CN105420656A - Metal/polymer composite coating and manufacturing method thereof - Google Patents
Metal/polymer composite coating and manufacturing method thereof Download PDFInfo
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- CN105420656A CN105420656A CN201510845103.2A CN201510845103A CN105420656A CN 105420656 A CN105420656 A CN 105420656A CN 201510845103 A CN201510845103 A CN 201510845103A CN 105420656 A CN105420656 A CN 105420656A
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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
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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
- C23C18/32—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
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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
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
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- General Chemical & Material Sciences (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
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Abstract
The invention discloses a metal/polymer composite coating which comprises a substrate and a composite layer on the surface of the substrate. The composite layer comprises, by volume, 5% to 50% of metal and 50% to 95% of a polymer, wherein the metal is copper or nickel, and the polymer is polyethylene or polypropylene or polytetrafluoroethylene or polyimide. The invention further discloses a manufacturing method of the metal/polymer composite coating. The method includes the following steps that metal/polymer composite microspheres are manufactured; the surface of the substrate is subjected to oil removal and roughing treatment; and the manufactured metal/polymer composite microspheres are thermally sprayed, so that a composite layer is manufactured on the treated surface of the substrate, and therefore the metal/polymer composite coating is obtained. The metal/polymer composite coating can be well combined with a base body, stain resistance and corrosion resistance can be effectively achieved, and the metal/polymer composite coating can be applied to outer surfaces of marine industrial parts and other occasions with the stain resistance and corrosion resistance requirements.
Description
Technical field
The present invention relates to metal and polymer composite coating technology field, particularly relate to a kind of metal/polymer compound coating and preparation method thereof.
Background technology
In recent years, along with the development of marine industry, biodeterioration and the etching problem of oceanographic engineering material become the focus of world attention, and especially China has abundant oceanic resources, should reduce the loss because marine biofouling brings while developing oceanic resources as far as possible.Both at home and abroad the etching problem of oceanographic engineering material being conducted extensive research, achieving good effect by selecting the method such as corrosion-resistant material, overlay coating, galvanic protection, coating protective system.Marine biofouling has great infringement to oceanographic engineering material, decreases the work-ing life of material, causes serious financial loss.Research shows, when marine organisms are attached to marine surface, the roughness of hull surface can be increased, reduce the speed of a ship or plane, increase fuel consumption etc., according to statistics, biodeterioration can make the fuel oil consumption of steamer increase by 40%, China has at least the financial loss of 90,000,000,000 yuan to be caused by corrosion every year, and the ratio of marine corrosion accounts for more than 30%, and wherein 30% of marine material corrosion total amount adheres to relevant to marine microorganism.Therefore, studying novel anti-soil corrosion protection coating technology to alleviate hull fouling problem is need the problem in science of solution badly, develops a kind of anti-corrosion, antifouling compound coating of having concurrently and technology of preparing is very important.
Hot-spraying techniques is a kind of surface strengthening technology, and its film forming efficiency is high, be applicable to industrialization scale operation, and the coating of acquisition has good bonding strength, excellent mechanical property and good functional performance, as anti-corrosion, fouling resistance, superhard, wear-resisting etc.In recent years, along with the reinforcement of people's environmental consciousness, the understanding of energy-saving and emission-reduction, the strategy of sustainable development, anti-corrosion, the anti-biological stained performance on oceanographic engineering material or marine settings surface becomes one of study hotspot.High molecular polymer has light, easy-formation, with low cost, resistance to chemical attack, the advantage such as lower temperature resistance and electrical isolation and being widely used because of it, but its lower wear resistance, weathering resistance limit the application of its association area.According to research reports, thermospray polymeric coating has good corrosion resistance nature to root, and the coating of cupric has good anti-biofouling performance.But polymkeric substance applies in hot-spraying techniques that often to there is dusty spray quality light, powder flowbility is poor, be sprayed into the problems such as membrane efficiency is low, thus limits the application of polymkeric substance in thermospray.Chinese invention patent (CN102776511A, publication date 2012.11.14) disclose the preparation method that a kind of pottery is the metal composite coating of matrix, this preparation method comprises the steps: a) alligatoring ceramic matrix, b) ultrasonic cleaning, c) thermospray middle layer, d) cleaning, drying, e) applies coating metal, f) sanding and polishing.Therefore, develop, improve polymer flowability, improve film forming efficiency, making it adapt to hot-spraying techniques is one of emphasis of current thermospray polymeric coating research.
