CN108002730A - A kind of hydrotalcite intercalation 5- methyl mercapto -1,3,4,-thiadiazoles -2- sulfydryls corrosion inhibitor and its application - Google Patents

A kind of hydrotalcite intercalation 5- methyl mercapto -1,3,4,-thiadiazoles -2- sulfydryls corrosion inhibitor and its application Download PDF

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CN108002730A
CN108002730A CN201711254566.7A CN201711254566A CN108002730A CN 108002730 A CN108002730 A CN 108002730A CN 201711254566 A CN201711254566 A CN 201711254566A CN 108002730 A CN108002730 A CN 108002730A
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corrosion inhibitor
thiadiazoles
corrosion
sulfydryl
hydrotalcite
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田惠文
李伟华
刘昂
侯保荣
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Institute of Oceanology of CAS
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/16Sulfur-containing compounds
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00Compounds of zinc
    • C01G9/006Compounds containing, besides zinc, two ore more other elements, with the exception of oxygen or hydrogen
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/60Agents for protection against chemical, physical or biological attack
    • C04B2103/61Corrosion inhibitors

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Abstract

The present invention relates to corrosion inhibitor, a kind of specifically 5 methyl mercapto 1 of hydrotalcite intercalation, 3,4,2 sulfydryl corrosion inhibitor of thiadiazoles and its application.In zinc-aluminum hydrotalcite interlayer by ion exchange, 5 methyl mercapto 1 of intercalation in a manner of hydrogen bond and Electrostatic Absorption, 3,4,2 sulfydryl anion of thiadiazoles, the compound of formation is corrosion inhibitor.Corrosion inhibitor using the present invention, can volume production, can accomplish controlled release and repair corrosion carbon steel, and there is long-term protective action, can effectively to carbon steel progress corrosion protection, have significant application value and vast market prospect.

Description

A kind of hydrotalcite intercalation 5- methyl mercapto -1,3,4,-thiadiazoles -2- sulfydryls corrosion inhibitor and It is applied
Technical field
The present invention relates to corrosion inhibitor, a kind of specifically hydrotalcite intercalation 5- methyl mercaptos -1,3,4,-thiadiazoles -2- mercaptos Base corrosion inhibitor and its application.
Background technology
Armored concrete is the material of main part of coastal and offshore engineering construction, under marine corrosion environment, by high concentration cl from The steel bar corrosion that son infiltration triggers, is the primary factor for causing concrete molecule to deteriorate.The method for completely cutting off Chloride Attack is very much, Reinforcing steel bar corrosion inhibitor is most simple and direct, economic and efficient aseptic technic.
Reinforcing steel bar corrosion inhibitor refers to add in concrete or brushes in concrete surface, can prevent or slow down the change of reinforcement corrosion Learn material.At present reinforcing steel bar corrosion inhibitor research and application be broadly divided into two classes:I.e. doped corrosion inhibitor (DCI) and migration-type resistance rust Agent (MCI), the former is mainly spiked into concrete, can also be used for recovery project for new construction, the latter is mainly sprayed at Concrete outer surface, the reparation for built engineering.However, big logarithm business corrosion inhibitor is all that function is single, some even can Ecological environment is destroyed, corrosion inhibitor long-term existence also occurs that in concrete in addition is lost in and fails.Although new reinforcing steel bar resistance rust Agent is always the emphasis of anticorrosion work person's research, but collects efficient, permanent, selfreparing and environmentally friendly novel and multifunctional resistance rust Agent slowly fails to come out, and in face of the strategy development requirement of national marine power and the marine environment of harshness, there is an urgent need to research and develop Multifunctional efficient green corrosion inhibitor.
Hydrotalcite, is also double-layered hydroxides, is a kind of anionite, it is separated by hybrid metal, by anion Positively charged hydroxide layer and hydrone composition, general formula is [M2+ 1-xM3+ x(OH)2]x+An- x/n·mH2O.Due to its point Son, size (nanoscale) and composition are adjustable, and have ion exchanging function, therefore have very big dive in field of corrosion prevention Power.
