CN105420656B - A kind of metal/polymer composite coating and preparation method thereof - Google Patents
A kind of metal/polymer composite coating and preparation method thereof Download PDFInfo
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- CN105420656B CN105420656B CN201510845103.2A CN201510845103A CN105420656B CN 105420656 B CN105420656 B CN 105420656B CN 201510845103 A CN201510845103 A CN 201510845103A CN 105420656 B CN105420656 B CN 105420656B
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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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
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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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
-
- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
Abstract
The invention discloses a kind of metal/polymer composite coatings, composite layer including substrate and substrate surface, the composite layer includes metal and polymer, and the volume fraction of the metal is 5~50vol.%, and the volume fraction of the polymer is 50~95vol.%；The metal is copper or nickel；The polymer be polyethylene, polypropylene, polytetrafluoroethylene (PTFE) or polyimides invention additionally discloses a kind of preparation method of metal/polymer composite coating, include the following steps：Prepare metal/polymer complex microsphere；Substrate is subjected to surface degreasing, roughening treatment；By the metal/polymer complex microsphere of preparation by heat spraying method, composite layer is prepared on processed substrate surface to get to metal/polymer composite coating.The metal/polymer composite coating can be well combined with matrix, can effectively anti-fouling and Corrosion Protection, can be applied to a variety of ocean industrial parts outer surface etc. need it is resistance to be stained, corrosion-resistant occasion.
Description
Technical field
The present invention relates to metals and polymer composite coating technology field more particularly to a kind of compound painting of metal/polymer
Layer and preparation method thereof.
Background technology
In recent years, with the continuous development of marine industry, the biodeterioration and etching problem of ocean engineering material have become
The focus of world attention, especially China possess abundant marine resources, should be reduced as possible while developing and using marine resources
The loss brought due to marine biofouling.Extensive research is had been carried out to the etching problem of ocean engineering material both at home and abroad,
By selecting the methods of corrosion resistant material, overlay coating, cathodic protection, coating anticorrosive paint to achieve preferable effect.It gives birth to ocean
Object is stained has great damage to ocean engineering material, reduces the service life of material, causes serious economic loss.Research
Show that the roughness of hull surface can be increased when marine organisms are attached to marine surface, reduces the speed of a ship or plane, increases fuel consumption
Amount etc., according to statistics, biodeterioration can make the fuel consumption of steamer increase by 40%, and at least 90,000,000,000 yuan of economy is damaged every year in China
Mistake is caused by corrosion, and the ratio of marine corrosion accounts for 30% or more, wherein 30% and marine microorganism of marine material corrosion total amount
Attachment is related.Therefore, novel anti-pollution corrosion-inhibiting coating technology is studied to mitigate the problem in science that hull fouling problem is urgent need to resolve,
Composite coating and its technology of preparing are very important both with exploitation one kind is anti-corrosion, antifouling.
Plasma spray technology is a kind of surface strengthening technology, and film forming efficiency is high, is suitble to industrialization large-scale production, acquisition
Coating has good bond strength, excellent mechanical performance and good functional performance, such as anti-corrosion, fouling resistance, superhard, wear-resisting
Deng.In recent years, with the reinforcement of people's environmental consciousness, energy-saving and emission-reduction, the strategy of sustainable development understanding, ocean engineering material
Or anti-corrosion, the anti-biological performance that is stained on marine settings surface is as one of research hotspot.High molecular polymer because its with it is light,
The advantages that easily molded, of low cost, resistant to chemical etching, lower temperature resistance and electrical isolation and be widely used, but its is lower wear-resisting
Property, weatherability limit the application of its related field.According to research reports, thermal spraying polymer coating has good corrosion resistant to root
The coating of corrosion energy, cupric has preferable anti-biofouling performance.But polymer is applied in plasma spray technology and is commonly present spraying
The problems such as powder quality is light, and powder flowbility is poor, spraying film forming efficiency is low, to limit polymer answering in thermal spraying
With.Chinese invention patent (CN102776511A, publication date 2012.11.14) discloses a kind of ceramic metal composite for matrix
The preparation method of coating, the preparation method include the following steps：A) it is roughened ceramic matrix, b) ultrasonic cleaning, c) in thermal spraying
Interbed, d) cleaning, drying, e) coating coating metal, f) sanding and polishing.Therefore, it develops, improve polymer flowability, improve film forming
Efficiency adapts it to one of the emphasis that hot-spraying technique is current thermal spraying polymer coating research.
