CN106868441A - A kind of polymer composite coating and its preparation method and application - Google Patents
A kind of polymer composite coating and its preparation method and application Download PDFInfo
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- CN106868441A CN106868441A CN201710041131.8A CN201710041131A CN106868441A CN 106868441 A CN106868441 A CN 106868441A CN 201710041131 A CN201710041131 A CN 201710041131A CN 106868441 A CN106868441 A CN 106868441A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D123/04—Homopolymers or copolymers of ethene
- C09D123/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
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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
- 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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Abstract
The invention discloses a kind of polymer composite coating and its preparation method and application, Inventive polymers composite coating possesses excellent Corrosion Protection and is stained performance with anti-biological, with wide spectrum, efficient, lasting antibacterial effect.Preparation method process is simple of the present invention, low in the pollution of the environment, efficiency high, spraying is not limited by workpiece size and shape, low cost, is adapted to large area and is prepared.Inventive polymers composite coating has a good application prospect and economic benefit in corrosion-resistant, anti-marime fouling field.
Description
Technical field
The present invention relates to the technical field of composite coating, more particularly to a kind of polymer composite coating and preparation method thereof and
Using.
Background technology
Recently as the industry such as maritime traffic, submarine oil and mineral products, sea-farming, desalinization, ocean power generation
Develop rapidly, marine biofouling and corrosion phenomenon are increasingly valued by people.When a kind of material or object immersion sea
After in water, surface is covered by the polymeric material of individual layer soon, forms adjusting film.And then, bacterium, single celled diatom
Can stick in adjusting film quickly, bacterial secretory exocellular polysaccharide, bacterium and matrix, bacterium and substrate are connected with each other, form one
The thin mucous membrane of layer.The housing of the underwaters such as ship, harbour for a long time and contact with sea water, is corroded by seawater, significantly shortens it
Service life；The attachment of marine organisms increases hull bottom roughness, causes ship resistance increase, energy consumption and discharge to aggravate
Even the blocking of some submarine pipelines, causes a series of economic loss.
Wherein, application anti-fouling material is to prevent and kill off biodeterioration most efficient method.Marine antifouling coating is a kind of extraordinary painting
Material, Main Function is to prevent being stained for marine organisms by progressively oozing out for anti-fouling agent in paint film (poison).But, previous is anti-
Dirty coating is suppressing also to cause secondary pollution to marine environment while marine organisms adhere to.Therefore, develop efficiently, wide spectrum,
Lasting environmental protection marine antifouling coating has turned into ocean science worker and technicians and has been devoted to what is solved jointly
Key issue.
Thermal spraying is a kind of important technology of material surface protection, is heated to sprayed on material using thermal source dissolving or semi-soluble
Change state, and with certain speed jet deposition to by pretreatment matrix surface formed coating, its have anti-corrosion, it is wear-resisting,
Various functions such as high temperature resistance, anti-oxidant, heat-insulated, insulation, anti-microwave radiation.Plasma spray technology is due to wide with sprayable material
General, base shape and size is unrestricted, technological operation simple, the features such as be easy to industrialization, be to confer to material surface particularity
The important means that can and strengthen.Also have in stock preparation process that reaction temperature is relatively low, low in the pollution of the environment, yield simultaneously
High, the low advantage of cost.High molecular polymer has light, easy-formation, with low cost, resistant to chemical etching, lower temperature resistance because of it
And be widely used the advantages of electric insulation.
At present, slow release anti-fouling agent is a kind of lossless effective means in anti-ocean in coating or coating, past several
In 10 years, brush the antifouling paint containing poisonous anti-fouling agents such as organotins and be once widely used, although this antifouling paint has very
Good anti-fouling effect, but, the poisonous anti-fouling agent such as organotin is stable in water and can accumulate, and can be endangered by bioconcentration
The evil marine eco-environment even human health.Therefore, International Maritime Organization (IMO) clear stipulaties, from 1 day January in 2008, institute
Having operation naval vessel must not use such coating.In consideration of it, having metal/metal composites, organic insecticidal including anti-fouling agent species
Agent, inorganic nanoparticles, ionic liquid, both sexes organic matter and natural extract etc..