The content of the invention
Present invention aims at providing a kind of hydrotalcite intercalation 5- methyl mercapto -1,3,4,-thiadiazoles -2- sulfydryls corrosion inhibitor and It is applied.
To achieve the above object, the technical solution adopted by the present invention is:
A kind of hydrotalcite intercalation 5- methyl mercaptos -1,3,4,-thiadiazoles -2- sulfydryl corrosion inhibitors, lead in zinc-aluminum hydrotalcite interlayer Ion exchange is crossed, intercalation 5- methyl mercaptos -1,3 in a manner of hydrogen bond and Electrostatic Absorption, 4,-thiadiazoles -2- sulfydryl anion, form Compound be corrosion inhibitor.
Zinc-aluminum hydrotalcite [the Zn0.67Al0.33(OH)2][(NO3)0.33·mH2O] reaction equation be:
Zn(NO3)2·6H2O+2NaOH=Zn (OH)2↓+2NaNO3+6H2O (1)
Al(NO3)3·9H2O+3NaOH=Al (OH)3↓+3NaNO3+9H2O (2)
0.67Zn(OH)2+0.33Al(OH)3+mH2O+0.33NaNO3=[Zn0.67Al0.33(OH)2][(NO3)0.33· mH2O]+0.33NaOH (3)
By the mixed solution A of zinc nitrate and aluminum nitrate, (amount of material compares Zn at room temperature:Al=2:1) it is slowly dropped to nitre (volume ratio A in acid sodium solution B:B=1:1.5-2), and using NaOH maintain the mixed system pH of solution A and solution B 10 ± 0.5.Then the suspension of acquisition is crystallized in 65-110 DEG C of heating water bath 8-24h, obtains zinc-aluminum hydrotalcite.
A kind of hydrotalcite intercalation 5- methyl mercapto -1,3,4, the preparation method of-thiadiazoles -2- sulfydryl corrosion inhibitors:
1) the organic corrosion inhibitor of deprotonation, by equimolar 5- methyl mercaptos -1,3,4,-thiadiazoles -2- sulfydryls are stirred with NaOH Mix mixing, obtain 5- methyl mercaptos -1,3,4,-thiadiazoles -2- sulfydryl anion;
2) by the mixed solution A of zinc nitrate and aluminum nitrate, (amount of material compares Zn at room temperature:Al=2:1) it is slowly dropped to (volume ratio A in sodium nitrate solution B:B=1:1.5-2), and using NaOH the mixed system pH of solution A and solution B is maintained 10 ±0.5.Then the suspension of acquisition is crystallized in 65-110 DEG C of heating water bath 8-24h, obtains zinc-aluminum hydrotalcite (Zn-Al-LDH- NO3)。
3) by the zinc-aluminum hydrotalcite (Zn-Al-LDH-NO of above-mentioned acquisition3) it is added to (matter in the corrosion inhibitor solution of protonation Measure ratio, zinc-aluminum hydrotalcite:Corrosion inhibitor=1:2-3), 24-48h is continuously stirred, hydrotalcite intercalation is obtained by ion-exchange reactions 5- methyl mercapto -1,3,4,-thiadiazoles -2- sulfydryl corrosion inhibitors.
A kind of hydrotalcite intercalation 5- methyl mercaptos -1,3,4, the application of-thiadiazoles -2- sulfydryl corrosion inhibitors, the corrosion inhibitor exists Application during concrete mild steel material and its reinforcing bar product are carried out corrosion protection, repaired.
The seawater corrosion inhibitor under concrete alkaline environment or corresponding alkaline condition to concrete mild steel material and Its reinforcing bar product carries out the application in corrosion protection, reparation.
The concrete alkaline environment or corresponding alkaline condition refer to that pH value is 9.5-13.5 in seawater or sodium chloride medium.