Electroless plating technology is that one kind being effectively improved polymer surfaces performance, and raising polymer performance, service life are most effective
One of method.Polymer chemistry plating possesses many advantages：Of low cost, technological operation is simple and practicable, production capacity is higher, changes
It is uniform to learn coated coating, it is strong with plastics binding force, it is suitable for the plastic products of arbitrarily complicated shape.The application range of chemical plating is very
Extensively, including metal and metal, metal and semiconductor, metal and insulator.Chinese invention patent (102296332 A of CN, it is open
Day 2011.12.28) disclose a kind of method of polyethylene surface direct plating conductive metal, Polyethylene Particles are by oil removing, thick
Change, reduction, presoak, activation and metal replacement, metal replacement are placed in electroplate liquid and are electroplated.Due to polyethylene heat resistance
Difference, in 100 DEG C or so easily meltings, conductive metal of the plating on Polyethylene Particles surface will lose substrate and lose the spy of electric conductivity
Property, the particle of polyethylene surface direct plating conductive metal is applied on lithium ion battery, is lived as positive electrode active materials or cathode
Property material conductive agent use, the technical solution primarily to improve electric conductivity.
Invention content
The technical problems to be solved by the invention are：A kind of novel metal/polymer composite coating and its preparation are provided
Method is stained performance to realize that composite coating has excellent Corrosion Protection with anti-biological.
Technical solution is used by the present invention solves above-mentioned technical problem：A kind of metal/polymer composite coating is provided,
Composite layer including substrate and substrate surface, the composite layer include metal and polymer, the volume point of the metal
Number is 5~50%, and the volume fraction of the polymer is 50~95%；The metal is copper or nickel；The polymer
For polyethylene, polypropylene, polytetrafluoroethylene (PTFE) or polyimides.
Preferably, the metal is copper, and volume fraction is 8~10%；The polymer is polyethylene, volume fraction
It is 90~92%.When the volume fraction of copper is 8~10%, the sterilization of composite coating and the performance of anti-biofouling are more excellent
It is different；When the volume fraction of polyethylene is 90~92%, the chemical stability and resistance to acid and alkali of composite coating are more excellent.
The substrate is：Q235 steel, Q345 steel, 45 steel, 304 stainless steels, 316 stainless steels or cast iron；Described is compound
The thickness of layer is 100 μm~1mm.
The advantages of this coating structure：The chemical stability of polymer in composite coating is good, and resistance to acid and alkali is strong, can be effective
Completely cut off corrosiveness of the corrosive medium to basis material；Metal in composite coating can be used as fungicide, play sterilization and resist
Biodeterioration.Metallic is uniformly distributed in composite coating, is conducive to the sustained release release of metallic and long-term release.
The present invention also provides a kind of preparation methods of metal/polymer composite coating, include the following steps：
1) metal/polymer complex microsphere is prepared；
2) substrate is subjected to surface degreasing, roughening treatment；
3) the metal/polymer complex microsphere for preparing step 1) is by heat spraying method, in the substrate of step 2) processing
Composite layer is prepared on surface to get to metal/polymer composite coating.
It is metallized by macromolecule surface, the mobility of irregular micron polymeric powder can be significantly improved, reduce heat
The granularity threshold of spraying polymeric powder, it is ensured that polymeric powder, which fully melts, obtains fine and close composite coating.It compares
In metal and macromolecule mechanical mixture powder as spraying raw material, this method can not avoided because of metal and macromolecule fusing point not
Match and caused by the problems such as metal molten is insufficient or macromolecule burning, and then obtain finer and close institutional framework, have simultaneously
Effect avoid macromolecule decompose and caused by performance decline.
The preparation method of the metal/polymer complex microsphere is：It is clear that polymer powder with acetone is subjected to ultrasonic wave
It washes, after the completion of cleaning, is deoiled, is roughened successively, is sensitized, activating pretreatment, then to pretreated polymer powder
Chemical plating metal is carried out in chemical plating metal liquid, it is neutral to adjust pH value with NaOH solution during plating, and plating metal is complete
Cheng Hou takes out, is rinsed with deionized water, dries to get to metal/polymer complex microsphere.
