CN109468645A - A kind of selfreparing corrosion inhibiter of Q235 steel and preparation method thereof - Google Patents
A kind of selfreparing corrosion inhibiter of Q235 steel and preparation method thereof Download PDFInfo
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- CN109468645A CN109468645A CN201811558232.3A CN201811558232A CN109468645A CN 109468645 A CN109468645 A CN 109468645A CN 201811558232 A CN201811558232 A CN 201811558232A CN 109468645 A CN109468645 A CN 109468645A
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- halloysite nanotubes
- corrosion inhibiter
- hydroxyquinoline
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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
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/173—Macromolecular compounds
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Abstract
The Q235 steel corrosion inhibiter for the pH sensitivity with self-healing ability that the invention discloses a kind of, this corrosion inhibiter is the halloysite nanotubes (HNTs) of 8-hydroxyquinoline (8-HQ) insertion, outside package polyelectrolyte, polyelectrolyte select poly styrene sulfonate (PSS) and polyallylamine hydrochlorides (PAH).When in corrosion process cathode reaction occurs for Q235 steel, local pH value changes, and 8-hydroxyquinoline, which can be released, forms complex compound with iron ion, adsorbs to fill up defect in Q235 steel surface.
Description
Technical field
The present invention relates to a kind of corrosion inhibiter, in particular to the Q235 steel corrosion inhibiter of a kind of pH sensitivity with self-healing ability and
Preparation method belongs to technical field of metal anti-corrosion.
Background technique
It is reduced since corrosion will lead to material failure, equipment closing, the wasting of resources, product loss or pollution, production efficiency
It is increased with maintenance cost, therefore the corrosion protection of metal and its alloy is one of sixty-four dollar question in industry and daily life.
It will once corrosive deposit is accumulated in protective layer although in the past few years, having studied various metal protection coatings
Metal surface is penetrated into, is occurred so as to cause continuous corrosion.Therefore in order to realize the metal surface of active healing ability
Digital preservation, self-healing coating are constantly subjected to extensive concern in recent years.
One of implementation method of self-healing coating is that corrosion inhibiter is encapsulated in micro-nano container, and outside microcapsules
Alternating deposit polyelectrolyte.When local environment changes or metal surface starts corrosion, the pH value around corrosion inhibiter will be sent out
Changing changes its electron density, the corrosion inhibiter of encapsulation will be straight from nano container to influence the functional group of polyelectrolyte
It connects and is discharged into affected area.The effect that corrosion inhibiting coating self-healing on the one hand can be played in this way, on the other hand can prevent encapsulation
Corrosion inhibiter leakage, reduces the barrier property of corrosion inhibition film.Common micro-nano container includes mesoporous SiO2Nano particle, carbon nanometer
Pipe, hydrotalcite, polymer hollow ball, halloysite nanotubes etc..
In various micro-nano containers, halloysite nanotubes (HNTs) are attracted wide attention, mainly since HNTs is
A kind of mesoporous clay material, hollow tubular structures can load effective component, have the excellent performances such as hypotoxicity.However, HNTs
Formation be heavily dependent on natural conditions, cause its size distribution uneven, this largely affects its dress
Load and releasability.The result shows that the HNTs of common corrosion inhibiter benzotriazole (BTA) and 2-mercaptobenzothiazole (MBT) is always born
Carrying is only 5wt.%.In order to further expansion HNTs internal diameter to increase load capacity, frequently with acid etching processes.
Existing many corrosion inhibiter have the defects that certain, such as high toxicity, carcinogenesis, will seriously endanger human body and are good for
Health and environment, therefore, there is an urgent need to find a kind of corrosion inhibiter that cost performance is high and environmentally friendly at present.8-hydroxyquinoline (8-HQ) conduct
A kind of typical organic matter is widely used as dyestuff, screening agent, while can be used for the metal deactivator of steel, copper and magnesium.8-HQ
It can easily be chelated with most metal ions, be effectively prevented corrosion, inhibition mechanism is ground by many
Study carefully personnel to study.Dopamine is a kind of effective adhesive, it can be attached to almost all of material surface, and gather automatically
Conjunction forms poly-dopamine (PDA) coating.The extensive use of PDA coating has benefited from its cross-linked structure and preparation method is simple, mechanical
Integrity and stability is good, simultaneously because its-NH2Functional group makes coating have surface hydrophobic.
