CN102219499A - Method for improving electrical property of zinc-oxide-based low voltage varister ceramic film - Google Patents
Method for improving electrical property of zinc-oxide-based low voltage varister ceramic film Download PDFInfo
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Abstract
The invention relates to varistor ceramics, and specifically relates to a method for improving the electrical property of a zinc-oxide-based low voltage varister ceramic film. The method is characterized in that: an aluminum foil, which is used as an absorption layer, is attached to the surface of a zinc-oxide-based low voltage varister ceramic film sample; a confinement medium is painted, stuck or covered on the aluminum foil; the ceramic film sample is then embedded on a mold; and laser impact is applied to the ceramic film sample, such that the electrical property of the zinc-oxide-based low voltage varister ceramic film is improved. According to the present invention, a laser impact treatment technology is employed in the surface treatment upon the zinc-oxide-based low voltage varister ceramic film. With the liquid confinement medium, non-linear coefficient of the zinc-oxide-based ceramic film is raised by 24% or above comparing to that before the laser impact treatment, varister voltage of the zinc-oxide-based ceramic film is reduced by 30% or above comparing to that before the laser impact treatment, and leakage current density of the zinc-oxide-based ceramic film is reduced by 35% or above comparing to that before the laser impact treatment. The advantage of the method is that: non-linear coefficient of the film is improved while the leakage current density of the film is reduced.
Description
Technical field
The present invention relates to voltage-sensitive ceramic, specifically a kind of method that improves Zinc oxide-base low voltage varistor ceramics thin-film electro performance.
Background technology
Laser shock processing (Laser Shock Processing is called for short LSP) is with high power density (10
9W/cm
2), short pulse (ns level) laser irradiation material, gasify rapidly in the additional coating of material surface and to form the plasma expansion blast and produce high-pressure shocking wave, make material generation microtexture or change in physical, thereby change a kind of novel surface treatment technology of material property.
At present laser shock processing is applied to the surface Hardening Treatment of metallic substance, as fields such as the industrial steel of various models, non-ferrous metal alloys, mainly improves material hardness, and is anticorrosive, mechanical propertys such as wear resistance and fatigue lifetime; Simultaneously also there are many scholars carry out the investigation of materials that laser-impact is handled various stupaliths, as improve stupalith hardness and compactness, and the phase transformation of material structure, mainly concentrate on aspects such as the machinery that improves material and mechanical property, relate to but also rarely have for the research of various lots of electricity stupalith.
Have good non-ohmic behavior as ZnO varistor, leakage current is little, and discharge capacity is big, time of response is fast, advantage such as cheap is the desirable device that is used to suppress instantaneous pressure, absorbs the surge electric energy, can be widely used in all kinds of power equipments and the electronic system; In recent years, along with electronic product develops to microminiaturization, slimming, direction integrated and multifunction, require piezoresistor low pressureization, the main method for preparing the ZnO low-voltage piezoresistor at present has: by the wafer-type low-voltage piezoresistor of control ZnO grain growing; Adopt the multi-layer stacks formula low-voltage piezoresistor of slice component technology of preparing; Adopt the ZnO low-voltage piezoresistor of film preparing technology; ZnO ceramic membrane thickness is minimum, can between the hundreds of nanometer is to several microns, regulate, therefore be lower than at the preparation pressure sensitive voltage and have very good potentiality and advantage aspect the small power voltage dependent resistor of 5V, when the thickness of zinc oxide-based ceramic film reduces, pressure sensitive voltage has reduced, but, nonlinear factor also decreases, when research ZnO low voltage varistor ceramics, for when reducing pressure sensitive voltage, obtain high nonlinear factor, the investigator has carried out number of research projects from optimizing material constituent element and aspects such as design of components and preparation treatment process, also obtain many scientific payoffss, but effect is desirable not to the utmost.
Therefore, explore a kind of pressure sensitive voltage that can effectively reduce the ZnO low voltage varistor ceramics, can effectively improve the succinct treatment process of its nonlinear factor again, become and comprehensively to improve ZnO low voltage varistor ceramics electrical property and make it obtain the gordian technique of wide range of industrial applications.
Summary of the invention
The purpose of this invention is to provide a kind of method that improves Zinc oxide-base low voltage varistor ceramics thin-film electro performance.