The heat spraying method includes：Flame-spraying, supersonic flame spraying or cold spraying.
The heat spraying method is preferably flame-spraying, and spray parameters are：Combustion-supporting gas is O2, combustion gas be acetylene, auxiliary
It is compressed air to help gas, and wherein pressure is respectively 0.2~1.0MPa, 0.05~0.4MPa, 0.3~6.0MPa, and powder feeding rate is
10~100g/min, spray distance be 100~300mm, flame gun 50~400mm/s of movement speed, coating spraying number 1~
30 times.
The metal/polymer complex microsphere is preferably polyethylene/copper complex microsphere；The side of the flame-spraying
Method, spray parameters are：Combustion-supporting gas is O2, pressure is 0.5~0.6MPa；Combustion gas is acetylene, and pressure is 0.07~0.08MPa；
Auxiliary gas is compressed air, and pressure is 0.75~0.85MPa；Powder feeding rate be 55~65g/min, spray distance be 240~
260mm, flame gun 190~210mm/s of movement speed, coating spraying number 5~7 times.When metal/polymer complex microsphere is
When polyethylene/copper complex microsphere, the spray parameters of flame-spraying are adjusted according to the complex microsphere of spraying so that obtain gold
Category/polymer composite coating has more outstanding anti-fouling and etch-proof performance.
Method of roughening in the step 2) is preferably sandblasting, cutting thread, annular knurl or electric plucking.
Currently, anti-fouling, erosion shield and preparation method thereof haves the shortcomings that respective, can effectively take into account i.e. anti-fouling
Anticorrosion again.Coating of the present invention and preparation method thereof compared with prior art, has the following advantages that：
(1) coating uniformly, fine and close can be prepared in a variety of substrate surfaces, is well combined with matrix, it can be effectively antifouling
Damage and Corrosion Protection, can be applied to a variety of ocean industrial parts outer surface etc. need it is resistance to be stained, corrosion-resistant occasion.
(2) composite coating is prepared using hot-spraying technique prepares coating, equipment cost is low, simple for process, efficient, fits
Site operation is closed, spraying is not limited by workpiece size and shape, at low cost.Therefore, the composite coating is in anti-corrosion sterilization, anti-life
Object is stained field and has a good application prospect and economic benefit.
Description of the drawings
Fig. 1 is metal/polymer microsphere particle shape appearance figure prepared by embodiment 5；
Fig. 2 is the section microscopic appearance figure of metal/polymer composite coating prepared by embodiment 2；
Fig. 3 is coating anti-fouling effect figure prepared by embodiment 2, and (a) is PE coatings, is (b) Ni coatings, (c) multiple for PE/Ni
Coating is closed, arrow is designated as bacterium；
Fig. 4 is coating antiseptic design sketch prepared by embodiment 1, and (a) is PE coatings, is (b) Cu coatings, (c) multiple for PE/Cu
Close coating.
Specific implementation mode
Present invention is further described in detail with reference to the accompanying drawings and embodiments:
For a kind of performance of metal/polymer composite coating in the characterization present invention, X-ray diffractometer (XRD) and field are utilized
Transmitting scanning electron microscope (SEM) characterizes the coating sample prepared, is specific method for testing performance below.
(1) coating substance mutually detects：The sample of preparation is placed in deionized water solution and is ultrasonically treated 10min, is then dried up,
Finally its object phase is detected using X-ray diffractometer.
(2) surface microscopic topographic is observed：The sample of preparation is placed in deionized water solution and is ultrasonically treated 30min, then
Drying, last surface spray Au, its surface microscopic topographic are observed using field emission scanning electron microscope.
(3) section microscopic appearance is observed：The sample of preparation is used into 400#, 800#, 1200#, 1500#, 2000# sand paper successively
Polishing, polishing, are subsequently placed in deionized water solution and are ultrasonically treated 5min, dry up, and Au is sprayed on last surface, is scanned using Flied emission
Its section microscopic appearance of electron microscope observation.
