CN109338355B - A kind of wear-resisting cladding layer preparation method on copper sheet surface - Google Patents
A kind of wear-resisting cladding layer preparation method on copper sheet surface Download PDFInfo
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- CN109338355B CN109338355B CN201811079813.9A CN201811079813A CN109338355B CN 109338355 B CN109338355 B CN 109338355B CN 201811079813 A CN201811079813 A CN 201811079813A CN 109338355 B CN109338355 B CN 109338355B
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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
Abstract
A kind of wear-resisting cladding layer preparation method on copper sheet surface adsorbs Ti ion using hydro-thermal high pressure, and in the case where GO carries functional group's effect, and TiO is obtained in after baking in water-less environment2Coat GO(anatase titanium dioxide).The thin iron powder of gained powder and Ti powder, Si powder and surplus adjusts the mixed-powder for being mixed to get gluing state with glycerine certain proportion.Copper sheet is polished with sand paper, and gluing state mixed-powder is uniformly applied to matrix face.Again with flame gun Quick uniform presintering powder in matrix surface.Then material is handled using laser melting coating in atmosphere, obtains cladding material.Copper sheet surface cladding material friction coefficient disclosed in this invention is smaller and has had both the features such as surface hardness is high, meanwhile, have many advantages, such as that simple, safety, low cost are easily operated and controllable.
Description
Technical field
The invention belongs to technical field of material.
Background technique
The two-dimensional material for the monoatomic layer thickness that graphene nanometer sheet is made of sp2 hydbridized carbon atoms, shows one
The unusual physical property of series.Graphene nanometer sheet causes physics, chemistry and materialogy because of its special two-dimensional structure
The great interest of boundary researcher, basic research and engineering Application Research in relation to graphene become research hotspot in recent years.
Since graphene has high intensity, tensile strength up to 130GPa, imply graphene have in material application study it is huge
Big application space.
In fact, enhancing using carbon material such as carbon nanotube or graphene the intensity and other mechanical properties of copper material
Research is carrying out always, and achieves a degree of progress.However, due to physical characteristics such as its intensity extremely outstanding, people
Ignore its excellent attribute in material abrasiveness and hardness instead.
With the development of national economy, people have harsher requirement to the properties of material.Such as requiring train
Or high-speed rail power grid contact line bears friction while power supply, and corresponding copper material is needed to have superior wear-resisting property and more
Good heat resistance etc..A large number of studies show that the correct selection of reinforced phase can directly improve the wear-resisting property and hardness of composite material.
And graphene oxide (GO) is due to the essential attribute of its carbon material, natural succession its self-lubricating and preferable thermal diffusivity etc. are no
It is same as the speciality of other reinforcing materials.Thus correctly using the loss that can efficiently reduce material.
The defect of right graphene oxide is also more obvious.Graphene oxide shows very poor profit similar to the structure of CNT
Moist, this directly results in not strong with metallic matrix interfacial bonding property, is unfavorable for the preparation of composite material.Thus, improve its with
The wetability of matrix simultaneously selects correct process to become the key using graphene enhancing metal_based material.
Graphene oxide, which improves wetability method, at present overlay coating etc., and such as chemical nickel plating, this method is mainly by carboxylic
The graphene of base is through sensitization plays, after activation, is put into plating in chemical plating fluid, as the progress of reaction can be in graphene oxide table
Face obtains graininess coating, but expensive, and commonly uses toxic reagent, not environmentally and high production cost, is not suitable for extensive
Production.
In publication CN106148949A, title are as follows: a kind of " laser-induction composite cladding graphene enhancing Ni3Ti
In the method for composite material ".Graphene is pre-processed using chemical plating to obtain the graphene of nickel plating.Powder is mixed again carries out routine
It is laser sintered.In fact this method due to chemical plating limitation, it is larger to human injury, and it also requires individually to graphene
Carboxylated, the production cycle is long, while utilizing is sintering process of dusting, higher for such powder waste degree, has certain office
It is sex-limited.
Therefore, still lack a kind of cost-effective graphene oxide enhancing copper sheet composite material preparation and forming skill at present
Art.
Summary of the invention
The object of the present invention is to provide a kind of new deposition technologies using graphene oxide enhancing copper-based material.It is
Substrate surface adds the methods of mixed-powder, makes powder form one layer of basis material in Copper substrate using the laser of certain power
Protective layer.With the process of the corrosion resistance or the hardness that reach reinforcing material etc..This method cladding layer controllability is high, fixed
Property processed is relatively strong, excellent bonding performance, and using new method and proportion addition graphene oxide in matrix surface, at low cost, low failure
Rate.Meanwhile being formed by SiC and being generated to be internal, binding performance is preferable.
