CN108047797A - Composite nano materials, its preparation method and application - Google Patents
Composite nano materials, its preparation method and application Download PDFInfo
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- CN108047797A CN108047797A CN201711209958.1A CN201711209958A CN108047797A CN 108047797 A CN108047797 A CN 108047797A CN 201711209958 A CN201711209958 A CN 201711209958A CN 108047797 A CN108047797 A CN 108047797A
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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
- C09D5/1612—Non-macromolecular compounds
- C09D5/1618—Non-macromolecular compounds inorganic
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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
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2262—Oxides; Hydroxides of metals of manganese
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2289—Oxides; Hydroxides of metals of cobalt
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The present invention relates to marine antifouling coating technical fields, specifically disclose a kind of composite nano materials.The composite nano materials of the present invention are by MnO, CoO and TiO2Composition, molar ratio are (1~15)：(1~15)：(1~100)；Composite nano materials are by transition metal element and rare earth doped；Using the quality of composite nano materials as 100%, the mass percent of the transition metal element of doping is 0.1%~5%, and the mass percent of the rare earth element of doping is 0.1%~3%.The composite nano materials of the present invention are at low concentrations respectively provided with marine microorganism, the soft fouling organism seaweed in ocean, ocean Macro-fouling Organismss mussel significant inhibition adhesion effect, show the efficient, antifouling activity of wide spectrum；Preparation process is simple, workable, while antifouling property protrudes, and has a extensive future.
Description
Technical field
The present invention relates to marine antifouling coating technical field, more particularly to a kind of composite nano materials, its preparation method and
Using.
Background technology
As the mankind to marine resources development and utilize increasingly deep, harm caused by marine biofouling has been drawn
Great attention and the extensive concern of countries in the world are played.Marine environment is a serious environment of burn into biodeterioration.It gives birth to ocean
Object is stained the marine organisms such as the microorganism referred in ocean, vegetalitas biology, animality biology and is adhered to hull or ocean structure
Object surface and make its be subject to destroy the phenomenon that.According to statistics, the whole world direct economic loss as caused by marine biofouling every year
Up to hundred million dollars of 300-500.The main harm of marine biofouling includes：(1) increase hull bottom roughness, ship's navigation is caused to hinder
Power increases, energy consumption is aggravated with discharge, and high risks are brought to ship's navigation.(2) accelerate the structural members such as marine facility, building dirty
Damage corrosion, significantly shortens their service life.(3) aquaculture net cage, mesh, the line clogging such as etting of fixation fishing are caused.(4) damage
Bad oceanographic instrumentation causes instrument transmission mechanism failure, distorted signals, reduced performance or even security risk, tremendous economic is caused to damage
It loses.Therefore, how effectively to inhibit marine biofouling to have become mankind's reasonable development and utilize marine resources urgently to be resolved hurrily
Key issue.At present, common means of defence mainly includes coating nonpolluting coating method, electrolytic seawater generates hypochlorite method,
Heavy metal method is electrolysed, method is manually or mechanically removed, works, conductive coat method etc. is made using anti-fouling material.At present, in hull
Or marine structure surface coating antifouling paint is come to inhibit the adherency of marine fouling organism and growth be to solve the problems, such as to be stained most
One of effective strategy.
Marine antifouling coating is a kind of sapecial coating, is mainly made of macromolecule resin, anti-fouling agent, color stuffing, solvent etc.,
Wherein anti-fouling agent is the nucleus that nonpolluting coating inhibits fouling organism adherency.With antifouling with high toxicity and teratogenesis
Agent organic tin compound is disabled by International Maritime Organization (IMO), and other anti-fouling agents such as cuprous oxide, isothiazolinone etc. is wide
General use, however find that these anti-fouling agents have the deficiencies of easy enrichment, difficult degradation, high toxicity in succession, dirt is caused to marine environment
Dye.
The content of the invention
It is contemplated that the defects of overcoming the prior art, provide one kind can inhibit marime fouling microorganism, marine algae,
The attachment of large-scale Fouling Animals, the excellent composite nano materials of antibacterial anti-algae performance.
To achieve the above object, the present invention uses following technical scheme：
On the one hand, the present invention provides a kind of composite nano materials, and the composite nano materials are by MnO, CoO and TiO2Group
Into；Described MnO, CoO and TiO2Molar ratio be (1~15)：(1~15)：(1~100)；The composite nano materials are by transition
Metallic element and rare earth doped；Using the quality of the composite nano materials as 100%, the transition metal element of doping
Mass percent for 0.1%~5%, the mass percent of the rare earth element of doping is 0.1%~3%.
In some embodiments, the transition metal element is selected from least one of platinum or palladium；The rare earth element is selected from
At least one of zirconium, lanthanum or cerium.
In some embodiments, the preparation method of the composite nano materials includes：The system of S1, presoma MnO@CoO@TiO2
It is standby；It is S2, transition element doped, obtain the composite nano materials intermediate of containing transition metal element；S3, rare earth element are mixed
It is miscellaneous.
In some embodiments, the presoma MnO@CoO@TiO2Preparation include：Manganese salt, cobalt salt are weighed in proportion, are matched somebody with somebody
Solution A processed；Under stiring, titanium tetrachloride, NaOH solution are slowly dropped into solution A, continue to be stirred to react 2h~6h, obtained
Even vitreosol is obtained by filtration sediment, and is washed with deionized；By the sediment in vacuum drying chamber, at 60 DEG C
Dry 6h~12h, is subsequently placed in crucible at a temperature of~100 DEG C, in lower 600 DEG C~1000 DEG C high-temperature calcination 4h of reducing atmosphere~
12h, cooled to room temperature.
In some embodiments, in the solution A concentration of manganese salt be 0.05mol/L~1.0mol/L, the cobalt salt it is dense
It spends for 0.05mol/L~1.0mol/L；The concentration of the NaOH solution is 0.05mol/L~2.0mol/L.
