CN106116204A - A kind of quaternary ammonium base cationoid corrosion inhibitor and application thereof - Google Patents
A kind of quaternary ammonium base cationoid corrosion inhibitor and application thereof Download PDFInfo
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- CN106116204A CN106116204A CN201610521762.5A CN201610521762A CN106116204A CN 106116204 A CN106116204 A CN 106116204A CN 201610521762 A CN201610521762 A CN 201610521762A CN 106116204 A CN106116204 A CN 106116204A
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- corrosion inhibitor
- quaternary ammonium
- ammonium base
- cationoid
- corrosion
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/12—Nitrogen containing compounds organic derivatives of hydrazine
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/60—Agents for protection against chemical, physical or biological attack
- C04B2103/61—Corrosion inhibitors
Abstract
The invention discloses a kind of quaternary ammonium base cationoid corrosion inhibitor as electrical mobility corrosion inhibitor, a kind of quaternary ammonium base cationoid is as the corrosion protection of Steel Bars in Concrete Structure and reparation.Quaternary ammonium base cationoid corrosion inhibitor of the present invention is the compound with quaternary ammonium base cationic structural, the effect by extra electric field of the described corrosion inhibitor, promotes the migration of quaternary ammonium base cation so that it is be enriched in around reinforcing bar, effectively protect reinforcing bar.Quaternary ammonium base cationoid corrosion inhibitor of the present invention, electromigration efficiency is high, and molecular structure stabilized does not changes with inside concrete environmental change, it is possible to effectively prevention and reparation built structure concrete reinforcement erosion, has significant using value and market prospect.
Description
Technical field
The present invention relates to a kind of reinforcement corrosion protection, with repair materials and application thereof, particularly one, there is quaternary ammonium base molecule
The cation of structure, is applied to reinforced concrete structure as electromigration corrosion inhibitor.
Background technology
Steel bar corrosion is as one of the main reason of reinforced concrete structure failure, it has also become whole world science and engineering
The hot that boundary pays close attention to.Around protection and the reparation of built Steel Bars in Concrete Structure corrosion, a lot of methods are applied the most, bag
Include electrochemical cathodic protection, electrochemical dechlorination, electrochemical realkalization, naturally migrate and electromigration corrosion inhibitor etc..At present, electrification
Learn cathodic protection and electrochemical dechlorination is acknowledged as effectively preventing the steel bar corrosion that chloride is induced.But, electrochemical dechlorination
The DC electric field used is (with 1A/m2), need to maintain 4～12 weeks could be reduced to critical by the chloride content around reinforcing bar
Below value；Cathodic protection requires used life cycle management to be persistently energized by protection structure, and maintenance cost is higher.Due to above-mentioned former
The application at home of cause, electrochemical dechlorination and cathode protection technology is actually rare.And nature migrating corrosion inhibitor uses due to it
Convenience, obtained studying largely and applying within a period of time.Patent US5427819 such as Cortec company of the U.S.
And US5326529, and the European patent EP 340807 of Sika company of Switzerland, all report a kind of organic carboxyl acid ammonium as migration
Property corrosion inhibitor, can directly be coated on concrete surface, by naturally osmotic and migrate arrive rebar surface, play corrosion inhibition
Effect.But in Practical Project, owing to concrete density is the highest, corrosion inhibitor is difficult to infiltrate into the bar list that protective layer is thicker
Face, application effect is not ideal enough.The research of electromigration corrosion inhibitor has been carried out for these a lot of scholars and engineers and technicians.Such as patent
CN1321793A, CN102924378A and document Construction and building materials 2013,39 (0):
2-8 all reports the electromigration corrosion inhibitor of the structure consisting of ion salt, imidazoles or imidazoline etc. that tradition hydramine acidifying is formed.
But, the anion neutralized due to above-mentioned electromigration corrosion inhibitor molecule is carboxylate radical or halide ion, its high-alkali at concrete
Under property environment, corrosion inhibitor molecular band electropositive is easily by concrete alkalescence environmental disruption, it is difficult to migrated by electric field acceleration, or because of
Its anion is halide ion and recontamination reinforcing bar, and actual effect is the most undesirable.
Summary of the invention
The invention aims to solve the defect of prior art, and a kind of cationic structural provided is stable, and just
Often high alkalinity concrete or carbonated concrete Environmental compatibility are the highest, the resistance not changed by the height of concrete alkaline environment
Rust agent molecule.The anion of corrosion inhibitor self is OH simultaneously-, the halide ion causing steel bar corrosion will not be introduced, stop coagulation
The risk of soil recontamination.
