CN103128284B - Reinforced method of carbon nanotubes (CNTs) of laser-induced composite fused deposition gradient content for copper matrix composite materials - Google Patents
Reinforced method of carbon nanotubes (CNTs) of laser-induced composite fused deposition gradient content for copper matrix composite materials Download PDFInfo
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Abstract
The invention discloses a reinforced method of carbon nanotubes (CNTs) of laser-induced composite fused deposition gradient content for copper matrix composite materials. The reinforced method of CNTs of the laser-induced composite fused deposition gradient content for the copper matrix composite materials is characterized by comprising the following steps: screening the CNTs by means of a method of rotating electrophoreses, and obtaining the CNTs of the same diameters and the same lengths; increasing the CNTs obtained by screening in a gradient mode by mass percent, and mixing the CNTs with copper alloy powder to be uniform on a planetary ball mill, conducting chemical nickel-plating processing, and preparing copper matrix composite powder with CNTs diffuse distributed; preparing reinforced copper matrix composite materials of CNTs of the gradient content by means of a method of laser-induced composite fused deposition. The reinforced method of CNTs of the laser-induced composite fused deposition gradient content for the copper matrix composite materials has the advantages that the defects that the CNTs are easy to gather, hard to disperse and hard to sift are overcome due to the fact that the CNTs are obtained by means of the method of rotating electrophoreses; gradient distribution of the content of the CNTs in the copper matrix composite materials can be achieved under the condition of increasing fused cladding efficiency by 5 times - 15 times; the method is a near net shape rapid manufacturing technology, precious materials can be markedly saved, manufacture cost is lowered, and manufacturing cycle is shortened.
Description
Technical field
The invention belongs to Rapid Manufacturing Technology field, particularly a kind of CNTs of laser-inductive composite melt sedimentation gradient content strengthens the method for Cu-base composites.
Background technology
Copper alloy has excellent conduction, heat conduction, corrosion resisting property and good processing characteristics, has a wide range of applications in fields such as leads of IC frame, high ferro contact wire, continuous cast molds.But intensity, high temperature resistance softening temperature and the wearability deficiency of copper alloy, greatly limit its application in industrial circle.As everyone knows, the high-strength and high relation that is conflicting of leading of copper alloy.Therefore, how, under the least possible conduction of reduction copper alloy and the prerequisite of heat conductivility, increasing substantially intensity, hardness, the wear-resisting and corrosion resisting property of copper alloy, is the target that domestic and international researcher unremitting effort is always pursued.
At present, conventionally adopt alloying or Second Phase Particle enhancing method to improve the intensity of copper alloy.According to conductivity theory, the old distortion of point that the atom of solid solution in copper matrix causes to the scattering process of electronics than Second Phase Particle to strong many of electron scattering effect.Therefore, Second Phase Particle strengthens copper alloy can obviously not reduce conduction and the heat conductivility of copper alloy, and can improve room temperature and the high-temperature behavior of copper alloy, becomes a kind of effective ways that improve copper alloy intensity.Especially from Japanese Iijima first with Hrtem Observation to (Iijima S. Helical microtubules of graphitic carbon. Nature since CNT, 1991,354:56-58), CNT goes out the performances such as extraordinary intensity, thermal conductivity, magnetic resistance with its unique structural expression, as the wild phase that has potentiality can form with metal have that intensity is high, modulus is high, high temperature resistant, thermal coefficient of expansion is little can wait by force the metal-base composites of feature with thermal denaturation resistant, has caused researcher's extensive concern
In recent years, the method of preparing CNTs enhancing Cu-base composites mainly contains: and powder metallurgic method (Wang Sen. the preparation of carbon nanotube reinforced copper-base composite material, master thesis, Lanzhou University, 2009, high-energy ball milling-high-temperature sintering process (Cai Xiaolan, Jiang Taiwei, Chen Yaguang, Wang Kaijun. a kind of preparation method of carbon nanotube reinforced copper-base composite material. Chinese invention patent, publication number: CN102628115A), pressure sintering (Chen Haiying. pressure sintering prepares carbon nano tube/copper microstructure of composite and performance shape is studied carefully. master thesis, Harbin Institute of Technology, 2006) etc.Above-mentioned three kinds of methods all exist in preparation process: easily reunion of CNT, skewness, with copper matrix wetability poor and complex process, be difficult to the problem such as carbon nanotube reinforced copper-base composite material of preparation large volume, especially be difficult to the Cu-base composites of preparation content of carbon nanotubes distribution gradient, be difficult to meet the demand of the copper alloy with high strength and high conductivity that industrial circle changes in gradient to performance.