To achieve these goals, technical scheme of the present invention is:
A kind of method that improves Zinc oxide-base low voltage varistor ceramics thin-film electro performance, it is characterized in that: on Zinc oxide-base low voltage varistor ceramics film sample surface, stick aluminium foil as absorption layer, after on aluminium foil surface, coating, paste or cover restraint layer the ceramic membrane sample is embedded on the mould, the ceramic membrane sample is carried out laser-impact, to improve the electrical property of Zinc oxide-base low voltage varistor ceramics film.
Described aluminum foil thickness is 0.1～0.3mm.
Described restraint layer thickness is 0.3～1.0mm.
Described laser spot size is 6mm, and wavelength is 1064nm, and pulse width is 10～22ns, and pulse energy is 3～10J.
In order to obtain better technique effect, promptly nonlinear factor is high simultaneously more more than impacting prerequisite; Pressure sensitive voltage is more than reducing before impacting; Leakage current density is more than reducing before impacting, and restraint layer adopts following method preparation:
1) alkaline process: in reactor, add dimethyl annular siloxane, chain termination agent hexamethyldisiloxane or trimethyl silicon based end capped dimethyl siloxane oligomer and catalyzer Tetramethylammonium hydroxide, the add-on of chain termination agent is 2.0 ~ 8.0% of a dimethyl annular siloxane quality, the add-on of catalyzer is 0.01 ~ 0.03% of a reactant total mass, under 80～90 ℃/60 mmhg, carry out telomerization, after reaction finishes, remove vacuum, be warming up to 150～200 ℃, destroy catalyzer and remove low-boiling-point substance, after the cooling, promptly get the liquid restraint layer.
2) acid system: the low-boiling-point substance, hexamethyldisiloxane and the concentration that add silicone oil or silicon rubber in reactor are 98% sulfuric acid, the add-on of hexamethyldisiloxane be silicone oil or silicon rubber the low-boiling-point substance quality 1.3 ~ 3.5%, concentration is that 98% sulfuric acid is 2 ~ 5% of reactant total mass, under agitation carry out telomerization in 50～60 ℃, after reaction finishes, put the disacidify water layer, oil-reservoir water is washed till neutrality, steam down in 150～200 ℃/10 mmhg then and remove low-boiling-point substance, the cooling back uses activated carbon decolorizing, decompress filter to get the liquid restraint layer.
The preferred dimethyl siloxane oligopolymer of the low-boiling-point substance of described silicone oil or silicon rubber, 200 ℃ of boiling points.
The above-mentioned liquid constrained layer material for preparing has following character:
1) constrained layer material is a colourless liquid;
2) can be by the laser of 1.06 mum wavelengths, transmittance is greater than water;
3) under the room temperature, viscosity is 500 CP;
4) under the room temperature, specific refractory power is 1400nd;
5) flash-point is greater than 300 ℃.
Using method of the present invention is:
On Zinc oxide-base low voltage varistor ceramics film sample surface, stick aluminium foil as absorption layer, utilize the viscosity of liquid constrained layer material then and from the levelling ability, this liquid constrained layer material is poured over the surface of coating, treat that it is behind levelling, it can form fluid film at workpiece surface, just can carry out shock peening to Zinc oxide-base low voltage varistor ceramics film sample surface with laser then and handle.
Or on Zinc oxide-base low voltage varistor ceramics film sample surface, stick aluminium foil as absorption layer, utilize spray gun that the liquid constrained layer material is painted on workpiece surface to be impacted, can form fluid film at workpiece surface, just can carry out shock peening to workpiece surface then and handle with laser.
The present invention carries out surface treatment by adopting laser shock processing to the zinc oxide-based ceramic film, the zinc oxide-based ceramic film that adopts above-mentioned liquid restraint layer to obtain, and its nonlinear factor is than having impacted the prerequisite height more than 24%; Pressure sensitive voltage has reduced more than 30% before impacting; Leakage current density has reduced more than 35% before impacting, and advantage of the present invention is when reducing the film pressure sensitive voltage, has improved the nonlinear factor of film.