The content of the invention
The invention discloses a kind of polymer composite coating and its preparation method and application, prepared polymer is compound to be applied
Layer possesses excellent Corrosion Protection and is stained performance with anti-biological, with wide spectrum, efficient, lasting antibacterial effect.And technique
Simply, low in the pollution of the environment, efficiency high, spraying is not limited by workpiece size and shape, low cost, is adapted to large area and is prepared.
A kind of polymer composite coating, constitutes the anti-staining agent of the polymer and 10~50wt% for 50~90wt%, described
Polymer is polyethylene, polypropylene or polytetrafluoroethylene (PTFE), and the anti-staining agent is allicin, capsicim, curcumin, chitin, pellet
At least one in peaceful acid, enzyme.
Preferably, described enzyme includes at least one in hydrolase, protease, carbohydrase and lipase.
The chemical stability of the polymer in the polymer composite coating is good, and resistance to acids and bases is strong, can effectively completely cut off corrosion
Corrosiveness of the medium to matrix material；The polymer forms special clad structure for anti-staining agent simultaneously, reaches and delays
Discharge and act on long-term effectively.
Preferably, the polymer is polyethylene, the chemical stability of polyethylene is good, and resistance to acids and bases is strong, can be effective
Corrosiveness of the isolation corrosive medium to matrix material.
The thickness of the polymer composite coating is 50~300 μm.Preferably, the thickness of the polymer composite coating
It is 50~80 μm.Cover light can not effective protection group bottom, the bond strength of blocked up influence coating is easy to fall off.
Present invention also offers a kind of preparation method of above-mentioned polymer composite coating, comprise the following steps that：
Step 1：Prepare spraying raw material；
The spraying raw material is polymer suspension or polymer compound powder end；
Step 2：Matrix carries out surface degreasing and roughening treatment；
Step 3：The spraying raw material that step 1 is prepared sprays shape by heat spraying method in the matrix surface of step 2 treatment
Into described polymer composite coating；Described heat spraying method includes：Flame-spraying, HVAF, plasma spray
Apply or cold spraying.
In step 1, the specific preparation technology of the polymer suspension is as follows：A certain amount of second is added in the polymer
Alcohol, is stirring evenly and then adding into anti-staining agent, obtains final product described polymer suspension.
In step 1, the specific preparation technology at the polymer compound powder end is as follows：Polymer powder is carried out into ultrasonic wave clear
Wash, add anti-staining agent, physical mixed uniformly to obtain described polymer compound powder end after drying.
In step 2, the substrate is Q235 steel, Q345 steel, 45 steel, 304 stainless steels, 316 stainless steels, cast iron, aluminium, glass
Or silicon chip.
In step 2, described roughening treatment is preferably sandblasting, cutting thread, annular knurl or electric plucking.
The spray parameters of the flame-spraying are：Combustion-supporting gas is O2, pressure is 0.2~1.0MPa；Combustion gas is acetylene, pressure
It is 0.05~0.4MPa；Auxiliary gas is compressed air, and pressure is 0.3~6.0MPa；Spray distance is 100~300mm, flame spray
Rifle 50~400mm/s of translational speed, coating spraying number of times 1~20 time.
When spraying raw material is polymer suspension, heat spraying method is preferably plasma spraying, by polymer suspension
It is sent in the flame stream that plasma gun is produced by nozzle, plasma liquid material spraying is carried out in the matrix surface of step 2 treatment.
Preferably, the spray parameters of the plasma spraying are：, used as main gas, hydrogen is used as secondary body, plasma for argon gas
The electric current of spraying is 300~650A, and voltage is 35~55V, and spray distance is 100~250mm, and plasma gun translational speed is
1000~1500mm/s, coating spraying pass is 10~35 times.
Preferably, the spraying raw material is polyethylene/allicin composite powder, heat spraying method uses flame-spraying,
Specifically spray parameters are：Combustion-supporting gas is O2, pressure is 0.2~1.0MPa；Combustion gas is acetylene, and pressure is 0.05~0.4MPa；It is auxiliary
Gas is helped for compressed air, pressure is 0.3~6.0MPa；Spray distance be 100~300mm, flame gun translational speed 50~
400mm/s, coating spraying number of times 2~5 times.
Preferably, the spraying raw material be polyethylene/allicin composite precursor slurry, heat spraying method using etc. from
Son is sprayed, and specific spray parameters are：The electric current of plasma spraying is 300~650A, and voltage is 35~55V, and spray distance is 100
~250mm, plasma gun translational speed is 1000~1500mm/s, and coating spraying pass is 2~10 times.
