CN109136913B - A method of improving titanium base material surface property - Google Patents
A method of improving titanium base material surface property Download PDFInfo
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- CN109136913B CN109136913B CN201811079812.4A CN201811079812A CN109136913B CN 109136913 B CN109136913 B CN 109136913B CN 201811079812 A CN201811079812 A CN 201811079812A CN 109136913 B CN109136913 B CN 109136913B
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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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
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Abstract
A method of titanium base material surface property is improved, in water-less environment, adsorbs Ti ion using hydro-thermal high pressure, and in the case where GO carries functional group's effect, and obtain GO@TiO in after baking2(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.Titanium plate 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.Material is handled using laser melting coating in atmosphere afterwards.Cladding material is obtained under the effect of correct technological parameter.Titanium plate surface cladding material friction coefficient of the present invention is smaller and has had both the features such as surface hardness is high, meanwhile, which has 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.
Enhance the intensity of titanium base material and grinding for other mechanical properties using carbon material such as carbon nanotube or graphene
Study carefully and carrying out always, and achieves a degree of progress.A large number of studies show that the correct selection of reinforced phase can be improved directly again
The wear-resisting property and hardness of condensation material.And graphene oxide (GO) is due to the essential attribute of its carbon material, natural succession its from
Lubrication and preferable thermal diffusivity etc. are different from the speciality of other reinforcing materials, and correct use can efficiently reduce material surface
Abrasion and increase the hardness of material.Material will be made to have using graphene as the overlay coating of metal material preferable wear-resisting
Property.
The defect of right graphene oxide or graphene is also more obvious.Graphene oxide is showed similar to the structure of CNT
Very poor wetability out, this directly result in it is not strong with metallic matrix interfacial bonding property, be unfavorable for composite material or surface plating
The preparation of layer.Thus, improve the wetability of itself and matrix and correct process is selected to become using graphene enhancing metal
The wear-resisting key of based composites.
On the other hand, high-energy ultrasonic dispersion may make melt to generate acoustic pressure as a kind of novel Dispersion of Reinforcement technology
Gradient simultaneously leads to instantaneous high pressure and microjet in melt, is effectively facilitated the dispersion of reinforced phase.Simultaneously as caused by ultrasound
Local temperature increases and molecular motion accelerated energy reduces the viscosity and surface tension of reinforced phase, it is thus possible to mention to a certain extent
The wetability of high melt and reinforced phase.
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 carboxylated graphene
Surface obtains graininess coating, but expensive, and commonly uses toxic reagent, not environmentally and high production cost, is not suitable for big rule
Mould 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, in conclusion still lacking a kind of preparation of cost-effective graphene coating titanium composite material at present
Technology.
Summary of the invention
The object of the present invention is to provide a kind of new titanium base material coating technologies.It is super by laser melting coating and high energy
Pre-made powder is sintered in titanium plate surface under the synergistic effect of sound, with the work of the corrosion resistance or the hardness that improve basis material etc.
Process.This method cladding layer controllability is high, customization is stronger, and using new method and proportion addition graphene oxide in matrix
Surface, at low cost, low failure rate.Graphene oxide has graphene oxide and protects to a certain degree since there is TiO2 coating on surface.
Meanwhile under high temperature, silicon phase (Si) and graphene oxide generate micro SiC in situ, and since it is generated to be internal, thus interface is clean
Net binding performance is preferable.In addition, can increase pool depth to a certain extent due to the effect of high-energy ultrasonic, improve reinforced phase
Dispersibility simultaneously improves wetting.
The present invention is achieved by the following technical solutions.
A kind of method improving titanium base material surface property 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 0.5~0.8:50.
(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 0.5~1.5h again.Among these, 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
25%~60%.It places into reacting furnace and heats, be warming up to 60~120 DEG C with 2~4 DEG C/min, keep the temperature 1~2h, then with 2~3
DEG C/after min is warming up to 165~170 DEG C, keep the temperature 10~15h；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 400~450 DEG C
Roasting, time control 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 4~9%, and titanium valve control is the 5~7% of total powder quality, and size Control is 5~10 μm,
The mass ratio of graphene oxide is 5~7.5%, and surplus is iron powder, and size Control is 4~8 μm.Glycerine is the 3 of total volume ratio
~6%, this is crucial for stomata control, and processing is whole without steam, and then with 1~3h of ultrasonic treatment.Obtain the mixing of gluing state
Powder.
(7) titanium plate 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 titanium surface, and prefabricated thickness control is 0.6~1.0mm.It is pre-sintered again with flame gun Quick uniform
Powder is in matrix surface.
(8) titanium plate material obtained by step (7) is put into argon gas guard box, titanium plate is fixed on the titanium that high-energy ultrasonic is arranged at bottom
It is fixed on sheet alloy and with fixture.
(9) laser melting and coating technique is recycled to handle material.Its process parameter control are as follows: laser power should be controlled strictly
It is made as 1.2~2.0Kw, scanning speed is 4~8mm/s, and spot diameter is 4~7mm.In cladding process, high-energy ultrasonic cooperate with into
Row, power are controllably the interruption ultrasound of 0.3~1.4Kw.
Hydrothermal reaction kettle liner described in step (3) of the present invention is polytetrafluoroethylene (PTFE).
The present invention has following uniqueness: (1) solution is using ethyl alcohol rather than water, participation reaction itself simultaneously increase volatilization
Property, pressure is bigger, beneficial to the surface tension for reducing solution.(2) in alcohol thermal response, prolonged low-temperature reduction can have the method
Effect abatement graphene oxide Guan Nengtuan extra after adsorbing metal ions.(3) this method is simple and effective is suitable for batch production.
