CN103205150A - Anticorrosive coating with polyaniline covering gas-phase nano-silica and preparation method thereof - Google Patents
Anticorrosive coating with polyaniline covering gas-phase nano-silica and preparation method thereof Download PDFInfo
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- CN103205150A CN103205150A CN2013100981421A CN201310098142A CN103205150A CN 103205150 A CN103205150 A CN 103205150A CN 2013100981421 A CN2013100981421 A CN 2013100981421A CN 201310098142 A CN201310098142 A CN 201310098142A CN 103205150 A CN103205150 A CN 103205150A
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Abstract
The invention belongs to the field of coatings and particularly relates to a preparation method and application of an anticorrosive additive with polyaniline covering gas-phase nano-silica. The anticorrosive additive has a core-shell structure, the core is nano-silica particles, the shell is polyaniline, and the thickness of polyaniline covering the surface of the gas-phase nano-silica particles is even. In terms of total mass of the anticorrosive additive, the anticorrosive additive comprises, by weight, 0.25-20% of polyaniline. Conductivity of the anticorrosive additive reaches 10-1S*cm-1. The preparation method includes: aniline monomer pre-attachment, polyreaction, post-treatment, undoping and secondary doping. The invention further comprises preparation of an anticorrosive coating with polyaniline covering gas-phase nano-silica. The anticorrosive coating can be sprayed as primer of various metallic matrixes, a compact anticorrosive coating can be achieved by baking the sprayed anticorrosive coating, and metal can be protected effectively.
Description
Technical field
The invention belongs to the protective system field, be specifically related to protective system of a kind of polyaniline coated silica and preparation method thereof.
Background technology
Since DeBerry etc. (sees document Journal of the Electrochemcal Society, 1985,132 (5): 1022～1026.; The Electrochemical Society, 1984,84 (3): 308-322) find that in 1985 polyaniline (PANI) has excellent antiseptic property since, countries in the world have begun the research as the gentle reagent of metallic surface corrosion protection coating to PANI in succession.Why the PANI protective system causes people's research enthusiasm, is because it is good with the consistency of matrix polymer, and the while anticorrosive coating has antistatic property concurrently, uses in seawater, also has the effect of the pollution that prevents marine microorganism.Existing many commercial PANI protective systems come out at present, but its application market also fails really to open.Mainly be owing to have phenyl ring on the PANI chain, interchain hydrogen bond interacts and the electric charge delocalization effect, cause the polymer chain rigidity insoluble not molten, its melt temperature is on decomposition temperature, melt-processed can not realize, the dissolving processing characteristics is relatively poor, and there are problems such as complex process, cost height, environmental pollution in the preparation process of PANI powder.People have very high enthusiasm to the modification of PANI always.The foreign study person has carried out a large amount of research (document Corrosion Sci. for example, 2007,49,3052-3063. to the preservative property of PANI; Electrochim.Acta, 2007,52,5392-5399.; Mater.Chem.Phys., 2009,113,685-689), and abroad the commodity of existing PANI protective system industrialization are reported, as Versicon, Ormecon, Corrpassive and Corepair etc.Domestic relevant protective system research also drops into very much, but really can be put to the few of practical application.Although domestic article one PANI protective system production line is also in Changsha investment construction, but because PANI dissolving processing characteristics is relatively poor, the preparation process of PANI powder exists complex process, cost height, and there are problems such as environmental pollution at aspects such as the volatilization of breakdown of emulsion stage emulsion splitter and filtrate discharges, make that the preparation cost of PANI coating is high, large-scale industrial application is subjected to severely restricts.
The pellet hardness of above-mentioned chemical oxidising polymerisation gained PANI is big and be difficult to be dispersed in problem in the coating matrix, remain the problem that can't avoid in the PANI of electrochemically oxidative polymerization, and the synthetic mode of production of electrochemically oxidative polymerization is difficult to extensiveization.