Present invention also offers a kind of application of above-mentioned polymer composite coating in anti-marime fouling.
Compared with prior art, the present invention has the advantages that：
1st, be wrapped in environmentally friendly anti-staining agent in itself system using polymer as a kind of " crosslinking agent " by the present invention
And it is securely attached to marine material surface.Effectively completely cut off the contact of substrate and air, oxygen, moisture, ion, delay base material
Corrosion rate, while have concurrently wide spectrum, continue antifouling capacity.Reduce the pollution to environment.
2nd, polymer composite coating is prepared using hot-spraying technique, its equipment cost is low, process is simple, efficiency high, environment
Pollution is few, is adapted to site operation, and spraying is not limited by workpiece size and shape, low cost, is adapted to large area and prepares.Therefore,
Polymer composite coating prepared by the method has a good application prospect and economic effect in corrosion-resistant, anti-marime fouling field
Benefit.
Brief description of the drawings
Fig. 1 is the SEM characterization results of polyethylene；
Fig. 2 is the SEM characterization results of garlic powder；
Fig. 3 is the SEM characterization results of polyethylene/garlic powder composite coating PE-50%Garlic；
Fig. 4 is the sterilized detection knot that coating prepared by comparative example 1 and embodiment 1~3 kills gram-positive bacteria bacillus
Really, wherein, (a) be blank group, (b) be PE groups, (c) be PE-10%Garlic groups, (d) be PE-40%Garlic groups, (e) is
PE-50%Garlic groups；
Fig. 5 is that the bacterium of the composite coating of PFA/ ginger powders prepared by embodiment 10 attaches SEM figures.
Specific embodiment
Below in conjunction with the accompanying drawings and embodiment is described in further detail to the present invention.
To characterize the performance of polymer composite coating in the present invention, using X-ray diffractometer (XRD), Flied emission scanning electricity
Sub- microscope (SEM) and contact angle tester, infrared (FTIR) are characterized to the coating sample for preparing, the following is specific
Method for testing performance：
(1) coating substance is mutually detected：The sample of preparation is placed in ultrasonically treated 10min in deionized water solution, is then dried up,
Finally its thing phase is detected using X-ray diffractometer.
(2) surface microscopic topographic observation：The sample of preparation is placed in ultrasonically treated 30min in deionized water solution, then
Au is sprayed on drying, last surface, and its surface microscopic topographic is observed using field emission scanning electron microscope.
(3) section microscopic appearance observation：The sample that will be prepared uses 400#, 800#, 1200#, 1500#, 2000# sand paper successively
Polishing, polishing, are subsequently placed in ultrasonically treated 5min in deionized water solution, dry up, and Au is sprayed on last surface, are scanned using Flied emission
Electron microscope observation its section microscopic appearance.
(4) surface contact angle (angle of wetting) test：Contact angle between testing coating and deionized water.
(5) infrared detection of polymer composite coating：The sample of preparation is placed in ultrasonically treated in deionized water solution
30min, then dries up, using the infrared absorption peak of Fourier infrared spectrograph determination sample.
(7) sterilized detection：The polymer composite coating of preparation is immersed in marine bacteria environment and cultivates a period of time, taken
Go out bacterium solution, be diluted to finite concentration, carry out coated plate, after certain hour, the bacteria colony count on observation culture plate is counted.
(8) bacteriological protection attaches detection：The sample of preparation is immersed in marine bacteria environment and cultivates a period of time, bacterium enters
Row glutaraldehyde is fixed, scanning electron microscopic observation is carried out after Gradient elution using ethanol, critical point drying, and it is attached in material surface, growth shape
State.
Comparative example 1
1st, polyethylene (PE) powder of 100g is weighed, ultrasound is dried；
2nd, matrix is cleaned with acetone, ethanol, deionized water successively, Q235 steel discs is entered using 60 mesh corundum sands
Row surface sand-blasting roughening treatment, the air pressure that sandblasting is respectively adopted is 0.5MPa, its roughness is reached spraying and requires；
3rd, using a diameter of 0.1mm atomizers, sent into after dried polyethylene powders are atomized in flame, finally existed
Matrix surface forms the PE coatings that thickness is about 80 μm.Wherein, the spray parameters for controlling flame-spraying are：Combustion-supporting gas is O2, combustion
Gas is acetylene, atomization gas are compressed air, and wherein pressure is respectively 0.5MPa, 0.1MPa, 0.1MPa, and spray distance is 200mm,
Flame gun translational speed 1200mm/s, wriggling pump rate 20rpm, coating spraying number of times 5 times.