Embodiment
EXAMPLE l
1) utilize the conventional sintering legal system to be equipped with the zinc oxide-based ceramic target: to prepare burden ZnO96.3%, Bi according to following molar percentage component
2O
30.9%, Sb
2O
31.0%, Co
2O
30.8%, Cr
2O
30.5%, MnO
20.5%; Adopt agate ball, stainless cylinder of steel, dehydrated alcohol is a ball-milling medium, agate ball: the batching powder: the mass ratio of dehydrated alcohol is 2.5:1:1, and wet-milling 5h in planetary high-energy ball mill, rotating speed are 300rpm; The slurry that ball milling is good becomes dry powder at 70 ℃ of insulation 24 h; After adding massfraction in the dry powder and be 2% the PVA aqueous solution,, make powder become base with the compacting of 70MPa pressure; Base substrate is put into the Si-Mo rod high-temperature electric resistance furnace, speed with 5 ℃/min rises to 500 ℃ from room temperature earlier, be incubated 120min in the air atmosphere, the back rises to 950 ℃ of sintering temperatures with the speed of 5 ℃/min, be incubated 120min in the air atmosphere, cool to room temperature with the furnace, promptly get the sputtering target material of φ 50 mm * 3mm.
2) utilize magnetron sputtering method to prepare Zinc oxide-base low voltage varistor ceramics thin-film material: substrate material is selected the Si(111 of single-sided polishing for use) substrate, its cleaning step is as follows: substrate is put into deionized water, ultrasonic cleaning 5～10min, twice; Ultrasonic cleaning 5～10min in acetone, twice; Ultrasonic cleaning 5～10min in dehydrated alcohol, twice; The substrate that cleans up is put into the beaker that fills dehydrated alcohol, and good seal is stand-by; Cleaned substrate is put into metal spraying equipment, vacuumize back spraying 5～10min, the preparation bottom electrode, it is rf magnetron sputtering that the sputter mode is adopted in experiment, sputtering target material is of a size of φ 50 mm * 3mm, sputter gas is high purity argon (Ar purity is 99.999%), and argon flow amount is 30sccm, and coating chamber base vacuum degree reaches 10
-5Pa, operating air pressure are 3.0Pa, and target-Ji spacing is 90mm, with Si(111) spraying of substrate faces up and is clamped on the pallet as substrate, and Si(111) substrate diameter is 6mm, and substrate does not heat, sputtering time is 1.5h, sputtering power 250W, and annealing temperature is 840 ℃, annealing time is 1h, film after the annealing is partly covered with aluminium foil, put into metal spraying equipment, vacuumize back spraying 5～10min, the preparation upper current conducting cap, the metal spraying area of upper current conducting cap is about 10mm
2, through performance test, nonlinear factor is 17.12, and pressure sensitive voltage is 3.87V, and leakage current density is 0.53 μ A/mm
2
3) the thick aluminium foil of 0.3mm is sticked as absorption layer in the film sample surface for preparing, aluminium foil surface is coated the liquid restraint layer of alkaline process preparation, thickness is about 0.5mm, afterwards film sample is embedded on the mould, film is carried out laser-impact, parameter is as follows: spot size is 6mm, wavelength is 1064nm, pulse width is 18ns, and pulse energy is 10J, at last aluminium foil is taken off; Through performance test, nonlinear factor increases to 21.26, and velocity of variation is 24.18%; Pressure sensitive voltage reduces to 2.35V, and velocity of variation is 39.28%; Leakage current density reduces to 0.25 μ A/mm
2, velocity of variation is 52.83%.
Embodiment 2
1) utilize the conventional sintering legal system to be equipped with the zinc oxide-based ceramic target: to prepare burden ZnO96.5%, Bi according to following molar percentage component
2O
30.7%, Sb
2O
31.0%, Co
2O
30.8%, Cr
2O
30.5%, MnO
20.5%; Adopt agate ball, stainless cylinder of steel, dehydrated alcohol is a ball-milling medium, agate ball: the batching powder: the mass ratio of dehydrated alcohol is 2.5:1:1, and wet-milling 6h in planetary high-energy ball mill, rotating speed are 250rpm; The slurry that ball milling is good becomes dry powder at 70 ℃ of insulation 24 h; After adding massfraction in the dry powder and be 2% the PVA aqueous solution,, make powder become base with the compacting of 65MPa pressure; Base substrate is put into the Si-Mo rod high-temperature electric resistance furnace, speed with 5 ℃/min rises to 600 ℃ from room temperature earlier, be incubated 120min in the air atmosphere, the back rises to 900 ℃ of sintering temperatures with the speed of 5 ℃/min, be incubated 120min in the air atmosphere, cool to room temperature with the furnace, promptly get the sputtering target material of φ 50 mm * 3mm.