Summary of the invention
Purpose of the present invention provides protective system of a kind of polyaniline coating micron silica and preparation method thereof, to overcome the deficiencies in the prior art.The protective system additive of polyaniline coated silica of the present invention is with aniline polymerization on silica substrate, makes PANI form coating layer and is wrapped in silica sphere, in order to be dispersed in the polymeric matrix easily when using.This preparation method of anticorrosion paint is convenient, can realize industrialization, and the PANI protective system of preparation is uniformly dispersed, system stable, and antiseptic property is good.
Reach other purposes to achieve these goals, the present invention adopts following technical scheme to realize.
The invention discloses the anticorrosive additive that a kind of polyaniline coats micron silica, described anticorrosive additive has nucleocapsid structure, nuclear is nano level silica dioxide granule, shell is polyaniline, and polyaniline is even at the coating thickness of gas phase nano silica particles, and in the total mass of anticorrosive additive, the content of polyaniline is 0.25wt%～20wt%, preferably, the content of polyaniline is 10wt%～20wt%, and the specific conductivity of this anticorrosive additive reaches 10
-2Scm
-1
The preparation method of described anticorrosive additive may further comprise the steps:
(1) adhering in advance of the derivatives monomer of aniline and aniline: earlier with ethanol the derivative of aniline and aniline is diluted to aniline solution, and soak into gas phase nano silicon-dioxide with this aniline solution, gas phase nano silicon-dioxide is put into baking oven and is baked to the ethanol volatilization totally after soaking into, and baking back gas phase nano silicon-dioxide is put into acidic medium again and stirred;
(2) polyreaction: will slowly splash under 0～5 ℃ of condition of above-mentioned system constant temperature the oxidizing agent solution reaction, and constantly be stirred to and react completely;
(3) aftertreatment: with reacting liquid filtering, wash colourless until washing lotion, the oven dry namely get ecosystem polyaniline coated silica mixture, be anticorrosive additive of the present invention.
Preparation method described above is further comprising the steps of:
(4) go to mix: ecosystem polyaniline coated silica mixture in the step (3) with alkaline soak and stirring, is filtered then, be washed with distilled water to neutrality;
(5) mix again: handle the filtration washing oven dry again with tosic acid PTSA solute doping.
In above-mentioned preparation method, the derivative of the aniline described in the step (1) and aniline is the compound of following structure, R wherein, R
1And R
2Be H or alkyl:
In the step (2), used oxygenant refers to the aqueous hydrochloric acid of the aqueous hydrochloric acid of ammonium persulphate, Sodium Persulfate, the hydrochloric acid soln of potassium bichromate, the salpeter solution of potassium bichromate or the acetic acid solution of potassium bichromate; The mol ratio of the derivative of solute and described aniline and aniline is 1:4～2:1 in the described oxygenant, is preferably 1:1.
The reaction times is 2～48h in the step (2).
Described acid reaction medium in the step (1) is the acidic aqueous solution of concentration 0.01～3.0mol/L, is preferably the hydrochloric acid soln of 1mol/L, and the buck in the step (4) is ammonia soln or NaOH solution, and buck concentration is 0.01～3.0mol/L.
PTSA in the above-mentioned step (5) uses when mixing again is the aqueous solution of PTSA or the ethanolic soln of PTSA, is preferably the ethanolic soln of PTSA.
The present invention's polymerization on the inorganic filler particle micron silica with aniline and derivative thereof, discovery is coating fully but does not exist under the free pure PANI particle situation, when joining in the coating matrix as anticorrosion activeconstituents additive, can be good at being dispersed in the coating system, can obtain the coating of antiseptic property excellence like this.Simultaneously, the polyaniline of nano thickness layer can effectively utilize the electroconductibility of polyaniline, saves the consumption of polyaniline.