(4) method introduces high-energy ultrasonic, can further improve the dispersion and wetability of graphene oxide.
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 0.5:50, 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 10:0.6.Hydro-thermal process is carried out later, wherein suspended
Liquid product accounts for the molten product 30% of reaction kettle.Place into reacting furnace and heat, be warming up to 80 DEG C with 2 DEG C/min, keep the temperature 2h, then with 2 DEG C/
After min is warming up to 165 DEG C, 10h 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 400 DEG C
Roasting.Time controls in 2h.The graphene oxide that surface has needle-shaped anatase type titanium oxide coating can be obtained.Gained powder is put
Enter in beaker and be added a certain amount of titanium valve, thin iron powder, fine silica powder, and a certain amount of glycerine is added, silicon powder controls among these
For total powder quality 5%, titanium valve control is the 5% of total powder quality, and size Control is 7 μm, and the mass ratio of graphene oxide is
6%, surplus is iron powder, and size Control is 6 μm.Glycerine is that calculating total volume ratio is 4%, this is crucial for stomata control, processing
Whole process then uses ultrasonic treatment 2h without steam.Obtain the mixed-powder of gluing state.
Titanium plate is polished in batches with 1500~2000 model sand paper, alcohol washes drying.Gained gluing state mixed powder
Last to be uniformly applied to matrix surface, prefabricated thickness control is 0.6mm.Again with flame gun Quick uniform presintering powder in matrix table
Face.Material is handled using laser melting coating and high-energy ultrasonic in argon gas guard box later.Its process parameter control are as follows:
Laser power is 0.9Kw, and scanning speed 5mm/s, spot diameter is about 5mm.High-energy ultrasonic power 1.5Kw, is ground by data
Damage experiment has dropped nearly 20.1% it is found that the coefficient of friction of coating is compared to matrix in load 200N.
Embodiment 2.
By graphene oxide in the analysis straight alcohol clock pre-dispersed 3h of ultrasound, temperature is room temperature, and whole-process control is without steam.Volume
Than being strict controlled in 0.7:50, 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 10:1.0.Hydro-thermal process is carried out later, wherein suspended
Liquid product accounts for the molten product 50% of reaction kettle.It places into reacting furnace and heats, be warming up to 100 DEG C with 4 DEG C/min, keep the temperature 1h, then with 3
DEG C/after min is warming up to 170 DEG C, keep the temperature 12h.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 450 DEG C under protection of argon gas of gained powder
Middle roasting.Time controls in 1h.The graphene oxide that surface has needle-shaped anatase type titanium oxide coating can be obtained.Gained powder is put
Enter in beaker and be added a certain amount of titanium valve, thin iron powder, fine silica powder, and a certain amount of glycerine is added, silicon powder controls among these
For total powder quality 8%, titanium valve control is the 7% of total powder quality, and size Control is 5 μm, and the mass ratio of graphene oxide is
7.5%, surplus is iron powder, and size Control is 8 μm.Glycerine is that calculating total volume ratio is 6%, this is crucial for stomata control, place
Reason whole process then uses ultrasonic treatment 3h without steam.Obtain the mixed-powder of gluing state.
Titanium plate is polished in batches with 1500~2000 model sand paper, alcohol washes drying.Gained gluing state mixed powder
Last to be uniformly applied to matrix surface, prefabricated thickness control is 0.9mm.Again with flame gun Quick uniform presintering powder in matrix table
Face.Material is handled using laser melting coating and high-energy ultrasonic in argon gas guard box later.Its process parameter control are as follows:
Laser power is 1.8Kw, and scanning speed 8mm/s, spot diameter is about 7mm.High-energy ultrasonic power 0.6Kw, is ground by data
Damage experiment has dropped nearly 18% it is found that the coefficient of friction of coating is compared to matrix in load 200N.It is compared to
Ultrasound is not imported, and hardness is greater than 15.4%.
Claims (1)
1. a kind of method for improving titanium base material surface property, 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 0.5~0.8:50；
(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 0.5~1.5h again；Wherein, glycerine and tetraisopropyl titanate volume ratio be 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 25%~
60%；It places into reacting furnace and heats, be warming up to 60~120 DEG C with 2~4 DEG C/min, keep the temperature 1~2h, then with 2~3 DEG C/min
After being warming up to 165~170 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 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 400~450 DEG C, the time under protection of argon gas
Control is 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, wherein
Silicon powder control is the 4~9% of total powder quality, and titanium valve control is the 5~7% of total powder quality, and size Control is 5~10 μm,
Graphene oxide is the 5~7.5% of powder quality, and surplus is iron powder, and size Control is 4~8 μm；Glycerine is total volume ratio
3~6%, processing whole process then uses 1~3h of ultrasonic treatment without steam；Obtain the mixed-powder of gluing state；
(7) titanium plate 1500~2000# sand paper is polished, alcohol washes drying；Then gluing state obtained by step (6) will be mixed
Powder is uniformly applied to titanium surface, and prefabricated thickness control is 0.6~1.0mm；Flame gun Quick uniform presintering powder is used again
In matrix surface；
(8) titanium plate material obtained by step (7) is put into argon gas guard box, titanium plate is fixed on the titanium alloy that high-energy ultrasonic is arranged at bottom
It is fixed on plate and with fixture；
(9) laser melting and coating technique is recycled to handle material；Its process parameter control are as follows: laser power is 1.2~2.0kW
, scanning speed is 4~8mm/s, and spot diameter is 4~7mm；In cladding process, high-energy ultrasonic collaboration is carried out, and power control is
The interruption ultrasound of 0.3~1.4kW；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 CN201811079812.4A patent/CN109136913B/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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