CN105525296B - A kind of anti-corrosion method for metal - Google Patents
A kind of anti-corrosion method for metal Download PDFInfo
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- CN105525296B CN105525296B CN201510982560.6A CN201510982560A CN105525296B CN 105525296 B CN105525296 B CN 105525296B CN 201510982560 A CN201510982560 A CN 201510982560A CN 105525296 B CN105525296 B CN 105525296B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
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Abstract
The invention discloses a kind of anti-corrosion method for metal, comprise the following steps：(1) preparation of conducting polymer composite：1) conducting polymer composite monomer solution is added in a reservoir, the dopant aqueous solution, stir, under agitation, aqueous oxidizing agent solution is added dropwise, continues to stir 3 5h, filtering at 05 DEG C, filter cake is repeatedly colourless to filtered fluid with absolute ethyl alcohol and distillation water washing successively, and 15 30h are dried at 60 80 DEG C；2) compression molding is the first conducting polymer composite under the conditions of 8 15Mpa；(2) conducting polymer composite is connected by plain conductor with metal.The method of the present invention is simple and easy, it can be protected before metal does not corrode, prevent or slow down the generation of metal erosion.To the antiseptic effect of metal up to more than 85%.
Description
Technical field
This method is related to a kind of anti-corrosion method for metal.
Background technology
Metal material is damaged by the effect of surrounding medium, referred to as metal erosion.Corrosion can significantly reduce metal material
The mechanical properties such as intensity, plasticity, toughness, the geometry of hardware is destroyed, increase the abrasion between part, deteriorate electricity and light
Etc. physical property, shortens the service life of equipment, or even cause the catastrophic failures such as fire, blast.Corrosion of metal phenomenon
Very universal, such as ironwork gets rusty, hickie occurs in aluminum products surface, copper product surface produces verdigris, silverware surface stain, its
Middle ironwork corrosion is most commonly seen.
The protective layer method use range of anti-corrosion of metal is the most extensive, and this anti-corrosion method is various in metallic surface manufacture
The protective layer of material, metal product and the corrosive medium in the external world are kept apart, prevent the effect metals of corrosion from preventing so as to reach
Rotten protective layer can by smearing, spraying, electroplating, hot dip, spraying plating the methods of form but the method for protective layer for it is long away from
From or large-scale metal then very consumptive material, and easy damaged, anticorrosion ability substantially reduces after damage.Another method is
Improve corrosive medium, such as remove harmful components in medium, improve medium character or corrosion inhibiter etc. is added in corrosive medium, but
This method is suitable only in the case where corrosive medium is limited, if corrosive medium is largely present, such as in atmosphere, then this
Method does not just apply to.Electrochemical protection is also one of method of preventing corrosion of metals, theoretical according to galvanic cell, is drawn as long as can eliminate
Play the reaction of the galvanic cell of chemical attack, so that it may draw existing for the anti-corrosion of metal but this method on condition that can eliminate to realize
The reaction of the galvanic cell of chemical attack is played, while it can cause the consumption of electrode metal, it is necessary to check continually on depositing for electrode metal
Amount with ensure electrochemistry can protective effect generation.
Therefore, new anti-corrosion method is developed, reduces the use of acid and corrosion inhibiter, reduces the corrosion of anode material, reduces life
Cost is produced, reduce environmental pollution turns into the task of top priority.
The content of the invention
The purpose of the present invention is the massive losses for avoiding metal erosion from bringing each side, there is provided a kind of anticorrosive metal side
Method.