The polyaniline of the present invention's preparation coats micron silica and has realized coating fully, and concrete manifestation is as follows: 1) in the microphotograph, and the viridescent coating in obvious granules of pigments surface; 2) particle size analyzer shows that the change of size before and after the pigment coating all is unimodal; 3) easily disperse of reaction product, material very easily are distributed to HEGMAN fineness about 8, if product has more solid polyaniline particle, the evidence fineness is difficult to reach this level.
Advantage after it realizes coating fully comprises: a) the inorganic filler particle silicon-dioxide specific surface area of polyaniline material that can greatly extend, thereby increase and interconnect the probability of realizing conducting between particle; B) polyaniline coating micron silica mixture has splendid dispersiveness and processing characteristics, is easy to sneak into various body materials, has avoided the characteristic of polyaniline indissoluble infusibility.
The specific conductivity that the ecosystem PANI that obtains among the present invention coats micron silica has certain specific conductivity, nonisulated body, and specific conductivity is 10
-2Scm
-1, specific conductivity is greatly improved, and it is good to illustrate as the performance of the passive film that forms after the anticorrosive additive film forming, and the rot-resistant performance is good.
The present invention has comprised that also a kind of polyaniline coats the micron silica protective system, and it comprises the anticorrosive additive among coating matrix and the present invention, and in the protective system total mass, described protective system content of additive is: 5wt%～20wt%; Described coating matrix is polyurethane coating, epoxypaint or polyacrylic acid coating; The protective system that the present invention obtains can be used as the priming paint spraying of various metallic matrixes, and baking processing in addition after the spraying can obtain fine and close corrosion protection coating.Protective system of the present invention can passive metal, and the anodic reaction of steel plate corrosion reaction is separated with cathodic reaction, can protect metal effectively.
The present invention utilizes easy chemical oxidising polymerisation to coat one deck electrically conductive polyaniline in silica particle surface, and the specific conductivity that the polyaniline of acquisition coats the micron silica anticorrosive additive can reach 10
-2Scm
-1, it is difficult dispersed to have improved PANI simultaneously, and the polyaniline of obtained to be uniformly dispersed, system is stable coats the protective system of gas phase nano silicon-dioxide.On the other hand, gas phase nano silicon-dioxide cost is extremely low, reduces the coating cost, simplifies technology, and because inorganic particulate silicon-dioxide density is big, is easy to be deposited in the coating bottom after the spraying, forms conductive layer thereby contact part with base material; So the protective system that obtains has good film forming properties, after placing 200h under the ASTM B117 salt fog condition, does not observe any rust staining on the base material.
Description of drawings
The grain size distribution curve of silicon-dioxide before and after Fig. 1 PANI coats;
Fig. 2 polyaniline coats the infared spectrum of quartz sand;
The blank coating of Fig. 3 is observed the antiseptic property of cold-rolled steel sheet;
Fig. 4 pure silicon dioxide coating is observed the antiseptic property of cold-rolled steel sheet;
Fig. 5 PANI coats the micron silica composite coating antiseptic property of cold-rolled steel sheet is observed.
Embodiment
Further set forth the present invention below in conjunction with specific embodiment, should be understood that these embodiment only are used for explanation the present invention and are not used in restriction protection scope of the present invention.
Used micron silica product type is 604 among the embodiment, white crystalline powder, specific surface area 1m
2G
-1, density 2.65gcm
-3
Embodiment 1:
Reaction conditions: temperature of reaction is 3 ℃, and the mol ratio of oxygenant and aniline monomer is 1:1, and reaction medium is the 1mol/L hydrochloric acid soln, and 1mL aniline is to 9g silicon-dioxide.
Add silicon-dioxide in three kinds of different modes under above polymerizing condition: (1) is according to aniline monomer preadsorption method of the present invention, namely with ethanol aniline is diluted earlier, and with this solution impregnation silicon-dioxide, put into the baking oven baking then and made the ethanol volatilization in 0.5 hour totally, then aniline can be attached to silica particles, put into acid medium again, add oxygenant and carry out polymerization; (2) the direct addition method of aniline monomer namely directly joins aniline in the reaction medium, stirs 5min and makes it to mix, and adds oxygenant and carries out polymerization; (3) blending method behind the aniline polymerization namely earlier carries out chemical oxidising polymerisation with aniline in the presence of no silicon-dioxide, polymkeric substance adding silicon-dioxide stir.
