CN104774537A - Reduction method spirulina nickel-loaded waterborne anticorrosive stealth coating and preparation method thereof - Google Patents

Reduction method spirulina nickel-loaded waterborne anticorrosive stealth coating and preparation method thereof Download PDF

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CN104774537A
CN104774537A CN201510209739.8A CN201510209739A CN104774537A CN 104774537 A CN104774537 A CN 104774537A CN 201510209739 A CN201510209739 A CN 201510209739A CN 104774537 A CN104774537 A CN 104774537A
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spirulina
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coating
agent
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王泽�
董观秀
徐修玲
卢雅琳
谈衡
叶霞
李仁兴
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Jiangsu University of Technology
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Abstract

The invention discloses a reduction-method nickel-loaded water-based anticorrosive stealth coating and a preparation method thereof, wherein the coating is composed of a component A and a component B according to the mass ratio of 1:1, and the component A comprises the following components in parts by mass: 80-120 parts of water-based epoxy resin; 0.2-0.8 part of defoaming agent; 5-15 parts of distilled water; the component B comprises the following components in parts by weight: 20-30 parts of a water-based epoxy curing agent; 0.08-0.15 part of defoaming agent; 1-1.5 parts of a dispersing agent; 20-30 parts of superfine talcum powder; 15-30 parts of zinc phosphate; 0-20 parts of iron oxide red; 15-30 parts of titanium dioxide; 15-30 parts of a spirulina chiral wave absorbing agent; the invention also discloses a preparation method of the coating, wherein the spirulina chiral wave absorbing agent is prepared by a reduction method, the coating prepared by the method has strong binding force with a matrix, has little pollution to the environment, has corrosion resistance and electromagnetic wave absorbability in the marine environment, and can be applied to corrosion prevention and invisibility of the surfaces of steel and iron components such as warships, submarines, underwater detectors, sea-crossing bridges and the like in the marine environment.

Description

Reduction method spirulina nickel-loaded water-repellent preservation invisible coating and preparation method thereof
Technical field
The present invention relates to a kind of coating technology, especially reduction method spirulina nickel-loaded water-repellent preservation invisible coating and preparation method thereof.
Background technology
Along with the development of World Developed Countries military technique, New World general layout is had higher requirement to naval of China military equipment and offshore operation platform, not only has resislance to corrosion from sea water but also has stealthy anti-strike function.Detecting means comparatively conventional in current military affairs have radar, infrared, visible ray, sound wave etc., and wherein extensive with radar, so in stealthy technique, the Radar Cross Section (RCS) of control objectives is important research content.Reducing RCS means utilizes absorbing material first hertzian wave to be sucked material internal, and then is other forms by electromagnetic energy.Due to the special construction of spiral, just form the effect of similar conductive helical circle, occur the magnetic polarization of material, the magnetic polarization of material can be coupled with incident electromagnetic wave, thus produces the effect of inhaling ripple.Metallic nickel has electroconductibility and magnetic simultaneously, a kind of desirable electromagnetic shielding and absorbing material, the special chiral helical structure of spirulina, general single frond diameter is scope is 6 ~ 10 μm, entire length scope is 200 ~ 300 μm, the wavelength of its chirality size range and microwave and infrared portion is close, can act on mutually in theory with incident electromagnetic wave.Combine the nickel with good electrical magnetic properties to be again expected to prepare there is wave-absorbing effect bio-based absorbing material.The most effective means of conventional hardware protection against corrosion is at metallic surface coating corrosion protection coating, isolated corrosive medium and metallic matrix.Along with marine economy and marine industries are upgraded further, require coating permanent protective property energy, low consumption of resources and environmental ecology friendly.Therefore, reduction method spirulina nickel-loaded water-repellent preservation invisible coating not only has anticorrosion Stealth Fighter, and has environmental ecology friendly.
Summary of the invention
Technical problem to be solved of the present invention is the defect overcoming prior art, and provide reduction method spirulina nickel-loaded water-repellent preservation invisible coating and preparation method thereof, this coating not only has anticorrosion Stealth Fighter, and has environmental ecology friendly.