Laser cladding technology includes selection proportion, the control of environment and the determination of the technological parameter three crucial rings of powder
Section, these three links are all linked with one another, all directly affect the quality of product.
In the present invention, graphene oxide is pre-processed using hydro-thermal method, the rear gluing state for recycling glycerine is protected
The adhesion for holding its dispersibility and material reaches during the mixed powder of reduction due to inhomogeneities caused by different densities.
Concrete principle of the invention are as follows: the high temperature generated by laser spreads powder rapid melting, in the high temperature of moment
Under, to reduce graphene oxide loss, surface of graphene oxide is handled by hydro-thermal method, its surface is made to adhere to TiO2Make
For stable particle protective layer.Meanwhile during prolonged low-temperature hydrothermal, graphene oxide activity can be effectively reduced, is made
Its chemical property is more stable.In addition, the addition of Si phase, may make surface of graphene oxide layer to generate micro SiC at high temperature
Particle can effectively improve the wearability and hardness of copper material coating.
The present invention is achieved by the following technical solutions.
A kind of wear-resisting cladding layer preparation method on copper sheet surface of the present invention, includes the following steps.
(1) by graphene oxide in analysis straight alcohol the pre-dispersed 1 ~ 2h of ultrasound, temperature is room temperature, and whole-process control is anhydrous
Vapour.Volume ratio is strict controlled in 0.3 ~ 0.6:50.
(2) by step (1) pretreated graphene oxide dispersion pour into glycerine and tetraisopropyl titanate composition
It is sealed in precursor liquid, and is ultrasonically treated 1 ~ 2h again.Wherein, glycerine and tetraisopropyl titanate volume ratio are 10:0.5 ~ 1.5.
(3) forerunner's suspension of step (2) is imported in hydrothermal reaction kettle, wherein suspension volume accounts for the molten product of reaction kettle
30%~60%.Place into reacting furnace and heat, be warming up to 80~120 DEG C with 2~6 DEG C/min, keep the temperature 1~2h, then with 1~3 DEG C/
After min is warming up to 170 ~ 190 DEG C, 10~15h is kept the temperature；It takes out, reaction kettle sealing is air-cooled.
(4) solution obtained by step (3) is taken out, centrifugal treating, and be repeatedly centrifuged by pouring into analysis straight alcohol to solution
Colourless, revolving speed is controlled in 9000 ~ 16000rpm.Whole process sealing guarantees without steam.
(5) the mixed-powder vacuum drying that step (4) is obtained, after will be in the powder under protection of argon gas 500 ~ 550 DEG C
Roasting.Time controls in 1 ~ 3h.The graphene oxide that surface has needle-shaped anatase type titanium oxide coating can be obtained.
(6) powder obtained by step (5) is put into beaker, titanium valve, thin iron powder, fine silica powder is added, and glycerine is added,
Middle silicon powder control is total powder quality 5 ~ 15%, and titanium valve control is the 3 ~ 5.5% of total powder quality, and size Control is 5 ~ 10 μm, oxygen
Graphite alkene is the 5 ~ 7.5% of total powder quality, and surplus is iron powder, and size Control is 5 ~ 8 μm.Glycerine is the 2.5 of total volume ratio
~ 5.0%, this is crucial for stomata control, and processing is whole without steam, and then with 1 ~ 3h of ultrasonic treatment.Obtain the mixed powder of gluing state
End.
(7) copper sheet 1500 ~ 2000# sand paper is polished, alcohol washes drying.It then will be gluing state obtained by step (6)
Mixed-powder is uniformly applied to copper material surface, and prefabricated thickness control is 0.4 ~ 0.8mm.Powder is pre-sintered with flame gun Quick uniform again
End is in matrix surface.
(8) step (7) resulting materials are put into argon gas guard box, material is handled using laser melting coating.Its work
Skill state modulator are as follows: it is 1.2 ~ 2.4Kw that laser power, which answers strict control, and scanning speed is 4 ~ 8mm/s, and spot diameter is 2 ~ 5mm.
Hydrothermal reaction kettle liner described in step (3) of the present invention is polytetrafluoroethylene (PTFE).
The present invention have following uniqueness: (1) the method reduce in conventional blending processes of powders as caused by density variation
Lamination.(2) the conventional caused dust pollution that dusts can be reduced using the viscosity of lipid itself, it is more environmentally-friendly.(3) should
Method reaction temperature is lower, and danger coefficient is smaller.(4) graphene oxide in coating is due to there is TiO2Protective effect, have
While more preferable interface, the wetability with metal is increased, further reduces graphene oxide reunion probability.
Specific embodiment
The present invention will be described further by following embodiment.
Embodiment 1.