It is an object of the invention to be achieved through the following technical solutions:
The invention provides a kind of quaternary ammonium base cationoid corrosion inhibitor, described corrosion inhibitor is for having quaternary ammonium base cationic structural
Compound, its structural formula is as follows:
Work as R1、R2、R3And R4Time identical, it is-(CH2)nCH3；
Work as R1、R2And R3Three is identical, is-(CH2)nCH3, R4For benzyl；
Work as R1And R2Both are identical, and both are-(CH2) simultaneouslynCH3, R3、R4Be respectively ethoxy, methylol ,-(CH2)mCH3, one or both in benzyl；Wherein by the regulation and control of alkane side chain lengths, reinforcement corrosion suppression can be reached and electricity moves
Move the unification of performance；
Wherein, n=0～18, m=0～12 ,-(CH2)nCH3With-(CH2)mCH3Can be linear paraffin, it is also possible to for propping up
Alkane.
The invention provides the application process of a kind of described quaternary ammonium base cationoid corrosion inhibitor, described corrosion inhibitor is applied to steel
In tendon concrete structure, using reinforcement in concrete as negative electrode, outside concrete cover, apply anodic dissolution, by described quaternary ammonium
Bases cation corrosion inhibitor adds use in the solution of anode region, and by DC Electric Field, is actively moved by cation corrosion inhibitor
Moving to rebar surface, suppress reinforcement corrosion, described field current density range is 0.1A/m2～5A/m2, conduction time be 7～
60d。
The application process of quaternary ammonium base cationoid corrosion inhibitor of the present invention, in the solution of described anode region quaternary ammonium bases sun from
The mass fraction of sub-corrosion inhibitor is 1～50%.Act not only as the corrosion protection of unattacked reinforcing bar, it is also possible to as corrosion
The reparation of reinforcing bar.
It is an advantage of the current invention that cation corrosion inhibitor molecular structure stabilized, application conditions do not answer concrete alkalescence strong and weak and
Changing, the anion that structure self has simultaneously is OH-, high with concrete Environmental compatibility, the corruption such as other halogens will not be introduced
Erosion property ion secondary pollution concrete.Strong with molecular configurational adjustability, it is possible to mate according to decay resistance and migration performance
Suitably molecular structure, has the most superior actual application value.Additionally, the cation corrosion inhibitor of the present invention can not only be to not
Corrosion Reinforcement carries out corrosion protection, can effectively suppress and reduce Corrosion Reinforcement corrosion rate, before having wide application simultaneously
Scape.
Accompanying drawing explanation
Fig. 1 is the cation corrosion inhibitor of the present invention impact on reinforcement corrosion speed.
Fig. 2 is that criticality chlorine ion concentration is affected by cation corrosion inhibitor of the present invention.
Fig. 3 is Electrotransport devices schematic diagram.
Wherein, Fig. 3 is respectively labeled as: 1 power supply, 2 cathode chambers, 3 concrete, 4 anodic dissolutions+corrosion inhibitor.
Fig. 4 is variety classes corrosion inhibitor transfer behavior under electric field action.
Detailed description of the invention
Conduct further description to the present invention below by embodiment:
Test uses corrosion inhibitor migration performance and reinforcing bar anticorrosion performance two parts to carry out.
Reinforcement corrosion protection and repairing performance evaluation:
The impact having synthesized compound to reinforcement corrosion performance is tested in Simulated pore solution.Test fluid is full
With aqua calcis sodium chloride Han mass fraction 3.5%, adding mass fraction is the corrosion inhibitor of 0.5%, utilizes flat board to corrode
Pond and electrochemistry linear polarization measuring technology, measure corrosion potential, the time dependent rule of electric current density, permissible by curve
Know the resistance rust efficiency of compound.Its empty is matched group, and S1 is n=0, R1、R2、R3And R4The most identical and be-CH3；S2 is n
=0, R1、R2、R3Identical and be-CH3, R4 is benzyl；S3 is n=1, m=11, R1And R2Identical and be-CH2CH3, R3 be hydroxyl second
Base, R4For (CH2)mCH3；AMA is commercially available common amino alcohol migration-type corrosion inhibitor (being mainly composed of dimethylethanolamine).
Electro-chemical test uses three-electrode system to carry out, and working electrode is reinforcing bar electrode, is paper tinsel net electrode to electrode, reference
Electrode is Ag/AgCl, uses linear polarisation curves to carry out decay resistance evaluation, and by Stern-Geary equation, calculates
To reinforcement corrosion electric current density, for evaluating the size of reinforcement corrosion speed, acquired results is as shown in Figure 1.
As seen from Figure 1, different time, the result that affects of reinforcement corrosion electric current density is shown by corrosion inhibitor, blank group
Reinforcement corrosion speed is gradually increased as time went on, and corrosion inhibitor can play certain inhibitory action, wherein S1, S2 after adding
Reducing reinforcement corrosion speed more substantially with S3, corrosion electric current density is significantly less than commercially available amino alcohol corrosion inhibitor.Result shows, this
Cation corrosion inhibitor described in invention has stronger corrosion inhibition and repair function.