To achieve these goals, the present invention by the following technical solutions: a kind of reduction method spirulina nickel-loaded water-repellent preservation invisible coating, described coating is that 1:1 is formed by the first and second two kinds of components according to quality proportioning;
According to the mass fraction, first component comprises following component:
Aqueous epoxy resins 80 ~ 120 parts;
Defoamer 0.2 ~ 0.8 part;
Distilled water 5 ~ 15 parts;
According to the mass fraction, second component comprises following component and content:
Aqueous epoxy curing agent 20 ~ 30 parts;
Defoamer 0.08 ~ 0.15 part;
Dispersion agent 1 ~ 1.5 part;
Superfine talcum powder 20 ~ 30 parts;
Zinc phosphate 15 ~ 30 parts;
Iron oxide red 0 ~ 20 part;
Titanium dioxide 15 ~ 30 parts;
Spirulina chirality wave absorbing agent 15 ~ 30 parts.
A kind of reduction method spirulina nickel-loaded water-repellent preservation invisible coating, described coating is that 1:1 is formed by the first and second two kinds of components according to quality proportioning;
According to the mass fraction, first component comprises following component and content:
Aqueous epoxy resins 100 parts;
Defoamer 0.5 part;
Distilled water 10 parts;
According to the mass fraction, second component comprises following component and content:
Aqueous epoxy curing agent 25 parts;
Defoamer 0.1 part;
Dispersion agent 1.2 parts;
Superfine talcum powder 25 parts;
Zinc phosphate 20 parts;
Iron oxide red 10 parts;
Titanium dioxide 20 parts;
Spirulina chirality wave absorbing agent 20 parts.
Described aqueous epoxy resins solid content is 60%, and epoxy equivalent (weight) is 730.
Described defoamer is BYK-018.
Described dispersion agent is BYK-190.
Described aqueous epoxy curing agent solid content is 60%, and amine hydrogen equivalent is 248.
Described spirulina chirality wave absorbing agent is the siliceous housing of nickel plating spirulina with spirane structure.
A preparation method for reduction method spirulina nickel-loaded water-repellent preservation invisible coating, comprises the following steps:
(1) spirulina chirality wave absorbing agent preparation:
A, prepare the substratum of growth of spirulina platensis in proportion, pour in the Erlenmeyer flask after sterilizing, add algae kind again and put into illumination box, illumination 12 hours, lucifuge 12 hours, temperature 37 DEG C of temperature constant states are cultivated to filter for 2 weeks and are used, and spirulina is fixed 4 hours at 4 DEG C by the glutaraldehyde solution with 2.5%, and spirulina isolated by whizzer, the rotating speed of whizzer is 1000 revs/min, and last spirulina is placed in loft drier drying treatment temperature 37 DEG C;
B, claim to obtain 15 parts of NiCl 26H 2o and spirulina are put into beaker and are added stirring solvent to dissolving to obtain A liquid completely.Claim to obtain 0.5 part of KBH 4put into beaker with 0.06 part of KOH and add the consoluet B liquid of stirring solvent.The beaker that A liquid is housed is carried out mechanical stirring, simultaneously the constant pressure funnel installing B liquid above A liquid beaker is being housed, mix up speed instillation A liquid, reaction terminates rear filtration, cleaning, drying, pulverizing are stand-by;
C, heat-treated in middle temperature tube furnace by nickel plating spirulina powder obtained for experiment, processing condition are: be incubated 1 hour at 450 DEG C.Spirulina chirality wave absorbing agent is obtained after cooling;
(2) add in agitator by the epoxy resin of formula ratio and defoamer, under the speed of 300 revs/min stir, then add deionized water dilution, high speed dispersion 30 minutes, obtains first component;
(3) by formula ratio solidifying agent added and get the raw materials ready in pot, stir under the speed of 1000 revs/min, add defoamer, dispersion agent, titanium dioxide, superfine talcum powder, zinc phosphate, iron oxide red, spirulina chirality wave absorbing agent and appropriate deionized water, first low speed dispersion on high speed dispersor, then high speed dispersion.Under the effect of high shear force, sand milling dispersion, until fineness is less than 10 μm, obtains second component;
(4) need be 1:1 by formula ratio quality proportioning by described first component, second component during construction, mixing, uniform stirring, slaking can use after 10 minutes.