2) utilize magnetron sputtering method to prepare Zinc oxide-base low voltage varistor ceramics thin-film material: substrate material is selected the Si(111 of single-sided polishing for use) substrate, its cleaning step is as follows: substrate is put into deionized water, ultrasonic cleaning 5～10min, twice; Ultrasonic cleaning 5～10min in acetone, twice; Ultrasonic cleaning 5～10min in dehydrated alcohol, twice; The substrate that cleans up is put into the beaker that fills dehydrated alcohol, and good seal is stand-by; Cleaned substrate is put into metal spraying equipment, vacuumize back spraying 5～10min, the preparation bottom electrode, it is rf magnetron sputtering that the sputter mode is adopted in experiment, sputtering target material is of a size of φ 50 mm * 3mm, sputter gas is high purity argon (Ar purity is 99.999%), and argon flow amount is 30sccm, and coating chamber base vacuum degree reaches 10
-5Pa, operating air pressure are 2.0Pa, and target-Ji spacing is 90mm, with Si(111) spraying of substrate faces up and is clamped on the pallet as substrate, Si(111) substrate diameter is 6mm, and substrate does not heat, and sputtering time is 2h, sputtering power 300W, annealing temperature is 800 ℃, annealing time is 1.5h.Film after the annealing is partly covered with aluminium foil, put into metal spraying equipment, vacuumize back spraying 5～10min, the preparation upper current conducting cap, the metal spraying area of upper current conducting cap is about 10mm
2, through performance test, nonlinear factor is 16.41, and pressure sensitive voltage is 2.99V, and leakage current density is 0.68 μ A/mm
2
3) the thick aluminium foil of 0.1mm is sticked as absorption layer in the film sample surface for preparing, aluminium foil surface is coated the liquid of acid system preparation as restraint layer, thickness is about 1mm, afterwards film sample is embedded on the mould, film is carried out laser-impact, parameter is as follows: spot size is 6mm, wavelength is 1064nm, pulse width is 22ns, and pulse energy is 8J, at last aluminium foil is taken off; The nonlinear factor of the Zinc oxide-base low voltage varistor ceramics film of preparing increases to 20.37, and velocity of variation is 24.13%; Pressure sensitive voltage reduces to 2.01V, and velocity of variation is 32.78%; Leakage current density reduces to 0.32 μ A/mm
2, velocity of variation is 52.94%.
Embodiment 3
1) utilize the conventional sintering legal system to be equipped with the zinc oxide-based ceramic target: to prepare burden ZnO96.7%, Bi according to following molar percentage component
2O
30.8%, Sb
2O
31.0%, Co
2O
30.5%, Cr
2O
30.5%, MnO
20.5%; Adopt agate ball, stainless cylinder of steel, dehydrated alcohol is a ball-milling medium, agate ball: the batching powder: the mass ratio of dehydrated alcohol is 2.5:1:1, and wet-milling 7h in planetary high-energy ball mill, rotating speed are 200rpm; The slurry that ball milling is good becomes dry powder at 70 ℃ of insulation 24 h; After adding massfraction in the dry powder and be 2% the PVA aqueous solution,, make powder become base with the compacting of 75MPa pressure; Base substrate is put into the Si-Mo rod high-temperature electric resistance furnace, speed with 5 ℃/min rises to 500 ℃ from room temperature earlier, be incubated 120min in the air atmosphere, the back rises to 850 ℃ of sintering temperatures with the speed of 5 ℃/min, be incubated 120min in the air atmosphere, cool to room temperature with the furnace, promptly get the sputtering target material of φ 50 mm * 3mm.