Embodiment 1：
In the present embodiment, basis material is the Q235 steel discs of thickness about 2mm, the thickness of matrix surface PE/Cu composite coatings
It it is 400 μm, coating is well combined with basis material；The specific preparation method of the PE/Cu composite coatings is as follows：
1, polyethylene powders are subjected to ultrasonic cleaning with acetone, after the completion of cleaning, deoiled, be roughened successively, is sensitized,
Then activating pretreatment carries out electroless copper, plating process to pretreated polyethylene powders in electroless copper plating solution
It is middle to adjust pH value with NaOH solution, after the completion of waiting for copper facing, takes out, rinsed, dried to get compound micro- to PE/Cu with deionized water
Ball；
2, matrix is cleaned with acetone, hydrochloric acid, deionized water successively, to Q235 steel discs using 60 mesh corundum sands into
Row surface sand-blasting roughening treatment, the air pressure that sandblasting is respectively adopted are 0.5MPa, so that its roughness is reached spraying and require；
3, using flame spraying method, using the PE/Cu microsphere particles of preparation as sprayed on material, thickness is formed in matrix surface
About 300 μm of PE/Cu composite coatings.Wherein, the spray parameters for controlling flame-spraying are：Combustion-supporting gas is O2, combustion gas be acetylene,
Auxiliary gas is compressed air, and wherein pressure is respectively 0.55MPa, 0.075MPa, 0.8MPa, powder feeding rate 60g/min, spraying
Distance is 250mm, flame gun movement speed 200mm/s, coating spraying number 6 times.
Following performance detection is carried out to the coating of above-mentioned preparation：
(1) coating cross sections microstructure morphology is observed：Coating cross sections are detected using field emission scanning electron microscope (SEM)
Microscopic appearance, it was demonstrated that coating layer thickness is 300 μm, and coating is well combined with matrix, and coating is fine and close.
(2) corrosion resistance coating is tested：Neutral salt spray test, experiment are carried out using the accurate salt spray testers of JK/60A
Condition is：35 DEG C of test temperature, solution concentration 50g/L, solution PH 6.9, atomisation pressure 1Kgf/cm2, as shown in Figure 4.It utilizes
Coating surface microscopic appearance after field emission scanning electron microscope (SEM) detection test, it was demonstrated that compared with copper coating and PE coatings,
The anti-corrosion effect of PE/Cu composite coatings is best.
(3) coating antifouling property is tested：Typical bacillus in ocean is selected to pass through Bacteria Culture successively as bacterium source
(2216E culture solutions, oscillation, constant incubator culture), bacterium attach and (sample are impregnated in the artificial seawater containing culture solution
In, constant temperature incubation 3 days), the processes such as fixed, dehydration.Utilize coating table after field emission scanning electron microscope (SEM) detection test
Face microscopic appearance, it was demonstrated that compared with PE coatings, the bacterial number that Cu/PE composite coatings surface attaches is few, good antifouling effect, with copper
Coating is suitable.
Embodiment 2：
In the present embodiment, basis material is 45 steel discs of thickness about 2mm, and the thickness of matrix surface PE/Ni composite coatings is
400 μm, coating is well combined with basis material；The specific preparation method of the PE/Ni composite coatings is as follows：
1, polyethylene powders are subjected to ultrasonic cleaning with acetone, after the completion of cleaning, are roughened successively, be sensitized, are activated
Then pretreated polyethylene powders are carried out chemical nickel plating by pretreatment in chemical nickel-plating plating solution, after the completion of waiting for nickel plating,
It takes out, is rinsed with deionized water, dried to get to PE/Ni complex microspheres；
2, matrix is cleaned with acetone, hydrochloric acid, deionized water successively, 45 steel discs is carried out using 60 mesh corundum sands
Surface sand-blasting roughening treatment, the air pressure that sandblasting is respectively adopted are 0.5MPa and 0.3MPa, so that its roughness is reached spraying and require；
3, using flame spraying method, using the PE/Ni microsphere particles of preparation as sprayed on material, thickness is formed in matrix surface
About 400 μm of PE/Ni composite coatings.Wherein, the spray parameters for controlling flame-spraying are：Combustion-supporting gas is O2, combustion gas be acetylene,
Auxiliary gas is compressed air, and wherein pressure is respectively 0.55MPa, 0.075MPa, 0.8MPa, powder feeding rate 60g/min, spraying
Distance is 250mm, flame gun movement speed 200mm/s, coating spraying number 6 times, the section of obtained PE/Ni composite coatings
Microscopic appearance figure is as shown in Figure 2.