Electroless plating technology is that one effectively improves polymer surfaces performance, improves one of polymkeric substance use properties, life-span most effective means.Polymer chemistry plating has many advantages: with low cost, technological operation is simple, throughput is higher, chemical plating coating is even, makes a concerted effort strong, be applicable to the plastics of any complicated shape with plastic tie.Being of wide application of electroless plating, comprises metal and metal, metal and semi-conductor, metal and isolator.Chinese invention patent (CN102296332A, publication date 2011.12.28) disclose a kind of method of polyethylene surface direct plating conducting metal, Polyethylene Particles is through oil removing, alligatoring, reduction, preimpregnation, activation and metal replacement, and metal replacement is placed in electroplate liquid and electroplates.Due to polyethylene poor heat resistance, about 100 DEG C easy meltings, the conducting metal of plating on Polyethylene Particles surface loses the characteristic of electroconductibility by losing substrate, the particulate of polyethylene surface direct plating conducting metal is applied on lithium ion battery, conductive agent as positive electrode active materials or negative active core-shell material uses, and this technical scheme is mainly in order to improve electroconductibility.
Summary of the invention
Technical problem to be solved by this invention is: provide a kind of novel metal/polymer compound coating and preparation method thereof, thus realizes compound coating and possess excellent Corrosion Protection and anti-biological stained performance.
The present invention solves the problems of the technologies described above adopted technical scheme: provide a kind of metal/polymer compound coating, comprise the composite bed of substrate and substrate surface, described composite bed comprises metal and polymkeric substance, the volume fraction of described metal is 5 ~ 50%, and the volume fraction of described polymkeric substance is 50 ~ 95%; Described metal is copper or nickel; Described polymkeric substance is polyethylene, polypropylene, tetrafluoroethylene or polyimide.
Be preferably, described metal is copper, and volume fraction is 8 ~ 10%; Described polymkeric substance is polyethylene, and volume fraction is 90 ~ 92%.When the volume fraction of copper is 8 ~ 10%, the sterilization of compound coating and the performance of anti-biofouling more excellent; When poly volume fraction is 90 ~ 92%, chemical stability and the resistance to acids and bases of compound coating are more excellent.
Described substrate is: Q235 steel, Q345 steel, 45 steel, 304 stainless steels, 316 stainless steels or cast iron; The thickness of described composite bed is 100 μm ~ 1mm.
The advantage of this coating structure: the chemical stability of the polymkeric substance in compound coating is good, resistance to acids and bases is strong, can effectively completely cut off the corrosive nature of corrosive medium to body material; Metal in compound coating as sterilant, can play sterilization and anti-biofouling.Metallics is uniformly distributed in compound coating, is conducive to the slowly-releasing release of metallics and long-term release.
The present invention also provides a kind of preparation method of metal/polymer compound coating, comprises the steps:
1) metal/polymer complex microsphere is prepared;
2) surface degreasing, roughening treatment are carried out in substrate;
3) by step 1) the metal/polymer complex microsphere prepared by heat spraying method, in step 2) substrate surface that processes prepares composite bed, namely obtain metal/polymer compound coating.
Metallized by macromolecule surface, the mobility of irregular micron polymeric powder can be significantly improved, reduce the granularity threshold of polymeric powder used for hot spraying, guarantee that polymeric powder fully melts and obtains fine and close compound coating.Be compared to metal and polymer mechanically mixing powder as spraying starting material, the method can avoid the problems such as the insufficient or polymer burning of the melting of metal that do not mate and cause because of metal and polymer fusing point, and then obtain finer and close weave construction, effectively avoid polymer to decompose and the degradation that causes simultaneously.
