CN104674324A - Preparation method of heteropolyacid doped polyaniline coating - Google Patents
Preparation method of heteropolyacid doped polyaniline coating Download PDFInfo
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- CN104674324A CN104674324A CN201510093857.7A CN201510093857A CN104674324A CN 104674324 A CN104674324 A CN 104674324A CN 201510093857 A CN201510093857 A CN 201510093857A CN 104674324 A CN104674324 A CN 104674324A
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Abstract
The invention provides a preparation method of a heteropolyacid doped polyaniline coating. First, polyaniline is deposited on the surface of metal through electropolymerization, then is de-doped through immersion in ammonia water, and is immersed in an acid solution containing heteropolyacid to obtain the heteropolyacid doped polyaniline coating. With the adoption of the method, a large area of the heteropolyacid doped polyaniline coating can be deposited directly and quickly on the surface of the metal. With the adoption of the coating prepared with the method, the anode protection effect is better than that of paint prepared from heteropolyacid doped polyaniline powder, and the preparation has good application prospect in the industries such as energy, petroleum, shipbuilding, maritime work and the like.
Description
Technical field
The present invention relates to anti-corrosion of metal field, specifically a kind of preparation method of heteropolyacid doped polyaniline coating.
Background technology
Polyaniline is a kind of conducting high polymers thing, has excellent stability, adjustable electric conductivity, and the advantage that production cost is low.Electropolymerization is synthesis and the deposition that under the condition of not adding other additives outside demonomerization and dopant acid, can realize polyaniline in metallic surface simultaneously, be a kind of can rapid large-area coating polyaniline coating green method.1985 years, Deberry reported first polyaniline in paper was used as the method for corrosion protection coating.After this, people have carried out much research to it.It is found that, at polyaniline after protonic acid doping, can be changed into the doping state of conduction by nonconducting ground state, and corrosion of metal current potential can be remained on passive area by the polyaniline of this doping state, anodic protection mechanism is provided.Heteropolyacid is a kind of by special metal and the nonmetal oxygen acid formed, and utilizes it can stable metal surface oxidation passivation layer as protonic acid doping polyaniline.Once had in report the filler laminar polyaniline that heteropolyacid adulterates be used in protective system, the polyaniline material prepared in report need add organic binder matter can in metallic surface film forming, and this weakens greatly by making the anodic protection effect of polyaniline.Electropolymerization is a kind of method that polyaniline can be deposited directly to metallic surface, does not need to add other organic substances.But because heteropolyacid and aniline monomer easily produce precipitation in the solution, therefore heteropolyacid can not be directly used in polyaniline electropolymerization.But the doping of polyaniline and dedoping completely reversibility, doping level by the impact of the factor such as pH value and current potential, and shows as the respective change of appearance color, can realize the doping of heteropolyacid by the secondary doping method of separating the doping-displacement dopant ion that adulterates again.
Summary of the invention
The invention discloses a kind of preparation method of heteropolyacid doped polyaniline coating, under the prerequisite not affecting coating performance, conciliate doping process, be doped to by heteropolyacid in polyaniline backbone by doping, improve the preservative effect of polyaniline, concrete steps are as follows:
Step 1: adopt cyclic voltammetry at needs antiseptic metallic surface electropolymerization one deck polyaniline coating, then clean remained on surface solution with deionized water;
Step 2: the material after processing through step 1 being put into concentration is that the ammoniacal liquor of M1 soaks 3 ~ 6 hours, then cleans remained on surface solution with deionized water, and under 20 ~ 35 DEG C and vacuum condition dry 4 ~ 8 hours;
Step 3: the material after processing through step 2 is put into the phosphoric acid that concentration is M2 and concentration is that M3 heteropolyacid mixing solutions soaks 6 ~ 12 hours, then cleans the solution of remained on surface with deionized water, and under 20 ~ 35 DEG C of conditions dry 4 ~ 8 hours.
Further, the preparation method of described a kind of heteropolyacid doped polyaniline coating, is characterized in that: in described cyclic voltammetry, electromotive force interval is-0.7 ~ 1.6V, and scanning speed is 5 ~ 50mV/S, circulates 5 ~ 50 times.
Further, described metal comprises one-component metal, binary or multicomponent alloy, and described surface is the surface of arbitrary shape.
Further, described electropolymerization need use protonic acid, and protonic acid is one or more mixing in sulfuric acid, phosphoric acid, nitric acid, oxalic acid more specifically, and concentration is 0.1 ~ 1M.