Embodiment 1~3
In three below embodiment, the polymer composite coating of preparation is polyethylene/garlic powder composite coating, wherein garlic
The mass fraction of powder is respectively 10%, 30%, 50%, and PE-10%Garlic, PE-30%Garlic and PE-50% are designated as successively
Garlic.Coating layer thickness is 80 μm, and matrix is the Q235 steel discs of thickness about 2mm, and coating is well combined with matrix material.
The specific preparation method of the polyethylene/garlic powder composite coating is as follows：
1st, polyethylene (PE) powder of 100g is weighed, ultrasound is dried；To being proportionally added into garlic powder in polyethylene powders
(size is 20 μm or so), mechanical agitation finally gives the mixed-powder of polyethylene/garlic powder to uniform；
2nd, matrix is cleaned with acetone, ethanol, deionized water successively, Q235 steel discs is entered using 60 mesh corundum sands
Row surface sand-blasting roughening treatment, the air pressure that sandblasting is respectively adopted is 0.5MPa, its roughness is reached spraying and requires, is conducive to applying
Layer is more firmly bonded in substrate；
3rd, using a diameter of 0.1mm atomizers, fire will be sent into after dried polyethylene/garlic powder mixed-powder atomization
In flame, finally polyethylene/garlic powder composite coating that thickness is about 80 μm is formed in matrix surface.Wherein, flame-spraying is controlled
Spray parameters be：Combustion-supporting gas is O2, combustion gas be that acetylene, atomization gas are compressed air, wherein pressure is respectively 0.5MPa,
0.1MPa, 0.1MPa, spray distance are 220mm, flame gun translational speed 1200mm/s, wriggling pump rate 20rpm, coating spray
Apply number of times 5 times.
Polyethylene/garlic powder composite coating to preparing carries out following performance detection：
(1) coating surface and section microstructure morphology are observed：Detected using field emission scanning electron microscope (SEM) and applied
Layer surface pattern and cross-section morphology, as a result as shown in Figures 1 to 3, wherein, Fig. 1 is the SEM results of polyethylene, and Fig. 2 is garlic
The SEM results of powder, Fig. 3 is the SEM results of polyethylene/garlic powder composite coating PE-50%Garlic.Can by SEM characterization results
Know, gained polyethylene/garlic powder composite coating thickness is about 80 μm, and coating is well combined with matrix, coating is fine and close, environment-friendly
Type anti-staining agent garlic is uniformly distributed in PE coatings.
(2) coating antifouling property test：From Gram-negative bacteria Escherichia coli and gram-positive bacteria bacillus,
Cultivated in nutrient solution, sample is put into certain density bacterium solution, after a period of time, take out sample, it is thin to what is attached on sample
Bacterium carry out glutaraldehyde fix, carry out after Gradient elution using ethanol, critical point drying scanning electron microscopic observation its attach in material surface, it is raw
Long status.Bacterium of drawing a conclusion is having on the coating of environmentally friendly anti-staining agent, and attaching is less, and thalli growth is presented unhealthy
State.
(3) the sterilized detection of coating：From Gram-negative bacteria Escherichia coli and gram-positive bacteria bacillus, will contrast
Coating prepared by example 1 and embodiment 1~3 cultivates a period of time in being immersed in marine bacteria environment, takes out bacterium solution, is diluted to certain
Concentration, carries out coated plate, and after certain hour, the bacteria colony count on observation culture plate is counted, and calculates the sterilizing rate of coating, as a result
As shown in figure 4, wherein, Fig. 4 (a) is blank group, Fig. 4 (b) is PE groups, and Fig. 4 (c) is PE-10%Garlic groups, and Fig. 4 (d) is
PE-30%Garlic groups, Fig. 4 (e) is PE-50%Garlic groups.
Draw a conclusion, with the increase of environmentally friendly anti-soil agent content, the sterilized effect of polyethylene/garlic powder composite coating
Fruit is obviously improved.In polyethylene/garlic powder composite coating, when the doping of garlic powder is 50wt%, for Gram-negative bacteria
The sterilizing rate of Escherichia coli and gram-positive bacteria bacillus reaches 75% or so.