The invention has the beneficial effects as follows: the reduction method spirulina nickel-loaded water-repellent preservation invisible coating of the present invention's development take aqueous epoxy resins as base-material, solidifying agent is the anticorrosion invisible coating of environment friendly of aqueous epoxy curing agent, be characterized in strong adhesion, metal surface rust cleaning is less demanding, there is high viscosity, the features such as high solids content, be constructed into film thickness for twice and can reach hundred microns, cost is low, and production technique is simple.
Aluminium nickel content in paint film is high, effectively serve in ocean environment surface electro-chemical protection function, be specially adapted to high temperature, high humidity ocean environment metal component surface anticorrosion.
Containing spirulina chirality wave absorbing agent in paint film, single spirulina chirality wave absorbing agent mean particle dia is scope is 6 ~ 10 μm, entire length scope is 200 ~ 300 μm, the wavelength of its chirality size range and microwave and infrared portion is close, have good shielding and sorption to hertzian wave, what reach metallic matrix is stealthy.Important application prospect is had in naval's military equipment and great marine drilling platform metal structure surface protection etc.
Adopt coating lacquer film thickness of the present invention more than 100 μm, through the accelerated corrosion simulation test resistance to neutral salt spray time: within more than 800 hours, paint film does not change.Electromagnetic parameter testing shows, and the change in dielectric constant of spirulina nickel-loaded is little, and the magnetic loss that changes greatly of magnetic permeability obviously strengthens.
Embodiment
In order to make content of the present invention more easily originally be expressly understood, below according to specific embodiment, the present invention is further detailed explanation,
Embodiment 1
Reduction method spirulina nickel-loaded water-repellent preservation invisible coating, it is that 1:1 is formed by the first and second two kinds of components according to quality proportioning.According to the mass fraction, first component comprises following component and content: aqueous epoxy resins 100 parts of defoamers 0.5 part; Distilled water 10 parts.According to the mass fraction, second component comprises following component and content: aqueous epoxy curing agent 25 parts; Defoamer 0.1 part; Dispersion agent 1.2 parts; Superfine talcum powder 25 parts; Zinc phosphate 20 parts; Iron oxide red 10 parts; Titanium dioxide 20 parts; Spirulina chirality wave absorbing agent 20 parts.
The preparation method of reduction method spirulina nickel-loaded water-repellent preservation invisible coating, step comprises:
(1) spirulina chirality wave absorbing agent preparation, 1) substratum of growth of spirulina platensis is prepared in proportion, pour in the Erlenmeyer flask after sterilizing, add algae kind again and put into illumination box, illumination 12 hours, lucifuge 12 hours, temperature 37 DEG C of temperature constant states are cultivated to filter for 2 weeks and are used, spirulina is fixed 4 hours at 4 DEG C by the glutaraldehyde solution with 2.5%, spirulina isolated by whizzer, and the rotating speed of whizzer is 1000 revs/min, and last spirulina is placed in loft drier drying treatment temperature 37 DEG C.2) 15 parts of NiCl are claimed to obtain 26H 2o and spirulina are put into beaker and are added stirring solvent to dissolving to obtain A liquid completely.Claim to obtain 0.5 part of KBH 4put into beaker with 0.06 part of KOH and add the consoluet B liquid of stirring solvent.The beaker that A liquid is housed is carried out mechanical stirring, simultaneously the constant pressure funnel installing B liquid above A liquid beaker is being housed, mix up speed instillation A liquid, reaction terminates rear filtration, cleaning, drying, pulverizing are stand-by.3) heat-treated in middle temperature tube furnace by the nickel plating spirulina powder that experiment is obtained, processing condition are: be incubated 1 hour at 450 DEG C.Spirulina chirality wave absorbing agent is obtained after cooling.
(2) add in agitator by the epoxy resin of formula ratio and defoamer, under the speed of 300 revs/min stir, then add deionized water dilution, high speed dispersion 30 minutes, obtains first component.
