CN106801225B - laser alloy coating, preparation method and laser alloying method - Google Patents
laser alloy coating, preparation method and laser alloying method Download PDFInfo
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- CN106801225B CN106801225B CN201710120760.XA CN201710120760A CN106801225B CN 106801225 B CN106801225 B CN 106801225B CN 201710120760 A CN201710120760 A CN 201710120760A CN 106801225 B CN106801225 B CN 106801225B
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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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- 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
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- 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
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Abstract
The invention discloses laser alloy coating, preparation method and laser alloying methods.The laser alloy coating includes the raw material of following mass parts: SiO220 ~ 30 parts, 20 ~ 25 parts of TiC, 20-25 parts of Ta, 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 that SiO2, TiC, Ta, W, Hf, Al, Si, Be and bentonite are crushed to granularity less than 3 microns respectively, 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.Laser alloying method is that mold is placed in certain time in above-mentioned laser alloy coating, then takes out mold, and carry out remelting with laser in logical argon and the laser alloying of die surface can be completed.
Description
Technical field
The invention belongs to material surface processing and reinforcement technique field, and in particular to laser alloy coating, preparation method with
Laser alloying 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 laser alloying, can be formed on the surface of hot die steel has good metallurgical bonding with matrix
Alloying layer, and obtain wear-resisting, high temperature resistant, impact-resistant hot forged mould alloying layer under suitable parameter, make hot-forging die
The service life of tool greatly improves.
Although the model of hot die steel, ingredient are more on the market, the alloy powder for mold laser alloying is few
It is again few.The reason is that the particularity of laser alloying, especially needs to consider its High-temperature-resandant andant wear-resistant, the reasonable transition with matrix
And be suitable for laser alloying characteristic requirements etc., conventional alloying component proportion is used in laser alloying or has stomata, folder
The defects of miscellaneous, crackle or service performance cannot be met the requirements.
Summary of the invention
In view of the above shortcomings of the prior art, the present invention provides a kind of laser alloy coating, to solve existing conjunction
Golden 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 being swashed using this
Light alloy coating carries out laser alloying method, short to solve the hot-work die service life that the prior art is surface-treated
Problem.
To achieve the goals above, The technical solution adopted by the invention is as follows:
A kind of laser alloy coating, the raw material including following mass parts: SiO2 20 ~ 30 parts, 20 ~ 25 parts of TiC, Ta 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.
TiC 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.
Ta, 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 TiC with preferable compatible
Property, after laser 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 TiC collective effect, can improve high temperature abrasion resistance, impact resistance, hot-cracking resistance, to improving
Die life.
Wherein, the SiO2, TiC, Ta, W, Hf, Al, Si, Be and bentonite be powder and granularity less than 3 microns.
A kind of preparation method of above-mentioned laser alloy coating, comprising the following steps:
1) by SiO2, TiC, Ta, 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
Laser alloy coating.
A kind of laser alloying method, this method are that mold is placed in certain time in above-mentioned laser alloy coating, then
Mold is taken out, and remelting is carried out to the die surface with laser in protection gas atmosphere, die surface is made to form alloy
Change coating, that is, completes the laser alloying 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 laser alloy coating, then taken out
The 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 laser 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 protection gas atmosphere, die surface is melted with laser
Solidifying processing stands the mold being cooled to room temperature to get having laser alloying coating to surface in protection gas atmosphere.Its
In, the power of the laser of laser transmitting is 1500 ~ 1900w, and sweep speed is 10 ~ 13 mm/s, and spot diameter is 3 ~ 4.5mm,
Overlapping rate is 20 ~ 25%.
Available fine and close, the higher coating of bond strength, the coating can improve making for mold after laser melting process
Use the service life.Such surface is high with hardness at high temperature, finish is good, coefficient of friction is low, hardly needs subsequent machining,
It can directly upper production line use.
The mold is hot-work die.The laser is the CO that maximum power is 5 kW2Laser can be selected
TJ-HL-T5000 type CO2Laser.
Protection gas atmosphere described in step (2) is argon atmosphere, wherein the flow for argon gas is 1.0 ~ 2.0 L/min.
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 laser 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 laser surface alloying, surface roughness can satisfy requirement.In addition to laser surface alloying
This process program, 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, machining ten
Divide difficulty, operability is low.And the present invention is by hot biofilm, laser consolidation treatment, surface is more smooth, does not need machining i.e.
It can be used, substantially increase operability, cost substantially reduces.
5, using the present invention to the laser alloying of hot-work die working face production efficiency, cost is relatively low, step is few, is convenient for
It promotes the use of.
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 3 times or more.
Specific embodiment
Invention is further described in detail combined with specific embodiments below.