It is described rare earth doped using directly joining method in some embodiments, it is included in presoma MnO@CoO@TiO2
Preparation in, after configuring solution A, with a small amount of deionized water by La (NO3)3·6H2O、Ce(NO3)3·6H2O、ZrOCl2·8H2O
It is dissolved into solution A, then under stiring, titanium tetrachloride, NaOH solution is slowly dropped into solution A.
In some embodiments, it is described it is transition element doped including：The presoma that will be prepared in step S1, with by platinum and/or
The transition metal powders of palladium composition are with ratio (20~100):1 is uniformly mixed, and tabletting is placed in crucible, in 1000 DEG C~1500
DEG C high-temperature calcination 1h~6h, cooled to room temperature.
In some embodiments, it is described it is rare earth doped use solid-state combustion method, including by La (NO3)3·6H2O、Ce
(NO3)3·6H2O、ZrOCl2·8H2O and transition metal powders, presoma ground and mixed are uniform, and tabletting is placed in crucible, in
500 DEG C~800 DEG C roasting temperature 5h~8h, cooled to room temperature.
It is described rare earth doped using dipping combustion method in some embodiments, including with a small amount of deionized water by La
(NO3)3·6H2O、Ce(NO3)3·6H2O、ZrOCl2·8H2O dissolves, by La (NO3)3·6H2O、Ce(NO3)3·6H2O、
ZrOCl2·8H2The mixed aqueous solution of O is impregnated into the composite nano materials intermediate of containing transition metal element, ultrasound leaching
It is dried in vacuo after stain 1h~2h at a temperature of 60 DEG C~100 DEG C, afterwards in 500 DEG C~800 DEG C roasting temperature 5h~8h.
Yet another aspect, the present invention provide a kind of application of above-mentioned composite nano materials, and the composite nano materials are used for
Prepare marine antifouling coating or marine antifoulant.
The beneficial effects of the present invention are：The composite nano materials of the present invention are at low concentrations to marine microorganism, ocean
Soft fouling organism seaweed, ocean Macro-fouling Organismss mussel are respectively provided with significant inhibition adhesion effect, show efficient, spectrum
Antifouling activity；There is phobotaxis to marine growth and without apparent lethal, it is environmentally friendly, low-toxicity marine anti-pollution can be used as
Agent is developed and application；Preparation process is simple, workable, while antifouling property protrudes, and has a extensive future.The present invention's answers
Close nano material not only can be applied to marine antifouling coating separately as anti-fouling agent, can also arrange in pairs or groups and play with other anti-fouling agents
Synergistic effect.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, below in conjunction with specific embodiment, to this
Invention is further elaborated.It should be appreciated that specific embodiment described herein is only to explain the present invention, without structure
Into limitation of the present invention.
The composite nano materials of the specific embodiment of the invention are by MnO, CoO and TiO2Composition；Wherein, MnO, CoO and TiO2's
Molar ratio is (1~15)：(1~15)：(1~100)；Composite nano materials are by transition metal element and rare earth doped；With
The quality of composite nano materials is 100%, and the mass percent of the transition metal element of doping is 0.1%~5%, doping
The rare earth element mass percent be 0.1%~3%.Transition metal element is selected from least one of platinum or palladium；It is dilute
Earth elements are selected from least one of zirconium, lanthanum or cerium.In preferred embodiment, transition metal element is simultaneously including platinum and palladium.
The preparation method of the composite nano materials of the specific embodiment of the invention includes：S1, presoma MnO@CoO@TiO2's
It prepares；It is S2, transition element doped, obtain the composite nano materials intermediate of containing transition metal element；S3, rare earth element are mixed
It is miscellaneous.The order of step S2 and S3 are not particularly limited, and can first carry out transition element doped, then are carried out rare earth element and are mixed
It is miscellaneous, transition elements and rare earth element can also be doped together.
Specifically, presoma MnO@CoO@TiO2Preparation include：Manganese salt, cobalt salt are weighed in proportion, prepare solution A, it is molten
The concentration of manganese salt is 0.05mol/L~1.0mol/L in liquid A, and the concentration of cobalt salt is 0.05mol/L~1.0mol/L, and manganese salt can be
Manganese nitrate, manganous chloride etc.；Cobalt salt can be cobalt nitrate or cobaltous dichloride etc.；Under stiring, it is titanium tetrachloride, NaOH solution is slow
It instills in solution A, the concentration of NaOH solution is 0.05mol/L~2.0mol/L, continues to be stirred to react 2h~6h, is obtained uniformly thoroughly
Sediment is obtained by filtration in bright colloidal sol, and is washed with deionized 3 times or more times；By the sediment in vacuum drying chamber,
Dry 6h~12h, is subsequently placed in crucible, is forged in lower 600 DEG C~1000 DEG C high temperature of reducing atmosphere at a temperature of 60 DEG C~100 DEG C
Burn 4h~12h, cooled to room temperature.
In addition to the above method, presoma MnO@CoO@TiO2Also can be prepared by other methods.Such as：Use tetrachloro
Change titanium (TiCl4), manganous chloride (MnCl2), cobaltous dichloride (CoCl2) with urea (CO (NH2)2), ammonium hydroxide (NH3.H2O)、NaOH
The alkaline solutions such as solution react, composite colloid can be generated, after washing or after convection drying, after high-temperature calcination can obtain by MnO,
CoO、TiO2Composite nano materials presoma of composition etc..
Specifically, it is transition element doped including：The presoma that will be prepared in step S1, with the mistake being made of platinum and/or palladium
Metal powder is crossed using mass ratio as (20~100):1 ratio is uniformly mixed, and tabletting is placed in crucible, in 1000 DEG C~1500
DEG C high-temperature calcination 1h~6h, cooled to room temperature.
