al, Si, Be and bentonite be crushed to granularity respectively less than 3 microns, then it is uniformly mixed and obtains alloy powder, by the shellac ethanol solution of a part of dehydrated alcohol melt into shellac, finally alloy powder, the ethanol solution of shellac and another part dehydrated alcohol are stirred evenly with blender.Mold electron beam alloyage method is that mold is placed in certain time in above-mentioned electron beam alloy coating, then carries out beam bombardment processing with surface of the pulsed electron beam device to mold in protection gas atmosphere.
Description
Technical field
The invention belongs to material surface processing and reinforcement technique fields, and in particular to a kind of surface alloying coating, preparation method
With mold electron beam alloyage method.
Background technique
Hot-work die bears varying stress and impact force at high temperature, and workpiece shaping temperature often at 1000 DEG C or more, is also wanted
It is subjected to high-temperature oxydation, scaling loss and is subjected to high wind-warm syndrome caused by cold and hot variation under strong water cooling condition.It is needed when being on active service
Bear high stress, thermal shock, defibrator process undermine the effects of the load such as corrosion, therefore die life is very low.To improve the service life, adopt at present
Main method is surface peening.Conventional method has quenching, carburizing, nitriding etc., but the effect of these methods is very limited, because
It is hot-work die work in hot environment, traditional quenching enters annealed condition again under high temperature environment.In addition, for carburizing
For this technique, penetrating into excessive carbon can be such that the toughness of hot-work die reduces.
Using the method for electron beam alloyage, can be formed on the surface of hot die steel has good metallurgical junction with matrix
The alloying layer of conjunction, and wear-resisting, high temperature resistant, impact-resistant hot forged mould alloying layer are obtained under suitable parameter, make to be hot-forged
The service life of mold greatly improves.
Although the model of hot die steel, ingredient are more on the market, it to be used for the alloy powder of mold electron beam alloyage
It is fewer and fewer.The reason is that the particularity of electron beam alloyage, especially need to consider its High-temperature-resandant andant wear-resistant, reasonable with matrix
Transition and it is suitable for electron beam alloyage characteristic requirements etc., conventional alloying component proportion is used in electron beam alloyage or has
Stomata, be mingled with, crackle the defects of or service performance cannot meet the requirements.
Summary of the invention
In view of the above shortcomings of the prior art, the present invention provides a kind of surface alloying coating, to solve existing alloy
Ingredient have stomata, be mingled with, crackle the defects of the technical issues of, and it is corresponding preparation method is provided, while providing and utilizing the electronics
Beam alloy coating carries out mold electron beam alloyage method, uses the longevity to solve the hot-work die that the prior art is surface-treated
Order short problem.
To achieve the goals above, The technical solution adopted by the invention is as follows:
A kind of surface alloying coating, the raw material including following mass parts: SiO220 ~ 30 parts, 20 ~ 25 parts of SiC, Nb 20 ~
25 parts, 20 ~ 25 parts of W, 20-25 parts of Hf, 20 ~ 25 parts of Al, 20 ~ 25 parts of Si, 20 ~ 25 parts of Be, 15 ~ 25 parts of bentonite, worm
6 ~ 10 parts of glue, 300 ~ 400 parts of dehydrated alcohol.
SiO2Effect in coating: auxiliary rheological agents in the construction process, since the solvent volatilization of coating edge is very fast, are led
It causes surface tension uneven, is easy to make coating to edge movement, and network of silica can effectively prevent the movement of coating
And webbing is formed, while also preventing the sagging phenomenon of coating in the curing process, make coating uniform.2, anti-settling agent, SiO2It is one
The ideal anti-settling agent of kind, for preventing the precipitating of pigment in coating system highly effective, especially for the system of mill base, suitably
Additive amount will greatly improve the stability of mill base, and the amount of wetting dispersing agent can be reduced, to improve the applicability of mill base,
And reduce influence of the mill base to coating system, SiO2Anti-settling effect to coating store highly beneficial, especially certain pigment,
Such as metal powder, all easily precipitates and cannot suspend completely, use SiO2It can guarantee that its dispersion does not precipitate.3, auxiliary agent is dispersed in powder
In last coating system, due to SiO2Small particle and high surface energy, they can be adsorbed on the surface of fine paint powders, and in powder
Surface formed a surface layer, improve powder obtain it is dispersed, therefore can be used as dispersing agent using in same coating system, be added
SiO2It can be obviously shortened jitter time, it is mono- it is noted that first by SiO to improve production efficiency2Disperse complete effect more preferably may be used
It is used together with other rheology host auxiliary agents of arranging in pairs or groups simultaneously, and adjusts SiO using alcohols solvent2Rheological property.4,SiO2May be used also
To improve weatherability, the resistance to marring of coating, the bond strength between coating and substrate is improved.