Further, described ammonia concn M1 is 0.5 ~ 1M.
Further, vacuum tightness is 0.01 ~ 0.05MPa.
Further, the solvent in described phosphoric acid and the mixing solutions of heteropolyacid is ethanol.
Further, described heteropolyacid comprises one or more in phospho-wolframic acid, phospho-molybdic acid, silicotungstic acid, silicomolybdic acid.
Further, described phosphoric acid concentration M2 is 0.5 ~ 1M, and the concentration M3 of heteropolyacid is 5 ~ 15mM.
Through the preparation method of a kind of heteropolyacid doped polyaniline corrosion protection coating that adulterates provided by the invention, at the polyaniline coating of metallic surface rapid large-area deposition heteropolyacid doping, can not add other organic substances.The present invention conciliates solvent and the soak time of doping by strict controlled doping, under the prerequisite not affecting coating antiseptic effect, is doped into by heteropolyacid in the main chain of polyaniline, improves the preservative effect of polyaniline.After method process of the present invention, metallic surface can form the oxidative deactivation layer of one deck densification, to protect metal, prevents it oxidized.
Specific embodiment
Embodiment 1: first at stainless steel surface cyclic voltammetry electropolymerization one deck polyaniline; Wherein protonic acid is the sulfuric acid of 0.1M, and scanning speed is 10mV/S, circulates 10 times.Then deionized water wash surface is used.Above-mentioned materials is put into 0.5M ammoniacal liquor to soak 5 hours, then taking-up deionized water wash, drying 4 hours under the vacuum tightnesss of 20 DEG C are 0.01MPa condition.Material is put into 0.5M phosphoric acid and 10mM phosphomolybdic acid ethanol solution to soak 9 hours, then taking-ups deionized water wash, drying 6 hours at 25 DEG C.Finally obtain green heteropolyacid doped polyaniline coating.
Embodiment 2: first at stainless steel surface cyclic voltammetry electropolymerization one deck polyaniline; Wherein protonic acid is the oxalic acid of 1M, and scanning speed is 50mV/S, circulates 30 times.Then deionized water wash surface is used.Above-mentioned materials is put into 1M ammoniacal liquor to soak 3 hours, then taking-up deionized water wash, drying 7.5 hours under the vacuum tightnesss of 35 DEG C are 0.05MPa condition.Material is put into 0.85M phosphoric acid and 13.5mM phosphomolybdic acid ethanol solution to soak 10.5 hours, then taking-ups deionized water wash, drying 8 hours at 20 DEG C.Finally obtain green heteropolyacid doped polyaniline coating.
Embodiment 3: first at surface of low-carbon steel cyclic voltammetry electropolymerization one deck polyaniline; Wherein protonic acid is the nitric acid of 0.5M, and scanning speed is 10mV/S, circulates 24 times.Then deionized water wash surface is used.Above-mentioned materials is put into 0.65M ammoniacal liquor to soak 6 hours, then taking-up deionized water wash, drying 5 hours under the vacuum tightnesss of 25 DEG C are 0.02MPa condition.Material is put into 0.55M phosphoric acid, 5mM phospho-wolframic acid and 5mM phosphomolybdic acid ethanol solution to soak 12 hours, then taking-up deionized water wash, drying 8 hours at 25 DEG C.Finally obtain green heteropolyacid doped polyaniline coating.
Embodiment 4: first at surface of low-carbon steel cyclic voltammetry electropolymerization one deck polyaniline; Wherein protonic acid is the phosphoric acid of 0.75M, and scanning speed is 50mV/S, circulates 50 times.Then deionized water wash surface is used.Above-mentioned materials is put into 1M ammoniacal liquor to soak 4 hours, then taking-up deionized water wash, drying 5 hours under the vacuum tightnesss of 30 DEG C are 0.04MPa condition.Material is put into 1M phosphoric acid, 5mM silicomolybdic acid, 5mM phospho-molybdic acid, and soak 6 hours in 5mM phospho-wolframic acid ethanolic soln, then taking-up deionized water wash, drying 6.5 hours at 35 DEG C.Finally obtain green heteropolyacid doped polyaniline coating.
Embodiment 5: first surface of low-carbon steel cyclic voltammetry electropolymerization one deck polyaniline; Wherein protonic acid is the oxalic acid of 0.75M, and scanning speed is 5mV/S, circulates 5 times.Then deionized water wash surface is used.Above-mentioned materials is put into 0.5M ammoniacal liquor to soak 6 hours, then taking-up deionized water wash, drying 8 hours under the vacuum tightnesss of 20 DEG C are 0.045MPa condition.Material is put into 0.5M phosphoric acid and 5mM silicotungstic acid ethanolic soln to soak 12 hours, then taking-ups deionized water wash, drying 8 hours at 20 DEG C.Finally obtain green heteropolyacid doped polyaniline coating.