Technical scheme is summarized as follows：
A kind of anti-corrosion method for metal, comprises the following steps：
(1) preparation of conducting polymer composite：
Conducting polymer composite is prepared with one kind of following two methods：
The preparation of the first conducting polymer composite：
1) the conducting polymer composite monomer-water-soluble for the 0.01-5M that volume content is 20%-60% is added in a reservoir
Liquid, volume content are 10%-50% 0.2-5M dopant-aqueous solution, are stirred, and under agitation, volume content are added dropwise
For 30%-60% 0.01-5M oxidant-aqueous solution, continue to stir 3-5h, filtering at 0-5 DEG C, filter cake uses nothing repeatedly successively
Water-ethanol and distillation water washing are colourless to filtered fluid, and 15-30h is dried at 60-80 DEG C；
2) compression molding is the first conducting polymer composite under the conditions of 8-15Mpa；
The preparation of second of conducting polymer composite：
1) 0.05-5M conducting polymer composites monomer-organic solvent solution is prepared；Addition 0.05-5M dopant-water-soluble
Liquid is well mixed to obtain solution one；Wherein the mol ratio of conducting polymer composite monomer and dopant is 1-3:1；
2) oxidant-aqueous solution for preparing 0.1-5M is solution two；
3) carrier is soaked into 5-30s in solution two, taken out, then 5-30s is soaked in solution one, taken out, place 5-
30min, cleaned with deionized water, 50-80 DEG C of dry 5-30min；
4) repeat step 3) 8-15 times, cleaned 3-5 times, 50-80 DEG C of dry 8-15h, obtained conductive high second with acetone
Molecular material；
(2) the first conducting polymer composite or second of conducting polymer composite are connected by plain conductor and metal
Connect.
At least one of the preferred stainless steel of metal, iron, chromium, aluminium, manganese and molybdenum.
Conducting polymer composite monomer is aniline, pyridine, thiophene, ethene or acetylene.
Dopant is iodine, hydrochloric acid, sulfuric acid, p-methyl benzenesulfonic acid, DBSA, camphorsulfonic acid, dodecyl sodium sulfonate
Sodium, cetyl trimethyl bromination alkane, ferric trichloride, arsenic pentafluoride, nitric acid, phosphoric acid, hydrofluoric acid, perchloric acid or acetic acid.
Oxidant is ferric trichloride, ferric perchlorate, ammonium persulfate, hydrogen peroxide, Peracetic acid, potassium permanganate, perchloric acid
Potassium, nitric acid, chromic acid or sodium dichromate.
Organic solvent is isopropanol, dimethyl sulfoxide (DMSO) or hexamethylene.
Carrier is that cellulose nitrate film, acetyl cellulose film, polyurethane film, carbon fiber sheet, polyvinyl chloride are thin
Film, polypropylene film, mylar, polyvinylidene difluoride film, silica gel thin film；It can also be that material is silica, carborundum,
Plate, block, rod or the pipe of silicon nitride, aluminum oxide, activated carbon, graphite, foamy carbon or C-base composte material.
The material of plain conductor is copper, aluminium, albronze or silver.
Advantages of the present invention：
The method of the present invention is simple and easy, it can be protected before metal does not corrode.Can to the antiseptic effect of metal
Up to more than 85%.
Embodiment
With reference to specific embodiment, the present invention is further illustrated.
Embodiment 1
A kind of anti-corrosion method for metal, comprises the following steps：
(1) preparation of conducting polymer composite：
1) ethene-aqueous solution for the 1M that volume content is 30% is added in a reservoir, and volume content is the iodo- of 30% 1M
The aqueous solution, stir, under agitation, the ferric trichloride-aqueous solution for the 1M that volume content is 40% is added dropwise, continues to stir at 3 DEG C
4h is mixed, is filtered, filter cake is repeatedly colourless to filtered fluid with absolute ethyl alcohol and distillation water washing successively, and 20h is dried at 70 DEG C；
2) compression molding is conducting polymer composite under the conditions of 10Mpa；
(2) conducting polymer composite is connected by copper conductor with stainless steel metal to be protected.
Embodiment 2
A kind of anti-corrosion method for metal, comprises the following steps：
(1) preparation of conducting polymer composite：
1) thiophene-aqueous solution for the 5M that volume content is 20% is added in a reservoir, and volume content is 50% 0.2M's
Hydrochloric acid-the aqueous solution, stirs, under agitation, be added dropwise volume content be 30% 5M ferric perchlorate-aqueous solution, 5 DEG C after
Continuous stirring 3h, filtering, filter cake is repeatedly colourless to filtered fluid with absolute ethyl alcohol and distillation water washing successively, and 15h is dried at 80 DEG C；
2) compression molding is conducting polymer composite under the conditions of 15Mpa；
(2) conducting polymer composite is connected by aluminum conductor with metallic aluminium to be protected.