The preparation method of described metal/polymer complex microsphere is: polymer powder acetone is carried out ultrasonic cleaning, after having cleaned, carry out successively deoiling, alligatoring, sensitization, activating pretreatment, then in chemical plating metal liquid, chemical plating metal is carried out to pretreated polymer powder, in plating process, regulate pH value to be neutral, after plating metal completes by NaOH solution, take out, with deionized water rinsing, dry, namely obtain metal/polymer complex microsphere.
Described heat spraying method comprises: flame plating, hypersonic flame spraying or cold spraying.
Described heat spraying method is preferably flame plating, and its spray parameters is: combustion-supporting gas is O
2, combustion gas is acetylene, assisted gas is pressurized air, wherein pressure is respectively 0.2 ~ 1.0MPa, 0.05 ~ 0.4MPa, 0.3 ~ 6.0MPa, powder feeding rate is 10 ~ 100g/min, and spray distance is 100 ~ 300mm, flame spray gun translational speed 50 ~ 400mm/s, coating spraying number of times 1 ~ 30 time.
Described metal/polymer complex microsphere is preferably polyethylene/copper complex microsphere; The method of described flame plating, its spray parameters is: combustion-supporting gas is O
2, pressure is 0.5 ~ 0.6MPa; Combustion gas is acetylene, and pressure is 0.07 ~ 0.08MPa; Assisted gas is pressurized air, and pressure is 0.75 ~ 0.85MPa; Powder feeding rate is 55 ~ 65g/min, and spray distance is 240 ~ 260mm, flame spray gun translational speed 190 ~ 210mm/s, coating spraying number of times 5 ~ 7 times.When metal/polymer complex microsphere is polyethylene/copper complex microsphere, the spray parameters of flame plating adjusts according to the complex microsphere of spraying, makes to obtain metal/polymer compound coating and has more outstanding anti-fouling and etch-proof performance.
Described step 2) in method of roughening be preferably sandblasting, cutting thread, annular knurl or electric plucking.
At present, there is respective shortcoming in anti-fouling, erosion shield and preparation method thereof, effectively can take into account i.e. anti-fouling but also protection against corrosion.Compared with prior art, tool has the following advantages coating of the present invention and preparation method thereof:
(1) even, fine and close coating can be prepared at multiple substrate surface, be combined with matrix well, can anti-fouling and Corrosion Protection effectively, can be applicable to multiple ocean industrial part outside surface etc. needs resistance to stained, corrosion-resistant occasion.
(2) adopt hot-spraying techniques to prepare coating and prepare compound coating, its equipment cost is low, and technique is simple, and efficiency is high, is applicable to site operation, and spraying is not subject to the restriction of workpiece size and shape, and cost is low.Therefore, this compound coating has a good application prospect and economic benefit in anti-corrosion sterilization, anti-biological stained field.
Accompanying drawing explanation
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 compound coating prepared by embodiment 2;
Fig. 3 is coating anti-fouling effect figure prepared by embodiment 2, and (a) is PE coating, and (b) is Ni coating, and (c) is PE/Ni compound coating, and arrow is designated as bacterium;
Fig. 4 is coating antiseptic design sketch prepared by embodiment 1, and (a) is PE coating, and (b) is Cu coating, and (c) is PE/Cu compound coating.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail:
For characterizing the performance of a kind of metal/polymer compound coating in the present invention, utilizing X-ray diffractometer (XRD) and field emission scanning electron microscope (SEM) to characterize the coating sample prepared, is below concrete method for testing performance.
(1) coating substance detects mutually: the sample of preparation is placed in deionized water solution supersound process 10min, then dries up, and finally utilizes X-ray diffractometer to detect its thing phase.
(2) surface microscopic topographic is observed: the sample of preparation is placed in deionized water solution supersound process 30min, then dries up, and last surface spray Au, utilizes field emission scanning electron microscope to observe its surface microscopic topographic.
(3) section microscopic appearance is observed: the sample of preparation is used 400#, 800#, 1200#, 1500#, 2000# sand papering, polishing successively, then deionized water solution supersound process 5min is placed in, dry up, last surface spray Au, utilizes field emission scanning electron microscope to observe its section microscopic appearance.