SiC is ceramic phase, improves coating hardness.Type, content and the matching with metal wetability of ceramic phase, are all bases
It is obtained in many experiments.
Nb, W, Hf, Al, Si, Be are prepared into alloy powder together, collectively form high-entropy alloy.High-entropy alloy includes heating power
" cocktail " in the distortion of lattice effect in high entropy effect, structure, sluggish diffusion effect kinetically, performance on
Effect.Using these characteristics, and binding isotherm calculates the high-entropy alloy designed with many experiments with SiC with preferable compatible
Property, after electron beam irradiation, coating structure can be refined, enhances toughness, the alloy-layer of formation is without empty crackle, alloy-layer and matrix
Metallurgical bonding, bond strength are high.With SiC collective effect, can improve high temperature abrasion resistance, impact resistance, hot-cracking resistance, to improving
Die life.
Wherein, the SiO2, SiC, Nb, W, Hf, Al, Si, Be and it is bentonitic be powder and granularity is micro- less than 3
Rice.
A kind of preparation method of above-mentioned surface alloying coating, comprising the following steps:
1) by SiO2, SiC, Nb, W, Hf, Al, Si, Be and bentonite be crushed to granularity respectively less than 3 microns, then mix
It closes uniformly, obtains alloy powder, it is spare.Micron powder can farthest avoid existing alloying component stomata,
Be mingled with, crackle the defects of generation.
2) a part of dehydrated alcohol of shellac is dissolved, obtains the ethanol solution of shellac, it is spare.Shellac can provide coating
Caking property, but uniform coating is formed, since commercially available shellac is solid, it is necessary to solution first be made and just advantageously form
The coating of suspended liquid status, and why using dehydrated alcohol make solvent, then it is the solubility due to shellac in dehydrated alcohol
It is higher, at the same dehydrated alcohol be easy to volatilize and it is substantially harmless to human body.
3) alloy powder, the ethanol solution of shellac and another part dehydrated alcohol are stirred evenly with blender to get arriving
Surface alloying coating.
A kind of mold electron beam alloyage method, this method are that mold is placed in certain time in above-mentioned surface alloying coating,
Mold is then taken out, and carries out beam bombardment processing with surface of the pulsed electron beam device to mold in protection gas atmosphere,
So that die surface is formed alloying coating, that is, completes the electron beam alloyage of die surface.Specifically includes the following steps:
(1) mold is first heated to 70 ~ 110 DEG C, then the mold is immersed in 1 ~ 3s in surface alloying coating, then take out this
Mold is stood to constant weight, is obtained to surface and is bonded with the mold of powder bed.Since mold is heated, when in electron beam alloy coating
Between it is shorter, when taking-up, still keeps hot, therefore under heat effect, the dehydrated alcohol of die surface can volatilize rapidly, and remaining at
One layer of mixed-powder being firmly bonded can be then formed on its surface by dividing, to facilitate lower step remelting.
(2) mold that surface is bonded with powder bed is placed in vacuum degree less than 6 × 10-3 In the vacuum chamber of Pa, then pass to
Inert gas carries out beam bombardment processing to die surface as protective gas, with pulsed electron beam device, i.e. completion mold
The electron beam alloyage on surface.
Wherein, the parameter of pulsed electron beam device are as follows: energy density 6-8J/cm2, pulse width 9-11 μ s, pulse number
200 ~ 300 times.
Available fine and close, the higher coating of bond strength, the coating can improve mold after beam bombardment is processed
Service life.Such surface is high with hardness at high temperature, finish is good, coefficient of friction is low, hardly needs subsequent machine and adds
Work, can directly upper production line use.
Hardness is high, finish is good, coefficient of friction is low at high temperature on the surface handled using electron beam alloyage of the present invention, several
Subsequent machining is not needed, it can directly upper production line use.
The mold is hot-work die；The protective gas is argon gas, helium or nitrogen.
Compared with prior art, the invention has the following beneficial effects:
1, the present invention uses micron powder for basic raw material, in this way after ethyl alcohol volatilization, can be formed and be caused in die surface
Close, bright and clean powder bed, avoid the stomata of existing alloying component, be mingled with, crackle the defects of generation.
2, preparation can be completed in electron beam alloy coating of the invention at room temperature, and simple production process is easy.
3, currently, hot-work die working face often will appear steel bonding problem after a period of time is used continuously in hot environment, make
With the present invention after steel cylinder ring moulds face surface forms new alloy-layer, the problem of steel bonding, is significantly improved.
4, using electron beam surface alloying, surface roughness can satisfy requirement.In addition to electron beam surface closes
This process program of aurification, also someone improves the service life of hot-work die by cladding Wear-resistant, high-temperature resistant powder, but its
Cladding layer is coarse, it is necessary to the online use of ability after the machinings such as vehicle, mill, and the very high cladding layer of hardness, machine add
Work is very difficult, and operability is low.And the present invention is handled by hot biofilm, beam bombardment, surface is more smooth, does not need machine
Processing can be used, and substantially increase operability, cost substantially reduces.