Embodiment 3
A kind of anti-corrosion method for metal, comprises the following steps：
(1) preparation of conducting polymer composite：
1) aniline-aqueous solution for the 0.01M that volume content is 60% is added in a reservoir, and volume content is 10% 5M's
Sulfuric acid-the aqueous solution, stirs, and under agitation, the ammonium persulfate-aqueous solution for the 0.01M that volume content is 60% is added dropwise, 0
DEG C continue to stir 5h, filtering, filter cake is repeatedly colourless to filtered fluid with absolute ethyl alcohol and distillation water washing successively, dry at 60 DEG C
30h；
2) compression molding is conducting polymer composite under the conditions of 8Mpa；
(2) conducting polymer composite is connected by copper aluminum alloy wire with crome metal to be protected.
Embodiment 4
A kind of anti-corrosion method for metal, comprises the following steps：
(1) preparation of conducting polymer composite：
1) the pyridine-water solution for the 1M that volume content is 30% is added in a reservoir, and volume content is 10% 5M pair
Toluenesulfonic acid-the aqueous solution, stirs, and under agitation, the hydrogen peroxide-aqueous solution for the 0.01M that volume content is 60% is added dropwise,
Continue to stir 4h at 3 DEG C, filtering, filter cake is repeatedly colourless to filtered fluid with absolute ethyl alcohol and distillation water washing successively, does at 70 DEG C
Dry 23h；
2) compression molding is conducting polymer composite under the conditions of 12Mpa；
(2) conducting polymer composite is connected by silver wire with metallic iron to be protected.
It is demonstrated experimentally that substituting the pyridine of the present embodiment with acetylene, other same the present embodiment, anti-corrosion can be carried out to metallic iron
Erosion protection.
It is demonstrated experimentally that with DBSA, camphorsulfonic acid, dodecyl sodium sulfate, cetyl trimethyl bromination
Alkane, ferric trichloride, arsenic pentafluoride, nitric acid, phosphoric acid, hydrofluoric acid, perchloric acid or acetic acid substitute respectively the present embodiment to toluene sulphur
Acid, other same the present embodiment, anti-corrosion protection can be carried out to metallic iron.
It is demonstrated experimentally that this reality is substituted respectively with Peracetic acid, potassium permanganate, potassium hyperchlorate, nitric acid, chromic acid or sodium dichromate
The hydrogen peroxide of example is applied, other same the present embodiment, anti-corrosion protection can be carried out to metallic iron.
Embodiment 5
(1) preparation of conducting polymer composite：
1) 1M pyridines-aqueous isopropanol is prepared；DBSA-the aqueous solution for adding 1M is well mixed to obtain solution
One；Wherein the mol ratio of pyridine and DBSA is 2:1；
2) nitric acid-aqueous solution for preparing 1M is solution two；
3) tubular type C-base composte material is soaked into 20s in solution two, taken out, then 20s is soaked in solution one, taken out,
10min is placed, is cleaned with deionized water, 60 DEG C of dry 20min；
4) repeat step 3) 10 times, cleaned 4 times with acetone, 70 DEG C of dry 10h, obtain conducting polymer composite；
(2) conducting polymer composite is connected by silver wire with manganese metal to be protected.
Embodiment 6
(1) preparation of conducting polymer composite：
1) 0.05M thiophene-dimethyl sulphoxide solution is prepared；Camphorsulfonic acid-the aqueous solution for adding 0.05M is moltenly well mixed
Liquid one；Wherein the mol ratio of thiophene and camphorsulfonic acid is 1:1；
2) potassium hyperchlorate-aqueous solution for preparing 0.1M is solution two；
3) silica plate is soaked into 5s in solution two, taken out, then 5s is soaked in solution one, taken out, place 5min,
Cleaned with deionized water, 50 DEG C of dry 30min；
4) repeat step 3) 8 times, cleaned 3 times with acetone, 50 DEG C of dry 15h, obtain conducting polymer composite；
(2) conducting polymer composite is connected by copper conductor with metal molybdenum to be protected.
Experiment proves：With
Carborundum, silicon nitride, aluminum oxide, activated carbon, graphite, plate, block, rod or the pipe of foamy carbon material substitute the present embodiment
Silica plate, other same the present embodiment, can to metal molybdenum carry out anti-corrosion protection.