Embodiment 4~6
In three below embodiment, the polymer composite coating of preparation is polyethylene/chilli powder composite coating, wherein capsicum
The mass fraction of powder is respectively 10%, 30%, 50%, and coating layer thickness is 80 μm, and matrix is the Q235 steel discs of thickness about 2mm,
Coating is well combined with matrix material.
The specific preparation method of the polyethylene/chilli powder composite coating is as follows：
1st, polyethylene (PE) powder of 100g is weighed, ultrasound is dried；To being proportionally added into chilli powder in polyethylene powders
(size is 20 μm or so), mechanical agitation finally gives the mixed-powder of polyethylene/chilli powder to uniform；
2nd, matrix is cleaned with acetone, ethanol, deionized water successively, Q235 steel discs is entered using 60 mesh corundum sands
Row surface sand-blasting roughening treatment, the air pressure that sandblasting is respectively adopted is 0.5MPa, its roughness is reached spraying and requires, is conducive to applying
Layer is more firmly bonded in substrate；
3rd, using a diameter of 0.1mm atomizers, fire will be sent into after dried polyethylene/chilli powder mixed-powder atomization
In flame, finally the PE/ chilli powder composite coatings that thickness is about 80 μm are formed in matrix surface.Wherein, the spray of flame-spraying is controlled
Applying parameter is：Combustion-supporting gas is O2, combustion gas be that acetylene, atomization gas are compressed air, wherein pressure is respectively 0.5MPa, 0.1MPa,
0.1MPa, spray distance is 220mm, flame gun translational speed 1200mm/s, wriggling pump rate 20rpm, coating spraying number of times 5
Time.
Polyethylene/chilli powder composite coating to preparing carries out following performance detection：
(1) coating surface and section microstructure morphology are observed：Detected using field emission scanning electron microscope (SEM) and applied
Layer surface pattern and cross-section morphology, from SEM characterization results, gained polyethylene/chilli powder composite coating thickness is about
80 μm, coating is well combined with matrix, and coating is fine and close, and environmentally friendly anti-staining agent chilli powder is uniformly distributed in PE coatings.
(2) coating antifouling property test：From Gram-negative bacteria Escherichia coli and gram-positive bacteria bacillus,
Cultivated in nutrient solution, sample is put into certain density bacterium solution, after a period of time, take out sample, it is thin to what is attached on sample
Bacterium carry out glutaraldehyde fix, carry out after Gradient elution using ethanol, critical point drying scanning electron microscopic observation its attach in material surface, it is raw
Long status.Bacterium of drawing a conclusion is having on the coating of environmentally friendly anti-staining agent, and attaching is less, and thalli growth is presented unhealthy
State.
(3) the sterilized detection of coating：From Gram-negative bacteria Escherichia coli and gram-positive bacteria bacillus, will prepare
Coating be immersed in a period of time cultivated in marine bacteria environment, take out bacterium solution, be diluted to finite concentration, carry out coated plate, necessarily
After time, the bacteria colony count on observation culture plate is counted, and calculates the sterilizing rate of coating.Draw a conclusion, with environmentally friendly
The increase of the content of anti-staining agent, the bactericidal effect of composite coating is obviously improved.
Embodiment 7~9
In three below embodiment, the polymer composite coating of preparation is polyethylene/ginger powder composite coating, wherein ginger
The mass fraction of powder is respectively 10%, 30%, 50%, and coating layer thickness is 80 μm, and matrix is the Q235 steel discs of thickness about 2mm,
Coating is well combined with matrix material.
The specific preparation method of the polyethylene/ginger powder composite coating is as follows：
1st, polyethylene (PE) powder of 100g is weighed, ultrasound is dried；To being proportionally added into ginger powder in polyethylene powders
(size is 20 μm or so), mechanical agitation finally gives the mixed-powder of polyethylene/ginger powder to uniform；
2nd, matrix is cleaned with acetone, ethanol, deionized water successively, Q235 steel discs is entered using 60 mesh corundum sands
Row surface sand-blasting roughening treatment, the air pressure that sandblasting is respectively adopted is 0.5MPa, its roughness is reached spraying and requires, is conducive to applying
Layer is more firmly bonded in substrate；
3rd, using a diameter of 0.1mm atomizers, fire will be sent into after dried polyethylene/ginger powder mixed-powder atomization
In flame, finally the PE/ ginger powder composite coatings that thickness is about 80 μm are formed in matrix surface.Wherein, the spray of flame-spraying is controlled
Applying parameter is：Combustion-supporting gas is O2, combustion gas be that acetylene, atomization gas are compressed air, wherein pressure is respectively 0.5MPa, 0.1MPa,
0.1MPa, spray distance is 220mm, flame gun translational speed 1200mm/s, wriggling pump rate 20rpm, coating spraying number of times 5
Time.