Carbon steel material and its reinforcing bar product are immersed in and added in the alkaline seawater solution or medium of corrosion inhibitor, bath temperature For 15-45 DEG C, wherein the amount of corrosion inhibitor compound is 0.5-2g/L.
The beneficial effects of the invention are as follows:
Corrosion inhibitor obtained by the present invention is green, efficient, persistently multi-functional in integral new resistance rust with selfreparing from obtaining Agent is started with, and uses hydrotalcite (double-layered hydroxides) as carrier, and intercalation load is carried out to thiazoles corrosion inhibitor molecule, it is therefore intended that A kind of reinforcing steel bar corrosion inhibitor for the multi-functional hydrotalcite intercalation thiadiazoles compound that Targeting delivery is carried out by ion exchange is provided, To suppress the corrosion of concrete medium carbon steel and its bar material product in seawater or sodium chloride medium under alkaline condition;Tool Body:
1. cost is low.The active ingredient of corrosion inhibitor of the present invention is hydrotalcite and 5- methyl mercapto -1,3,4,-thiadiazoles -2- mercaptos Base complex, the compound synthesis material derive from a wealth of sources, are of low cost, and industrially a large amount of productions, and preparation method is simple, Yield is high, can be produced in enormous quantities, therefore integrated application cost is cheap.
2. environment Small side effects.Between corrosion inhibitor is supported on hydrotalcite bilayer by the present invention, there is preferable Environmental compatibility, On the one hand the loss and failure of corrosion inhibitor can be reduced, on the other hand, corrosion inhibitor active ingredient is exposed under strong light or in soil With it is degradable in organism be innocuous substance, load will not be brought to environment, meet the trend of green corrosion inhibitor development.
3. strong applicability.Corrosion inhibitor of the present invention it is applied widely, in higher salinity, higher temperature and wider alkali Excellent anticorrosion performance is respectively provided with the range of property pH.
4. high efficiency.This corrosion inhibitor compound yield is high, and dosage is few, can large area be added in concrete, and can have Effect suppresses carbon steel material or its destruction of corresponding reinforcing bar product in corrosive medium.
5. self-repairability.Corrosion inhibitor of the present invention is applied in corrosive medium, can carry out Corrosion Repair to Corrosion Reinforcement, Reinforcing bar is prevented further to corrode.
6. durability is good.Between corrosion inhibitor is supported on hydrotalcite bilayer by the present invention, have to erosion carbon dioxide (chlorine in environment Ion) response release ability, erosion carbon dioxide in medium (chlorion) can also be captured while discharging corrosion inhibitor, when can be long Between keep higher resistance to become rusty efficiency in alkaline environment.
Brief description of the drawings
Fig. 1 is the synthetic route of corrosion inhibitor compound provided in an embodiment of the present invention.
Embodiment
Further explanation is made to the present invention with reference to the accompanying drawings and examples.
Corrosion inhibitor is intercalation into hydrotalcite layers by the present invention, acts in corrosive medium, not only environmental response can be released Corrosion inhibitor is put, protection metal exempts from erosion, and can also capture erosion carbon dioxide chlorion in medium by ion exchange, in addition Release of the harmful substance to environment can also be reduced using hydrotalcite intercalation corrosion inhibitor, the loss and failure of corrosion inhibitor is reduced, reaches To extended protection effect.
And then using hydrotalcite nano material as carrier, organic corrosion inhibitor molecule is object, nano-device load resistance rust is prepared Agent, discharges corrosion inhibitor by ion exchange, improves corrosion inhibitor to the long-effective corrosion performance of carbon steel, possess sufficient theoretical foundation and Technical feasibility.