The specific conductivity of these the three kinds of resultant PANI coated silica of method mixtures is listed in table 1.Can be seen that by table 1 blending method products therefrom color is more shallow behind the aniline polymerization, specific conductivity is low, and aniline monomer preadsorption method can obtain the black composite of the highest specific conductivity.
Specific conductivity and the knifing color of gained PANI coated silica mixture under three kinds of adding modes of table 1 aniline monomer
Embodiment 2:
Reactions steps is as follows among the embodiment:
(1) adhering in advance of aniline monomer: earlier with ethanol the derivative of aniline and aniline is diluted to aniline solution, and soak into gas phase nano silicon-dioxide with this aniline solution, gas phase nano silicon-dioxide is put into baking oven and is baked to the ethanol volatilization totally after soaking into, and baking back gas phase nano silicon-dioxide is put into acidic medium again and stirred;
(2) polyreaction: will slowly splash under 3 ℃ of conditions of above-mentioned system constant temperature the oxidizing agent solution reaction, the mol ratio of oxygenant and aniline monomer is 1:1, reaction medium is the hydrochloric acid of 1mol/L, and constantly is stirred to and reacts completely;
(3) aftertreatment: with reacting liquid filtering, wash colourlessly until washing lotion, oven dry namely gets ecosystem polyaniline coated silica mixture.
Feed than having synthesized four kinds of PANI coated silica anticorrosive additives that polyaniline PANI content is different with silicon-dioxide with four kinds of different aniline according to above step, their specific conductivity sees Table 2.
The PANI content of table 2PANI coated silica mixture and the specific conductivity of mixture
Can find out, along with the increase of aniline add-on, the product specific conductivity rises gradually, and aniline content is 10% when following, the specific conductivity ascendant trend is obvious, being the order of magnitude increases, and when aniline content 10% when above, the specific conductivity ascendant trend reduces, particularly the coating product of PTSA doping attitude at aniline content 10% when above, conductivity variations is little, therefore considers that from the angle that reduces cost the proper consumption of aniline monomer is 20%.This ratio and Theoretical Calculation result differ greatly, and are nonconducting according to the resulting coating product of Theoretical Calculation ratio.This is that particle diameter is tens times of individual layer PANI thickness because silica dioxide granule is bigger, if having only individual layer PANI to be coated on particle surface, PANI shared volume ratio in particle is too small, can't realize good electrical conductivity, so specific conductivity is very low.And when the mass ratio of silicon-dioxide and aniline monomer was 9:1, PANI shared volume ratio in particle was bigger, therefore can obtain higher specific conductivity.
Be that 10% embodiment product is tested the size distribution that records PANI coated silica mixture with LS230 type laser particle size analyzer (U.S. Beckman Coulter Inc.) and seen Fig. 1 to the aniline monomer consumption, grain size distribution curve shape basically identical before and after coating, translation has taken place than coating preceding curve to big particle diameter direction in the grain size distribution curve after PANI coats, and proves whole the change greatly of coating back particle.The silicon-dioxide median size is 2.51 μ m, and it is 3.27 μ m that PANI coats micron silica mixture median size.If coat calculating according to sphere, coating thickness is about 380nm.In addition, if there is the PANI particle of " dissociating " in the coating product, then coat and generally can occur two peaks in the product grain size distribution curve, be respectively PANI coated silica mixture size distribution peak and PANI size distribution peak, and in the coating product grain size distribution curve that we record, do not find second peak, this has shown that PANI has been coated on silica particles, does not form the PANI of " dissociating ", and more even at the coating thickness of silica particles.