2) utilize magnetron sputtering method to prepare Zinc oxide-base low voltage varistor ceramics thin-film material: substrate material is selected the Si(111 of single-sided polishing for use) substrate, its cleaning step is as follows: substrate is put into deionized water, ultrasonic cleaning 5～10min, twice; Ultrasonic cleaning 5～10min in acetone, twice; Ultrasonic cleaning 5～10min in dehydrated alcohol, twice; The substrate that cleans up is put into the beaker that fills dehydrated alcohol, and good seal is stand-by; Cleaned substrate is put into metal spraying equipment, vacuumize back spraying 5～10min, the preparation bottom electrode, it is rf magnetron sputtering that the sputter mode is adopted in experiment, sputtering target material is of a size of φ 50 mm * 3mm, sputter gas is high purity argon (Ar purity is 99.999%), and argon flow amount is 30sccm, and coating chamber base vacuum degree reaches 10
-5Pa, operating air pressure are 2.5Pa, and target-Ji spacing is 90mm, with Si(111) spraying of substrate faces up and is clamped on the pallet as substrate, and Si(111) substrate diameter is 6mm, and substrate does not heat, sputtering time is 1h, sputtering power 200W, and annealing temperature is 900 ℃, annealing time is 0.5h, film after the annealing is partly covered with aluminium foil, put into metal spraying equipment, vacuumize back spraying 5～10min, the preparation upper current conducting cap, the metal spraying area of upper current conducting cap is about 10mm
2, through performance test, nonlinear factor is 15.74, and pressure sensitive voltage is 2.62V, and leakage current density is 0.79 μ A/mm
2
3) the thick aluminium foil of 0.2mm is sticked as absorption layer in the film sample surface for preparing, aluminium foil surface is sticked K9 glass as restraint layer, and thickness is about 0.6mm, afterwards film sample is embedded on the mould, film is carried out laser-impact, parameter is as follows: spot size is 6mm, and wavelength is 1064nm, and pulse width is 12ns, pulse energy is 5J, at last aluminium foil is taken off, the nonlinear factor of the Zinc oxide-base low voltage varistor ceramics film of preparing increases to 18.101, and velocity of variation is 15.00%; Pressure sensitive voltage reduces to 2.096V, and velocity of variation is 20.00%; Leakage current density reduces to 0.6123 μ A/mm
2, velocity of variation is 22.5%, though adopt restraint layer K9 glass commonly used also can improve nonlinear factor as can be seen, reduces pressure sensitive voltage simultaneously, effect is not as the liquid restraint layer of alkaline process of the present invention or acid system preparation.
Embodiment 4
Step 1 and 2 is with embodiment 3, and the restraint layer in the step 3 is a water, and water layer thickness is 0.9mm, and other are with embodiment 3, and the nonlinear factor of the Zinc oxide-base low voltage varistor ceramics film of preparing increases to 18.57, and velocity of variation is 18.00%; Pressure sensitive voltage reduces to 2.04V, and velocity of variation is 22.00%; Leakage current density reduces to 0.59 μ A/mm
2, velocity of variation is 25%, though adopt restraint layer water commonly used also can improve nonlinear factor as can be seen, reduces pressure sensitive voltage simultaneously, and is slightly better than K9 glass, effect is not as the liquid restraint layer of alkaline process of the present invention or acid system preparation.
Claims (10)
1. method that improves Zinc oxide-base low voltage varistor ceramics thin-film electro performance, it is characterized in that: on Zinc oxide-base low voltage varistor ceramics film sample surface, stick aluminium foil as absorption layer, after on aluminium foil surface, coating, paste or cover restraint layer the ceramic membrane sample is embedded on the mould, the ceramic membrane sample is carried out laser-impact, to improve the electrical property of Zinc oxide-base low voltage varistor ceramics film.
2. a kind of method that improves Zinc oxide-base low voltage varistor ceramics thin-film electro performance as claimed in claim 1, it is characterized in that: described aluminum foil thickness is 0.1～0.3mm.
3. a kind of method that improves Zinc oxide-base low voltage varistor ceramics thin-film electro performance as claimed in claim 1, it is characterized in that: described restraint layer thickness is 0.3～1.0mm.
4. a kind of method that improves Zinc oxide-base low voltage varistor ceramics thin-film electro performance as claimed in claim 1, it is characterized in that: described laser spot size is 6mm, and wavelength is 1064nm, and pulse width is 10～22ns, and pulse energy is 3～10J.
5. a kind of method that improves Zinc oxide-base low voltage varistor ceramics thin-film electro performance as claimed in claim 1, it is characterized in that: described constrained layer material is a colourless liquid, can be by the laser of 1.06 mum wavelengths, transmittance is greater than water, viscosity is 500 CP under the room temperature, specific refractory power is 1400nd under the room temperature, and flash-point is greater than 300 ℃.
6. a kind of method that improves Zinc oxide-base low voltage varistor ceramics thin-film electro performance as claimed in claim 5 is characterized in that: restraint layer adopts following method preparation:
In reactor, add dimethyl annular siloxane, chain termination agent hexamethyldisiloxane or trimethyl silicon based end capped dimethyl siloxane oligomer and catalyzer Tetramethylammonium hydroxide, the add-on of chain termination agent is 2.0 ~ 8.0% of a dimethyl annular siloxane quality, the add-on of catalyzer is 0.01 ~ 0.03% of a reactant total mass, under 80～90 ℃/60 mmhg, carry out telomerization, after reaction finishes, remove vacuum, be warming up to 150～200 ℃, destroy catalyzer and remove low-boiling-point substance, after the cooling, promptly get the liquid restraint layer.