Embodiment one
The raw material for preparing laser alloy coating is calculated using following mass parts: SiO2 21 parts, 25 parts of TiC, 24 parts of Ta, W
23 parts, 25 parts of Hf, 21 parts of Al, 25 parts of Si, 20 parts of Be, 18 parts of bentonite, 9 parts of commercially available shellac, dehydrated alcohol 380
Part.Wherein: SiO2, TiC, Ta, W, Hf, Al, Si, Be and bentonite be powdery, granularity is at 3 microns or less.
The specific preparation step of laser alloy coating are as follows:
1) by SiO2, TiC, Ta, 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
Laser alloy coating.
The Laser Alloying Treatment of die surface is carried out using above-mentioned laser alloy coating:
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 100 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) laser irradiation die surface is used.Use maximum power for the TJ-HL-T5000 type CO of 5 kW2Laser is to mold
Surface carries out remelting, uses argon gas to be cooled down and protected during consolidation, and flow is 1.8 L/min, adjusts laser function
Rate is 1800w, and sweep speed is 13 mm/s, spot diameter 4.5mm, overlapping rate 25%, can be with after laser melting process
Obtain fine and close, the higher coating of bond strength.
The present embodiment handled after alloying surface at 900 DEG C hardness average value be HRC38, 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 3.3 times.
Embodiment two
The raw material for preparing laser alloy coating is calculated using following mass parts: SiO2 24 parts, 21 parts of TiC, 21 parts of Ta, W
21 parts, 20 parts of Hf, 25 parts of Al, 22 parts of Si, 24 parts of Be, 16 parts of bentonite, 8 parts of commercially available shellac, 330 parts of dehydrated alcohol.
Wherein: SiO2, TiC, Ta, W, Hf, Al, Si, Be and bentonite be powdery, granularity is at 3 microns or less.
The specific preparation step of laser alloy coating are as follows:
1) by SiO2, TiC, Ta, 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
Laser alloy coating.
The Laser Alloying Treatment of die surface is carried out using above-mentioned laser alloy coating:
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 80 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) laser irradiation die surface is used.Use maximum power for the TJ-HL-T5000 type CO of 5 kW2Laser is to mold
Surface carries out remelting, uses argon gas to be cooled down and protected during consolidation, and flow is 1.5 L/min, adjusts laser function
Rate is 1700w, and sweep speed is 12 mm/s, spot diameter 4mm, and overlapping rate 20% can obtain after laser melting process
To fine and close, the higher coating of bond strength.
The present embodiment handled after alloying surface at 900 DEG C hardness average value be HRC39, 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 3.5 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 (7)
1. a kind of laser alloy coating, which is characterized in that the raw material including following mass parts: SiO2 20 ~ 30 parts, TiC 20 ~ 25
Part, 20-25 parts of Ta, 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 laser alloy coating is prepared by following methods:
1) by SiO2, TiC, Ta, 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 laser is arrived
Alloy coating.
2. laser alloy coating according to claim 1, which is characterized in that the SiO2、TiC、Ta、W、Hf、Al、Si、
Be and bentonitic granularity are less than 3 microns.
3. a kind of laser alloying method, which is characterized in that mold is placed in a timing in the laser alloy coating of claim 1
Between, mold is then taken out, and remelting is carried out to the die surface with laser in protection gas atmosphere, makes die surface shape
At alloying coating, that is, complete the laser alloying of die surface.
4. laser alloying 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 laser alloy coating, then take out the mould
Tool is stood to constant weight, is obtained to surface and is bonded with the mold of powder bed；
(2) mold that surface is bonded with powder bed is placed in protection gas atmosphere, die surface is carried out at consolidation with laser
Reason stands in protection gas atmosphere and is cooled to room temperature, that is, completes the laser alloying of die surface；
Wherein, laser transmitting laser power be 1500 ~ 1900W, sweep speed be 10 ~ 13 mm/s, spot diameter be 3 ~
4.5mm, overlapping rate are 20 ~ 25%.
5. laser alloying method according to claim 4, which is characterized in that the laser is that maximum power is 5
The CO of kW2Laser.
6. laser alloying method according to claim 4, which is characterized in that protection gas atmosphere described in step (2) is
Argon atmosphere, wherein the flow of argon gas is 1.0 ~ 2.0 L/min.
7. laser alloying method according to claim 4, which is characterized in that the mold is hot-work die.
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| JPS60138041A (en) * | 1983-12-27 | 1985-07-22 | Ibiden Co Ltd | Ceramic-metal composite body and its manufacture |
| US6986810B1 (en) * | 2002-11-21 | 2006-01-17 | Mohammad Behi | Aqueous binder formulation for metal and ceramic feedstock for injection molding and aqueous coating composition |
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| CN101418445A (en) * | 2008-12-16 | 2009-04-29 | 贵州大学 | Adhesive agent for preset coating for laser surface alloying as well as preparation method and use thereof |
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