Embodiment 6: first use cyclic voltammetry electropolymerization one deck polyaniline on ferro-aluminium surface; Wherein protonic acid is the sulfuric acid of 0.1M, and scanning speed is 5mV/S, circulates 20 times.Then deionized water wash surface is used.Above-mentioned materials is put into 0.65M ammoniacal liquor to soak 3 hours, then taking-up deionized water wash, drying 4 hours under the vacuum tightnesss of 35 DEG C are 0.01MPa condition.Material is put into 0.65M phosphoric acid and 12.5mM phosphomolybdic acid ethanol solution to soak 8 hours, then taking-ups deionized water wash, drying 4.5 hours at 30 DEG C.Finally obtain green heteropolyacid doped polyaniline coating.
Embodiment 7: first use cyclic voltammetry electropolymerization one deck polyaniline on ferro-aluminium surface; Wherein protonic acid is the nitric acid of 0.25M, and scanning speed is 10mV/S, circulates 20 times.Then deionized water wash surface is used.Above-mentioned materials is put into 0.75M ammoniacal liquor to soak 5.5 hours, then taking-up deionized water wash, drying 6 hours under the vacuum tightnesss of 35 DEG C are 0.015MPa condition.Material is put into 0.65M phosphoric acid 5.5mM silicotungstic acid and 5mM silicomolybdic acid ethanolic soln to soak 7.5 hours, then taking-ups deionized water wash, drying 5.5 hours at 25 DEG C.Finally obtain green heteropolyacid doped polyaniline coating.
Embodiment 8: first use cyclic voltammetry electropolymerization one deck polyaniline on ferro-aluminium surface; Wherein protonic acid is the sulfuric acid of 0.7M, and scanning speed is 35mV/S, circulates 36 times.Then deionized water wash surface is used.Above-mentioned materials is put into 0.55M ammoniacal liquor to soak 6 hours, then taking-up deionized water wash, drying 4.5 hours under the vacuum tightnesss of 20 DEG C are 0.01MPa condition.Material is put into 0.55M phosphoric acid and 12.5mM phosphomolybdic acid ethanol solution to soak 10.5 hours, then taking-ups deionized water wash, drying 7.5 hours at 30 DEG C.Finally obtain green heteropolyacid doped polyaniline coating.
Embodiment 9: first at surface of magnesium aluminium alloy cyclic voltammetry electropolymerization one deck polyaniline; Wherein protonic acid is the mixing acid of 0.55M sulfuric acid and 0.2M oxalic acid, and scanning speed is 5mV/S, circulates 24 times.Then deionized water wash surface is used.Above-mentioned materials is put into 1M ammoniacal liquor to soak 3 hours, then taking-up deionized water wash, drying 5 hours under the vacuum tightnesss of 25 DEG C are 0.035MPa condition.Material is put into 0.65M phosphoric acid and 5.5mM silicomolybdic acid ethanolic soln to soak 12 hours, then taking-ups deionized water wash, drying 8 hours at 20 DEG C.Finally obtain green heteropolyacid doped polyaniline coating.
Embodiment 10: first use cyclic voltammetry electropolymerization one deck polyaniline on copper surface; Wherein protonic acid is the mixing acid of 0.35M sulfuric acid, 0.35M nitric acid and 0.1M oxalic acid, and scanning speed is 15mV/S, circulates 16 times.Then deionized water wash surface is used.Above-mentioned materials is put into 0.65M ammoniacal liquor to soak 4.5 hours, then taking-up deionized water wash, drying 5 hours under the vacuum tightnesss of 30 DEG C are 0.01MPa condition.Material is put into 0.85M phosphoric acid and 10mM phosphomolybdic acid ethanol solution to soak 9 hours, then taking-ups deionized water wash, drying 7 hours at 20 DEG C.Finally obtain green heteropolyacid doped polyaniline coating.