Summary of the invention
The object of the present invention is to provide a kind of CNTs of laser-inductive composite melt sedimentation gradient content to strengthen the method for Cu-base composites.Laser-inductive composite melt deposition technique of the present invention, is that laser-inductive composite melt coating technique and RP technique are combined, a kind of Rapid Manufacturing Technology of manufacturing the fine and close parts of high-performance forming.In addition, the present invention adopts the method for rotation electrophoresis to filter out the identical CNT identical with length of diameter, then increase and mix through ball mill with copper alloy powder respectively in gradient by mass percentage, the copper base composite powder that form good fluidity after chemical nickel plating, be applicable to automatic powder feeding, CNTs disperse distributes, finally carry out multiple tracks multilayer laser-inductive composite meltization deposition, preparation strengthens Cu-base composites along the CNTs of thickness direction content distribution gradient.
The present invention is achieved like this, and its method and step are:
(1) screening of CNT: adopt the method screening of rotation electrophoresis to obtain the CNT of same diameter and equal length, be specially:
1) adopting 30 ~ 70% sulfuric acid of volume ratio 1:1 and the mixed liquor of 40 ~ 80% nitric acid, is that 2 ~ 100nm and length are CNT pickling 3 ~ 10h of 5 ~ 100 μ m to diameter, obtains the CNT of purifying;
2) CNT after purifying is joined to concentration is housed is that 0.5 ~ 2.0g/L and temperature are in the surface modification groove of softex kw solution of 40 ~ 90 DEG C, on ultrasonic disperser, disperse 2 ~ 8h, make the CNT after purifying positively charged after surface modification;
3) top electrode of rotation electrophoretic apparatus connects power cathode, be 5 ~ 10 revs/min of rotations along its central shaft taking speed, its lower surface is provided with the permeable membrane that material is polyamide, bottom electrode connects positive source, in the scope that is 10 ~ 30V at DC voltage, choose the voltage of rotation electrophoretic apparatus and fix, the CNT that diameter is identical and length is identical electrode movement upwards under the effect of electric field force, and be adsorbed on permeable membrane surface;
4) permeable membrane that absorption is had to a CNT from power on lower surface of the utmost point takes out, and being dissolved in volume ratio is completely in the phenol of 1:1 and the mixed solvent of glacial acetic acid, filters with deionized water and washs, vacuum drying 2 ~ 4h;
(2) preparation of the copper base composite powder that CNTs disperse distributes: the CNT that screening is obtained increases and mixes on planetary ball mill with copper alloy powder respectively in gradient by mass percentage, then carry out chemical nickel plating processing, the copper base composite powder that be prepared into good fluidity, be applicable to automatic powder feeding, CNTs disperse distributes;
(3) CNTs of gradient content strengthens the preparation of Cu-base composites: the copper base composite powder that the CNTs disperse of preparation is distributed adopts the method for multiple tracks multilayer laser-inductive composite meltization deposition, the CNTs of preparation gradient content strengthens Cu-base composites, and the laser instrument of use is crossing current CO
2laser instrument, the induction heater using is integration module type high frequency induction heater, and concrete technology parameter is: laser power 1 ~ 10kW, laser scanning speed 1 ~ 8m/min, spot diameter 0.5 ~ 5mm, induction heating power 10 ~ 150kW, powder feeding rate 30 ~ 300g/min, 45 ~ 53 ° of jet angles, overlapping rate 40 ~ 60%.
CNTs of the present invention is 0.05 ~ 20wt% gradient along thickness direction and distributes, and the content of outermost layer CNTs is 20wt%.
The present invention, in the time carrying out described step (1), is provided with rotation electrophoretic apparatus in surface modification groove, the upper and lower electrode of rotation electrophoretic apparatus is that diameter is the circle of 100 ~ 500mm, and bottom electrode is positioned at the bottom of surface modification groove.
The present invention is in the time carrying out described step (2), and the chemical composition of copper alloy powder is: Zr 0.1 ~ 0.35wt%, Al 0.8 ~ 5wt%, Ni 0.1 ~ 0.25wt%, Y 0.01 ~ 0.025wt%, Hf 0.01 ~ 0.035wt%, surplus are Cu.