Summary of the invention
The technical problems to be solved by the invention: there are high toxicity, carcinogenicities etc. for existing corrosion inhibiter, seriously endanger human body
Health and environment.
In order to solve the above-mentioned technical problem, the first aspect of the present invention provides a kind of steel corrosion inhibiter, for Q235 steel
Selfreparing, constituent component include:
Halloysite nanotubes；
8-hydroxyquinoline is embedded in inside halloysite nanotubes；
Polyelectrolyte is wrapped in outside halloysite nanotubes.
Further, polyelectrolyte uses poly styrene sulfonate (PSS) and polyallylamine hydrochlorides (PAH).
The second aspect of the present invention provides the preparation method of above-mentioned steel corrosion inhibiter, includes the following steps:
(1) acidification is carried out to halloysite nanotubes；
(2) 8-hydroxyquinoline is filled in halloysite nanotubes, obtains the halloysite nanotubes for being packaged with 8-hydroxyquinoline；
(3) polyelectrolyte is coated in the external of the halloysite nanotubes for being packaged with 8-hydroxyquinoline.
Further, step (1) includes following subdivided step: halloysite nanotubes are immersed in inorganic acid solution, stirring,
It filters, is dry；It is multiple to repeat the above acidization；Finally rinsed with deionized water, it is dry.
Further, in step (1), inorganic acid solution uses 2mol/L sulfuric acid solution, stirs 12 hours, 50 degrees Celsius of items
It is dry under part.
Further, step (2) includes following subdivided step: the acetone that 8-hydroxyquinoline is added in halloysite nanotubes is satisfied
In solution, is stirred under reduced pressure at room temperature, 8-hydroxyquinoline is enable to be inhaled into halloysite nanotubes；Then deionized water is used
Halloysite nanotubes are cleaned, are centrifuged, it is dry.
Further, in step (2), the halloysite nanotubes of 5 parts by volume are added to the third of the 8-hydroxyquinoline of 1 parts by volume
It is dry under 60 degrees celsius in ketone saturated solution.
Further, in step (3), polystyrene is alternately coated outside halloysite nanotubes using laminated assembling technology
Sulfonate and polyallylamine hydrochlorides.
Further, step (3) includes following subdivided step:
(3-1) takes the halloysite nanotubes for being packaged with 8-hydroxyquinoline after drying to be scattered in sodium-chloride water solution, surpasses
Sound dispersion, obtains mixed liquor；
Mixed liquor and poly styrene sulfonate solution are thoroughly mixed by (3-2), and product is centrifugated, deionized water
It rinses 3 times, obtains semi-finished product；
Semi-finished product and polyallylamine hydrochlorides solution are sufficiently mixed by (3-3)；It rinses, is repeated 3 times above after centrifugation；It is dry
After obtain corrosion inhibiter finished product.
Further, in step (3-1), halloysite nanotubes 0.02g, the aqueous sodium chloride for the use of concentration being 0.5M are used
Liquid 10mL；Ultrasonic treatment 5 minutes or more；
In step (3-2), the poly styrene sulfonate solution 10mL for the use of concentration being 2mg/mL, after being mixed with mixed liquor,
Magnetic stirring 15 minutes or more；
In step (3-3), the polyallylamine hydrochlorides solution 5mL for the use of concentration being 2mg/mL.
The beneficial effects of the present invention are: being prepared for a kind of Q235 steel of pH sensitivity using the method that polyelectrolyte assembles layer by layer
Corrosion inhibiter, the corrosion inhibiter are realized release of the 8-HQ in acid and alkaline solution, can be improved by the HNTs of load 8-HQ
The antiseptic property of Q235 steel surface.