Embodiment 1:
In the present embodiment, body material is the Q235 steel disc that thickness is about 2mm, and the thickness of matrix surface PE/Cu compound coating is 400 μm, and coating is combined with body material well; The concrete preparation method of this PE/Cu compound coating is as follows:
1, polyethylene powders acetone is carried out ultrasonic cleaning, after having cleaned, carry out successively deoiling, alligatoring, sensitization, activating pretreatment, then in electroless copper plating solution, electroless copper is carried out to pretreated polyethylene powders, regulate pH value by NaOH solution in plating process, after copper facing completes, take out, with deionized water rinsing, dry, namely obtain PE/Cu complex microsphere;
2, cleaned with acetone, hydrochloric acid, deionized water successively by matrix, adopt 60 order corundum sands to carry out surface sand-blasting roughening treatment to Q235 steel disc, the air pressure that sandblasting adopts respectively is 0.5MPa, makes its roughness reach spraying requirement;
3, adopt flame spraying method, with the PE/Cu microsphere particle prepared for spray material, form at matrix surface the PE/Cu compound coating that thickness is about 300 μm.Wherein, the spray parameters controlling flame plating is: combustion-supporting gas is O
2, combustion gas is acetylene, assisted gas is pressurized air, wherein pressure is respectively 0.55MPa, 0.075MPa, 0.8MPa, and powder feeding rate is 60g/min, and spray distance is 250mm, flame spray gun translational speed 200mm/s, coating spraying number of times 6 times.
Following Performance Detection is carried out to the coating of above-mentioned preparation:
(1) coating cross sections microstructure morphology is observed: utilize field emission scanning electron microscope (SEM) to detect coating cross sections microscopic appearance, and confirm that coat-thickness is 300 μm, coating is combined with matrix well, and coating is fine and close.
(2) corrosion resistance coating test: utilize the accurate salt spray tester of JK/60A to carry out neutral salt spray test, experiment condition is: probe temperature 35 DEG C, strength of solution 50g/L, solution PH 6.9, spray pressure 1Kgf/cm
2, as shown in Figure 4.Utilize field emission scanning electron microscope (SEM) to detect the rear coatingsurface microscopic appearance of test, confirm to compare with PE coating with copper coating, the preservative effect of PE/Cu compound coating is best.
(3) coating antifouling property test: to select in ocean typical genus bacillus as bacterium source, the process such as (being impregnated in by sample in the artificial seawater containing nutrient solution, constant temperature culture 3 days), fixing, dehydration is attached successively through microbial culture (2216E nutrient solution, vibration, constant incubator are cultivated), bacterium.Utilize field emission scanning electron microscope (SEM) to detect the rear coatingsurface microscopic appearance of test, confirm compared with PE coating, the bacterial number that Cu/PE compound coating surface attaches is few, and good antifouling effect is suitable with copper coating.
Embodiment 2:
In the present embodiment, body material is 45 steel discs that thickness is about 2mm, and the thickness of matrix surface PE/Ni compound coating is 400 μm, and coating is combined with body material well; The concrete preparation method of this PE/Ni compound coating is as follows:
1, polyethylene powders acetone is carried out ultrasonic cleaning, after having cleaned, carry out alligatoring, sensitization, activating pretreatment successively, then in chemical nickel-plating plating solution, chemical nickel plating is carried out to pretreated polyethylene powders, after nickel plating completes, take out, with deionized water rinsing, dry, namely obtain PE/Ni complex microsphere;
2, cleaned with acetone, hydrochloric acid, deionized water successively by matrix, adopt 60 order corundum sands to carry out surface sand-blasting roughening treatment to 45 steel discs, the air pressure that sandblasting adopts respectively is 0.5MPa and 0.3MPa, makes its roughness reach spraying requirement;
3, adopt flame spraying method, with the PE/Ni microsphere particle prepared for spray material, form at matrix surface the PE/Ni compound coating that thickness is about 400 μm.Wherein, the spray parameters controlling flame plating is: combustion-supporting gas is O
2, combustion gas is acetylene, assisted gas is pressurized air, wherein pressure is respectively 0.55MPa, 0.075MPa, 0.8MPa, powder feeding rate is 60g/min, and spray distance is 250mm, flame spray gun translational speed 200mm/s, coating spraying number of times 6 times, the section microscopic appearance figure of the PE/Ni compound coating obtained 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: utilize field emission scanning electron microscope (SEM) to detect coating cross sections microscopic appearance, and confirm that coat-thickness is 300 μm, coating is combined with matrix well, and coating is fine and close.