The present invention is in the time carrying out described step (3), the complete one deck of every deposition, by laser-inductive composite melt processing head along the Z axis distance equating with CAD two-dimensional slice thickness that rises, in automatic powder feeding device, rejoin the copper base composite powder that CNTs disperse distributes simultaneously, wherein CNTs increases by 0.05 ~ 5wt% at the content in composite powder compared with deposition is when last layer, then carry out laser-inductive composite meltization deposition according to the track while scan of lower one deck, after all two-dimensional slice have all been scanned, the CNTs that forms three-dimensional content distribution gradient strengthens Cu-base composites.
Compared with prior art, advantage of the present invention is: (1) CNT used screens acquisition through the method for rotating electrophoresis, has the identical feature identical with length of diameter, has overcome the problem that CNT is easily reunited, difficulty is disperseed and difficulty is screened; (2) the copper base composite powder that CNTs disperse distributes has passed through chemical nickel plating processing, has improved the wettability of its high temperature resistance oxygen performance and CNTs and acid bronze alloy; (3) can improve under the condition of 5 ~ 15 times in cladding efficiency, preparation have concurrently high strength and high rigidity, high abrasion with high anti-corrosion, high conduct electricity and the content of high heat conduction, pore-free and flawless, CNTs along the Cu-base composites of thickness direction distribution gradient; (4) be near-net-shape Rapid Manufacturing Technology, the CNTs for preparing content distribution gradient strengthens Cu-base composites only to be needed a small amount of fine finishining or not to need processing, can significantly save precious materials, reduces manufacturing cost and shorten the manufacturing cycle.
Detailed description of the invention
embodiment 1
Adopt laser-inductive composite meltization deposition, the CNTs of preparation gradient content strengthens copper-based composite material parts, the gradient that wherein CNTs is 0.05 ~ 20wt% along thickness direction distributes, this part is hollow cylinder: internal diameter and external diameter are respectively 80mm and 83mm, be highly 10.2mm, the CAD two-dimensional slice thickness that adopts microtomy to obtain is 1.02mm, in ground floor, the content of CNTs is 2wt%, in later layer, the content of CNTs increases 2wt% than the content of CNTs in front one deck, 10 layers of total codepositions, specific implementation process is as follows:
(1) screening of CNT: adopt the method screening of rotation electrophoresis to obtain the CNT of same diameter and equal length, be specially:
1) adopting 35% sulfuric acid of volume ratio 1:1 and the mixed liquor of 80% nitric acid, is that 2 ~ 100nm and length are the CNT pickling 4h of 5 ~ 100 μ m to diameter, obtains the CNT of purifying;
2) CNT after purifying is joined to concentration is housed is that 0.8g/L and temperature are in the surface modification groove of softex kw solution of 90 DEG C, on ultrasonic disperser, disperse 3h, make the CNT after purification positively charged after surface modification;
3) rotation electrophoretic apparatus is arranged in surface modification groove, the upper and lower electrode of rotation electrophoretic apparatus is that diameter is the circle of 100mm, bottom electrode is positioned at the bottom of surface modification groove, top electrode connects power cathode, be 5 revs/min of rotations along its central shaft taking speed, its lower surface is provided with the permeable membrane that material is polyamide, bottom electrode connects positive source, the voltage of choosing rotation electrophoretic apparatus is 10V, the CNT that diameter is identical and length is identical electrode movement upwards under the effect of electric field force, and be adsorbed on permeable membrane surface;
4) permeable membrane that absorption is had to a CNT from power on lower surface of the utmost point takes out, and being dissolved in volume ratio is completely in the phenol of 1:1 and the mixed solvent of glacial acetic acid, filters with deionized water and washs, vacuum drying 2h;
(2) preparation of the copper base composite powder that CNTs disperse distributes: the CNT that screening is obtained increases and mixes on planetary ball mill with copper alloy powder respectively in gradient by mass percentage, then carry out chemical nickel plating processing, the copper base composite powder that be prepared into good fluidity, be applicable to automatic powder feeding, CNTs disperse distributes, wherein, the chemical composition of copper alloy powder is that Zr 0.15wt%, Al 0.8wt%, Ni 0.15wt%, Y 0.015wt%, Hf 0.015wt%, surplus are Cu;
(3) CNTs of gradient content strengthens the preparation of Cu-base composites: in the process of multiple tracks multilayer laser-inductive composite meltization deposition, the laser instrument of use is crossing current CO
2laser instrument, the induction heater using is integration module type high frequency induction heater, and concrete technology parameter is: laser power 5kW, laser scanning speed 3m/min, spot diameter 1.5mm, induction heating power 60kW, powder feeding rate 120g/min, 45 ° of jet angles, overlapping rate 40%; In addition, the complete one deck of every deposition, by laser-inductive composite melt processing head along the Z axis 1.02mm that rises, in automatic powder feeding device, rejoin the copper base composite powder that CNTs disperse distributes simultaneously, wherein CNTs increases 2wt% at the content in composite powder compared with deposition is when last layer, then carry out laser-inductive composite meltization deposition according to the track while scan of lower one deck, after all two-dimensional slice have all been scanned, the CNTs that forms three-dimensional content distribution gradient strengthens Cu-base composites.