Detailed description of the invention
Fig. 1 is the preparation technology flow chart of selfreparing corrosion inhibiter of the present invention；
In Fig. 2, a and b are respectively SEM and the TEM figure of untreated HNTs, and c and d are respectively the HNTs and HNTs/ being acidified
The TEM of 8-HQ/PSS/PAH schemes.
Fig. 3 is the zeta potential control for being acidified HNTs, HNTs/8-HQ, HNTs/8-HQ/PSS and HNTs/8-HQ/PSS/PAH
Figure.
Specific embodiment
It is described further below with reference to technical effect of the attached drawing to design of the invention, specific structure and generation, with
It is fully understood from the purpose of the present invention, feature and effect.
Supported corrosion inhibitor 8-HQ realizes the controlled release to encapsulation type corrosion inhibiter from HNTs internal leakage in order to prevent,
In several alternate polyelectrolyte film (poly styrene sulfonates/polyallylamine salt of outside deposition of the HNTs of load 8-HQ
Hydrochlorate).As the intelligent switch of control corrosion inhibiter release, Q235 steel corrosion causes the variation of local ph that will trigger polyelectrolyte
The functional group of film changes its electron density, thus the corrosion inhibiter that release wherein encapsulates.Steps are as follows for specific experiment:
The surface preparation of Q235 steel
Experiment is 0.0314cm with analysis area2Epoxy sealing Q235 rod iron as working electrode.Firstly, with containing
500- and 1000- SiC paper polishes to Q235 steel electrode, removes the oxide/hydroxide layer of metal surface.So
Afterwards, electrode surface is polished using 0.3 μm of aluminium oxide.Finally, electrode surface is rinsed with deionized water, ethyl alcohol and deionized water,
To remove metal oxide and oxidation residue of aluminum.
Galapectite processing
HNTs is immersed in 2mol/L sulfuric acid, 12h is gently mixed.Suction filtration is dried overnight, reacidizing process.Finally use
Deionized water flushes three times, and is heated to 50 DEG C of dryings.
The preparation of corrosion inhibiter
50mg HNTs is added first in the acetone saturated solution of 10mL 8-hydroxyquinoline, stirs 30 under reduced pressure at room temperature
Minute, so that 8-HQ is inhaled into HNTs.Circulating repetition three times, to ensure to load sufficient amount of corrosion inhibiter.Then clear with water
HNTs is washed, is centrifuged, overnight, the HNTs (8-HQ/HNTs) for being packaged with 8-HQ is made in 60 DEG C of drying.
Then, using layer assembly (LbL) technology, polyelectrolyte PSS and PAH are alternately coated.Firstly, after taking drying
0.02g 8-HQ/HNTs is scattered in 10mL 0.5M NaCl aqueous solution, is ultrasonically treated 5 minutes.Then by the solution and 10mL
PSS solution (2mg/mL) mix 15min under magnetic stirring, will first coat one layer of negatively charged polyelectrolyte PSS, be made
Sample HNTs/8-HQ/PSS.It is centrifugated the sample, distilled water flushing 3 times.Then by the PAH solution of 5mLn concentration 2mg/mL
It is mixed with HNT/8-HQ/PSS sample, sufficiently after absorption, mixture (HNTs/8-HQ/PSS/PAH) is rinsed and is centrifuged 3
It is secondary.Finally, sample is dried at room temperature for.
PDA self-healing coating
Q235 steel electrode is first dipped into 10mL and contains 0.01g HNTs/8-HQ/PSS/PAH and 2mg/mL dopamine Tris-
In HCl (pH=8.5) buffer solution.Then 12h is stirred at room temperature, is finally rinsed with deionized water, dries in air, makes
Obtain sample Q235@HNT/8-HQ/PSS/PAH@PDA.The Q235 steel electrode of blank is immersed into 10mL dopamine Tris-HCl (pH=
8.5) in buffer solution, 12h (Q235@PDA) is stirred at room temperature, as a control group.