The present invention is according to GB10124-88《Uniform Corrosion Method of Laboratory Immersion Test method》Carry out zero-G test, And carry out anticorrosion performance characterization using two kinds of electrochemical methods of electrochemical alternate impedance spectrum and potentiodynamic polarization.Although three kinds of methods Obtained resistance rust efficiency has different, and what it is mainly due to weight-loss method test is average corrosion rate, and electrochemical method is tested Be corrosion efficiency in transient process, but the general morphologictrend of various methods is consistent, it can be seen that in different salinity, resistance rust The compound is respectively provided with excellent anticorrosion performance under agent concentration, temperature, pH value condition.Used experimental test procedures come from text Offer【1】With【2】:【1】W.Li,L.Hu,S.Zhang,B.Hou,Effects of two fungicides on the Corrosion resistance of copper in 3.5%NaCl solution under various conditions [J],Corros.Sci.2011,53:735-745 (weightless test, electrochemical impedance spectroscopy measuring resistance rust efficiency);【2】 H.Tian,W.Li,B.Hou.Novel application of a hormone biosynthetic inhibitor for the corrosion resistance enhancement of copper in synthetic seawater[J] .Corros.Sci.2011,53:3435-3445 (dynamic potential polarization curve measuring resistance rust efficiency).
Embodiment 1
Hydrotalcite intercalation 5- methyl mercapto -1,3,4, the preparation of-thiadiazoles -2- sulfydryl corrosion inhibitors.
The first step:Zinc-aluminum hydrotalcite is synthesized, reaction is as follows:
Zn(NO3)2·6H2O+2NaOH=Zn (OH)2↓+2NaNO3+6H2O (1)
Al(NO3)3·9H2O+3NaOH=Al (OH)3↓+3NaNO3+9H2O (2)
0.67Zn(OH)2+0.33Al(OH)3+mH2O+0.33NaNO3=[Zn0.67Al0.33(OH)2][(NO3)0.33· mH2O]+0.33NaOH (3)
First, by 14.85g Zn (NO3)2·6H2O and 9.38g Al (NO3)3·9H2O is dissolved into 100mL distilled water, Obtain mixing salt solution A;Again by 25.5g NaNO3It is dissolved into 200mL distilled water, obtains solution B;It is afterwards that 8g NaOH is molten Solution obtains aqueous slkali C into 100mL distilled water.
Then, solution A is slowly dropped in solution B, while aqueous slkali C is added dropwise, maintain the pH=10 of mixed system ± 0.5, rear system is during which stirred strongly, and high pure nitrogen is constantly passed through into mixed system.
Then, the suspension obtained after the completion of titration is put into 65 DEG C of water-baths and handles 24h crystallizations.
Finally, product is by centrifuging (4500rpm, 10min), and is cleaned four times with distilled water, 70 DEG C of vacuum dryings (24h) is simultaneously ground, and obtains zinc-aluminum hydrotalcite.
To avoid introducing CO3 2-, all solution are using the distilled water configuration boiled.
Second step:Synthesize zinc-aluminum hydrotalcite intercalation 5- methyl mercapto -1,3,4,-thiadiazoles -2- sulfydryl corrosion inhibitor compounds.
It is 5- methyl mercapto -1,3,4 first, the preparation (deprotonation) of-thiadiazoles -2- sulfydryl sodium salt solutions:By equimolar 5- methyl mercaptos -1,3,4,-thiadiazoles -2- sulfydryls and NaOH are added in 100mL distilled water, maintain the pH=10 of solution ± 0.5, stir 30min;
Secondly by zinc-aluminum hydrotalcite Zn-Al-LDH-NO3(half is in the amount of corrosion inhibitor), is added to above-mentioned 5- methyl mercapto -1, 3,4, in-thiadiazoles -2- sulfydryl sodium salt solutions, mixed liquor is continuously stirred into reaction 24h, pH value of solution maintains 10, end product Centrifugation recycling, cleaning, drying are simultaneously ground (with zinc-aluminum hydrotalcite recycling step), obtain corrosion inhibitor.
Adjusting its reaction condition in the way of above-described embodiment is recorded can obtain the corrosion inhibitor.