Claims (9)
1. a preparation method for heteropolyacid doped polyaniline coating, it comprises the steps:
Step 1: adopt cyclic voltammetry at needs antiseptic metallic surface electropolymerization one deck polyaniline coating, then clean remained on surface solution with deionized water;
Step 2: the material after processing through step 1 being put into concentration is that the ammoniacal liquor of M1 soaks 3 ~ 6 hours, then cleans remained on surface solution with deionized water, and under 20 ~ 35 DEG C and vacuum condition dry 4 ~ 8 hours;
Step 3: the material after processing through step 2 is put into the phosphoric acid that concentration is M2 and concentration is that M3 heteropolyacid mixing solutions soaks 6 ~ 12 hours, then cleans the solution of remained on surface with deionized water, and under 20 ~ 35 DEG C of conditions dry 4 ~ 8 hours.
2. the preparation method of a kind of heteropolyacid doped polyaniline coating according to claim 1, is characterized in that: in described cyclic voltammetry, electromotive force interval is-0.7 ~ 1.6V, and scanning speed is 5 ~ 50mV/S, circulates 5 ~ 50 times.
3. the preparation method of a kind of heteropolyacid doped polyaniline coating according to claim 1, it is characterized in that: described metal comprises one-component metal, binary or multicomponent alloy, described surface is the surface of arbitrary shape.
4. the preparation method of a kind of heteropolyacid doped polyaniline coating according to claim 1, it is characterized in that: described electropolymerization need use protonic acid, protonic acid is one or more mixing in sulfuric acid, phosphoric acid, nitric acid, oxalic acid more specifically, and concentration is 0.1 ~ 1M.
5. the preparation method of a kind of heteropolyacid doped polyaniline coating according to claim 1, is characterized in that: described ammonia concn M1 is 0.5 ~ 1M.
6. the preparation method of a kind of heteropolyacid doped polyaniline coating according to claim 1, is characterized in that: vacuum tightness is 0.01 ~ 0.05MPa.
7. the preparation method of a kind of heteropolyacid doped polyaniline coating according to claim 1, is characterized in that: the solvent in described phosphoric acid and the mixing solutions of heteropolyacid is ethanol.
8. the preparation method of a kind of heteropolyacid doped polyaniline coating according to claim 1, is characterized in that: described heteropolyacid comprises one or more in phospho-wolframic acid, phospho-molybdic acid, silicotungstic acid, silicomolybdic acid.
9. according to the preparation method of a kind of heteropolyacid doped polyaniline coating described in claim 1, it is characterized in that: described phosphoric acid concentration M2 is 0.5 ~ 1M, the concentration M3 of heteropolyacid is 5 ~ 15mM.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107142507A (en) * | 2017-05-03 | 2017-09-08 | 中国东方电气集团有限公司 | A kind of preparation method of lithium ion battery collector |
| CN109423683A (en) * | 2017-08-30 | 2019-03-05 | 广东新会中集特种运输设备有限公司 | The finishing system of container and the coating process of container |
| CN110252361A (en) * | 2019-06-25 | 2019-09-20 | 东北师范大学 | A kind of catalyst cellulose of polyacid containing molybdenum of doped polyaniline prepares the technology of lactic acid |
| CN110255674A (en) * | 2019-07-03 | 2019-09-20 | 辽宁科技学院 | A kind of anode material and preparation method for wastewater treatment |
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| CN103361704A (en) * | 2013-07-22 | 2013-10-23 | 兰州理工大学 | Preparation method and use of copper ion electrochemical doped polyaniline material |
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| CN103361704A (en) * | 2013-07-22 | 2013-10-23 | 兰州理工大学 | Preparation method and use of copper ion electrochemical doped polyaniline material |
Non-Patent Citations (2)
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| 刘万民等: "循环伏安法制备掺杂聚苯胺涂层的防腐性研究", 《表面技术》 * |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107142507A (en) * | 2017-05-03 | 2017-09-08 | 中国东方电气集团有限公司 | A kind of preparation method of lithium ion battery collector |
| CN107142507B (en) * | 2017-05-03 | 2019-01-01 | 中国东方电气集团有限公司 | A kind of preparation method of lithium ion battery collector |
| CN109423683A (en) * | 2017-08-30 | 2019-03-05 | 广东新会中集特种运输设备有限公司 | The finishing system of container and the coating process of container |
| CN109423683B (en) * | 2017-08-30 | 2021-03-23 | 广东新会中集特种运输设备有限公司 | Container coating system and container coating method |
| CN110252361A (en) * | 2019-06-25 | 2019-09-20 | 东北师范大学 | A kind of catalyst cellulose of polyacid containing molybdenum of doped polyaniline prepares the technology of lactic acid |
| CN110255674A (en) * | 2019-07-03 | 2019-09-20 | 辽宁科技学院 | A kind of anode material and preparation method for wastewater treatment |
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