(3) by formula ratio solidifying agent added and get the raw materials ready in pot, stir under the speed of 1000 revs/min, add defoamer, dispersion agent, titanium dioxide, superfine talcum powder, zinc phosphate, iron oxide red, spirulina chirality wave absorbing agent and appropriate deionized water, low speed dispersion on high speed dispersor, then high speed dispersion.Under the effect of high shear force, sand milling dispersion, until fineness is less than 10 μm, obtains second component.
(4) need be 1:1 by formula ratio quality proportioning by described first component, second component during construction, mixing, uniform stirring, slaking can use after 10 minutes.
Coating paint film test result: resistance to neutral salt spray time: 850 hours.Dielectric loss: maximum absorption band is at 9.1GHz, and reflectivity is-17.12dB.
Embodiment 2
Reduction method spirulina nickel-loaded water-repellent preservation invisible coating, it is that 1:1 is formed by the first and second two kinds of components according to quality proportioning.According to the mass fraction, first component comprises following component and content: aqueous epoxy resins 100 parts; Defoamer 0.5 part; Distilled water 10 parts.According to the mass fraction, second component comprises following component and content: aqueous epoxy curing agent 25 parts; Defoamer 0.1 part; Dispersion agent 1.2 parts; Superfine talcum powder 25 parts; Zinc phosphate 25 parts; Iron oxide red 10 parts; Titanium dioxide 20 parts; Spirulina chirality wave absorbing agent 25 parts.
The preparation method of reduction method spirulina nickel-loaded water-repellent preservation invisible coating, step comprises:
(1) spirulina chirality wave absorbing agent preparation, 1) substratum of growth of spirulina platensis is prepared in proportion, pour in the Erlenmeyer flask after sterilizing, add algae kind again and put into illumination box, illumination 12 hours, lucifuge 12 hours, temperature 37 DEG C of temperature constant states are cultivated to filter for 2 weeks and are used, spirulina is fixed 4 hours at 4 DEG C by the glutaraldehyde solution with 2.5%, spirulina isolated by whizzer, and the rotating speed of whizzer is 1000 revs/min, and last spirulina is placed in loft drier drying treatment temperature 37 DEG C.2) 15 parts of NiCl are claimed to obtain 26H 2o and spirulina are put into beaker and are added stirring solvent to dissolving to obtain A liquid completely.Claim to obtain 0.5 part of KBH 4put into beaker with 0.06 part of KOH and add the consoluet B liquid of stirring solvent.The beaker that A liquid is housed is carried out mechanical stirring, simultaneously the constant pressure funnel installing B liquid above A liquid beaker is being housed, mix up speed instillation A liquid, reaction terminates rear filtration, cleaning, drying, pulverizing are stand-by.3) heat-treated in middle temperature tube furnace by the nickel plating spirulina powder that experiment is obtained, processing condition are: be incubated 1 hour at 450 DEG C.Spirulina chirality wave absorbing agent is obtained after cooling.
(2) add in agitator by the epoxy resin of formula ratio and defoamer, under the speed of 300 revs/min stir, then add deionized water dilution, high speed dispersion 30 minutes, obtains first component.
(3) by formula ratio solidifying agent added and get the raw materials ready in pot, stir under the speed of 1000 revs/min, add defoamer, dispersion agent, titanium dioxide, superfine talcum powder, zinc phosphate, iron oxide red, spirulina chirality wave absorbing agent and appropriate deionized water, low speed dispersion on high speed dispersor, then high speed dispersion.Under the effect of high shear force, sand milling dispersion, until fineness is less than 10 μm, obtains second component.
(4) need be 1:1 by formula ratio quality proportioning by described first component, second component during construction, mixing, uniform stirring, slaking can use after 10 minutes.
Coating paint film test result: resistance to neutral salt spray time: 900 hours.Dielectric loss: maximum absorption band is at 9.1GHz, and reflectivity is-18.19dB.