7. a kind of method that improves Zinc oxide-base low voltage varistor ceramics thin-film electro performance as claimed in claim 5 is characterized in that: restraint layer adopts following method preparation:
The low-boiling-point substance, hexamethyldisiloxane and the concentration that add silicone oil or silicon rubber in reactor are 98% sulfuric acid, the add-on of hexamethyldisiloxane be silicone oil or silicon rubber the low-boiling-point substance quality 1.3 ~ 3.5%, concentration is that 98% sulfuric acid is 2 ~ 5% of reactant total mass, under agitation carry out telomerization in 50～60 ℃, after reaction finishes, put the disacidify water layer, oil-reservoir water is washed till neutrality, steam down in 150～200 ℃/10 mmhg then and remove low-boiling-point substance, the cooling back uses activated carbon decolorizing, decompress filter to get the liquid restraint layer.
8. a kind of method that improves Zinc oxide-base low voltage varistor ceramics thin-film electro performance as claimed in claim 7, it is characterized in that: the low-boiling-point substance of described silicone oil or silicon rubber is the dimethyl siloxane oligopolymer, 200 ℃ of boiling points.
9. a kind of method that improves Zinc oxide-base low voltage varistor ceramics thin-film electro performance as claimed in claim 5, it is characterized in that: the using method of described restraint layer is as follows: stick aluminium foil as absorption layer on Zinc oxide-base low voltage varistor ceramics film sample surface, utilize the viscosity of liquid constrained layer material then and from the levelling ability, this liquid constrained layer material is poured over the surface of coating, treat that it is behind levelling, it can form fluid film at workpiece surface, with laser shock peening is carried out on Zinc oxide-base low voltage varistor ceramics film sample surface then and handles.
10. a kind of method that improves Zinc oxide-base low voltage varistor ceramics thin-film electro performance as claimed in claim 5, it is characterized in that: the using method of described restraint layer is as follows: stick aluminium foil as absorption layer on Zinc oxide-base low voltage varistor ceramics film sample surface, utilize spray gun that the liquid constrained layer material is painted on workpiece surface to be impacted, can form fluid film at workpiece surface, with laser workpiece surface be carried out shock peening then and handle.
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| CN102432281A (en) * | 2011-09-21 | 2012-05-02 | 江苏大学 | Method for improving electrical properties of zinc oxide-based low voltage-sensitive ceramic film |
| CN103726046A (en) * | 2013-12-24 | 2014-04-16 | 江苏大学 | Method for preparing compound coatings through laser shock induced chemical reaction |
| CN106222650A (en) * | 2016-07-29 | 2016-12-14 | 苏州大学张家港工业技术研究院 | The surface reinforcing method of laser-impact graphite oxide ene coatings |
| CN110280672A (en) * | 2019-07-11 | 2019-09-27 | 华中科技大学 | A kind of metal plate like piece connection and forming composite manufacturing method based on high speed impact |
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| CN1404954A (en) * | 2002-09-25 | 2003-03-26 | 江苏大学 | Flexible lamina for laser impact treatment |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432281A (en) * | 2011-09-21 | 2012-05-02 | 江苏大学 | Method for improving electrical properties of zinc oxide-based low voltage-sensitive ceramic film |
| CN103726046A (en) * | 2013-12-24 | 2014-04-16 | 江苏大学 | Method for preparing compound coatings through laser shock induced chemical reaction |
| CN103726046B (en) * | 2013-12-24 | 2017-02-01 | 江苏大学 | Method for preparing compound coatings through laser shock induced chemical reaction |
| CN106222650A (en) * | 2016-07-29 | 2016-12-14 | 苏州大学张家港工业技术研究院 | The surface reinforcing method of laser-impact graphite oxide ene coatings |
| WO2018018655A1 (en) * | 2016-07-29 | 2018-02-01 | 苏州大学张家港工业技术研究院 | Surface strengthening method by laser shock on graphene or graphene oxide coating |
| CN110280672A (en) * | 2019-07-11 | 2019-09-27 | 华中科技大学 | A kind of metal plate like piece connection and forming composite manufacturing method based on high speed impact |
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