Following performance detection is carried out to the coating of above-mentioned preparation：
(1) coating cross sections microstructure morphology is observed：Coating cross sections are detected using field emission scanning electron microscope (SEM)
Microscopic appearance, it was demonstrated that coating layer thickness is 300 μm, and coating is well combined with matrix, and coating is fine and close.
(2) corrosion resistance coating is tested：Neutral salt spray test, experiment are carried out using the accurate salt spray testers of JK/60A
Condition is：35 DEG C of test temperature, solution concentration 50g/L, solution PH 6.7, atomisation pressure 1Kgf/cm2.It is scanned using Flied emission
Coating surface microscopic appearance after electron microscope (SEM) detection test, it was demonstrated that compared with nickel coating and PE coatings, PE/Ni is compound
The anti-corrosion effect of coating is best.
(3) coating antifouling property is tested：Typical bacillus in ocean is selected to pass through Bacteria Culture successively as bacterium source
(2216E culture solutions, oscillation, constant incubator culture), bacterium attach and (sample are impregnated in the artificial seawater containing culture solution
In, constant temperature incubation 3 days), the processes such as fixed, dehydration.Utilize coating table after field emission scanning electron microscope (SEM) detection test
Face microscopic appearance, as shown in Figure 3, it was demonstrated that compared with nickel coating and PE coatings, the bacterial number of PE/Ni composite coatings surface attaching
At least, anti-fouling effect is best.
Embodiment 3：
In the present embodiment, basis material is the Q345 steel discs of thickness about 2mm, the thickness of matrix surface PP/Cu composite coatings
Degree is 400 μm, and coating is well combined with basis material；The specific preparation method of the PP/Cu composite coatings is as follows：
1, polypropylene powder is subjected to ultrasonic cleaning with acetone, after the completion of cleaning, deoiled, be roughened successively, is sensitized,
Then activating pretreatment carries out electroless copper, plating process to pretreated polypropylene powder in electroless copper plating solution
It is middle to adjust pH value with NaOH solution, after the completion of waiting for copper facing, takes out, rinsed, dried to get compound micro- to PP/Cu with deionized water
Ball；
2, matrix is cleaned with acetone, hydrochloric acid, deionized water successively, to Q345 steel discs using 60 mesh corundum sands into
Row surface sand-blasting roughening treatment, the air pressure that sandblasting is respectively adopted are 0.5MPa and 0.3MPa, so that its roughness is reached spraying and require；
3, using flame spraying method, using the PP/Cu microsphere particles of preparation as sprayed on material, thickness is formed in matrix surface
About 400 μm of PP/Cu composite coatings.Wherein, the spray parameters for controlling flame-spraying are：Combustion-supporting gas is O2, combustion gas be acetylene,
Auxiliary gas is compressed air, and wherein pressure is respectively 0.55MPa, 0.075MPa, 0.8MPa, powder feeding rate 60g/min, spraying
Distance is 250mm, flame gun movement speed 200mm/s, coating spraying number 6 times.
Following performance detection is carried out to the coating of above-mentioned preparation：
(1) coating cross sections microstructure morphology is observed：Coating cross sections are detected using field emission scanning electron microscope (SEM)
Microscopic appearance, it was demonstrated that coating layer thickness is 300 μm, and coating is well combined with matrix, and coating is fine and close.
(2) corrosion resistance coating is tested：Neutral salt spray test, experiment are carried out using the accurate salt spray testers of JK/60A
Condition is：35 DEG C of test temperature, solution concentration 50g/L, solution PH 7.0, atomisation pressure 1Kgf/cm2.It is scanned using Flied emission
Coating surface microscopic appearance after electron microscope (SEM) detection test, it was demonstrated that compared with copper coating and PP coatings, PP/Cu is compound
The anti-corrosion effect of coating is best.
(3) coating antifouling property is tested：Typical bacillus in ocean is selected to pass through Bacteria Culture successively as bacterium source
(2216E culture solutions, oscillation, constant incubator culture), bacterium attach and (sample are impregnated in the artificial seawater containing culture solution
In, constant temperature incubation 3 days), the processes such as fixed, dehydration.Utilize coating table after field emission scanning electron microscope (SEM) detection test
Face microscopic appearance, it was demonstrated that compared with PP coatings, the bacterial number that PP/Cu composite coatings surface attaches is few, good antifouling effect, with copper
Coating is suitable.