Embodiment 3:
Be that 10% embodiment product carries out examination of infrared spectrum with Nicolet FT-IR Nexsus470 instrument to the aniline monomer consumption, the gained infared spectrum is seen Fig. 2.At 3440cm
-1～3445cm
-1About a wide absorption peak is arranged, be the charateristic avsorption band of – NH – stretching vibration, show imino-in the polymkeric substance (– NH –), amino (– NH
2) existence of group.1470cm
-1～1560cm
-1Absorption peak be the quinoid of aromatic carbon (C=C) and benzene formula (C – C) stretching vibration on the phenyl ring in the polymer molecular chain, 1000cm
-1About and 780cm
-1About the corresponding phenyl ring face of absorption peak in and the out-of-plane deformation vibration characteristic absorption band.The existence of phenyl ring in the molecular chain is described.At 1300cm
-1The absorption peak at place is corresponding to C – N stretching vibration.These absorption features are identical with pure polyaniline, and the polyaniline really of synthetic resulting polymkeric substance is described.And the quartz sand after the polyaniline coating is at 1050cm
-1And 800cm
-1Charateristic avsorption band is also arranged, and they absorb all overlapping coincidence the to some extent with the phenyl ring face is interior with out-of-plane deformation vibration.
Embodiment 4:
Gained doping PANI coated silica among the embodiment 2 is moved in the beaker, add ammoniacal liquor magnetic agitation 24h, filter, use a large amount of distilled water washs to neutral again, filter, the attitude PANI coated silica that must go to mix will go doped P ANI coated silica mixture to mix with the tosic acid PTSA aqueous solution, and the doping consumption is that the mol ratio of each structural unit and tosic acid is 1:0.7 among the PANI.Obtain cyan tosic acid doped P ANI coated silica mixture.Its specific conductivity sees Table 2.As seen the specific conductivity of back mixture of mixing all has raising in various degree, slightly descends but the aniline monomer consumption is the specific conductivity of 20% mixture.
When mixing again with PTSA, if use the alcoholic solution of PTSA to mix again, about 7 times in the aqueous solution that the mixture specific conductivity that then obtains is, this is because polymer molecule long-chain form in ethanol is unfolded more, the group steric hindrance is less, PTSA is easier to be doped on the molecular chain, thereby obtains better doping effect.Use when therefore, PANI coated silica mixture mixes again and use ethanol to make medium.
Embodiment 5:
The PANI coating is carried out aftertreatments such as drying, grinding, it is joined in the filmogens such as priming paint such as urethane (PU) polyacrylic ester as the anti-corrosion function component form coating system, its prescription sees Table 3.
Table 3 has the primer base prescription of anti-corrosion function
On the cold-rolled steel sheet base material, respectively carry out the simultaneous test of three groups of coating:
1) blank coating is namely directly at the two-layer PU varnish of base material spraying;
2) pure micron silica coating namely uses the silicon-dioxide that does not have coating as anti-corrosion function priming paint, sprays one deck PU varnish again as finish paint;
3) coat the micron silica coating, namely the micron silica that coats with PANI sprays one deck PU varnish as finish paint again as anti-corrosion function priming paint.
According to above-mentioned 3 kinds of modes, paint spay-coating on tinplate and cold-rolled steel sheet, is put into 60 ℃ of oven for drying, the about 50 μ m of coat-thickness.Draw two cuts in the paint film intersection, cut place air can directly contact with base material.Put it into salt fog cabinet and carry out corrosion test, the salt fog condition is ASTM B117, namely constantly on the plate 35 ℃ of concentration of spray be 5% NaCl salt solution, take out its corrosion situation of observation behind the 200h, see Fig. 3～Fig. 5.The antiseptic power grade of naked eyes objective evaluation coating is carried out according to table 4.