Embodiment 3
Reduction method spirulina nickel-loaded water-repellent preservation invisible coating, it is that 1:1 is formed by the first and second two kinds of components according to quality proportioning.According to the mass fraction, first component comprises following component and content: aqueous epoxy resins 100 parts; Defoamer 0.5 part; Distilled water 10 parts.According to the mass fraction, second component comprises following component and content: aqueous epoxy curing agent 25 parts; Defoamer 0.1 part; Dispersion agent 1.2 parts; Superfine talcum powder 25 parts; Zinc phosphate 30 parts; Iron oxide red 10 parts; Titanium dioxide 20 parts; Spirulina chirality wave absorbing agent 30 parts.
The preparation method of reduction method spirulina nickel-loaded water-repellent preservation invisible coating, step comprises:
(1) spirulina chirality wave absorbing agent preparation, 1) substratum of growth of spirulina platensis is prepared in proportion, pour in the Erlenmeyer flask after sterilizing, add algae kind again and put into illumination box, illumination 12 hours, lucifuge 12 hours, temperature 37 DEG C of temperature constant states are cultivated to filter for 2 weeks and are used, spirulina is fixed 4 hours at 4 DEG C by the glutaraldehyde solution with 2.5%, spirulina isolated by whizzer, and the rotating speed of whizzer is 1000 revs/min, and last spirulina is placed in loft drier drying treatment temperature 37 DEG C.2) 15 parts of NiCl are claimed to obtain 26H 2o and spirulina are put into beaker and are added stirring solvent to dissolving to obtain A liquid completely.Claim to obtain 0.5 part of KBH 4put into beaker with 0.06 part of KOH and add the consoluet B liquid of stirring solvent.The beaker that A liquid is housed is carried out mechanical stirring, simultaneously the constant pressure funnel installing B liquid above A liquid beaker is being housed, mix up speed instillation A liquid, reaction terminates rear filtration, cleaning, drying, pulverizing are stand-by.3) heat-treated in middle temperature tube furnace by the nickel plating spirulina powder that experiment is obtained, processing condition are: be incubated 1 hour at 450 DEG C.Spirulina chirality wave absorbing agent is obtained after cooling.
(2) add in agitator by the epoxy resin of formula ratio and defoamer, under the speed of 300 revs/min stir, then add deionized water dilution, high speed dispersion 30 minutes, obtains first component.
(3) by formula ratio solidifying agent added and get the raw materials ready in pot, stir under the speed of 1000 revs/min, add defoamer, dispersion agent, titanium dioxide, superfine talcum powder, zinc phosphate, iron oxide red, spirulina chirality wave absorbing agent and appropriate deionized water, low speed dispersion on high speed dispersor, then high speed dispersion.Under the effect of high shear force, sand milling dispersion, until fineness is less than 10 μm, obtains second component.
(4) need be 1:1 by formula ratio quality proportioning by described first component, second component during construction, mixing, uniform stirring, slaking can use after 10 minutes.
Coating paint film test result: resistance to neutral salt spray time: 1002 hours.Dielectric loss: maximum absorption band is at 9.1GHz, and reflectivity is-19.04dB.
Through this kind of reduction method spirulina nickel-loaded water-repellent preservation invisible coating prepared by above-mentioned 3 kinds of embodiments and many experiments, not only there is anticorrosion Stealth Fighter, and there is environmental ecology friendly.
Important application prospect is had in naval's military equipment and great marine drilling platform metal structure surface protection etc.
Above-described specific embodiment; object of the present invention, technical scheme and beneficial effect are further described; be understood that; the foregoing is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (8)

1. a reduction method spirulina nickel-loaded water-repellent preservation invisible coating, is characterized in that: described coating is that 1:1 is formed by the first and second two kinds of components according to quality proportioning;
According to the mass fraction, first component comprises following component:
Aqueous epoxy resins 80 ~ 120 parts;
Defoamer 0.2 ~ 0.8 part;
Distilled water 5 ~ 15 parts;
According to the mass fraction, second component comprises following component and content:
Aqueous epoxy curing agent 20 ~ 30 parts;
Defoamer 0.08 ~ 0.15 part;
Dispersion agent 1 ~ 1.5 part;
Superfine talcum powder 20 ~ 30 parts;
Zinc phosphate 15 ~ 30 parts;
Iron oxide red 0 ~ 20 part;
Titanium dioxide 15 ~ 30 parts;
Spirulina chirality wave absorbing agent 15 ~ 30 parts.