Additionally, also by the cumulative test of chloride ion, have studied different structure cation corrosion inhibitor chlorine critical to reinforcement corrosion
The impact of ion concentration, result of the test is as shown in Figure 2.It can be seen that reinforcement corrosion criticality chlorine ion concentration is carried by AMA
Ascending effect is inconspicuous, and when chlorine ion concentration increases to about 0.05mol/L, the corrosion electric current density of reinforcing bar is higher than 0.2uA/
cm2.S1 and S2 can promote criticality chlorine ion concentration respectively to 0.15mol/L and 0.2mol/L.Cation of the present invention hinders
Rust agent has superior corrosion-resistant ability and corrosion prevention function.
Electromigration behavioral study:
Being tested by electric field acceleration, have studied the electromigration rule of variety classes cation corrosion inhibitor, migration tests selects
Selecting in xoncrete structure and carry out, concrete mix used is shown in Table 1.
Table 1 concrete sample match ratio
| W/C | Water/kg | Cement/kg | Sand/kg | Handstone/kg | Big stone/kg | NaCl/g |
| 0.53 | 2.88 | 5.4 | 10.83 | 6.495 | 9.35 | 108 (2%) |
Concrete sample uses cement Carnis Rapanae thomasianae 42.5, according to table 1 mix, inside mixes the chemical pure sodium chloride of cement quality 2%,
Maintenance 28 days.Section, protective layer thickness is followed successively by the concrete block of 4cm as migrating objects.
As shown in Figure 3, test specimen is clipped in the middle of device experiment Electrotransport devices used, all adds about in the cavity of device both sides
150mL saturated Ca (OH) 2 solution, anode region adds the organic corrosion inhibitor of quaternary ammonium bases of 2.5% mass fraction, added electric current density
For 3A/m2, as a comparison, another device is not added with electric current, carries out nature migration.Use Multi N/C3100 organic after a period of time
Carbon analyzer measures the carbon content on cathode chamber, is characterized the Transport of cation corrosion inhibitor by the change of carbon content.
Fig. 4 is under electric field action, cathode chamber variety classes corrosion inhibitor concentration rule over time.Can from figure
Going out, prolongation over time, under electric field action, S1 and S3 is more obvious in cathode chamber rebar surface concentration increase, migration rate
Comparatively fast, higher concentration can quickly be reached.And in front 28d increase obvious, after 28d, corrosion inhibitor concentration reaches a phase
To stationary value.Blank for not having under electric field action, cathode chamber rebar surface corrosion inhibitor concentration change rule, result shows, does not has
Electric field action, slowly, in whole test period, cathode chamber is basic for commercially available AMA alkamine corrosion inhibitor nature migration rate
Not having corrosion inhibitor to migrate in the past, commercially available AMA alkamine corrosion inhibitor exists with the corrosion inhibitor having certain content under electric field action
Cathode chamber is enriched with, but measures less, is extremely difficult to protect the effect of reinforcing bar in 60d.Result shows, electric field can be obviously
Increase the transfer ability of corrosion inhibitor, and along with the prolongation of action time, arriving rebar surface corrosion inhibitor concentration can be more and more higher, table
Bright electromigration corrosion inhibitor can be as the steel bar corrosion protection of chloride ion induction in built structure and one of important means repaired.
Claims (3)
1. a quaternary ammonium base cationoid corrosion inhibitor, it is characterised in that described corrosion inhibitor is to have quaternary ammonium base cationic structural
Compound, its structural formula is as follows:
Work as R1、R2、R3And R4Time identical, it is-(CH2)nCH3；
Work as R1、R2And R3Three is identical, is-(CH2)nCH3, R4For benzyl；
Work as R1And R2Both are identical, and both are-(CH2) simultaneouslynCH3, R3、R4Be respectively ethoxy, methylol ,-(CH2)mCH3, benzyl
One or both in base；
Wherein, n=0 ~ 18, m=0 ~ 12 ,-(CH2)nCH3With-(CH2)mCH3Can be linear paraffin, it is also possible to for branched paraffin.
2. the application process of a kind of quaternary ammonium base cationoid corrosion inhibitor described in claim 1, it is characterised in that: described corrosion inhibitor
It is applied in reinforced concrete structure, using reinforcement in concrete as negative electrode, outside concrete cover, applies anodic dissolution, will
Described quaternary ammonium base cationoid corrosion inhibitor adds use in the solution of anode region, and by DC Electric Field, by cation resistance rust
Agent active migration is to rebar surface, and described field current density range is 0.1A/m2~5A/m2, conduction time is 7 ~ 60d.
The application process of a kind of quaternary ammonium base cationoid corrosion inhibitor the most according to claim 2, it is characterised in that described sun
In polar region solution, the mass fraction of quaternary ammonium base cationoid corrosion inhibitor is 1 ~ 50%.
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| CN106116204B (en) | 2018-08-31 |
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