The corresponding corrosion situation of each corrosion level that table 4 sets up on their own
Can see not having yellow rust staining all to have occurred at the cut place on the plate at coating place of anticorrosive additive of the present invention, not observe rust staining and added on the plate at coating place of anticorrosive additive of the present invention.Anticorrosion grade according to coating in the table 5 sees Table 5.Can be seen that by table 5 plate that PANI coats micron silica mixture corrosion protection coating place does not corrode fully, corrosion has all taken place in other plate, and the pure silicon dioxide coating is more serious than the corrosion situation of blank coating.This is because adding pure silicon dioxide particle can reduce the adhesive ability of coating in coating, makes the shielding effect variation of coating, thereby the preservative property variation; But after adding PANI coated silica mixture is made protective system in coating, PANI coated silica mixture forms continuous conducting layers at matrix surface, this conductive layer and metallic contact, form the oxide film of one deck densification, it is passive film, this tunic can prevent that following metal from further corroding, thereby reaches anticorrosion purpose.
The corrosion level of table 5 after tinplate and three kinds of coatings of cold-rolled steel sheet spraying
Claims (10)
1. a polyaniline coats the anticorrosive additive of micron silica, it is characterized in that, described anticorrosive additive has nucleocapsid structure, nuclear is micron-sized silica dioxide granule, shell is polyaniline, and polyaniline is even at the coating thickness of silica particles, and in the total mass of anticorrosive additive, the content of polyaniline is 0.25wt%～20wt%, and the specific conductivity of this anticorrosive additive reaches 10
-2Scm
-1
2. the preparation method of an anticorrosive additive as claimed in claim 1 is characterized in that, described preparation method may further comprise the steps:
(1) adhering in advance of the derivatives monomer of aniline and aniline: earlier with ethanol the derivative of aniline and aniline is diluted to aniline solution, and soak into gas phase nano silicon-dioxide with this aniline solution, gas phase nano silicon-dioxide is put into baking oven and is baked to the ethanol volatilization totally after soaking into, and baking back gas phase nano silicon-dioxide is put into acidic medium again and stirred;
(2) polyreaction: will slowly splash under 0～5 ℃ of condition of above-mentioned system constant temperature the oxidizing agent solution reaction, and constantly be stirred to and react completely;
(3) aftertreatment: with reacting liquid filtering, wash colourlessly until washing lotion, oven dry namely gets ecosystem polyaniline coated composites.
3. the preparation method of anticorrosive additive as claimed in claim 2 is characterized in that, described preparation method is further comprising the steps of:
(4) go to mix: ecosystem polyaniline coated composites in the step (3) with alkaline soak and stirring, is filtered then, be washed with distilled water to neutrality;
(5) mix again: handle the filtration washing oven dry again with tosic acid PTSA solute doping.
4. the preparation method of anticorrosive additive as claimed in claim 2 is characterized in that, in the step (1), the derivative of described aniline and aniline is the compound of following structure, R wherein, R
1And R
2Be H or alkyl:
5. the preparation method of anticorrosive additive as claimed in claim 2, it is characterized in that, in the step (2), used oxygenant refers to the aqueous hydrochloric acid of the aqueous hydrochloric acid of ammonium persulphate, Sodium Persulfate, the hydrochloric acid soln of potassium bichromate, the salpeter solution of potassium bichromate or the acetic acid solution of potassium bichromate; The mol ratio of the derivative of solute and described aniline and aniline is 1:4～2:1 in the described oxygenant.
6. the preparation method of anticorrosive additive as claimed in claim 2 is characterized in that, the described acid reaction medium in the step (1) is the acidic aqueous solution of concentration 0.01～3.0mol/L, and the buck in the step (4) is ammonia soln or NaOH solution.
7. coat the anticorrosive additive of micron silica in the application in protective system field as the arbitrary described polyaniline of claim 1-6.
8. a protective system comprises that the arbitrary described polyaniline of coating matrix and claim 1-7 coats the protective system additive of micron silica, and in the protective system total mass, described protective system content of additive is: 5wt%～20wt%.
9. protective system as claimed in claim 8 is characterized in that, described coating matrix is polyurethane coating, epoxypaint or polyacrylic acid coating.