Embodiment 7
(1) preparation of conducting polymer composite：
1) 5M ethene-cyclohexane solution is prepared；Dodecyl sodium sulfate-the aqueous solution for adding 5M is well mixed to obtain solution
One；Wherein the mol ratio of ethene and dodecyl sodium sulfate is 3:1；
2) potassium permanganate-aqueous solution for preparing 5M is solution two；
3) acetyl cellulose film is soaked into 30s in solution two, taken out, then 30s is soaked in solution one, taken out, put
30min is put, is cleaned with deionized water, 80 DEG C of dry 5min；
4) repeat step 3) 15 times, cleaned 5 times with acetone, 80 DEG C of dry 8h, obtain conducting polymer composite；
(2) conducting polymer composite is connected by copper aluminum alloy wire with metallic aluminium to be protected.
Embodiment 8
(1) preparation of conducting polymer composite：
1) 2M acetylene-cyclohexane solution is prepared；The cetyl trimethyl bromination alkane-aqueous solution for adding 2M is well mixed
Solution one；The mol ratio of wherein acetylene and cetyl trimethyl bromination alkane is 2:1；
2) Peracetic acid-aqueous solution for preparing 2M is solution two；
3) cellulose nitrate film is soaked into 20s in solution two, taken out, then 20s is soaked in solution one, taken out, put
10min is put, is cleaned with deionized water, 70 DEG C of dry 10min；
4) repeat step 3) 12 times, cleaned 4 times with acetone, 70 DEG C of dry 12h, obtain conducting polymer composite；
(2) conducting polymer composite is connected by aluminum conductor with metallic iron to be protected.
It is demonstrated experimentally that substituting the acetylene of the present embodiment with aniline, other same the present embodiment, anti-corrosion can be carried out to metallic iron
Erosion protection.
It is demonstrated experimentally that with iodine, hydrochloric acid, sulfuric acid, p-methyl benzenesulfonic acid, ferric trichloride, arsenic pentafluoride, nitric acid, phosphoric acid, hydrogen fluorine
Acid, perchloric acid or acetic acid substitute the cetyl trimethyl bromination alkane of the present embodiment respectively, and other same the present embodiment can be to gold
Belong to iron and carry out anti-corrosion protection.
It is demonstrated experimentally that substituted respectively with ferric trichloride, ferric perchlorate, ammonium persulfate, hydrogen peroxide, chromic acid or sodium dichromate
The Peracetic acid of the present embodiment, other same the present embodiment, anti-corrosion protection can be carried out to metallic iron.
It is demonstrated experimentally that with polyurethane film, carbon fiber sheet, polyvinyl chloride film, polypropylene film, mylar, poly-
Vinylidene film, silica gel thin film substitute the cellulose nitrate film of the present embodiment respectively, and other same the present embodiment can be to gold
Belong to iron and carry out anti-corrosion protection.
It is demonstrated experimentally that substitute the iron of the present embodiment respectively with stainless steel, chromium, other same the present embodiment, can to stainless steel,
Chromium carries out anti-corrosion protection.
It is in three-electrode system, the metal of connection and conducting polymer composite is (each using 0.2-5M acid as corrosive liquid
What embodiment obtained：Conducting polymer composite passes through plain conductor and metal connection product to be protected) it is used as working electrode, lead to
Cross and be connected with AUTOLAB systems, measure corresponding polarization curve, the polarization that it is measured with metal separately as working electrode
Curve is made comparisons, and show that conducting polymer composite can to the protection effect of metal by weight metal change in corrosivity acid solution
Up to more than 85%.
The acid of corrosive liquid includes hydrochloric acid, sulfuric acid, perchloric acid, phosphoric acid, sulfurous acid.It is shown in Table 1
Table 1
| Embodiment | Condition | Protection effect of the conducting polymer composite to metal |
| 1 | 20 DEG C of sulfuric acid of 1M | 95.42% |
| 2 | 20 DEG C of sulfurous acid of 1M | 98.87% |
| 3 | 40 DEG C of phosphoric acid of 2M | 92.43% |
| 4 | 60 DEG C of hydrochloric acid of 0.5M | 90.21% |
| 5 | 50 DEG C of perchloric acid of 0.5M | 89.21% |
| 6 | 50 DEG C of sulfuric acid of 2M | 85.32% |
| 7 | 20 DEG C of hydrochloric acid of 2M | 88.62% |
| 8 | 30 DEG C of sulfuric acid of 0.2M | 98.95% |
Claims (9)
- A kind of 1. anti-corrosion method for metal, it is characterized in that comprising the following steps：(1) preparation of conducting polymer composite：1) 0.05-5M conducting polymer composites monomer-organic solvent solution is prepared；Dopant-the aqueous solution for adding 0.05-5M mixes Close uniform solution one；Wherein the mol ratio of conducting polymer composite monomer and dopant is 1-3:1；2) oxidant-aqueous solution for preparing 0.1-5M is solution two；3) carrier is soaked into 5-30s in solution two, taken out, then 5-30s is soaked in solution one, taken out, place 5-30min, Cleaned with deionized water, 50-80 DEG C of dry 5-30min；4) repeat step 3) 8-15 times, cleaned 3-5 times with acetone, 50-80 DEG C of dry 8-15h, obtain conducting polymer composite； (2) conducting polymer composite is connected by plain conductor with metal.