Directly joining method, solid-state combustion method or dipping combustion method, directly joining method, work can be used in the doping of rare earth element
Skill step is simple；And the antibacterial antifouling activity higher for the composite nano materials that solid-state combustion method is prepared with dipping combustion method,
The antibacterial antifouling activity for impregnating nano material prepared by combustion method is more prominent.During using directly joining method, it is included in presoma
MnO@CoO@TiO2Preparation in, with a small amount of deionized water by La (NO3)3·6H2O、Ce(NO3)3·6H2O、ZrOCl2·8H2O
It is dissolved into solution A, then carries out subsequent operation.During using solid-state combustion method, including by La (NO3)3·6H2O、Ce(NO3)3·
6H2O、ZrOCl2·8H2O and transition metal powders, presoma ground and mixed are uniform, then carry out subsequent operation.It is fired using dipping
During burning method, including with a small amount of deionized water by La (NO3)3·6H2O、Ce(NO3)3·6H2O、ZrOCl2·8H2O dissolves, by La
(NO3)3·6H2O、Ce(NO3)3·6H2O、ZrOCl2·8H2The mixed aqueous solution of O is impregnated into answering for containing transition metal element
It closes in nano material intermediate, is dried in vacuo, is put into Muffle furnace at a temperature of 60 DEG C~100 DEG C after ultrasonic immersing 1h~2h,
Afterwards in 500 DEG C~800 DEG C roasting temperature 5h~8h, final composite nano materials are obtained.
The composite nano materials of the present invention are at low concentrations to marine microorganism, the soft fouling organism seaweed in ocean, ocean
Macro-fouling Organismss mussel is respectively provided with significant inhibition adhesion effect, shows the efficient, antifouling activity of spectrum, can be used as low toxicity
Type marine antifoulant is developed and application.Antifouling paint made of the composite nano materials of the present invention, shallow sea soak test result
Show it with significant anti-fouling effect.Composite nano materials provided by the invention, not only can one-component for marine anti-pollution apply
The preparation of material can also compound with other anti-fouling agents, enhance its anti-fouling effect.
The present invention composite nano materials can be in marine biofouling be prevented application, using include but not limited to making
Standby marine antifouling coating, marine antifoulant etc., contain composite nano materials in marine antifouling coating, can by impregnating, spray or
The usual manners such as coating apply the antifouling paint to artificial ocean facility surface.It in addition, also can be by the composite Nano of the present invention
Material, which is applied to, carries out the antifouling marine Artificial facilities of environmental protection, includes but not limited to：Ship, offshore oil and gas platform, buoy, code
Head, bridge pier, dock, seawater pipeline, timber and net cage for sea farming etc..
It is described in detail below in conjunction with specific embodiment.
Embodiment 1：
With molar ratio n (Mn)：n(Co)：N (Ti)=1：1：Preparation reaction is carried out based on 1.First, nitre is weighed in proportion
Sour manganese, cobalt nitrate prepare solution A, wherein Mn (NO3)2Concentration is 0.05mol/L, Co (NO3)2Concentration is 0.05mol/L；So
Afterwards, under stiring, titanium tetrachloride, the NaOH solution that concentration is 0.05mol/L are slowly dropped into A liquid, continue to be stirred to react 2h,
Homogeneous transparent colloidal sol, filtering precipitate are obtained, and is washed with deionized 3 times；Finally, by gained sediment in vacuum drying chamber
In, 60 DEG C of dryings are subsequently placed in crucible, in the lower 600 DEG C of high-temperature calcination 4h of reducing atmosphere, cooled to room temperature, i.e.,
Obtain presoma MnO@CoO@TiO2。
Embodiment 2：
With molar ratio n (Mn)：n(Co)：N (Ti)=15：9：Preparation reaction is carried out based on 100.First, weigh in proportion
Manganese nitrate, cobalt nitrate prepare solution A, wherein Mn (NO3)2Concentration is 1mol/L, Co (NO3)2Concentration is 1mol/L；Then, exist
Under stirring, titanium tetrachloride, the NaOH solution that concentration is 2mol/L are slowly dropped into A liquid, continues to be stirred to react 6h, obtain uniformly
Vitreosol, filtering precipitate, and be washed with deionized 3 times；Finally, by gained sediment in vacuum drying chamber, 100 DEG C
It is dry, it is subsequently placed in crucible, in the lower 1000 DEG C of high-temperature calcination 12h of reducing atmosphere, cooled to room temperature is to get before
Drive body MnO@CoO@TiO2。
Embodiment 3：
With molar ratio n (Mn)：n(Co)：N (Ti)=10：15：Preparation reaction is carried out based on 50.First, weigh in proportion
Manganese nitrate, cobalt nitrate prepare solution A, wherein Mn (NO3)2Concentration is 0.5mol/L, Co (NO3)2Concentration is 0.5mol/L；So
Afterwards, under stiring, titanium tetrachloride, the NaOH solution that concentration is 1.0mol/L are slowly dropped into A liquid, continue to be stirred to react 4h,
Homogeneous transparent colloidal sol, filtering precipitate are obtained, and is washed with deionized 3 times；Finally, by gained sediment in vacuum drying chamber
In, 80 DEG C of dryings are subsequently placed in crucible, in the lower 800 DEG C of high-temperature calcination 8h of reducing atmosphere, cooled to room temperature, i.e.,
Obtain presoma MnO@CoO@TiO2。
Embodiment 4：
Step S1：With molar ratio n (Mn)：n(Co)：N (Ti)=10：15：Preparation reaction is carried out based on 50.First, press
Ratio weighs manganese nitrate, cobalt nitrate, prepares solution A, wherein Mn (NO3)2Concentration is 0.5mol/L, Co (NO3)2Concentration is
0.5mol/L；Then, under stiring, titanium tetrachloride, the NaOH solution that concentration is 1.0mol/L are slowly dropped into A liquid, continued
4h is stirred to react, obtains homogeneous transparent colloidal sol, filtering precipitate, and is washed with deionized 3 times；Finally, by gained sediment
In vacuum drying chamber, 80 DEG C of dryings are subsequently placed in crucible, naturally cold in the lower 800 DEG C of high-temperature calcinations 8h of reducing atmosphere
But to room temperature to get including MnO, CoO, TiO2The presoma of three kinds of oxides.