By graphene oxide in the analysis straight alcohol clock pre-dispersed 1h of ultrasound, temperature is room temperature, and whole-process control is without steam.Volume
Than being strict controlled in 0.3:50, after that gained dispersion liquid poured into sealing in the precursor liquid of glycerine and tetraisopropyl titanate composition is super
Sonication 1h.Among these, glycerine and tetraisopropyl titanate volume ratio are 10:0.8.Hydro-thermal process is carried out later, wherein suspended
Liquid product accounts for the molten product 30% of reaction kettle.It places into reacting furnace and heats, be warming up to 90 DEG C with 3 DEG C/min, keep the temperature 2h, then with 1.5
DEG C/after min is warming up to 175 DEG C, keep the temperature 10h.It is air-cooled after taking-up reaction kettle.Gained solution takes out, centrifugal treating, and by pouring into
Analysis straight alcohol is repeatedly centrifuged colourless to solution.Whole process sealing guarantees without steam.Afterwards by 500 DEG C under protection of argon gas of gained powder
Middle roasting.Time controls in 2h.The graphene oxide that surface has needle-shaped anatase type titanium oxide coating can be obtained.
Later by gained powder and titanium valve, thin iron powder, silicon powder matches in beaker, and a certain amount of glycerine is added, this
Wherein silicon powder control is total powder quality 8%, and titanium valve control is the 4% of total powder quality, and size Control is about 5 μm, graphite oxide
The mass ratio of alkene is 5%, and surplus is iron powder, and size Control is 5 μm.Glycerine is that calculating total volume ratio is 2.5%, handles whole nothing
Steam, and then with ultrasonic treatment 1h.Obtain the mixed-powder of gluing state.Copper sheet is beaten in batches with 1500 ~ 2000# sand paper
Mill, alcohol washes drying.Gained gluing state mixed-powder is uniformly applied to matrix surface, prefabricated thickness control is 0.5mm.Again
With flame gun Quick uniform presintering powder in matrix surface.Material is carried out using laser melting coating in argon gas guard box later
Processing.Its process parameter control are as follows: laser power 1.5Kw, scanning speed 5mm/s, spot diameter are about 3mm.Pass through mill
Damage experiment has dropped nearly 25.9% it is found that the coefficient of friction of coating is compared to matrix in load 300N.
Embodiment 2.
By graphene oxide in the analysis straight alcohol clock pre-dispersed 2h of ultrasound, temperature is room temperature, and whole-process control is without steam.Volume
Than being strict controlled in 0.6:50, after that gained dispersion liquid poured into sealing in the precursor liquid of glycerine and tetraisopropyl titanate composition is super
Sonication 2h.Among these, glycerine and tetraisopropyl titanate volume ratio are 10:1.2.Hydro-thermal process is carried out later, wherein suspended
Liquid product accounts for the molten product 50% of reaction kettle.Place into reacting furnace and heat, be warming up to 120 DEG C with 5 DEG C/min, keep the temperature 1h, then with 3 DEG C/
After min is warming up to 190 DEG C, 15h is kept the temperature.It is air-cooled after taking-up reaction kettle.Gained solution takes out, centrifugal treating, and by pouring into point
Analysis straight alcohol is repeatedly centrifuged colourless to solution.Whole process sealing guarantees without steam.It afterwards will be in gained powder under protection of argon gas 550 DEG C
Roasting.Time controls in 3h.The graphene oxide that surface has needle-shaped anatase type titanium oxide coating can be obtained.
Later by gained powder and titanium valve, thin iron powder, silicon powder matches in beaker, and a certain amount of glycerine is added, this
Wherein silicon powder control is total powder quality 12%, and titanium valve control is the 5.5% of total powder quality, and size Control is about 10 μm, oxidation
The mass ratio of graphene is 7%, and surplus is iron powder, and size Control is 8 μm.Glycerine is that calculating total volume ratio is 4.5%, and processing is complete
Journey then uses ultrasonic treatment 3h without steam.Obtain the mixed-powder of gluing state.In batches with 1500 ~ 2000# sand paper by copper sheet
Polishing, alcohol washes drying.Gained gluing state mixed-powder is uniformly applied to matrix surface, prefabricated thickness control is 0.8mm.
Again with flame gun Quick uniform presintering powder in matrix surface.Later in argon gas guard box using laser melting coating to material into
Row processing.Its process parameter control are as follows: laser power 2Kw, scanning speed 7mm/s, spot diameter are about 5mm.Pass through mill
Damage experiment has dropped nearly 19.2% it is found that the coefficient of friction of coating is compared to matrix in load 300N.