Polyethylene/ginger powder composite coating to preparing carries out following performance detection：
(1) coating surface and section microstructure morphology are observed：Detected using field emission scanning electron microscope (SEM) and applied
Layer surface pattern and cross-section morphology, from SEM characterization results, gained polyethylene/ginger powder composite coating thickness is about
80 μm, coating is well combined with matrix, and coating is fine and close, and environmentally friendly additive ginger powder is uniformly distributed in PE coatings.
(2) coating antifouling property test：From Gram-negative bacteria Escherichia coli and gram-positive bacteria bacillus,
Cultivated in nutrient solution, sample is put into certain density bacterium solution, after a period of time, take out sample, it is thin to what is attached on sample
Bacterium carry out glutaraldehyde fix, carry out after Gradient elution using ethanol, critical point drying scanning electron microscopic observation its attach in material surface, it is raw
Long status.Bacterium of drawing a conclusion is having on the coating of environmentally friendly anti-staining agent, and attaching is less, and thalli growth is presented unhealthy
State.
(3) the sterilized detection of coating：From Gram-negative bacteria Escherichia coli and gram-positive bacteria bacillus, will prepare
Coating be immersed in a period of time cultivated in marine bacteria environment, take out bacterium solution, be diluted to finite concentration, carry out coated plate, necessarily
After time, the bacteria colony count on observation culture plate is counted, and calculates the sterilizing rate of coating.Draw a conclusion, with environmentally friendly
The increase of the content of anti-staining agent, the bactericidal effect of composite coating is obviously improved.
Embodiment 10~12
In three below embodiment, the polymer composite coating of preparation is polytetrafluoroethylene (PTFE)/ginger powder composite coating, wherein
The mass fraction of ginger powder is respectively 10%, 30%, 50%, and coating layer thickness is 80 μm, and matrix is the Q235 steel of thickness about 2mm
Piece, coating is well combined with matrix material.
The specific preparation method of the polytetrafluoroethylene (PTFE)/ginger powder composite coating is as follows：
1st, polytetrafluoroethylene (PTFE) (PFA) powder of 100g is weighed, ultrasound is dried；Added in polytetrafluorethylepowder powder
The alcohol of 1000ml, it is uniform with magnetic stirrer；
2nd, to being proportionally added into ginger powder (size be 20 μm or so), mechanical agitation in the alcohol suspension of polytetrafluoroethylene (PTFE)
To uniform, the suspension of polytetrafluoroethylene (PTFE)/ginger powder is finally given；
3rd, matrix is cleaned with acetone, ethanol, deionized water successively, Q235 steel discs is entered using 60 mesh corundum sands
Row surface sand-blasting roughening treatment, the air pressure that sandblasting is respectively adopted is 0.5MPa, its roughness is reached spraying and requires, is conducive to applying
Layer is more firmly bonded in substrate；
4th, using a diameter of 0.1mm atomizers, flame will be sent into after the suspension atomization of polytetrafluoroethylene (PTFE)/ginger powder
In, finally form the PFA/ ginger powder composite coatings that thickness is about 80 μm in matrix surface.Wherein, the spraying of flame-spraying is controlled
Parameter is：Combustion-supporting gas is O2, combustion gas be that acetylene, atomization gas are compressed air, wherein pressure is respectively 0.5MPa, 0.1MPa,
0.1MPa, spray distance is 220mm, flame gun translational speed 1200mm/s, wriggling pump rate 20rpm, coating spraying number of times 5
Time.
Polytetrafluoroethylene (PTFE)/ginger powder composite coating to preparing carries out following performance detection：
(1) coating surface and section microstructure morphology are observed：Detected using field emission scanning electron microscope (SEM) and applied
Layer surface pattern and cross-section morphology, from SEM characterization results, gained polytetrafluoroethylene (PTFE)/ginger powder composite coating thickness
About 80 μm, coating is well combined with matrix, and coating is fine and close, and environmentally friendly additive ginger powder is uniform in PFA coatings
Distribution.