Step S2：By the presoma prepared in step S1 and the transition metal powders that are made of platinum (Pt), palladium (Pd) with than
Example 1000:1 is uniformly mixed, and transition elements platinum (Pt), the codope mass percent of palladium (Pd) are 0.1%, and tabletting is placed on earthenware
In crucible, in 1500 DEG C of high-temperature calcination 1h, cooled to room temperature is to get to containing transition metal elements platinum (Pt) and palladium (Pd)
Composite nano materials intermediate.
Embodiment 5：
Step S1：With molar ratio n (Mn)：n(Co)：N (Ti)=10：15：Preparation reaction is carried out based on 50.First, press
Ratio weighs manganese nitrate, cobalt nitrate, prepares solution A, wherein Mn (NO3)2Concentration is 0.5mol/L, Co (NO3)2Concentration is
0.5mol/L；Then, under stiring, titanium tetrachloride, the NaOH solution that concentration is 1.0mol/L are slowly dropped into A liquid, continued
4h is stirred to react, obtains homogeneous transparent colloidal sol, filtering precipitate, and is washed with deionized 3 times；Finally, by gained sediment
In vacuum drying chamber, 80 DEG C of dryings are subsequently placed in crucible, naturally cold in the lower 800 DEG C of high-temperature calcinations 8h of reducing atmosphere
But to room temperature to get including MnO, CoO, TiO2The presoma of three kinds of oxides.
Step S2：By the presoma prepared in step S1 and the transition metal powders that are made of platinum (Pt), palladium (Pd) with than
Example 20:1 is uniformly mixed, and transition elements platinum (Pt), the codope mass percent of palladium (Pd) are 5%, and tabletting is placed in crucible,
In 1000 DEG C of high-temperature calcination 6h, cooled to room temperature is to get to the compound of containing transition metal elements platinum (Pt) and palladium (Pd)
Nano material intermediate.
Embodiment 6：
Step S1：With molar ratio n (Mn)：n(Co)：N (Ti)=10：15：Preparation reaction is carried out based on 50.First, press
Ratio weighs manganese nitrate, cobalt nitrate, prepares solution A, wherein Mn (NO3)2Concentration is 0.5mol/L, Co (NO3)2Concentration is
0.5mol/L；Then, under stiring, titanium tetrachloride, the NaOH solution that concentration is 1.0mol/L are slowly dropped into A liquid, continued
4h is stirred to react, obtains homogeneous transparent colloidal sol, filtering precipitate, and is washed with deionized 3 times；Finally, by gained sediment
In vacuum drying chamber, 80 DEG C of dryings are subsequently placed in crucible, naturally cold in the lower 800 DEG C of high-temperature calcinations 8h of reducing atmosphere
But to room temperature to get including MnO, CoO, TiO2The presoma of three kinds of oxides.
Step S2：By the presoma prepared in step S1 and the transition metal powders that are made of platinum (Pt), palladium (Pd) with than
Example 100:1 is uniformly mixed, and transition elements platinum (Pt), the codope mass percent of palladium (Pd) are 1%, and tabletting is placed on crucible
In, in 1200 DEG C of high-temperature calcination 3h, cooled to room temperature is to get answering to containing transition metal elements platinum (Pt) and palladium (Pd)
Close nano material intermediate.
Embodiment 7：
A kind of composite nano materials intermediate of containing transition metal elements platinum (Pt), wherein the transition elements adulterated is platinum
(Pt) and doping mass percent is 1%, remaining is same as Example 6.
Embodiment 8：
A kind of composite nano materials, doped with transition elements platinum (Pt), palladium (Pd) and rare earth element zirconium (Zr), lanthanum (La),
Cerium (Ce) by MnO, CoO, TiO2The composite nano materials of composition, the molar ratio of principal component is MnO：CoO：TiO2=10：15：
50, and the codope mass percent of transition elements is 1%, the codope mass percent of rare earth element is 1%.Rare earth element
Doping method is dipping combustion method.
Step S1：With molar ratio n (Mn)：n(Co)：N (Ti)=10：15：Preparation reaction is carried out based on 50.First, press
Ratio weighs manganese nitrate, cobalt nitrate, prepares solution A, wherein Mn (NO3)2Concentration is 0.5mol/L, Co (NO3)2Concentration is
0.5mol/L；Then, under stiring, titanium tetrachloride, the NaOH solution that concentration is 1.0mol/L are slowly dropped into A liquid, continued
4h is stirred to react, obtains homogeneous transparent colloidal sol, filtering precipitate, and is washed with deionized 3 times；Finally, by gained sediment
In vacuum drying chamber, 80 DEG C of dryings are subsequently placed in crucible, naturally cold in the lower 800 DEG C of high-temperature calcinations 8h of reducing atmosphere
But to room temperature to get including MnO, CoO, TiO2The presoma of three kinds of oxides.
Step S2：By the presoma prepared in step S1 and the transition metal powders that are made of platinum (Pt), palladium (Pd) with than
Example 100:1 is uniformly mixed, and tabletting is placed in crucible, and in 1200 DEG C of high-temperature calcination 3h, cooled to room temperature is to get to doping
Transition metal element platinum (Pt), palladium (Pd) include MnO, CoO, TiO2Composite nano materials.
Step S3：It is rare earth doped to the nano material intermediate progress prepared in step S2 using dipping combustion method,
Specially：With a small amount of water by La (NO3)3·6H2O、Ce(NO3)3·6H2O、ZrOCl2·8H2O dissolves, by La (NO3)3·6H2O、
Ce(NO3)3·6H2O、ZrOCl2·8H2The mixed aqueous solution of O is impregnated among the nano material intermediate of step S2 preparations, is surpassed
It is dried in vacuo, is put into Muffle furnace at 80 DEG C after sound dipping 2h, 6h is roasted at 650 DEG C, cooled to room temperature is to get multiple
Close nano material.