5, using the present invention to hot-work die working face electron beam alloyage production efficiency, cost is relatively low, step is few, just
In popularization and use.
6, the present invention is more than 1 year through production testing, it was demonstrated that the hot-work die red hardness after processed by the invention can be very
It is good, rank of the roughness close to smart car.Using effect is shown, can improve die life to original 2.5 times or more.
Specific embodiment
Invention is further described in detail combined with specific embodiments below.
Embodiment one
The raw material for preparing surface alloying coating is calculated using following mass parts: SiO221 parts, 25 parts of SiC, 25 parts of Nb, W
20 parts, 20 parts of Hf, 25 parts of Al, 24 parts of Si, 21 parts of Be, 23 parts of bentonite, 10 parts of shellac, 380 parts of dehydrated alcohol.Its
Middle SiO2, SiC, Nb, W, Hf, Al, Si, Be and bentonite be powdery, granularity is at 3 microns or less.
The specific preparation step of electron beam alloy coating are as follows:
1) by SiO2, SiC, Nb, W, Hf, Al, Si, Be and bentonite be crushed to granularity respectively less than 3 microns, then mix
It closes uniformly, obtains alloy powder, it is spare.
2) a part of dehydrated alcohol of shellac is dissolved, obtains the ethanol solution of shellac, it is spare.
3) alloy powder, the ethanol solution of shellac and another part dehydrated alcohol are stirred evenly with blender to get arriving
Surface alloying coating.
It is handled using the electron beam alloyage that above-mentioned electron beam alloy coating carries out die surface:
1) hot-work die is worked into the size of needs.
2 surface alloying coating is added in the container for being greater than mold.
3) hot-work die is heated to 110 DEG C with chamber type electric resistance furnace, is put into after taking-up in the container equipped with surface alloying coating,
It allows coating to flood mold and takes out mold from coating after 1 second, under heat effect, the ethyl alcohol of die surface can volatilize rapidly, stay
The next layer of firm mixed-powder of bonding.
4) use electron beam irradiation die surface: sample is put on the station of vacuum chamber, vacuumizes on fixture, until
The vacuum degree P < 6 × 10 of vacuum chamber-3Then Pa is filled with inert gas as protective gas, such as argon gas, helium into vacuum chamber
Deng；Starting impulse electron beam equipment loads high pressure (20-25kv), carries out beam bombardment processing to the surface of mold.Pulse electricity
The main parameters ranges of beamlet surface treatment: energy density 8J/cm2, pulse width 9 μ s, pulse number 220 times；Vacuum chamber is opened,
Take out the part through E.B surface treatment.
The present embodiment handled after alloying surface at 900 DEG C hardness average value be HRC33, do not carry out surface conjunction
Aurification processing has and is obviously improved, and does not carry out the working face of the surface alloying processing hardness average value at 900 DEG C and is
HRC17.Through production testing, the present embodiment can improve die life to original 2.8 times.
Embodiment two
The raw material for preparing surface alloying coating is calculated using following mass parts: SiO225 parts, 22 parts of SiC, 21 parts of Nb, W
24 parts, 24 parts of Hf, 21 parts of Al, 20 parts of Si, 24 parts of Be, 23 parts of bentonite, 10 parts of shellac, 380 parts of dehydrated alcohol.Its
In: SiO2, SiC, Nb, W, Hf, Al, Si, Be and bentonite be powdery, granularity is at 3 microns or less.
The specific preparation step of electron beam alloy coating are as follows:
1) by SiO2, SiC, Nb, W, Hf, Al, Si, Be and bentonite be crushed to granularity respectively less than 3 microns, then mix
It closes uniformly, obtains alloy powder, it is spare.
2) a part of dehydrated alcohol of shellac is dissolved, obtains the ethanol solution of shellac, it is spare.
3) alloy powder, the ethanol solution of shellac and another part dehydrated alcohol are stirred evenly with blender to get arriving
Electron beam alloy coating.
It is handled using the electron beam alloyage that above-mentioned electron beam alloy coating carries out die surface:
1) hot-work die is worked into the size of needs.
2 surface alloying coating is added in the container for being greater than mold.
3) hot-work die is heated to 85 DEG C with chamber type electric resistance furnace, is put into after taking-up in the container equipped with surface alloying coating,
It allows coating to flood mold and takes out mold from coating after 3 seconds, under heat effect, the ethyl alcohol of die surface can volatilize rapidly, stay
The next layer of firm mixed-powder of bonding.