(2) corrosion resistance coating test: utilize the accurate salt spray tester of JK/60A to carry out neutral salt spray test, experiment condition is: probe temperature 35 DEG C, strength of solution 50g/L, solution PH 6.7, spray pressure 1Kgf/cm
2.Utilize field emission scanning electron microscope (SEM) to detect the rear coatingsurface microscopic appearance of test, confirm to compare with PE coating with nickel coating, the preservative effect of PE/Ni compound coating is best.
(3) coating antifouling property test: to select in ocean typical genus bacillus as bacterium source, the process such as (being impregnated in by sample in the artificial seawater containing nutrient solution, constant temperature culture 3 days), fixing, dehydration is attached successively through microbial culture (2216E nutrient solution, vibration, constant incubator are cultivated), bacterium.Utilize field emission scanning electron microscope (SEM) to detect the rear coatingsurface microscopic appearance of test, as shown in Figure 3, confirm to compare with PE coating with nickel coating, the bacterial number that PE/Ni compound coating surface attaches is minimum, and anti-fouling effect is best.
Embodiment 3:
In the present embodiment, body material is the Q345 steel disc that thickness is about 2mm, and the thickness of this matrix surface PP/Cu compound coating is 400 μm, and coating is combined with body material well; The concrete preparation method of this PP/Cu compound coating is as follows:
1, polypropylene powder acetone is carried out ultrasonic cleaning, after having cleaned, carry out successively deoiling, alligatoring, sensitization, activating pretreatment, then in electroless copper plating solution, electroless copper is carried out to pretreated polypropylene powder, regulate pH value by NaOH solution in plating process, after copper facing completes, take out, with deionized water rinsing, dry, namely obtain PP/Cu complex microsphere;
2, cleaned with acetone, hydrochloric acid, deionized water successively by matrix, adopt 60 order corundum sands to carry out surface sand-blasting roughening treatment to Q345 steel disc, the air pressure that sandblasting adopts respectively is 0.5MPa and 0.3MPa, makes its roughness reach spraying requirement;
3, adopt flame spraying method, with the PP/Cu microsphere particle prepared for spray material, form at matrix surface the PP/Cu compound coating that thickness is about 400 μm.Wherein, the spray parameters controlling flame plating is: combustion-supporting gas is O
2, combustion gas is acetylene, assisted gas is pressurized air, wherein pressure is respectively 0.55MPa, 0.075MPa, 0.8MPa, and powder feeding rate is 60g/min, and spray distance is 250mm, flame spray gun translational speed 200mm/s, coating spraying number of times 6 times.
Following Performance Detection is carried out to the coating of above-mentioned preparation:
(1) coating cross sections microstructure morphology is observed: utilize field emission scanning electron microscope (SEM) to detect coating cross sections microscopic appearance, and confirm that coat-thickness is 300 μm, coating is combined with matrix well, and coating is fine and close.
(2) corrosion resistance coating test: utilize the accurate salt spray tester of JK/60A to carry out neutral salt spray test, experiment condition is: probe temperature 35 DEG C, strength of solution 50g/L, solution PH 7.0, spray pressure 1Kgf/cm
2.Utilize field emission scanning electron microscope (SEM) to detect the rear coatingsurface microscopic appearance of test, confirm to compare with PP coating with copper coating, the preservative effect of PP/Cu compound coating is best.