Embodiment 9：
A kind of composite nano materials, wherein rare earth doped mass percent is 0.1%, remaining and 8 phase of embodiment
Together.
Embodiment 10：
A kind of composite nano materials, wherein rare earth doped mass percent is 3%, remaining is same as Example 8.
Embodiment 11：
A kind of composite nano materials, doped with transition elements platinum (Pt), palladium (Pd) and rare earth element zirconium (Zr), lanthanum (La),
Cerium (Ce) by MnO, CoO, TiO2The composite nano materials of composition, the molar ratio of principal component is MnO：CoO：TiO2=10：15：
50, and the codope mass percent of transition elements is 1%, the codope mass percent of rare earth element is 1%.Rare earth element
Doping method is directly joining method.
Step S1：With molar ratio n (Mn)：n(Co)：N (Ti)=10：15：Preparation reaction is carried out based on 50.First, press
Ratio weighs manganese nitrate, cobalt nitrate, La (NO3)3·6H2O、Ce(NO3)3·6H2O、ZrOCl2·8H2O dissolves, and prepares solution A,
2 concentration of wherein Mn (NO3) is that 2 concentration of 0.5mol/L, Co (NO3) is 0.5mol/L；Then, under stiring, by titanium tetrachloride, dense
The NaOH solution spent for 1.0mol/L is slowly dropped into A liquid, continues to be stirred to react 4h, obtains homogeneous transparent colloidal sol, filtering precipitation
Object, and be washed with deionized 3 times；Finally, by gained sediment in vacuum drying chamber, 80 DEG C of dryings are subsequently placed at
In crucible, in the lower 800 DEG C of high-temperature calcination 8h of reducing atmosphere, cooled to room temperature is to get including MnO, CoO, TiO2Three kinds
The presoma of oxide.
Step S2：By the presoma prepared in step S1 and the transition metal powders that are made of platinum (Pt), palladium (Pd) with than
Example 100:1 is uniformly mixed, and tabletting is placed in crucible, and in 1200 DEG C of high-temperature calcination 3h, cooled to room temperature is received to get compound
Rice material.
Embodiment 12：
A kind of composite nano materials, doped with transition elements platinum (Pt), palladium (Pd) and rare earth element zirconium (Zr), lanthanum (La),
Cerium (Ce) by MnO, CoO, TiO2The composite nano materials of composition, the molar ratio of principal component is MnO：CoO：TiO2=10：15：
50, and the codope mass percent of transition elements is 1%, the codope mass percent of rare earth element is 1%.Rare earth element
Doping method is solid-state combustion method.
Step S1：With molar ratio n (Mn)：n(Co)：N (Ti)=10：15：Preparation reaction is carried out based on 50.First, press
Ratio weighs manganese nitrate, cobalt nitrate, prepares solution A, wherein Mn (NO3)2Concentration is 0.5mol/L, Co (NO3)2Concentration is
0.5mol/L；Then, under stiring, titanium tetrachloride, the NaOH solution that concentration is 1.0mol/L are slowly dropped into A liquid, continued
4h is stirred to react, obtains homogeneous transparent colloidal sol, filtering precipitate, and is washed with deionized 3 times；Finally, by gained sediment
In vacuum drying chamber, 80 DEG C of dryings are subsequently placed in crucible, naturally cold in the lower 800 DEG C of high-temperature calcinations 8h of reducing atmosphere
But to room temperature to get including MnO, CoO, TiO2The presoma of three kinds of oxides.
Step S2：By La (NO3)3·6H2O、Ce(NO3)3·6H2O、ZrOCl2·8H2O and transition metal powders, presoma
Ground and mixed is uniform, adds tabletting and is placed in crucible, and in 1200 DEG C of high-temperature calcination 3h, cooled to room temperature is to get multiple
Close nano material.
Embodiment 13：
A kind of composite nano materials, doped with transition elements platinum (Pt), palladium (Pd) and rare earth element zirconium (Zr), lanthanum (La),
Cerium (Ce) by MnO, CoO, TiO2The composite nano materials of composition, the molar ratio of principal component is MnO：CoO：TiO2=10：15：
50, and the codope mass percent of transition elements is 1%, the codope mass percent of rare earth element is 1%.Rare earth element
Doping method is dipping combustion method.
Step S1：With molar ratio n (Mn)：n(Co)：N (Ti)=10：15：Preparation reaction is carried out based on 50.First, press
Ratio weighs manganese nitrate, cobalt nitrate, prepares solution A, wherein Mn (NO3)2Concentration is 0.5mol/L, Co (NO3)2Concentration is
0.5mol/L；Then, under stiring, titanium tetrachloride, the NaOH solution that concentration is 1.0mol/L are slowly dropped into A liquid, continued
4h is stirred to react, obtains homogeneous transparent colloidal sol, filtering precipitate, and is washed with deionized 3 times；Finally, by gained sediment
In vacuum drying chamber, 80 DEG C of dryings are subsequently placed in crucible, naturally cold in the lower 800 DEG C of high-temperature calcinations 8h of reducing atmosphere
But to room temperature to get including MnO, CoO, TiO2The presoma of three kinds of oxides.
Step S2：By the presoma prepared in step S1 and the transition metal powders that are made of platinum (Pt), palladium (Pd) with than
Example 100:1 is uniformly mixed, and tabletting is placed in crucible, and in 1200 DEG C of high-temperature calcination 3h, cooled to room temperature is to get to doping
Transition metal element platinum (Pt), palladium (Pd) include MnO, CoO, TiO2Composite nano materials.