4) use electron beam irradiation die surface: sample is put on the station of vacuum chamber, vacuumizes on fixture, until
The vacuum degree P < 6 × 10 of vacuum chamber-3Then Pa is filled with inert gas as protective gas, such as argon gas, helium into vacuum chamber
Deng；Starting impulse electron beam equipment loads high pressure (20-25kv), carries out beam bombardment processing to the surface of mold.Pulse electricity
The main parameters ranges of beamlet surface treatment: energy density 8J/cm2, pulse width 9 μ s, pulse number 220 times；Vacuum chamber is opened,
Take out the part through E.B surface treatment.
The present embodiment handled after alloying surface at 900 DEG C hardness average value be HRC35, do not carry out surface conjunction
Aurification processing has and is obviously improved, and does not carry out the working face of the surface alloying processing hardness average value at 900 DEG C and is
HRC17.Through production testing, the present embodiment can improve die life to original 3.0 times.
The above embodiment of the present invention is only example to illustrate the invention, and is not to implementation of the invention
The restriction of mode.For those of ordinary skill in the art, other can also be made not on the basis of the above description
With the variation and variation of form.Here all embodiments can not be exhaustive.It is all to belong to technical solution of the present invention
Changes and variations that derived from are still in the scope of protection of the present invention.
Claims (6)
1. a kind of surface alloying coating, which is characterized in that the raw material including following mass parts: SiO220 ~ 30 parts, SiC 20 ~ 25
Part, 20 ~ 25 parts of Nb, 20 ~ 25 parts of W, 20-25 parts of Hf, 20 ~ 25 parts of Al, 20 ~ 25 parts of Si, 20 ~ 25 parts of Be, bentonite 15
~ 25 parts, 6 ~ 10 parts of shellac, 300 ~ 400 parts of dehydrated alcohol；
The alloying coating is prepared using following methods:
1) by SiO2, SiC, Nb, W, Hf, Al, Si, Be and bentonite be crushed to granularity respectively less than 3 microns, then mixing is equal
It is even, alloy powder is obtained, it is spare；
2) a part of dehydrated alcohol of shellac is dissolved, obtains the ethanol solution of shellac, it is spare；
3) alloy powder, the ethanol solution of shellac and another part dehydrated alcohol are stirred evenly with blender to get alloy is arrived
Change coating.
2. surface alloying coating according to claim 1, which is characterized in that the SiO2、SiC、Nb、W、Hf、Al、Si、Be
With bentonitic granularity less than 3 microns.
3. a kind of mold electron beam alloyage method, which is characterized in that mold to be placed in one in the surface alloying coating of claim 1
It fixes time, then takes out mold, and carry out electron beam with surface of the pulsed electron beam device to mold in protection gas atmosphere and bang
Processing is hit, so that die surface is formed alloying coating, that is, completes the electron beam alloyage of die surface.
4. mold electron beam alloyage method according to claim 3, which comprises the following steps:
(1) mold is first heated to 70 ~ 110 DEG C, then the mold is immersed in 1 ~ 3s in surface alloying coating, then take out the mold
It stands to constant weight, obtains to surface and be bonded with the mold of powder bed；
(2) mold that surface is bonded with powder bed is placed in vacuum degree less than 6 × 10-3 In the vacuum chamber of Pa, inertia is then passed to
Gas carries out beam bombardment processing to die surface as protective gas, with pulsed electron beam device, i.e. completion die surface
Electron beam alloyage；
Wherein, the parameter of pulsed electron beam device are as follows: energy density 6-8J/cm2, pulse width 9-11 μ s, pulse number 200-
300 times.
5. mold electron beam alloyage method according to claim 4, which is characterized in that the mold is Forming Die
Tool.
6. mold electron beam alloyage method according to claim 4, which is characterized in that the protective gas is argon
Gas, helium or nitrogen.
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| CN108864779A (en) * | 2018-07-19 | 2018-11-23 | 江苏久祥汽车电器集团有限公司 | A kind of electron beam alloyage coating composition and its preparation, application method |
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| US8034153B2 (en) * | 2005-12-22 | 2011-10-11 | Momentive Performances Materials, Inc. | Wear resistant low friction coating composition, coated components, and method for coating thereof |
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Effective date of registration: 20221223 Address after: 110200 Gate 3, No. 10A, Donghuan Street, Puxi Street, Liaozhong District, Shenyang, Liaoning Patentee after: Shenyang Xinyuxuan Trading Co.,Ltd. Address before: No.33, Lane 159, Taiye Road, Fengxian District, Shanghai, 201400 Patentee before: Shanghai Yuanbao Industrial Design Co.,Ltd. Effective date of registration: 20221223 Address after: No.33, Lane 159, Taiye Road, Fengxian District, Shanghai, 201400 Patentee after: Shanghai Yuanbao Industrial Design Co.,Ltd. Address before: No. 69 lijiatuo Chongqing District of Banan City Road 400054 red Patentee before: Chongqing University of Technology |