(3) coating antifouling property test: to select in ocean typical genus bacillus as bacterium source, the process such as (being impregnated in by sample in the artificial seawater containing nutrient solution, constant temperature culture 3 days), fixing, dehydration is attached successively through microbial culture (2216E nutrient solution, vibration, constant incubator are cultivated), bacterium.Utilize field emission scanning electron microscope (SEM) to detect the rear coatingsurface microscopic appearance of test, confirm compared with PP coating, the bacterial number that PP/Cu compound coating surface attaches is few, and good antifouling effect is suitable with copper coating.
Embodiment 4:
In the present embodiment, body material is 304 stainless steel substrates that thickness is about 2mm, and the thickness of this matrix surface PP/Ni compound coating is 400 μm, and coating is combined with body material well; The concrete preparation method of this PP/Ni compound coating is as follows:
1, polypropylene powder acetone is carried out ultrasonic cleaning, after having cleaned, carry out alligatoring, sensitization, activating pretreatment successively, then in chemical nickel-plating plating solution, chemical nickel plating is carried out to pretreated polypropylene powder, after nickel plating completes, take out, with deionized water rinsing, dry, namely obtain PP/Ni complex microsphere;
2, cleaned with acetone, hydrochloric acid, deionized water successively by matrix, adopt 60 order corundum sands to carry out surface sand-blasting roughening treatment to 304 stainless steel substrates, the air pressure that sandblasting adopts respectively is 0.5MPa and 0.3MPa, makes its roughness reach spraying requirement;
3, adopt flame spraying method, with the PP/Ni microsphere particle prepared for spray material, form at matrix surface the PP/Ni compound coating that thickness is about 400 μm.Wherein, the spray parameters controlling flame plating is: combustion-supporting gas is O
2, combustion gas is acetylene, assisted gas is pressurized air, wherein pressure is respectively 0.55MPa, 0.075MPa, 0.8MPa, and powder feeding rate is 60g/min, and spray distance is 250mm, flame spray gun translational speed 200mm/s, coating spraying number of times 6 times.
Following Performance Detection is carried out to the coating of above-mentioned preparation:
(1) coating cross sections microstructure morphology is observed: utilize field emission scanning electron microscope (SEM) to detect coating cross sections microscopic appearance, and confirm that coat-thickness is 300 μm, coating is combined with matrix well, and coating is fine and close.
(2) corrosion resistance coating test: utilize the accurate salt spray tester of JK/60A to carry out neutral salt spray test, experiment condition is: probe temperature 35 DEG C, strength of solution 50g/L, solution PH 7.2, spray pressure 1Kgf/cm
2.Utilize field emission scanning electron microscope (SEM) to detect the rear coatingsurface microscopic appearance of test, confirm to compare with PP coating with nickel coating, the preservative effect of PP/Ni compound coating is best.
(3) coating antifouling property test: to select in ocean typical genus bacillus as bacterium source, the process such as (being impregnated in by sample in the artificial seawater containing nutrient solution, constant temperature culture 3 days), fixing, dehydration is attached successively through microbial culture (2216E nutrient solution, vibration, constant incubator are cultivated), bacterium.Utilize field emission scanning electron microscope (SEM) to detect the rear coatingsurface microscopic appearance of test, confirm to compare with PP coating with nickel coating, the bacterial number that PP/Ni compound coating surface attaches is minimum, and anti-fouling effect is best.