Step S3：It is rare earth doped to the nano material intermediate progress prepared in step S2 using dipping combustion method,
Specially：With a small amount of water by La (NO3)3·6H2O、Ce(NO3)3·6H2O、ZrOCl2·8H2O dissolves, by La (NO3)3·6H2O、
Ce(NO3)3·6H2O、ZrOCl2·8H2The mixed aqueous solution of O is impregnated among the nano material intermediate of step S2 preparations, is surpassed
Be dried in vacuo after sound dipping 1h at 100 DEG C, be put into Muffle furnace, roast 8h at 500 DEG C, cooled to room temperature to get
Composite nano materials.
Embodiment 14：
A kind of composite nano materials, doped with transition elements platinum (Pt), palladium (Pd) and rare earth element zirconium (Zr), lanthanum (La),
Cerium (Ce) by MnO, CoO, TiO2The composite nano materials of composition, the molar ratio of principal component is MnO：CoO：TiO2=10：15：
50, and the codope mass percent of transition elements is 1%, the codope mass percent of rare earth element is 1%.Rare earth element
Doping method is dipping combustion method.
Step S1：With molar ratio n (Mn)：n(Co)：N (Ti)=10：15：Preparation reaction is carried out based on 50.First, press
Ratio weighs manganese nitrate, cobalt nitrate, prepares solution A, wherein Mn (NO3)2Concentration is 0.5mol/L, Co (NO3)2Concentration is
0.5mol/L；Then, under stiring, titanium tetrachloride, the NaOH solution that concentration is 1.0mol/L are slowly dropped into A liquid, continued
4h is stirred to react, obtains homogeneous transparent colloidal sol, filtering precipitate, and is washed with deionized 3 times；Finally, by gained sediment
In vacuum drying chamber, 80 DEG C of dryings are subsequently placed in crucible, naturally cold in the lower 800 DEG C of high-temperature calcinations 8h of reducing atmosphere
But to room temperature to get including MnO, CoO, TiO2The presoma of three kinds of oxides.
Step S2：By the presoma prepared in step S1 and the transition metal powders that are made of platinum (Pt), palladium (Pd) with than
Example 100:1 is uniformly mixed, and tabletting is placed in crucible, and in 1200 DEG C of high-temperature calcination 3h, cooled to room temperature is to get to doping
The composite nano materials for including MnO, CoO, TiO2 of transition metal element platinum (Pt), palladium (Pd).
Step S3：It is rare earth doped to the nano material intermediate progress prepared in step S2 using dipping combustion method,
Specially：With a small amount of water by La (NO3)3·6H2O、Ce(NO3)3·6H2O、ZrOCl2·8H2O dissolves, by La (NO3)3·6H2O、
Ce(NO3)3·6H2O、ZrOCl2·8H2The mixed aqueous solution of O is impregnated among the nano material intermediate of step S2 preparations, is surpassed
It is dried in vacuo, is put into Muffle furnace at 60 DEG C after sound dipping 2h, 5h is roasted at 800 DEG C, cooled to room temperature is to get multiple
Close nano material.
Embodiment 15：
A kind of composite nano materials, wherein rare earth doped element is zirconium (Zr), remaining is same as Example 8.
Comparative example 1
A kind of marine antifoulant cuprous oxide.
Comparative example 2
A kind of marine antifoulant nano-titanium dioxide.
Performance test
1st, composite nano materials are to the inhibitory action of marime fouling microorganism
The biological detection model of the miniature fouling organism in ocean uses most important miniature fouling organism --- ocean in ocean
Biofouling bacterium.
Marine pseudomonas D2217 is inoculated in 2216E fluid nutrient mediums, shaking table culture is collected by centrifugation thin after overnight
Bacterium is washed with antiseptic sea water and suspension is made, bacterial concentration about 107~109/mL.By embodiment 1-15 resulting materials
It is first dissolved in 2216E fluid nutrient mediums respectively with the anti-fouling agent of comparative example 1-2, then by 0.1,1.0,5.0,15.0,50.0 μ
The concentration of g/mL is mixed with bacterial suspension obtained, is added in culture dish.Using the culture dish of refinement bacterium suspension as control group.
Each experimental group is all provided with 3 parallel cups with control group, and 3h is cultivated at 30 DEG C, and culture dish is gently washed repeatedly with antiseptic sea water.With
4% formalin impregnates culture dish, with distilled water flushing, then dyes 5min with the DAPI of 0.5 μ g/mL.In fluorescence microscopy
10 visuals field is taken to count under mirror at random, obtain the attachment quantity of bacterium, as shown in table 1.
1 each material of table inhibits attachment concentration to the half of marine bacteria D2217
By table 1 as it can be seen that the composite nano materials of the present invention can significantly inhibit marime fouling bacterium D2217 at low concentrations
Attachment, and the antibiotic property of the composite nano materials prepared in the present embodiment 8-15 better than embodiment 1-3 prepare presoma, reality
Apply nano cupric oxide, the nanometer titanic oxide material in the intermediate prepared in a 4-7 and comparative example.
2nd, composite nano materials are to the inhibitory action of the soft fouling organism seaweed in ocean
The biological detection model of the soft fouling organism in ocean represents biological seaweed --- boat-shaped algae using it.Boat-shaped algae is commercially available
In the aquatic institute's algae storehouse of the Chinese Academy of Sciences or isolated from Shenzhen waters acquisition.
Boat-shaped algae is inoculated in Erdchreiber ' s culture mediums, the algae solution cultivated to exponential phase of growth is trained with algae
Nutrient solution is diluted to certain concentration, shakes up spare.By the anti-fouling agent of the material obtained by embodiment 1-15 and comparative example 1-2 respectively first
It is dissolved in Erdchreiber ' s culture mediums, then the concentration by 0.5,5.0,10.0,25,50 μ g/mL and boat-shaped algae obtained
Suspension mixes, and adds in culture dish.To add the culture dish of boat-shaped algae suspension as control group.Each experimental group and control group are all provided with
3 parallel cups, 20 DEG C, culture culture 7 days under conditions of 30001x, culture dish is gently washed with antiseptic sea water repeatedly.Utilize leaf
The characteristic of green element autofluorescence, under fluorescence microscope takes 10 visuals field to count, obtains the attachment quantity of boat-shaped algae, such as table at random
Shown in 2.