In Fig. 2, a and b are respectively SEM and the TEM figure of untreated HNTs.C and d is respectively the HNTs and HNTs/ being acidified
The TEM of 8-HQ/PSS/PAH schemes.From c as can be seen that the processed HNTs internal diameter (about 25nm) of acid is greater than in b original HNTs (about
17nm), this is because sulfuric acid can be from internal etch away sections HNTs.C and d is compared, discovery is coated with PSS and PAH layers of polyelectrolyte
HNTs outer diameter it is bigger (from 50nm to 65nm), illustrate that HNTs/8-HQ/PSS/PAH is successfully prepared.
The zeta potential for being acidified HNTs, HNTs/8-HQ, HNTs/8-HQ/PSS and HNTs/8-HQ/PSS/PAH is as shown in Figure 3.
The zeta potential for the HNTs that sulfuric acid treatment is crossed is -22.8mV, and zeta current potential becomes+1.1mV after being loaded with 8-HQ.Deposit polyelectrolyte
After PSS, zeta current potential becomes -32.0mV.Finally, after assembling PAH, zeta current potential is+29.9mV again.The change of zeta current potential
Change shows that 8-HQ is loaded successfully, the success of PSS and PAH covering.
The preferred embodiment of the present invention has been described in detail above.It should be appreciated that those skilled in the art without
It needs creative work according to the present invention can conceive and makes many modifications and variations.Therefore, all technologies in the art
Personnel are available by logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea
Technical solution, all should be within the scope of protection determined by the claims.
Claims (10)
1. a kind of steel corrosion inhibiter, which is characterized in that constituent component includes:
Halloysite nanotubes；
8-hydroxyquinoline is embedded in inside the halloysite nanotubes；
Polyelectrolyte is wrapped in outside the halloysite nanotubes.
2. a kind of steel corrosion inhibiter according to claim 1, which is characterized in that the polyelectrolyte uses polystyrolsulfon acid
Salt and polyallylamine hydrochlorides.
3. a kind of preparation method of steel corrosion inhibiter according to claim 2, which comprises the steps of:
(1) acidification is carried out to the halloysite nanotubes；
(2) 8-hydroxyquinoline is filled in the halloysite nanotubes, obtains the halloysite nanotubes for being packaged with 8-hydroxyquinoline；
(3) polyelectrolyte is coated in the external of the halloysite nanotubes for being packaged with 8-hydroxyquinoline.
4. a kind of preparation method of steel corrosion inhibiter according to claim 3, which is characterized in that the step (1) includes such as
Lower subdivided step: the halloysite nanotubes are immersed in inorganic acid solution, and stirring filters, is dry；Repeat the above acidization
Repeatedly；Finally rinsed with deionized water, it is dry.
5. a kind of preparation method of steel corrosion inhibiter according to claim 4, which is characterized in that described inorganic in step (1)
Acid solution uses 2mol/L sulfuric acid solution, stirs 12 hours, dry under 50 degrees celsius.
6. a kind of preparation method of steel corrosion inhibiter according to claim 3, which is characterized in that the step (2) includes such as
Lower subdivided step: the halloysite nanotubes being added in the acetone saturated solution of 8-hydroxyquinoline, stirred under reduced pressure at room temperature,
8-hydroxyquinoline is set to be inhaled into the halloysite nanotubes；Then the halloysite nanotubes are cleaned with deionized water,
Centrifugation, it is dry.
7. a kind of preparation method of steel corrosion inhibiter according to claim 6, which is characterized in that in step (2), by 5 volumes
The halloysite nanotubes of part are added in the acetone saturated solution of the 8-hydroxyquinoline of 1 parts by volume, 60 degrees celsius
Lower drying.
8. a kind of preparation method of steel corrosion inhibiter according to claim 3, which is characterized in that in step (3), using layer by layer
Package technique alternately coats poly styrene sulfonate and polyallylamine hydrochlorides outside the halloysite nanotubes.