Embodiment 4：
In the present embodiment, basis material is 304 stainless steel substrates of thickness about 2mm, matrix surface PP/Ni composite coatings
Thickness is 400 μm, and coating is well combined with basis material；The specific preparation method of the PP/Ni composite coatings is as follows：
1, polypropylene powder is subjected to ultrasonic cleaning with acetone, after the completion of cleaning, is roughened successively, be sensitized, is activated
Pretreatment, then carries out chemical nickel plating to pretreated polypropylene powder in chemical nickel-plating plating solution, after the completion of waiting for nickel plating,
It takes out, is rinsed with deionized water, dried to get to PP/Ni complex microspheres；
2, matrix is cleaned with acetone, hydrochloric acid, deionized water successively, 60 mesh Brown Alundums is used to 304 stainless steel substrates
Sand carries out surface sand-blasting roughening treatment, and the air pressure that sandblasting is respectively adopted is 0.5MPa and 0.3MPa, its roughness is made to reach spraying
It is required that；
3, using flame spraying method, using the PP/Ni microsphere particles of preparation as sprayed on material, thickness is formed in matrix surface
About 400 μm of PP/Ni composite coatings.Wherein, the spray parameters for controlling flame-spraying are：Combustion-supporting gas is O2, combustion gas be acetylene,
Auxiliary gas is compressed air, and wherein pressure is respectively 0.55MPa, 0.075MPa, 0.8MPa, powder feeding rate 60g/min, spraying
Distance is 250mm, flame gun movement speed 200mm/s, coating spraying number 6 times.
Following performance detection is carried out to the coating of above-mentioned preparation：
(1) coating cross sections microstructure morphology is observed：Coating cross sections are detected using field emission scanning electron microscope (SEM)
Microscopic appearance, it was demonstrated that coating layer thickness is 300 μm, and coating is well combined with matrix, and coating is fine and close.
(2) corrosion resistance coating is tested：Neutral salt spray test, experiment are carried out using the accurate salt spray testers of JK/60A
Condition is：35 DEG C of test temperature, solution concentration 50g/L, solution PH 7.2, atomisation pressure 1Kgf/cm2.It is scanned using Flied emission
Coating surface microscopic appearance after electron microscope (SEM) detection test, it was demonstrated that compared with nickel coating and PP coatings, PP/Ni is compound
The anti-corrosion effect of coating is best.
(3) coating antifouling property is tested：Typical bacillus in ocean is selected to pass through Bacteria Culture successively as bacterium source
(2216E culture solutions, oscillation, constant incubator culture), bacterium attach and (sample are impregnated in the artificial seawater containing culture solution
In, constant temperature incubation 3 days), the processes such as fixed, dehydration.Utilize coating table after field emission scanning electron microscope (SEM) detection test
Face microscopic appearance, it was demonstrated that compared with nickel coating and PP coatings, the bacterial number that PP/Ni composite coatings surface attaches is minimum, antifouling
Effect is best.
Embodiment 5：
In the present embodiment, basis material is the Q235 steel discs of thickness about 2mm, the thickness of matrix surface PI/Cu composite coatings
Degree is 300 μm, and coating is well combined with basis material；The specific preparation method of the PI/Cu composite coatings is as follows：
1, polyimide plastic powder is subjected to ultrasonic cleaning with acetone, after the completion of cleaning, is deoiled successively, slightly
Change, be sensitized, activating pretreatment, is rinsed with deionized water between each step, then pretreated polyimide powder is being changed
It learns and carries out electroless copper in plating copper electrolyte, pH value is adjusted with NaOH solution during plating, after the completion of waiting for copper facing, take out, spend
Ionized water rinses, and dries to get to PI/Cu complex microspheres, the pattern of specific PI/Cu complex microspheres is as shown in Figure 1；
2, matrix is cleaned with acetone, hydrochloric acid, deionized water successively, to Q235 steel discs using 60 mesh corundum sands into
Row surface sand-blasting roughening treatment, the air pressure that sandblasting is respectively adopted are 0.5MPa and 0.3MPa, so that its roughness is reached spraying and require；
3, using supersonic flame spraying method, using the PI/Cu microsphere particles of preparation as sprayed on material, in matrix surface shape
The PI/Cu composite coatings for being about 400 μm at thickness.Wherein, the spray parameters for controlling supersonic flame spraying are：Combustion-supporting gas is
O2, combustion gas be propane, accelerate gas be compressed air, pressure is respectively 1MPa, 0.6MPa, 0.7MPa, and flow is respectively
240slpm, 70slpm, 300slpm, powder feeding gas N2Flow is 15slpm, and powder delivery rate is 50g/min, and spray distance is
300mm is sprayed 6 times.