(2) coating antifouling property test：From Gram-negative bacteria Escherichia coli and gram-positive bacteria bacillus,
Cultivated in nutrient solution, sample is put into certain density bacterium solution, after a period of time, take out sample, it is thin to what is attached on sample
Bacterium carry out glutaraldehyde fix, carry out after Gradient elution using ethanol, critical point drying scanning electron microscopic observation its attach in material surface, it is raw
Long status.Experimental result is as shown in figure 5, be the bacterium of rupture at A in figure, it was therefore concluded that bacterium is having environmentally friendly anti-staining agent
Coating on, attach less, and thalli growth is presented unsound state.
(3) the sterilized detection of coating：From Gram-negative bacteria Escherichia coli and gram-positive bacteria bacillus, will prepare
Coating be immersed in a period of time cultivated in marine bacteria environment, take out bacterium solution, be diluted to finite concentration, carry out coated plate, necessarily
After time, the bacteria colony count on observation culture plate is counted, and calculates the sterilizing rate of coating.Draw a conclusion, with environmentally friendly
The increase of the content of anti-staining agent, the bactericidal effect of composite coating is obviously improved.
Embodiment 13~15
In three below embodiment, the polymer composite coating of preparation is polyethylene/garlic powder composite coating, wherein garlic
The mass fraction of powder is respectively 10%, 30%, 50%, and coating layer thickness is 80 μm, and matrix is the Q235 steel discs of thickness about 2mm,
Coating is well combined with matrix material.
The specific preparation method of the polyethylene/garlic powder composite coating is as follows：
1st, polyethylene (PE) powder of 100g is weighed, ultrasound is dried；To being proportionally added into garlic powder in polyethylene powders
(size is 20 μm or so), mechanical agitation finally gives the mixed-powder of polyethylene/garlic powder to uniform；
2nd, matrix is cleaned with acetone, ethanol, deionized water successively, Q235 steel discs is entered using 60 mesh corundum sands
Row surface sand-blasting roughening treatment, the air pressure that sandblasting is respectively adopted is 0.5MPa, its roughness is reached spraying and requires, is conducive to applying
Layer is more firmly bonded in substrate；
3rd, using plasma spraying method, its spray parameters is：Electric current is 550A, and voltage is 50V, and powder feeding rate is 40g/
Min, spray distance is 150mm, and plasma gun translational speed is 1500mm/s, and coating spraying pass is 5 times.
Polyethylene/garlic powder composite coating to preparing carries out following performance detection：
(1) coating surface and section microstructure morphology are observed：Detected using field emission scanning electron microscope (SEM) and applied
Layer surface pattern and cross-section morphology, coating layer thickness are about 80 μm, and coating is well combined with matrix, and coating is fine and close, environment friend
Good type additive garlic is uniformly distributed in PE coatings.
(2) coating antifouling property test：From Gram-negative bacteria Escherichia coli and gram-positive bacteria bacillus,
Cultivated in nutrient solution, sample is put into certain density bacterium solution, after a period of time, take out sample, it is thin to what is attached on sample
Bacterium carry out glutaraldehyde fix, carry out after Gradient elution using ethanol, critical point drying scanning electron microscopic observation its attach in material surface, it is raw
Long status.Bacterium of drawing a conclusion is having on the coating of environmentally friendly anti-staining agent, and attaching is less, and thalli growth is presented unhealthy
State.
(3) the sterilized detection of coating：From Gram-negative bacteria Escherichia coli and gram-positive bacteria bacillus, will prepare
Coating be immersed in a period of time cultivated in marine bacteria environment, take out bacterium solution, be diluted to finite concentration, carry out coated plate, necessarily
After time, the bacteria colony count on observation culture plate is counted, and calculates the sterilizing rate of coating.Draw a conclusion, with environmentally friendly
The increase of the content of anti-staining agent, the bactericidal effect of composite coating is obviously improved.Adulterate the composite coating of 50% garlic powder, for leather
The sterilizing rate of Lan Shi negative bacterium E. colis and gram-positive bacteria bacillus reaches 75% or so.