9. a kind of preparation method of steel corrosion inhibiter according to claim 8, which is characterized in that step (3) includes following thin
Step by step:
(3-1) takes the halloysite nanotubes for being packaged with 8-hydroxyquinoline after drying to be scattered in sodium-chloride water solution, surpasses
Sound dispersion, obtains mixed liquor；
The mixed liquor and poly styrene sulfonate solution are thoroughly mixed by (3-2), and product is centrifugated, deionized water
It rinses 3 times, obtains semi-finished product；
The semi-finished product and polyallylamine hydrochlorides solution are sufficiently mixed by (3-3)；It rinses, is repeated 3 times above after centrifugation；It is dry
After obtain the corrosion inhibiter finished product.
10. a kind of preparation method of steel corrosion inhibiter according to claim 9, which is characterized in that
In step (3-1), the halloysite nanotubes 0.02g, the sodium-chloride water solution 10mL for the use of concentration being 0.5M are used；It is super
Sonication 5 minutes or more；
In step (3-2), the poly styrene sulfonate solution 10mL for the use of concentration being 2mg/mL, after being mixed with the mixed liquor,
Magnetic stirring 15 minutes or more；
In step (3-3), the polyallylamine hydrochlorides solution 5mL for the use of concentration being 2mg/mL.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113215576A (en) * | 2021-06-22 | 2021-08-06 | 中国石油大学(华东) | Preparation method and application of rare earth doped silicon dioxide intelligent corrosion inhibition system |
| CN113245166A (en) * | 2021-03-24 | 2021-08-13 | 吉林大学 | Bionic intelligent repeatable self-repairing coating and drop coating process method thereof |
| CN113667340A (en) * | 2021-07-29 | 2021-11-19 | 华南理工大学 | Corrosion inhibition material and application thereof |
| CN114602995A (en) * | 2022-02-25 | 2022-06-10 | 江苏铭展特钢制造有限公司 | High-pressure-resistant corrosion-resistant stainless steel bar and processing technology thereof |
| CN114656044A (en) * | 2021-09-26 | 2022-06-24 | 天津科技大学 | Environment-friendly nano-fluid scale inhibitor and preparation method and application thereof |
| CN115537084A (en) * | 2022-11-16 | 2022-12-30 | 华东理工大学 | Mussel bionic modified HNT composite water-based anticorrosive paint and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113245166A (en) * | 2021-03-24 | 2021-08-13 | 吉林大学 | Bionic intelligent repeatable self-repairing coating and drop coating process method thereof |
| CN113215576A (en) * | 2021-06-22 | 2021-08-06 | 中国石油大学(华东) | Preparation method and application of rare earth doped silicon dioxide intelligent corrosion inhibition system |
| CN113215576B (en) * | 2021-06-22 | 2022-04-22 | 中国石油大学(华东) | Preparation method and application of rare earth doped silicon dioxide intelligent corrosion inhibition system |
| CN113667340A (en) * | 2021-07-29 | 2021-11-19 | 华南理工大学 | Corrosion inhibition material and application thereof |
| CN114656044A (en) * | 2021-09-26 | 2022-06-24 | 天津科技大学 | Environment-friendly nano-fluid scale inhibitor and preparation method and application thereof |
| CN114656044B (en) * | 2021-09-26 | 2023-07-18 | 天津科技大学 | Environment-friendly nano fluid scale inhibitor and preparation method and application thereof |
| CN114602995A (en) * | 2022-02-25 | 2022-06-10 | 江苏铭展特钢制造有限公司 | High-pressure-resistant corrosion-resistant stainless steel bar and processing technology thereof |
| CN114602995B (en) * | 2022-02-25 | 2023-12-26 | 江苏铭展特钢制造有限公司 | High-pressure-resistant corrosion-resistant stainless steel rod and processing technology thereof |
| CN115537084A (en) * | 2022-11-16 | 2022-12-30 | 华东理工大学 | Mussel bionic modified HNT composite water-based anticorrosive paint and preparation method thereof |
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Application publication date: 20190315 |