Embodiment 5:
In the present embodiment, body material is the Q235 steel disc that thickness is about 2mm, and the thickness of this matrix surface PI/Cu compound coating is 300 μm, and coating is combined with body material well; The concrete preparation method of this PI/Cu compound coating is as follows:
1, polyimide plastic powder acetone is carried out ultrasonic cleaning, after having cleaned, carry out successively deoiling, alligatoring, sensitization, activating pretreatment, with deionized water rinsing between each step, then in electroless copper plating solution, electroless copper is carried out to pretreated polyimide powder, regulate pH value by NaOH solution in plating process, after copper facing completes, take out, with deionized water rinsing, dry, namely obtain PI/Cu complex microsphere, the pattern of concrete PI/Cu complex microsphere as shown in Figure 1;
2, cleaned with acetone, hydrochloric acid, deionized water successively by matrix, adopt 60 order corundum sands to carry out surface sand-blasting roughening treatment to Q235 steel disc, the air pressure that sandblasting adopts respectively is 0.5MPa and 0.3MPa, makes its roughness reach spraying requirement;
3, adopt supersonic flame spraying method, with the PI/Cu microsphere particle prepared for spray material, form at matrix surface the PI/Cu compound coating that thickness is about 400 μm.Wherein, the spray parameters controlling hypersonic flame spraying is: combustion-supporting gas is O
2, combustion gas is propane, acceleration gas is pressurized air, its pressure is respectively 1MPa, 0.6MPa, 0.7MPa, and flow is respectively 240slpm, 70slpm, 300slpm, powder feeding gas N
2flow is 15slpm, and powder transfer rate is 50g/min, and spray distance is 300mm, sprays 6 times.
Following Performance Detection is carried out to the coating of above-mentioned preparation:
(1) coating cross sections microstructure morphology is observed: utilize field emission scanning electron microscope (SEM) to detect coating cross sections microscopic appearance, and confirm that coat-thickness is 300 μm, coating is combined with matrix well, and coating is fine and close.
(2) corrosion resistance coating test: utilize the accurate salt spray tester of JK/60A to carry out neutral salt spray test, experiment condition is: probe temperature 35 DEG C, strength of solution 50g/L, solution PH 6.5, spray pressure 1Kgf/cm
2.Utilize field emission scanning electron microscope (SEM) to detect the rear coatingsurface microscopic appearance of test, confirm to compare with PI coating with copper coating, the preservative effect of PI/Cu compound coating is best.
(3) coating antifouling property test: to select in ocean typical genus bacillus as bacterium source, the process such as (being impregnated in by sample in the artificial seawater containing nutrient solution, constant temperature culture 3 days), fixing, dehydration is attached successively through microbial culture (2216E nutrient solution, vibration, constant incubator are cultivated), bacterium.Utilize field emission scanning electron microscope (SEM) to detect the rear coatingsurface microscopic appearance of test, confirm compared with PI coating, the bacterial number that PI/Cu compound coating surface attaches is few, and good antifouling effect is suitable with copper coating.
Embodiment 6:
In the present embodiment, body material is 45 steel discs that thickness is about 2mm, and the thickness of this matrix surface PI/Ni compound coating is 400 μm, and coating is combined with body material well; The concrete preparation method of this PI/Ni compound coating is as follows:
1, polyimide plastic powder acetone is carried out ultrasonic cleaning, after having cleaned, carry out alligatoring, sensitization, activating pretreatment successively, with deionized water rinsing between each step, then in chemical nickel-plating plating solution, chemical nickel plating is carried out, after nickel plating completes to pretreated polyimide powder, take out, with deionized water rinsing, dry, namely obtain PI/Ni complex microsphere;
2, cleaned with acetone, hydrochloric acid, deionized water successively by matrix, adopt 60 order corundum sands to carry out surface sand-blasting roughening treatment to 45 steel discs, the air pressure that sandblasting adopts respectively is 0.5MPa and 0.3MPa, makes its roughness reach spraying requirement;
3, adopt cold spray-coating method, with the PI/Ni microsphere particle prepared for spray material, form at matrix surface the PI/Ni compound coating that thickness is about 400 μm.Wherein, the spray parameters controlling cold spraying is: nitrogen is main gas, temperature 500 DEG C, pressure 3MPa; Argon gas is powder feeding gas, room temperature, pressure 3.1MPa; Powder mass flow 50g/min, spray distance 30mm, cold spray gun translational speed 200mm/s, coating spraying number of times 6 times.
Following Performance Detection is carried out to the coating of above-mentioned preparation:
(1) coating cross sections microstructure morphology is observed: utilize field emission scanning electron microscope (SEM) to detect coating cross sections microscopic appearance, and confirm that coat-thickness is 400 μm, coating is combined with matrix well, and coating is fine and close.