Claims (10)
1. a kind of polymer composite coating, it is characterised in that the composition of the polymer composite coating is poly- for 50~90wt%'s
The anti-staining agent of compound and 10~50wt%, the polymer is polyethylene, polypropylene or polytetrafluoroethylene (PTFE), and the anti-staining agent is big
At least one in allicin, capsicim, curcumin, chitin, tannic acid, enzyme.
2. polymer composite coating according to claim 1, it is characterised in that the thickness of the polymer composite coating is
50~300 μm.
3. a kind of preparation method of polymer composite coating according to claim 1 and 2, it is characterised in that specific steps
It is as follows：
Step 1：Prepare spraying raw material；
The spraying raw material is polymer suspension or polymer compound powder end；
Step 2：Matrix carries out surface degreasing and roughening treatment；
Step 3：The spraying raw material that step 1 is prepared sprays to form institute by heat spraying method in the matrix surface of step 2 treatment
The polymer composite coating stated；Described heat spraying method includes：Flame-spraying, HVAF, plasma spraying or
Cold spraying.
4. the preparation method of polymer composite coating according to claim 3, it is characterised in that in step 1, the polymerization
The specific preparation technology of thing suspension is as follows：A certain amount of ethanol is added in the polymer, is stirring evenly and then adding into anti-staining agent, i.e.,
Obtain described polymer suspension.
5. the preparation method of polymer composite coating according to claim 3, it is characterised in that in step 1, the polymerization
The specific preparation technology of composite powder is as follows：Polymer powder is carried out into ultrasonic wave cleaning, anti-staining agent, physics are added after drying
It is well mixed to obtain described polymer compound powder end.
6. the preparation method of polymer composite coating according to claim 3, it is characterised in that the spray of the flame-spraying
Applying parameter is：Combustion-supporting gas is O2, pressure is 0.2~1.0MPa；Combustion gas is acetylene, and pressure is 0.05~0.4MPa；Auxiliary gas be
Compressed air, pressure is 0.3~6.0MPa；Spray distance be 100~300mm, flame gun 50~400mm/s of translational speed,
Coating spraying number of times 1~20 time.
7. the preparation method of polymer composite coating according to claim 3, it is characterised in that the plasma spraying
Spray parameters are：Used as main gas, used as secondary body, the electric current of plasma spraying is 300~650A to hydrogen to argon gas, voltage is 35~
55V, spray distance is 100~250mm, and plasma gun translational speed is 1000~1500mm/s, and coating spraying pass is 10
~35 times.
8. the preparation method of polymer composite coating according to claim 3, it is characterised in that the spraying raw material is poly-
Ethene/allicin composite powder, heat spraying method uses flame-spraying, and specific spray parameters are：Combustion-supporting gas is O2, pressure is
0.2~1.0MPa；Combustion gas is acetylene, and pressure is 0.05~0.4MPa；Auxiliary gas is compressed air, and pressure is 0.3~6.0MPa；
Spray distance is 100~300mm, flame gun 50~400mm/s of translational speed, coating spraying number of times 2~5 times.
9. the preparation method of polymer composite coating according to claim 3, it is characterised in that the spraying raw material is poly-
Ethene/allicin composite precursor slurry, heat spraying method uses plasma spraying, and specific spray parameters are：Plasma spraying
Electric current be 300~650A, voltage be 35~55V, spraying raw material flow be 15~40ml/min, spray distance be 100~
250mm, plasma gun translational speed is 1000~1500mm/s, and coating spraying pass is 2~10 times.
10. application of a kind of polymer composite coating according to claim 1 and 2 in anti-marime fouling.
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| CN108047911A (en) * | 2017-12-15 | 2018-05-18 | 苏州赛斯德工程设备有限公司 | A kind of preparation method of environment-friendly type antifouling of ship's hull coating |
| CN108610892A (en) * | 2018-05-05 | 2018-10-02 | 海南大学 | A kind of ocean steel construction anticorrosion and antifouling water paint and preparation method thereof |
| CN109530192A (en) * | 2018-12-10 | 2019-03-29 | 中国航发贵州黎阳航空动力有限公司 | A kind of casing coat processing method |
| CN112689687A (en) * | 2018-10-09 | 2021-04-20 | 深圳市柔宇科技股份有限公司 | Mask plate and preparation method of mask plate coating |
| CN113969081A (en) * | 2021-09-29 | 2022-01-25 | 中国科学院宁波材料技术与工程研究所 | Polymer-based antifouling coating based on thermal spraying technology, preparation method and application thereof |
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