Following performance detection is carried out to the coating of above-mentioned preparation：
(1) coating cross sections microstructure morphology is observed：Coating cross sections are detected using field emission scanning electron microscope (SEM)
Microscopic appearance, it was demonstrated that coating layer thickness is 300 μm, and coating is well combined with matrix, and coating is fine and close.
(2) corrosion resistance coating is tested：Neutral salt spray test, experiment are carried out using the accurate salt spray testers of JK/60A
Condition is：35 DEG C of test temperature, solution concentration 50g/L, solution PH 6.5, atomisation pressure 1Kgf/cm2.It is scanned using Flied emission
Coating surface microscopic appearance after electron microscope (SEM) detection test, it was demonstrated that compared with copper coating and PI coatings, PI/Cu is compound
The anti-corrosion effect of coating is best.
(3) coating antifouling property is tested：Typical bacillus in ocean is selected to pass through Bacteria Culture successively as bacterium source
(2216E culture solutions, oscillation, constant incubator culture), bacterium attach and (sample are impregnated in the artificial seawater containing culture solution
In, constant temperature incubation 3 days), the processes such as fixed, dehydration.Utilize coating table after field emission scanning electron microscope (SEM) detection test
Face microscopic appearance, it was demonstrated that compared with PI coatings, the bacterial number that PI/Cu composite coatings surface attaches is few, good antifouling effect, with copper
Coating is suitable.
Embodiment 6：
In the present embodiment, basis material is 45 steel discs of thickness about 2mm, the thickness of matrix surface PI/Ni composite coatings
It it is 400 μm, coating is well combined with basis material；The specific preparation method of the PI/Ni composite coatings is as follows：
1, polyimide plastic powder is subjected to ultrasonic cleaning with acetone, after the completion of cleaning, is roughened successively, is quick
Change, activating pretreatment, is rinsed with deionized water between each step, then to pretreated polyimide powder in chemical nickel plating
Chemical nickel plating is carried out in plating solution, after the completion of waiting for nickel plating, is taken out, is rinsed with deionized water, dries to get to PI/Ni complex microspheres；
2, matrix is cleaned with acetone, hydrochloric acid, deionized water successively, 45 steel discs is carried out using 60 mesh corundum sands
Surface sand-blasting roughening treatment, the air pressure that sandblasting is respectively adopted are 0.5MPa and 0.3MPa, so that its roughness is reached spraying and require；
3, using cold spraying method, using the PI/Ni microsphere particles of preparation as sprayed on material, thickness is formed about in matrix surface
For 400 μm of PI/Ni composite coatings.Wherein, the spray parameters for controlling cold spraying are：Gas based on nitrogen, 500 DEG C of temperature, pressure
3MPa；Argon gas is powder feeding gas, room temperature, pressure 3.1MPa；Powder mass flow 50g/min, spray distance 30mm, cold spray gun movement speed
200mm/s, coating spraying number 6 times.
Following performance detection is carried out to the coating of above-mentioned preparation：
(1) coating cross sections microstructure morphology is observed：Coating cross sections are detected using field emission scanning electron microscope (SEM)
Microscopic appearance, it was demonstrated that coating layer thickness is 400 μm, and coating is well combined with matrix, and coating is fine and close.
(2) corrosion resistance coating is tested：Neutral salt spray test, experiment are carried out using the accurate salt spray testers of JK/60A
Condition is：35 DEG C of test temperature, solution concentration 50g/L, solution PH 6.6, atomisation pressure 1Kgf/cm2.It is scanned using Flied emission
Coating surface microscopic appearance after electron microscope (SEM) detection test, it was demonstrated that compared with nickel coating and PI coatings, PI/Ni is compound
The anti-corrosion effect of coating is best.