- 2. according to the method for claim 1, it is characterized in that the metal be stainless steel, iron, chromium, aluminium, manganese and molybdenum at least It is a kind of.
- 3. according to the method for claim 1, it is characterized in that the conducting polymer composite monomer be aniline, pyridine, thiophene, Ethene or acetylene.
- 4. according to the method for claim 1, it is characterized in that the dopant is iodine, hydrochloric acid, sulfuric acid, p-methyl benzenesulfonic acid, ten Dialkyl benzene sulfonic acids, camphorsulfonic acid, dodecyl sodium sulfate, cetyl trimethyl bromination alkane, ferric trichloride, arsenic pentafluoride, Nitric acid, phosphoric acid, hydrofluoric acid, perchloric acid or acetic acid.
- 5. according to the method for claim 1, it is characterized in that the oxidant be ferric trichloride, ferric perchlorate, ammonium persulfate, Hydrogen peroxide, Peracetic acid, potassium permanganate, potassium hyperchlorate, nitric acid, chromic acid or sodium dichromate.
- 6. according to the method for claim 1, it is characterized in that the organic solvent is isopropanol, dimethyl sulfoxide (DMSO) or hexamethylene Alkane.
- 7. the method according to claim 11, it is characterized in that the carrier is cellulose nitrate film, cellulose acetate is thin Film, polyurethane film, carbon fiber sheet, polyvinyl chloride film, polypropylene film, mylar, polyvinylidene difluoride film, silica gel Film.
- 8. according to the method for claim 1, it is characterized in that it is silica that the carrier, which is material, carborundum, silicon nitride, Plate, block, rod or the pipe of aluminum oxide, activated carbon, graphite, foamy carbon or C-base composte material.
- A kind of 9. method according to claim 1, it is characterized in that the material of the plain conductor is copper, aluminium, albronze Or silver.
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| CN108060155A (en) * | 2017-12-29 | 2018-05-22 | 舟山富晟食品科技有限公司 | The protease extracted from squid viscera |
| WO2020037450A1 (en) * | 2018-08-20 | 2020-02-27 | 唐建 | Method for manufacturing surface corrosion-resistant film |
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| CN1624200A (en) * | 2004-10-29 | 2005-06-08 | 武汉大学 | Application of conductive polyaniline in anode protection technology |
| CN1671803A (en) * | 2002-07-24 | 2005-09-21 | Geo泰克化学技术有限公司 | Method for applying a coating that acts as an electrolytic barrier and cathodic corrosion prevention system |
| CN2775094Y (en) * | 2004-05-20 | 2006-04-26 | 赵全玺 | Anti-corrosion fire-proof cable |
| CN106164338A (en) * | 2014-03-31 | 2016-11-23 | 藤森工业株式会社 | Anode for corrosion prevention, and corrosion prevention structure and corrosion prevention method for concrete structure using same |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1671803A (en) * | 2002-07-24 | 2005-09-21 | Geo泰克化学技术有限公司 | Method for applying a coating that acts as an electrolytic barrier and cathodic corrosion prevention system |
| CN2775094Y (en) * | 2004-05-20 | 2006-04-26 | 赵全玺 | Anti-corrosion fire-proof cable |
| CN1624200A (en) * | 2004-10-29 | 2005-06-08 | 武汉大学 | Application of conductive polyaniline in anode protection technology |
| CN106164338A (en) * | 2014-03-31 | 2016-11-23 | 藤森工业株式会社 | Anode for corrosion prevention, and corrosion prevention structure and corrosion prevention method for concrete structure using same |
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