2. a reduction method spirulina nickel-loaded water-repellent preservation invisible coating, is characterized in that: described coating is that 1:1 is formed by the first and second two kinds of components according to quality proportioning;
According to the mass fraction, first component comprises following component and content:
Aqueous epoxy resins 100 parts;
Defoamer 0.5 part;
Distilled water 10 parts;
According to the mass fraction, second component comprises following component and content:
Aqueous epoxy curing agent 25 parts;
Defoamer 0.1 part;
Dispersion agent 1.2 parts;
Superfine talcum powder 25 parts;
Zinc phosphate 20 parts;
Iron oxide red 10 parts;
Titanium dioxide 20 parts;
Spirulina chirality wave absorbing agent 20 parts.
3. coating according to claim 1 and 2, is characterized in that: described aqueous epoxy resins solid content is 60%, and epoxy equivalent (weight) is 730.
4. coating according to claim 1 and 2, is characterized in that: described defoamer is BYK-018.
5. coating according to claim 1 and 2, is characterized in that: described dispersion agent is BYK-190.
6. coating according to claim 1 and 2, is characterized in that: described aqueous epoxy curing agent solid content is 60%, and amine hydrogen equivalent is 248.
7. coating according to claim 1 and 2, is characterized in that: described spirulina chirality wave absorbing agent is the siliceous housing of nickel plating spirulina with spirane structure.
8. the preparation method of reduction method spirulina nickel-loaded water-repellent preservation invisible coating according to claim 1 or 2, is characterized in that comprising the following steps:
(1) spirulina chirality wave absorbing agent preparation:
A, prepare the substratum of growth of spirulina platensis in proportion, pour in the Erlenmeyer flask after sterilizing, add algae kind again and put into illumination box, illumination 12 hours, lucifuge 12 hours, temperature 37 DEG C of temperature constant states are cultivated to filter for 2 weeks and are used, and spirulina is fixed 4 hours at 4 DEG C by the glutaraldehyde solution with 2.5%, and spirulina isolated by whizzer, the rotating speed of whizzer is 1000 revs/min, and last spirulina is placed in loft drier drying treatment temperature 37 DEG C;
B, claim to obtain 15 parts of NiCl 26H 2o and spirulina are put into beaker and are added stirring solvent to dissolving to obtain A liquid completely.Claim to obtain 0.5 part of KBH 4put into beaker with 0.06 part of KOH and add the consoluet B liquid of stirring solvent; The beaker that A liquid is housed is carried out mechanical stirring, simultaneously the constant pressure funnel installing B liquid above A liquid beaker is being housed, mix up speed instillation A liquid, reaction terminates rear filtration, cleaning, drying, pulverizing are stand-by;
C, heat-treated in middle temperature tube furnace by nickel plating spirulina powder obtained for experiment, processing condition are: be incubated 1 hour at 450 DEG C, obtain spirulina chirality wave absorbing agent after cooling;
(2) add in agitator by the epoxy resin of formula ratio and defoamer, under the speed of 300 revs/min stir, then add deionized water dilution, high speed dispersion 30 minutes, obtains first component;
(3) by formula ratio solidifying agent added and get the raw materials ready in pot, stir under the speed of 1000 revs/min, add defoamer, dispersion agent, titanium dioxide, superfine talcum powder, zinc phosphate, iron oxide red, spirulina chirality wave absorbing agent and appropriate deionized water, first low speed dispersion on high speed dispersor, then high speed dispersion, under the effect of high shear force, sand milling dispersion, until fineness is less than 10 μm, obtains second component;
(4) need be 1:1 by formula ratio quality proportioning by described first component, second component during construction, mixing, uniform stirring, slaking can use after 10 minutes.
CN201510209739.8A 2015-04-28 2015-04-28 Reduction method spirulina nickel-loaded waterborne anticorrosive stealth coating and preparation method thereof Pending CN104774537A (en)

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Application publication date: 20150715