embodiment 2
Adopt laser-inductive composite meltization deposition, the CNTs of preparation gradient content strengthens copper-based composite material parts, the gradient that wherein CNTs is 0.05 ~ 20wt% along thickness direction distributes, this part is hollow cylinder: internal diameter and external diameter are respectively 120mm and 125mm, be highly 50.49mm, the CAD two-dimensional slice thickness that adopts microtomy to obtain is 0.99mm, in ground floor, the content of CNTs is 2wt%, in later layer, the content of CNTs increases 0.36wt% than the content of CNTs in front one deck, 51 layers of total codepositions, specific implementation process is as follows:
(1) screening of CNT: adopt the method screening of rotation electrophoresis to obtain the CNT of same diameter and equal length, be specially:
1) adopting 50% sulfuric acid of volume ratio 1:1 and the mixed liquor of 60% nitric acid, is that 2 ~ 100nm and length are the CNT pickling 6h of 5 ~ 100 μ m to diameter, obtains the CNT of purifying;
2) CNT after purifying is joined to concentration is housed is that 1.5g/L and temperature are in the surface modification groove of softex kw solution of 70 DEG C, on ultrasonic disperser, disperse 6h, make the CNT after purification positively charged after surface modification;
3) rotation electrophoretic apparatus is arranged in surface modification groove, the upper and lower electrode of rotation electrophoretic apparatus is that diameter is the circle of 300mm, bottom electrode is positioned at the bottom of surface modification groove, top electrode connects power cathode, be 7 revs/min of rotations along its central shaft taking speed, its lower surface is provided with the permeable membrane that material is polyamide, bottom electrode connects positive source, choose the voltage 20V of rotation electrophoretic apparatus, the CNT that diameter is identical and length is identical electrode movement upwards under the effect of electric field force, and be adsorbed on permeable membrane surface;
4) permeable membrane that absorption is had to a CNT from power on lower surface of the utmost point takes out, and being dissolved in volume ratio is completely in the phenol of 1:1 and the mixed solvent of glacial acetic acid, filters with deionized water and washs, vacuum drying 3h;
(2) preparation of the copper base composite powder that CNTs disperse distributes: the CNT that screening is obtained increases and mixes on planetary ball mill with copper alloy powder respectively in gradient by mass percentage, then carry out chemical nickel plating processing, the copper base composite powder that be prepared into good fluidity, be applicable to automatic powder feeding, CNTs disperse distributes, wherein, the chemical composition of copper alloy powder is that Zr 0.25wt%, Al 2.5wt%, Ni 0.2wt%, Y 0.02wt%, Hf 0.025wt%, surplus are Cu;
(3) CNTs of gradient content strengthens the preparation of Cu-base composites: in the process of multiple tracks multilayer laser-inductive composite meltization deposition, the laser instrument of use is crossing current CO
2laser instrument, the induction heater using is integration module type high frequency induction heater, and concrete technology parameter is: laser power 7kW, laser scanning speed 5m/min, spot diameter 2.5mm, induction heating power 100kW, powder feeding rate 200g/min, 50 ° of jet angles, overlapping rate 50%; In addition, the complete one deck of every deposition, by laser-inductive composite melt processing head along Z axis rising 0.99mm mm, in automatic powder feeding device, rejoin the copper base composite powder that CNTs disperse distributes simultaneously, wherein CNTs increases 0.36wt% at the content in composite powder compared with deposition is when last layer, then carry out laser-inductive composite meltization deposition according to the track while scan of lower one deck, after all two-dimensional slice have all been scanned, the CNTs that forms three-dimensional content distribution gradient strengthens Cu-base composites.