Embodiment 2
Corrosion inhibitor compound is obtained to above-described embodiment and is measured its resistance rust efficiency, is specially:
Condition:Experiment material is carbon steel (Fe:99.5%, Mn:0.4-0.5%, C:0.1-0.2%), effective corrosion inhibitor into It is divided into above-described embodiment and obtains zinc-aluminum hydrotalcite intercalation 5- methyl mercaptos -1,3,4,-thiadiazoles -2- sulfydryl corrosion inhibitors, medium is 3.5% sodium chloride solution, dosage 1L, the effective content for adding corrosion inhibitor are 0.5g, and temperature is 25 DEG C, pH=11.5, during submergence Between be 60 days.
It is respectively weightlessness 89.1% to obtain resistance rust efficiency by experiment test according to above-mentioned mensuration mode, electrochemistry resistance Anti- spectrum 89.7%, dynamic potential polarization curve 90.5%, shows compound for low, the efficient corrosion inhibitor of dosage.
Embodiment 3
Condition:Experiment material is carbon steel (Fe:99.5%, Mn:0.4-0.5%, C:0.1-0.2%), effective corrosion inhibitor into It is divided into above-described embodiment and obtains zinc-aluminum hydrotalcite intercalation 5- methyl mercaptos -1,3,4,-thiadiazoles -2- sulfydryl corrosion inhibitors, medium is 3.5% sodium chloride solution, dosage 1L, the effective content for adding corrosion inhibitor are 1g, and temperature is 25 DEG C, pH=11.5, Immersion time For 60 days.
It is respectively weightlessness 91.5% to obtain resistance rust efficiency by experiment test according to above-mentioned mensuration mode, electrochemistry resistance Anti- spectrum 92.3%, dynamic potential polarization curve 93.4%, shows compound for low, the efficient corrosion inhibitor of dosage.
Embodiment 4
Condition:Experiment material is carbon steel (Fe:99.5%, Mn:0.4-0.5%, C:0.1-0.2%), effective corrosion inhibitor into It is divided into above-described embodiment and obtains zinc-aluminum hydrotalcite intercalation 5- methyl mercaptos -1,3,4,-thiadiazoles -2- sulfydryl corrosion inhibitors, medium is 3.5% sodium chloride solution, dosage 1L, the effective content for adding corrosion inhibitor are 1.5g, and temperature is 25 DEG C, pH=11.5, during submergence Between be 60 days.
It is respectively weightlessness 91.6% to obtain resistance rust efficiency by experiment test according to above-mentioned mensuration mode, electrochemistry resistance Anti- spectrum 92.7%, dynamic potential polarization curve 93.5%, shows compound for low, the efficient corrosion inhibitor of dosage.
Embodiment 5
Condition:Experiment material is carbon steel (Fe:99.5%, Mn:0.4-0.5%, C:0.1-0.2%), effective corrosion inhibitor into It is divided into above-described embodiment and obtains zinc-aluminum hydrotalcite intercalation 5- methyl mercaptos -1,3,4,-thiadiazoles -2- sulfydryl corrosion inhibitors, medium is 3.5% sodium chloride solution, dosage 1L, the effective content for adding corrosion inhibitor are 2g, and temperature is 25 DEG C, pH=11.5, Immersion time For 60 days.
It is respectively weightlessness 92.2% to obtain resistance rust efficiency by experiment test according to above-mentioned mensuration mode, electrochemistry resistance Anti- spectrum 93.1%, dynamic potential polarization curve 94.3%, shows compound for low, the efficient corrosion inhibitor of dosage.
Embodiment 6
Condition:Experiment material is carbon steel (Fe:99.5%, Mn:0.4-0.5%, C:0.1-0.2%), corrosion inhibitor component is imitated For above-described embodiment obtain zinc-aluminum hydrotalcite intercalation 5- methyl mercaptos -1,3,4,-thiadiazoles -2- sulfydryl corrosion inhibitors, medium 3.5% Sodium chloride solution, dosage 1L, the effective content for adding corrosion inhibitor are 1g, and temperature is 15 DEG C, pH=11.5, Immersion time 60 My god.