(2) corrosion resistance coating test: utilize the accurate salt spray tester of JK/60A to carry out neutral salt spray test, experiment condition is: probe temperature 35 DEG C, strength of solution 50g/L, solution PH 6.6, spray pressure 1Kgf/cm
2.Utilize field emission scanning electron microscope (SEM) to detect the rear coatingsurface microscopic appearance of test, confirm to compare with PI coating with nickel coating, the preservative effect of PI/Ni compound coating is best.
(3) coating antifouling property test: to select in ocean typical genus bacillus as bacterium source, the process such as (being impregnated in by sample in the artificial seawater containing nutrient solution, constant temperature culture 3 days), fixing, dehydration is attached successively through microbial culture (2216E nutrient solution, vibration, constant incubator are cultivated), bacterium.Utilize field emission scanning electron microscope (SEM) to detect the rear coatingsurface microscopic appearance of test, confirm to compare with PI coating with nickel coating, the bacterial number that PI/Ni compound coating surface attaches is minimum, and anti-fouling effect is best.
Claims (8)
1. a metal/polymer compound coating, is characterized in that, comprises the composite bed of substrate and substrate surface, and described composite bed comprises metal and polymkeric substance, and the volume fraction of described metal is 5 ~ 50%, and the volume fraction of described polymkeric substance is 50 ~ 95%; Described metal is copper or nickel; Described polymkeric substance is polyethylene, polypropylene, tetrafluoroethylene or polyimide.
2. metal/polymer compound coating according to claim 1, is characterized in that, described metal is copper, and volume fraction is 8 ~ 10%; Described polymkeric substance is polyethylene, and volume fraction is 90 ~ 92%.
3. metal/polymer compound coating according to claim 1, is characterized in that, the thickness of described composite bed is 100 μm ~ 1mm.
4. a preparation method for the metal/polymer compound coating as described in claims 1 to 3, is characterized in that, comprise the steps:
1) metal/polymer complex microsphere is prepared;
2) surface degreasing, roughening treatment are carried out in substrate;
3) by step 1) the metal/polymer complex microsphere prepared by heat spraying method, in step 2) substrate surface that processes prepares composite bed, namely obtain metal/polymer compound coating.
5. the preparation method of metal/polymer compound coating according to claim 4, it is characterized in that, the preparation method of described metal/polymer complex microsphere is: polymer powder acetone is carried out ultrasonic cleaning, carry out successively deoiling, alligatoring, sensitization, activating pretreatment, then in chemical plating metal liquid, chemical plating metal is carried out to pretreated polymer powder, pH value is regulated to be neutral by NaOH solution in plating process, after plating metal completes, namely obtain metal/polymer complex microsphere.
6. the preparation method of metal/polymer compound coating according to claim 4, is characterized in that, described heat spraying method comprises: flame plating, hypersonic flame spraying or cold spraying.
7. the preparation method of metal/polymer compound coating according to claim 6, is characterized in that, the method for described flame plating, and its spray parameters is: combustion-supporting gas is O
2, pressure is 0.2 ~ 1.0MPa; Combustion gas is acetylene, and pressure is 0.05 ~ 0.4MPa; Assisted gas is pressurized air, and pressure is 0.3 ~ 6.0MPa; Powder feeding rate is 10 ~ 100g/min, and spray distance is 100 ~ 300mm, flame spray gun translational speed 50 ~ 400mm/s, coating spraying number of times 1 ~ 30 time.
8. the preparation method of metal/polymer compound coating according to claim 7, is characterized in that, described metal/polymer complex microsphere is polyethylene/copper complex microsphere, the method for described flame plating, and its spray parameters is: combustion-supporting gas is O
2, pressure is 0.5 ~ 0.6MPa; Combustion gas is acetylene, and pressure is 0.07 ~ 0.08MPa; Assisted gas is pressurized air, and pressure is 0.75 ~ 0.85MPa; Powder feeding rate is 55 ~ 65g/min, and spray distance is 240 ~ 260mm, flame spray gun translational speed 190 ~ 210mm/s, coating spraying number of times 5 ~ 7 times.
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