Claims (1)
1. a kind of wear-resisting cladding layer preparation method on copper sheet surface, it is characterized in that the following steps are included:
(1) by graphene oxide in analysis straight alcohol the pre-dispersed 1 ~ 2h of ultrasound, temperature is room temperature, and whole-process control is without steam；Body
Product ratio is strict controlled in 0.3 ~ 0.6: 50；
(2) step (1) pretreated graphene oxide dispersion is poured into the forerunner of glycerine and tetraisopropyl titanate composition
It is sealed in liquid, and is ultrasonically treated 1 ~ 2h again；Wherein, glycerine and tetraisopropyl titanate volume ratio are 10:0.5 ~ 1.5；
(3) forerunner's suspension of step (2) is imported in hydrothermal reaction kettle, wherein suspension volume account for the molten product of reaction kettle 30%~
60%；It places into reacting furnace and heats, be warming up to 80~120 DEG C with 2~6 DEG C/min, keep the temperature 1~2h, then with 1~3 DEG C/min liter
Temperature keeps the temperature 10~15h to after 170 ~ 190 DEG C；It takes out, reaction kettle sealing is air-cooled；
(4) solution obtained by step (3) is taken out, centrifugal treating, and by pour into analysis straight alcohol be repeatedly centrifuged it is colourless to solution,
Revolving speed is controlled in 9000 ~ 16000rpm；Whole process sealing guarantees without steam；
(5) then the mixed-powder vacuum drying that step (4) is obtained roasts in 500 ~ 550 DEG C under protection of argon gas；Time control
System is in 1 ~ 3h；Obtain the graphene oxide that surface has needle-shaped anatase type titanium oxide coating；
(6) powder obtained by step (5) is put into beaker, titanium valve, thin iron powder, fine silica powder is added, and glycerine is added, wherein silicon
Powder control is total powder quality 5 ~ 15%, and titanium valve control is the 3 ~ 5.5% of total powder quality, and size Control is 5 ~ 10 μm, aoxidizes stone
Black alkene is the 5 ~ 7.5% of total powder quality, and surplus is iron powder, and size Control is 5 ~ 8 μm；Glycerine be total volume ratio 2.5 ~
5.0%, processing whole process then uses 1 ~ 3h of ultrasonic treatment without steam；Obtain the mixed-powder of gluing state；
(7) copper sheet 1500 ~ 2000# sand paper is polished, alcohol washes drying；Then gluing state obtained by step (6) will be mixed
Powder is uniformly applied to copper material surface, and prefabricated thickness control is 0.4 ~ 0.8mm；Again with flame gun Quick uniform presintering powder in
Matrix surface；
(8) step (7) resulting materials are put into argon gas guard box, material is handled using laser melting coating；Its technique ginseng
Numerical control is made as: it is 1.2 ~ 2.4kW that laser power, which answers strict control, and scanning speed is 4 ~ 8mm/s, and spot diameter is 2 ~ 5mm；
Hydrothermal reaction kettle liner described in step (3) is polytetrafluoroethylene (PTFE).
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102496700A (en) * | 2011-12-20 | 2012-06-13 | 中国科学院新疆理化技术研究所 | Graphene-titanium dioxide nanotube composite material and preparation method thereof |
| CN106532014A (en) * | 2016-12-26 | 2017-03-22 | 天津大学 | Method for preparing composite material that stannic oxide nano-particles attach to graphene oxide |
| KR20180057323A (en) * | 2016-11-22 | 2018-05-30 | 재단법인 한국탄소융합기술원 | Method of manufacturing metal-loaded TiO2/graphene composites through one-pot hydrothermal synthesis and the TiO2/graphene composites manufactured by the same |
| CN108127123A (en) * | 2018-01-16 | 2018-06-08 | 武汉理工大学 | A kind of composite coating material applied to semimetal iron-based brake block and preparation method thereof |
-
2018
- 2018-09-17 CN CN201811079813.9A patent/CN109338355B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102496700A (en) * | 2011-12-20 | 2012-06-13 | 中国科学院新疆理化技术研究所 | Graphene-titanium dioxide nanotube composite material and preparation method thereof |
| KR20180057323A (en) * | 2016-11-22 | 2018-05-30 | 재단법인 한국탄소융합기술원 | Method of manufacturing metal-loaded TiO2/graphene composites through one-pot hydrothermal synthesis and the TiO2/graphene composites manufactured by the same |
| CN106532014A (en) * | 2016-12-26 | 2017-03-22 | 天津大学 | Method for preparing composite material that stannic oxide nano-particles attach to graphene oxide |
| CN108127123A (en) * | 2018-01-16 | 2018-06-08 | 武汉理工大学 | A kind of composite coating material applied to semimetal iron-based brake block and preparation method thereof |
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