(3) coating antifouling property is tested：Typical bacillus in ocean is selected to pass through Bacteria Culture successively as bacterium source
(2216E culture solutions, oscillation, constant incubator culture), bacterium attach and (sample are impregnated in the artificial seawater containing culture solution
In, constant temperature incubation 3 days), the processes such as fixed, dehydration.Utilize coating table after field emission scanning electron microscope (SEM) detection test
Face microscopic appearance, it was demonstrated that compared with nickel coating and PI coatings, the bacterial number that PI/Ni composite coatings surface attaches is minimum, antifouling
Effect is best.
Claims (4)
1. a kind of preparation method of metal/polymer composite coating, which is characterized in that the metal/polymer composite coating packet
The composite layer of substrate and substrate surface is included, the composite layer includes metal and polymer, the volume fraction of the metal
It is 5~50%, the volume fraction of the polymer is 50~95%；The metal is copper or nickel；The polymer is
Polyethylene, polypropylene, polytetrafluoroethylene (PTFE) or polyimides；
Specifically comprise the following steps：
1) polymer powder is subjected to ultrasonic cleaning with acetone, is deoiled, is roughened successively, is sensitized, activating pretreatment, then
Chemical plating metal is carried out in chemical plating metal liquid to pretreated polymer powder, with NaOH solution tune during plating
It is neutrality to save pH values, to get to metal/polymer complex microsphere after the completion of plating metal；
2) substrate is subjected to surface degreasing, roughening treatment；
3) the metal/polymer complex microsphere for preparing step 1) is by heat spraying method, in the substrate surface of step 2) processing
On prepare composite layer to get to metal/polymer composite coating.
2. the preparation method of metal/polymer composite coating according to claim 1, which is characterized in that the thermal jet
Coating method includes：Flame-spraying or cold spraying.
3. the preparation method of metal/polymer composite coating according to claim 2, which is characterized in that the flame
The method of spraying, spray parameters are：Combustion-supporting gas is O2, pressure is 0.2~1.0MPa；Combustion gas is acetylene, pressure is 0.05~
0.4MPa；Auxiliary gas is compressed air, and pressure is 0.3~6.0MPa；Powder feeding rate is 10~100g/min, and spray distance is
100~300mm, flame gun 50~400mm/s of movement speed, coating spraying number 1~30 time.
4. the preparation method of metal/polymer composite coating according to claim 3, which is characterized in that the metal/
Polymer composite microsphere is polyethylene/copper complex microsphere, and the method for the flame-spraying, spray parameters are：Combustion-supporting gas is
O2, pressure is 0.5~0.6MPa；Combustion gas is acetylene, and pressure is 0.07~0.08MPa；Auxiliary gas is compressed air, and pressure is
0.75~0.85MPa；Powder feeding rate is 55~65g/min, and spray distance is 240~260mm, flame gun movement speed 190
~210mm/s, coating spraying number 5~7 times.
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| CN105838239B (en) * | 2016-04-13 | 2018-11-23 | 中国科学院宁波材料技术与工程研究所 | A kind of polyimides composite coating and its preparation method and application |
| CN105903650B (en) * | 2016-04-13 | 2019-07-16 | 中国科学院宁波材料技术与工程研究所 | A kind of method and products thereof preparing polyimide coating using plasma spray technology |
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| CN106868441A (en) * | 2017-01-17 | 2017-06-20 | 中国科学院宁波材料技术与工程研究所 | A kind of polymer composite coating and its preparation method and application |
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| CN107620027A (en) * | 2017-05-10 | 2018-01-23 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of metal/high-molecular composite coating |
| CN110542350B (en) * | 2018-05-28 | 2022-03-08 | 中国科学院宁波材料技术与工程研究所 | Bullet-proof vest nail piece and preparation method thereof |
| CN110542351B (en) * | 2018-05-28 | 2022-03-08 | 中国科学院宁波材料技术与工程研究所 | Bulletproof helmet and preparation method thereof |
| CN110206823B (en) * | 2019-06-01 | 2021-03-19 | 大连理工大学 | Hot spraying resin-based composite material water-lubricated bearing and manufacturing method thereof |
| CN110643984B (en) * | 2019-10-11 | 2021-08-03 | 中国石油大学(华东) | Method for rapidly preparing copper oxide/polytetrafluoroethylene super-amphiphobic coating |
| CN113073365A (en) * | 2021-03-25 | 2021-07-06 | 北京冬曦既驾科技咨询有限公司 | High-corrosion-resistance magnesium alloy electroplated layer and preparation method thereof |
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