2 each material of table inhibits attachment concentration to the half of boat-shaped algae
Experimental result in table 2 confirms that composite nano materials of the present invention can significantly inhibit the attached of boat-shaped algae at low concentrations
It, and anti-algae property is substantially better than nano cupric oxide, the nanometer titanic oxide material in comparative example, is prepared in the present embodiment 8-15
The anti-algae property of composite nano materials is also better than the intermediate prepared in the presoma of embodiment 1-3 preparations, embodiment 4-7.
3rd, composite nano materials are to the inhibitory action of large ocean fouling organism
The biological detection model of ocean Macro-fouling Organismss represents biological Mytilus galloprovincialis using it.Mytilus galloprovincialis adult is in Qingdao City
It gathers and obtains on the reef of marine site, the young cultivates acquisition in laboratory.By the material obtained by embodiment 1-15 and comparative example 1-2
Anti-fouling agent be dissolved in respectively in antiseptic sea water, be configured to 0.5,2.5,5,10 μ g/mL, each solution of 10mL taken to be added to culture respectively
In ware, the antiseptic sea water of 10mL is separately taken to be added in blank culture dish, be set to corresponding control group, each experimental group and control group are all provided with
3 parallel cups, every glass of addition young 30~80.After putting into young 48h, with the adhesion condition of the stereomicroscope observation young,
As a result as shown in table 3.
3 each material of table inhibits attachment concentration to the half of Mytilus galloprovincialis
| Sequence number | EC50/μg/mL | Sequence number | EC50/μg/mL |
| Embodiment 1 | 25.95±0.37 | Embodiment 10 | 5.92±0.20 |
| Embodiment 2 | 23.57±0.45 | Embodiment 11 | 6.88±0.24 |
| Embodiment 3 | 21.18±0.62 | Embodiment 12 | 7.16±0.19 |
| Embodiment 4 | 16.72±0.33 | Embodiment 13 | 6.13±0.25 |
| Embodiment 5 | 12.37±0.29 | Embodiment 14 | 5.96±0.26 |
| Embodiment 6 | 10.49±0.21 | Embodiment 15 | 6.55±0.22 |
| Embodiment 7 | 11.14±0.35 | Comparative example 1 | 45.79±2.15 |
| Embodiment 8 | 5.58±0.24 | Comparative example 2 | 1542.43±17.28 |
| Embodiment 9 | 7.24±0.27 |
Experimental result in table 3 confirms that the composite nano materials can significantly inhibit the attachment of Mytilus galloprovincialis at low concentrations,
And the composite nano materials prepared in the material prepared in the present embodiment 1-15, especially embodiment 8-15 are stained life to large size
The inhibitory action of object Mytilus galloprovincialis is significantly better than nano cupric oxide, nanometer titanic oxide material in comparative example, in embodiment 8-15
The composite nano materials of preparation to the inhibitory action of Macro-fouling Organismss Mytilus galloprovincialis also superior to presoma prepared by embodiment 1-3,
The intermediate prepared in embodiment 4-7.
4th, composite nano materials are to the environment friendly of large ocean fouling organism
After the Mytilus galloprovincialis tested in 3 is handled 3 days in composite nano materials solution, Mytilus galloprovincialis is transferred to fresh seawater
In, seawater is replaced daily, counts byssus number, observes byssus adhesive rate.The result shows that after 3 days embodiment 1-15 prepare it is compound
When the nano-titanium dioxide concentration of nano material and comparative example 2 is less than 25ug/mL, Mytilus galloprovincialis byssus can recover to control group water
It is flat, and when the nano cupric oxide in comparative example 1 acts on Mytilus galloprovincialis with 25ug/mL concentration, Mytilus galloprovincialis byssus is unable to full recovery
It is horizontal (52%) to control group, illustrate that composite nano materials prepared by the present invention are environmentally friendly.
5th, the marine hanging plate test of a kind of novel nano marine antifouling coating containing composite nano materials
With reference to national standard《Anti-fouling paint model shallow sea soak test method》(GB/T 5370-2007) examines this compound to receive
Rice material is as antifouling efficiency of the marine antifoulant in Shenzhen sea area.Using epoxy resin as film forming matter, embodiment is separately added into
Composite nano materials prepare nano antifouling coating and comparative example marine antifoulant, Yu Haiyang fouling organism vigorous summer
Panel experiment is carried out, wherein control group is the panel experiment for blank plate, on natural sea area hanging plate 3 months, computing board
Fouling organism coverage, as a result as shown in table 4.
The marine antifouling coating sea hanging plate test result of 4 each material preparation of table
It can be seen that the test piece for being coated with embodiment 8-15 composite nano-material antifouling coating by data in table 4
The biodeterioration coverage average out to 5% on surface, substantially less than embodiment 1-7 presomas, intermediate nano material are prepared anti-
Dirty coating sample board, comparative example sample board and control group model are especially substantially less than control model (blank plate) average out to
97.8% biodeterioration coverage, showing the composite nano materials of the present invention has good anti-fouling effect.
In summary, composite nano materials of the invention are at low concentrations to marine microorganism, the soft fouling organism in ocean
Seaweed, ocean Macro-fouling Organismss Mytilus galloprovincialis are respectively provided with significant inhibition adhesion effect, show efficient, the antifouling work of spectrum
Property；In addition, also indicating that composite nano materials that there is phobotaxis to the recovery of Mytilus galloprovincialis experiment without lethal, low-toxicity can be used as
Marine antifoulant is developed and application.Antifouling paint made of composite nano materials, shallow sea soak test result also indicate that it has
Significant anti-fouling effect.Composite nano materials provided by the invention, not only can one-component be used for marine antifouling coating preparation,
It can be compounded with other anti-fouling agents, enhance its anti-fouling effect.