10. as the application of the arbitrary described protective system of claim 8-9 as the priming paint of various metallic matrixes.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105646895A (en) * | 2015-12-04 | 2016-06-08 | 中国科学院宁波材料技术与工程研究所 | Attapulgite coated polyaniline anticorrosive material, preparation method and applications thereof |
| WO2018232269A1 (en) * | 2017-06-16 | 2018-12-20 | SAS Nanotechnologies LLC | Emeraldine base composite for corrosion inhibition |
| CN109627826A (en) * | 2018-11-29 | 2019-04-16 | 江南大学 | A kind of compound shell material microcapsules and preparation method thereof with dual corrosion proof function |
| CN110628045A (en) * | 2019-09-02 | 2019-12-31 | 长春工业大学 | Polyaniline-coated silicon dioxide core-shell microsphere toughened hydrogel and preparation method thereof |
| CN115895409A (en) * | 2023-01-04 | 2023-04-04 | 浙江双金粉末涂料有限公司 | Preparation and film forming method of low-temperature curing anticorrosive powder coating |
| CN116239905A (en) * | 2022-06-21 | 2023-06-09 | 青岛科技大学 | Preparation method of marine anti-corrosion and anti-fouling multi-effect coating material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100078779A (en) * | 2008-12-30 | 2010-07-08 | 서울대학교산학협력단 | A preparation method of ink for inkjet printing using silica-polyaniline core-shell nanoparticle |
-
2013
- 2013-03-25 CN CN201310098142.1A patent/CN103205150B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100078779A (en) * | 2008-12-30 | 2010-07-08 | 서울대학교산학협력단 | A preparation method of ink for inkjet printing using silica-polyaniline core-shell nanoparticle |
Non-Patent Citations (2)
| Title |
|---|
| 《材料工程》 20040125 井新利等 "二氧化硅/聚苯胺复合粒子的制备与性能" 第1.1，1.2，3节 1-10 , 第1期 * |
| 井新利等: ""二氧化硅/聚苯胺复合粒子的制备与性能"", 《材料工程》 * |
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| CN105646895A (en) * | 2015-12-04 | 2016-06-08 | 中国科学院宁波材料技术与工程研究所 | Attapulgite coated polyaniline anticorrosive material, preparation method and applications thereof |
| WO2018232269A1 (en) * | 2017-06-16 | 2018-12-20 | SAS Nanotechnologies LLC | Emeraldine base composite for corrosion inhibition |
| CN111201290A (en) * | 2017-06-16 | 2020-05-26 | Sas纳米技术有限公司 | Emeraldine base composites for corrosion inhibition |
| US11208567B2 (en) | 2017-06-16 | 2021-12-28 | SAS Nanotechnologies LLC | Emeraldine base composite for corrosion inhibition |
| CN109627826A (en) * | 2018-11-29 | 2019-04-16 | 江南大学 | A kind of compound shell material microcapsules and preparation method thereof with dual corrosion proof function |
| CN110628045A (en) * | 2019-09-02 | 2019-12-31 | 长春工业大学 | Polyaniline-coated silicon dioxide core-shell microsphere toughened hydrogel and preparation method thereof |
| CN116239905A (en) * | 2022-06-21 | 2023-06-09 | 青岛科技大学 | Preparation method of marine anti-corrosion and anti-fouling multi-effect coating material |
| CN116239905B (en) * | 2022-06-21 | 2024-01-26 | 青岛科技大学 | Preparation method of marine anti-corrosion and anti-fouling multi-effect coating material |
| CN115895409A (en) * | 2023-01-04 | 2023-04-04 | 浙江双金粉末涂料有限公司 | Preparation and film forming method of low-temperature curing anticorrosive powder coating |
| CN115895409B (en) * | 2023-01-04 | 2023-09-12 | 浙江双金粉末涂料有限公司 | Preparation and film forming method of low-temperature curing anti-corrosion powder coating |
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