embodiment 3
Adopt laser-inductive composite meltization deposition, the CNTs of preparation gradient content strengthens copper-based composite material parts, the gradient that wherein CNTs is 0.05 ~ 20wt% along thickness direction distributes, this part is hollow cylinder: internal diameter and external diameter are respectively 300mm and 310mm, be highly 102.01mm, the CAD two-dimensional slice thickness that adopts microtomy to obtain is 1.01mm, in ground floor, the content of CNTs is 1.0wt%, in later layer, the content of CNTs increases 0.19wt% than the content of CNTs in front one deck, 101 layers of total codepositions, specific implementation process is as follows:
(1) screening of CNT: adopt the method screening of rotation electrophoresis to obtain the CNT of same diameter and equal length, be specially:
1) adopting 65% sulfuric acid of volume ratio 1:1 and the mixed liquor of 40% nitric acid, is that 2 ~ 100nm and length are the CNT pickling 8h of 5 ~ 100 μ m to diameter, obtains the CNT of purifying;
2) CNT after purifying is joined to concentration is housed is that 2.0g/L and temperature are in the surface modification groove of softex kw solution of 50 DEG C, on ultrasonic disperser, disperse 8h, make the CNT after purification positively charged after surface modification;
3) rotation electrophoretic apparatus is arranged in surface modification groove, the upper and lower electrode of rotation electrophoretic apparatus is that diameter is the circle of 500mm, bottom electrode is positioned at the bottom of surface modification groove, top electrode connects power cathode, be 9 revs/min of rotations along its central shaft taking speed, its lower surface is provided with the permeable membrane that material is polyamide, bottom electrode connects positive source, choose the voltage 30V of rotation electrophoretic apparatus, the CNT that diameter is identical and length is identical electrode movement upwards under the effect of electric field force, and be adsorbed on permeable membrane surface;
4) permeable membrane that absorption is had to a CNT from power on lower surface of the utmost point takes out, and being dissolved in volume ratio is completely in the phenol of 1:1 and the mixed solvent of glacial acetic acid, filters with deionized water and washs, vacuum drying 4h;
(2) preparation of the copper base composite powder that CNTs disperse distributes: the CNT that screening is obtained increases and mixes on planetary ball mill with copper alloy powder respectively in gradient by mass percentage, then carry out chemical nickel plating processing, the copper base composite powder that be prepared into good fluidity, be applicable to automatic powder feeding, CNTs disperse distributes, wherein, the chemical composition of copper alloy powder is that Zr 0.35wt%, Al 4.5wt%, Ni 0.25wt%, Y 0.025wt%, Hf 0.03wt%, surplus are Cu;
(3) CNTs of gradient content strengthens the preparation of Cu-base composites: in the process of multiple tracks multilayer laser-inductive composite meltization deposition, the laser instrument of use is crossing current CO
2laser instrument, the induction heater using is integration module type high frequency induction heater, and concrete technology parameter is: laser power 10kW, laser scanning speed 5m/min, spot diameter 5mm, induction heating power 150kW, powder feeding rate 300g/min, 53 ° of jet angles, overlapping rate 60%; In addition, the complete one deck of every deposition, by laser-inductive composite melt processing head along Z axis rising 1.01mm mm, in automatic powder feeding device, rejoin the copper base composite powder that CNTs disperse distributes simultaneously, wherein CNTs increases 0.19wt% at the content in composite powder compared with deposition is when last layer, then carry out laser-inductive composite meltization deposition according to the track while scan of lower one deck, after all two-dimensional slice have all been scanned, the CNTs that forms three-dimensional content distribution gradient strengthens Cu-base composites.