It is respectively weightlessness 91.6% to obtain resistance rust efficiency by experiment test according to above-mentioned mensuration mode, electrochemistry resistance Anti- spectrum 92.4%, dynamic potential polarization curve 93.3%, shows compound for low, the efficient corrosion inhibitor of dosage.
Embodiment 7
Condition:Experiment material is carbon steel (Fe:99.5%, Mn:0.4-0.5%, C:0.1-0.2%), corrosion inhibitor component is imitated For above-described embodiment obtain zinc-aluminum hydrotalcite intercalation 5- methyl mercaptos -1,3,4,-thiadiazoles -2- sulfydryl corrosion inhibitors, medium 3.5% Sodium chloride solution, dosage 1L, the effective content for adding corrosion inhibitor are 1g, and temperature is 35 DEG C, pH=11.5, Immersion time 60 My god.
It is respectively weightlessness 91.8% to obtain resistance rust efficiency by experiment test according to above-mentioned mensuration mode, electrochemistry resistance Anti- spectrum 92.7%, dynamic potential polarization curve 93.6%, shows compound for low, the efficient corrosion inhibitor of dosage.
Embodiment 8
Condition:Experiment material is carbon steel (Fe:99.5%, Mn:0.4-0.5%, C:0.1-0.2%), corrosion inhibitor component is imitated For above-described embodiment obtain zinc-aluminum hydrotalcite intercalation 5- methyl mercaptos -1,3,4,-thiadiazoles -2- sulfydryl corrosion inhibitors, medium 3.5% Sodium chloride solution, dosage 1L, the effective content for adding corrosion inhibitor are 1g, and temperature is 45 DEG C, pH=11.5, Immersion time 60 My god.
It is respectively weightlessness 91.5% to obtain resistance rust efficiency by experiment test according to above-mentioned mensuration mode, electrochemistry resistance Anti- spectrum 92.4%, dynamic potential polarization curve 93.5%, shows compound for low, the efficient corrosion inhibitor of dosage.
Embodiment 9
Condition:Experiment material is carbon steel (Fe:99.5%, Mn:0.4-0.5%, C:0.1-0.2%), corrosion inhibitor component is imitated For above-described embodiment obtain zinc-aluminum hydrotalcite intercalation 5- methyl mercaptos -1,3,4,-thiadiazoles -2- sulfydryl corrosion inhibitors, medium 3.5% Sodium chloride solution, dosage 1L, the effective content for adding corrosion inhibitor are 1g, and temperature is 25 DEG C, pH=9.5, and Immersion time is 60 days.
It is respectively weightlessness 90.5% to obtain resistance rust efficiency by experiment test according to above-mentioned mensuration mode, electrochemistry resistance Anti- spectrum 91.3%, dynamic potential polarization curve 92.1%, shows compound for low, the efficient corrosion inhibitor of dosage.
Embodiment 10
Condition:Experiment material is carbon steel (Fe:99.5%, Mn:0.4-0.5%, C:0.1-0.2%), corrosion inhibitor component is imitated For above-described embodiment obtain zinc-aluminum hydrotalcite intercalation 5- methyl mercaptos -1,3,4,-thiadiazoles -2- sulfydryl corrosion inhibitors, medium 3.5% Sodium chloride solution, dosage 1L, the effective content for adding corrosion inhibitor are 1g, and temperature is 25 DEG C, pH=10.5, Immersion time 60 My god.
It is respectively weightlessness 91.1% to obtain resistance rust efficiency by experiment test according to above-mentioned mensuration mode, electrochemistry resistance Anti- spectrum 91.8%, dynamic potential polarization curve 92.5%, shows compound for low, the efficient corrosion inhibitor of dosage.