The specific embodiment of present invention described above, is not intended to limit the scope of the present invention..Any basis
Various other corresponding changes and deformation made by the technical concept of the present invention, should be included in the guarantor of the claims in the present invention
In the range of shield.
Claims (10)
1. a kind of composite nano materials, which is characterized in that the composite nano materials are by MnO, CoO and TiO2Composition；The MnO,
CoO and TiO2Molar ratio be (1~15)：(1~15)：(1~100)；The composite nano materials by transition metal element and
It is rare earth doped；Using the quality of the composite nano materials as 100%, the quality percentage of the transition metal element of doping
Than being 0.1%~3% for the mass percent of 0.1%~5%, the rare earth element of doping.
2. composite nano materials as described in claim 1, which is characterized in that the transition metal element is in platinum or palladium
It is at least one；The rare earth element is selected from least one of zirconium, lanthanum or cerium.
A kind of 3. preparation method of composite nano materials as described in claim 1, which is characterized in that the preparation method bag
It includes：
S1, presoma MnO@CoO@TiO2Preparation；It is S2, transition element doped, it obtains the compound of containing transition metal element and receives
Rice material intermediate；It is S3, rare earth doped.
4. preparation method as claimed in claim 3, which is characterized in that the presoma MnO@CoO@TiO2Preparation include：It presses
Ratio weighs manganese salt, cobalt salt, prepares solution A；Under stiring, titanium tetrachloride, NaOH solution are slowly dropped into solution A, continued
2h~6h is stirred to react, obtains homogeneous transparent colloidal sol, sediment is obtained by filtration, and is washed with deionized；By the sediment
In vacuum drying chamber, dry 6h~12h, is subsequently placed in crucible, 600 under reducing atmosphere at a temperature of 60 DEG C~100 DEG C
DEG C~1000 DEG C of high-temperature calcination 4h~12h, cooled to room temperature.
5. preparation method as claimed in claim 4, which is characterized in that in the solution A concentration of manganese salt for 0.05mol/L~
1.0mol/L, the concentration of the cobalt salt is 0.05mol/L~1.0mol/L；The concentration of the NaOH solution for 0.05mol/L~
2.0mol/L。
6. preparation method as claimed in claim 4, which is characterized in that described rare earth doped using directly joining method, bag
It includes in presoma MnO@CoO@TiO2Preparation in, after configuring solution A, with a small amount of deionized water by La (NO3)3·6H2O、Ce
(NO3)3·6H2O、ZrOCl2·8H2O is dissolved into solution A, then under stiring, titanium tetrachloride, NaOH solution is slowly dropped into molten
In liquid A.
7. preparation method as claimed in claim 3, which is characterized in that it is described it is transition element doped including：It will be made in step S1
Standby presoma, with the transition metal powders that are made of platinum and/or palladium with mass ratio (20~100):1 is uniformly mixed, after tabletting
It is placed in crucible, in 1000 DEG C~1500 DEG C high-temperature calcination 1h~6h, cooled to room temperature.
8. preparation method as claimed in claim 3, which is characterized in that described rare earth doped using solid-state combustion method, bag
It includes La (NO3)3·6H2O、Ce(NO3)3·6H2O、ZrOCl2·8H2O and transition metal powders, presoma ground and mixed are uniform,
Tabletting is placed in crucible, in 500 DEG C~800 DEG C roasting temperature 5h~8h, cooled to room temperature.
9. preparation method as claimed in claim 3, which is characterized in that described rare earth doped using dipping combustion method, bag
It includes La (NO with a small amount of deionized water3)3·6H2O、Ce(NO3)3·6H2O、ZrOCl2·8H2O dissolves, by La (NO3)3·
6H2O、Ce(NO3)3·6H2O、ZrOCl2·8H2The mixed aqueous solution of O is impregnated into the composite Nano of containing transition metal element
It in material intermediate, is dried in vacuo after ultrasonic immersing 1h~2h at a temperature of 60 DEG C~100 DEG C, afterwards in 500 DEG C~800 DEG C temperature
The lower roasting 5h~8h of degree.
10. a kind of application of composite nano materials as described in claim 1, which is characterized in that the composite nano materials are used
In preparing marine antifouling coating or marine antifoulant.
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| CN110157267A (en) * | 2019-05-30 | 2019-08-23 | 廊坊师范学院 | The preparation method of energy-saving and emission-reduction functional paint and processing method to core plate with holes |
| CN110726804A (en) * | 2019-07-11 | 2020-01-24 | 浙江省海洋开发研究院 | Quick evaluation method for antifouling performance of bionic and low-surface-energy marine antifouling coating |
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| CN101161705A (en) * | 2006-10-13 | 2008-04-16 | 中国科学院化学研究所 | Functional polymer nano composite material and preparation method and uses thereof |
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| CN101563294A (en) * | 2006-10-11 | 2009-10-21 | 巴斯夫欧洲公司 | Method for the production of surface-modified, nanoparticulate metal oxides, metal hydroxides and/or metal oxyhydroxides |
| CN101161705A (en) * | 2006-10-13 | 2008-04-16 | 中国科学院化学研究所 | Functional polymer nano composite material and preparation method and uses thereof |
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| CN110157267A (en) * | 2019-05-30 | 2019-08-23 | 廊坊师范学院 | The preparation method of energy-saving and emission-reduction functional paint and processing method to core plate with holes |
| CN110157267B (en) * | 2019-05-30 | 2021-02-26 | 廊坊师范学院 | Preparation method of energy-saving emission-reducing functional coating and treatment method of core plate with holes |
| CN110726804A (en) * | 2019-07-11 | 2020-01-24 | 浙江省海洋开发研究院 | Quick evaluation method for antifouling performance of bionic and low-surface-energy marine antifouling coating |
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