Claims (5)
1. the CNTs of laser-inductive composite melt sedimentation gradient content strengthens a method for Cu-base composites, and its method step is:
(1) screening of CNT: adopt the method screening of rotation electrophoresis to obtain the CNT of same diameter and equal length, be specially:
1) adopting 30 ~ 70% sulfuric acid of volume ratio 1:1 and the mixed liquor of 40 ~ 80% nitric acid, is that 2 ~ 100nm and length are CNT pickling 3 ~ 10h of 5 ~ 100 μ m to diameter, obtains the CNT of purifying;
2) CNT after purifying is joined to concentration is housed is that 0.5 ~ 2.0g/L and temperature are in the surface modification groove of softex kw solution of 40 ~ 90 DEG C, on ultrasonic disperser, disperse 2 ~ 8h, make the CNT after purifying positively charged after surface modification;
3) top electrode of rotation electrophoretic apparatus connects power cathode, be 5 ~ 10 revs/min of rotations along its central shaft taking speed, its lower surface is provided with the permeable membrane that material is polyamide, bottom electrode connects positive source, in the scope that is 10 ~ 30V at DC voltage, choose the voltage of rotation electrophoretic apparatus and fix, the CNT that diameter is identical and length is identical electrode movement upwards under the effect of electric field force, and be adsorbed on permeable membrane surface;
4) permeable membrane that absorption is had to a CNT from power on lower surface of the utmost point takes out, and being dissolved in volume ratio is completely in the phenol of 1:1 and the mixed solvent of glacial acetic acid, filters with deionized water and washs, vacuum drying 2 ~ 4h;
(2) preparation of the copper base composite powder that CNTs disperse distributes: the CNT that screening is obtained increases and mixes on planetary ball mill with copper alloy powder respectively in gradient by mass percentage, then carry out chemical nickel plating processing, the copper base composite powder that be prepared into good fluidity, be applicable to automatic powder feeding, CNTs disperse distributes;
(3) CNTs of gradient content strengthens the preparation of Cu-base composites: the copper base composite powder that the CNTs disperse of preparation is distributed adopts the method for multiple tracks multilayer laser-inductive composite meltization deposition, the CNTs disperse of preparation gradient content strengthens Cu-base composites, and the laser instrument of use is crossing current CO
2laser instrument, the induction heater using is integration module type high frequency induction heater, and concrete technology parameter is: laser power 1 ~ 10kW, laser scanning speed 1 ~ 8m/min, spot diameter 0.5 ~ 5mm, induction heating power 10 ~ 150kW, powder feeding rate 30 ~ 300g/min, 45 ~ 53 ° of jet angles, overlapping rate 40 ~ 60%.
2. the CNTs of laser-inductive composite melt sedimentation gradient content according to claim 1 strengthens the method for Cu-base composites, it is characterized in that CNTs is 0.05 ~ 20wt% gradient along thickness direction and distributes, and the content of outermost layer CNTs is 20wt%.
3. the CNTs of laser-inductive composite melt sedimentation gradient content according to claim 1 strengthens the method for Cu-base composites, while it is characterized in that carrying out described step (1), rotation electrophoretic apparatus is installed in surface modification groove, the upper and lower electrode of rotation electrophoretic apparatus is that diameter is the circle of 100 ~ 500mm, and bottom electrode is positioned at the bottom of surface modification groove.
4. the CNTs of laser-inductive composite melt sedimentation gradient content according to claim 1 strengthens the method for Cu-base composites, while it is characterized in that carrying out described step (2), the chemical composition of copper alloy powder is: Zr 0.1 ~ 0.35wt%, Al 0.8 ~ 5wt%, Ni 0.1 ~ 0.25wt%, Y 0.01 ~ 0.025wt%, Hf 0.01 ~ 0.035wt%, surplus are Cu.
5. the CNTs of laser-inductive composite melt sedimentation gradient content according to claim 1 strengthens the method for Cu-base composites, while it is characterized in that carrying out described step (3), the complete one deck of every deposition, by laser-inductive composite melt processing head along the Z axis distance equating with CAD two-dimensional slice thickness that rises, in automatic powder feeding device, rejoin the copper base composite powder that CNTs disperse distributes simultaneously, wherein CNTs increases by 0.05 ~ 5wt% at the content in composite powder compared with deposition is when last layer, then carry out laser-inductive composite meltization deposition according to the track while scan of lower one deck, after all two-dimensional slice have all been scanned, the CNTs that forms three-dimensional content distribution gradient strengthens Cu-base composites.
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| CN104084583B (en) * | 2014-07-28 | 2016-06-15 | 中国科学院重庆绿色智能技术研究院 | The laser preparing apparatus of a kind of Metal Substrate carbon nano-composite material and method |
| CN106702375B (en) * | 2016-12-05 | 2019-01-01 | 天津工业大学 | A kind of device of laser-inductive composite melt deposit fiber enhancing metal-base composites |
| CN107454815B (en) * | 2017-06-09 | 2020-05-22 | 安徽理工大学 | Cu2O/MWCNTs composite material, preparation method and electromagnetic wave absorption application |
| CN107224973B (en) * | 2017-06-09 | 2020-07-21 | 安徽理工大学 | Cu2O/MWCNTs composite material, preparation method and catalytic application |
| CN107649682A (en) * | 2017-09-04 | 2018-02-02 | 西安交通大学 | The method of ultrasonic impact and sensing heating refining laser increasing material manufacturing titanium alloy crystal grain |
| CN111378964A (en) * | 2020-04-20 | 2020-07-07 | 浙江工业大学 | Method for preparing carbon nanotube reinforced coating by supersonic laser deposition |
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