Embodiment 11
Condition:Experiment material is carbon steel (Fe:99.5%, Mn:0.4-0.5%, C:0.1-0.2%), corrosion inhibitor component is imitated For above-described embodiment obtain zinc-aluminum hydrotalcite intercalation 5- methyl mercaptos -1,3,4,-thiadiazoles -2- sulfydryl corrosion inhibitors, medium 3.5% Sodium chloride solution, dosage 1L, the effective content for adding corrosion inhibitor are 1g, and temperature is 25 DEG C, pH=12.5, Immersion time 60 My god.
It is respectively weightlessness 91.9% to obtain resistance rust efficiency by experiment test according to above-mentioned mensuration mode, electrochemistry resistance Anti- spectrum 93.7%, dynamic potential polarization curve 94.6%, shows compound for low, the efficient corrosion inhibitor of dosage.
Embodiment 12
Condition:Experiment material is carbon steel (Fe:99.5%, Mn:0.4-0.5%, C:0.1-0.2%), corrosion inhibitor component is imitated For above-described embodiment obtain zinc-aluminum hydrotalcite intercalation 5- methyl mercaptos -1,3,4,-thiadiazoles -2- sulfydryl corrosion inhibitors, medium 3.5% Sodium chloride solution, dosage 1L, the effective content for adding corrosion inhibitor are 1g, and temperature is 25 DEG C, pH=13.5, Immersion time 60 My god.
It is respectively weightlessness 92.1% to obtain resistance rust efficiency by experiment test according to above-mentioned mensuration mode, electrochemistry resistance Anti- spectrum 93.8%, dynamic potential polarization curve 94.5%, shows compound for low, the efficient corrosion inhibitor of dosage.
Using hydrotalcite nano material as carrier, the organic corrosion inhibitor of thiazoles becomes rusty the present invention for the seawater resistance of chemical load object Agent, the application under concrete alkaline environment or corresponding alkaline condition.Corrosion inhibitor is applied in concrete environment or corresponding alkalescence Under the conditions of, organic corrosion inhibitor ion is discharged by hydrotalcite layers ion exchange process, to the carbon in seawater or sodium chloride medium Steel material and its reinforcing bar product carry out Corrosion Repair, while capture erosion carbon dioxide chlorion in medium.Resistance using the present invention Become rusty agent, can volume production, can accomplish controlled release and repair corrosion carbon steel, and there is long-term protective action, can be effectively Corrosion protection is carried out to carbon steel, there is significant application value and vast market prospect.

Claims (7)

1. a kind of hydrotalcite intercalation 5- methyl mercaptos -1,3,4,-thiadiazoles -2- sulfydryl corrosion inhibitors, it is characterised in that:In zinc-aluminium neatly By ion exchange between rock layers, intercalation 5- methyl mercaptos -1,3 in a manner of hydrogen bond and Electrostatic Absorption, 4,-thiadiazoles -2- sulfydryls are cloudy Ion, the compound of formation is corrosion inhibitor.
2. zinc-aluminum hydrotalcite intercalation 5- methyl mercaptos -1,3 as described in claim 1,4,-thiadiazoles -2- sulfydryl corrosion inhibitors, it is special Sign is:The zinc-aluminum hydrotalcite ([Zn0.67Al0.33(OH)2][(NO3)0.33·mH2O]) reaction equation be:
Zn(NO3)2·6H2O+2NaOH=Zn (OH)2↓+2NaNO3+6H2O (1)
Al(NO3)3·9H2O+3NaOH=Al (OH)3↓+3NaNO3+9H2O (2)
0.67Zn(OH)2+0.33Al(OH)3+mH2O+0.33NaNO3
=[Zn0.67Al0.33(OH)2][(NO3)0.33·mH2O]+0.33NaOH (3)
By the mixed solution A of zinc nitrate and aluminum nitrate, (amount of material compares Zn at room temperature:Al=2:1) it is slowly dropped to sodium nitrate (volume ratio A in solution B:B=1:1.5-2), and using NaOH the mixed system pH of solution A and solution B is maintained 10 ± 0.5, Then the suspension of acquisition is crystallized in 65-110 DEG C of heating water bath 8-24h, obtains zinc-aluminum hydrotalcite.
3. a kind of hydrotalcite intercalation 5- methyl mercapto -1,3,4 as described in claim 1, the system of-thiadiazoles -2- sulfydryl corrosion inhibitors Preparation Method, it is characterised in that:
1) the organic corrosion inhibitor of deprotonation, by equimolar 5- methyl mercaptos -1,3,4,-thiadiazoles -2- sulfydryls and NaOH stirrings are mixed Close, acquisition 5- methyl mercaptos -1,3,4,-thiadiazoles -2- sulfydryl anion;
2) mixed solution A of zinc nitrate and aluminum nitrate is slowly dropped in sodium nitrate solution B (volume ratio A at room temperature:B= 1:1.5-2), and using NaOH maintain the mixed system pH of solution A and solution B 10 ± 0.5, then by the suspension of acquisition in 65-110 DEG C of heating water bath 8-24h crystallization, obtains zinc-aluminum hydrotalcite (Zn-Al-LDH-NO3);
3) by the zinc-aluminum hydrotalcite (Zn-Al-LDH-NO of above-mentioned acquisition3) be added in the corrosion inhibitor solution of protonation (mass ratio, Zinc-aluminum hydrotalcite:Corrosion inhibitor=1:2-3), 24-48h is continuously stirred, hydrotalcite intercalation 5- first sulphur is obtained by ion-exchange reactions Base -1,3,4,-thiadiazoles -2- sulfydryl corrosion inhibitors.
4. hydrotalcite intercalation 5- methyl mercaptos -1,3 described in a kind of claim 1,4, the application of-thiadiazoles -2- sulfydryl corrosion inhibitors, It is characterized in that:The corrosion inhibitor answering in concrete mild steel material and its reinforcing bar product are carried out corrosion protection, repaired With.
5. hydrotalcite intercalation 5- methyl mercaptos -1,3 as described in claim 4,4, the application of-thiadiazoles -2- sulfydryl corrosion inhibitors, its It is characterized in that:The seawater corrosion inhibitor under concrete alkaline environment or corresponding alkaline condition to concrete mild steel material and Its reinforcing bar product carries out the application in corrosion protection, reparation.
6. hydrotalcite intercalation 5- methyl mercaptos -1,3 as described in claim 5,4, the application of-thiadiazoles -2- sulfydryl corrosion inhibitors, its It is characterized in that:The concrete alkaline environment or corresponding alkaline condition refer to that pH value is 9.5- in seawater or sodium chloride medium 13.5。
7. hydrotalcite intercalation 5- methyl mercaptos -1,3 as described in claim 6,4, the application of-thiadiazoles -2- sulfydryl corrosion inhibitors, its It is characterized in that:Carbon steel material and its reinforcing bar product are immersed in and added in the alkaline seawater solution or medium of corrosion inhibitor, submergence temperature Spend for 15-45 DEG C, wherein the amount of corrosion inhibitor compound is 0.5-2g/L.
CN201711254566.7A 2017-11-29 2017-11-29 A kind of hydrotalcite intercalation 5- methyl mercapto -1,3,4,-thiadiazoles -2- sulfydryls corrosion inhibitor and its application Pending CN108002730A (en)

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CN114933322A (en) * 2022-06-28 2022-08-23 青岛理工大学 Calcium-aluminum type hydrotalcite of intercalation rust inhibitor and preparation method and application thereof
RU2813268C1 (en) * 2022-12-27 2024-02-08 федеральное государственное бюджетное образовательное учреждение высшего образования "Воронежский государственный университет" (ФГБОУ ВО "ВГУ") Corrosion inhibitor of copper and copper-containing alloys

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