CN102295426A - Organic composite nano-diameter sepiolite fiber reinforced concrete corrosion inhibitor, and preparation method and application thereof - Google Patents
Organic composite nano-diameter sepiolite fiber reinforced concrete corrosion inhibitor, and preparation method and application thereof Download PDFInfo
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- CN102295426A CN102295426A CN 201110271403 CN201110271403A CN102295426A CN 102295426 A CN102295426 A CN 102295426A CN 201110271403 CN201110271403 CN 201110271403 CN 201110271403 A CN201110271403 A CN 201110271403A CN 102295426 A CN102295426 A CN 102295426A
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Abstract
The invention relates to an organic composite nano-diameter sepiolite fiber reinforced concrete corrosion inhibitor, and a preparation method and application thereof. The corrosion inhibitor is obtained by the steps of: stirring an organic corrosion inhibitor and inorganic nano-diameter r sepiolite fibers in high speed, and homogenizing; the mass ratio of the organic corrosion inhibitor to the inorganic nano-diameter sepiolite fibers is (1-1.5):(2.0-2.5); the invention solves the problem of low penetration resistance capacity of concrete in the prior art; and a comparison experiment result shows that the organic composite nano-diameter sepiolite fiber reinforced concrete corrosion inhibitor has rust resistance capacity under the conditions of choride ions and carbonization, improves the corrosion limit content of reinforcing steel bars, the anti-permeability capacity of a reinforced concrete protection layer, and the performance of an interfacial zone of concrete and reinforcing steel bars, and ensures that the reinforced concrete has high durability and long engineering service life, and various electrochemistry parameters completely meet the rust and corrosion resistance requirements of reinforced steel bars in the reinforced concrete.
Description
Technical field
The present invention relates to a kind of organic composite Nano diameter sepiolite fibre antirust for reinforced concrete, preparation method and application thereof.
Background technology
Skeleton construction is a topmost structure formation during national basis is built, and is widely used in each field such as traffic, water conservancy, industry, agricultural, national defence.Yet, the corrosion of invar muscle causes the military service performance degradation of concrete structure, and engineering does not reach design requirements and too early destruction work-ing life, this has become a big disaster of whole world growing interest and the great difficult scientific problems of civil engineering field, and reinforcement corrosion destroys has become worldwide problem.Among numerous factors that influence concrete durability, reinforcement corrosion is made number one.
Reinforcement corrosion is mainly electrochemical reaction in the concrete, comprises two kinds of reactions of anode and negative electrode.The mechanism of action of rust inhibitor is preferentially to participate in and to stop these two kinds or wherein a kind of reaction, and energy stable for extended periods of time state, thereby effectively stops the corrosion of reinforcing bar.
Anode type rust inhibitor can suppress the rust inhibitor of corrosion cell anodic reaction.Anodic polarization being increased, reduced anodic reaction speed, is that corrosion of metal is subjected to the intensive inhibition.Phosphoric acid salt, borate, carbonate, benzoate, cinnamate etc. all have corrosion inhibition to corrosion of metal, but they itself do not have oxidisability, play corrosion inhibition, in the solution dissolved oxygen must be arranged.These negatively charged ion rust inhibitors mostly are strong base-weak acid salt, and hydrolysis produces hydroxide ion and forms passivating oxide in the metallic surface in water, utilizes them effectively to stop iron and alloy corrosion thereof.Work as OH
-When concentration is enough, only rely on OH
-In oxygen just can form passivating oxide.
The cathode type rust inhibitor is important to the corrosion inhibition of metal in corrosive medium to be to increase to starve cathodic polarization in the galvanic corrosion, hinders the carrying out of cathodic process, and corrosion potential is moved to negative direction, reduces corrosion speed.The external negative electrode rust inhibitor of usefulness has: amido alcohol, alkylamino ethanol, fatty acid ester.
The reinforcing bar rust inhibitor is a kind of admixture that reduces and stop steel bar corrosion, works by being spiked in the concrete or spreading upon concrete surface, and it more and more becomes a kind of means that prevent steel bar corrosion now.Japan beginning in 1973 uses the reinforcing bar rust inhibitor to resist in the oceanographic engineering villaumite to the infringement of reinforcing bar in heavy construction.In the U.S., in the time of the beginning of the seventies, use the epoxy coating reinforcing bar in a large number, yet,, bring into use rust inhibitor at the end of the seventies because its industrial economic target and environmental protection index can not be satisfactory, use in each engineering in a large number during to the eighties.The mode classification of reinforcing bar rust inhibitor has many kinds, and according to chemical composition difference can be divided into inorganic type, organic type and compound; Can be divided into anode type, cathode type and both mixed types by the mechanism of action; Can be divided into infitration type (DCI) and osmosis type (MCI) according in use mode.
Early stage reinforcing bar rust inhibitor product mainly comprises Sodium Nitrite, chromic salt and Sodium Benzoate, but they are to concrete coagulating time, morning, late period, intensity all had negative impact in various degree.U.S.'s the mid-1970s, by experimental results demonstrate the superior anticorrosion performance of calcium nitrite, but its damaging effect to human body (carcinogenic) makes some country ban use of as countries such as Germany.Early stage nitrite commonly used is done the major ingredient of reinforcing bar rust inhibitor.Nitrite is typical anode rust inhibitor, its effect be by with metal reaction, generate passive film in the metallic surface, the protection reinforcing bar is not by corrosion.
Enter the nineties, some developed countries are continuous mutually to have developed such as sodium monoflurophosphate (Na
2PO
3Novel rust inhibitor such as F).Hansson etc. have investigated Na
2PO
3F is added in the concrete resistance rust effect to reinforcing bar, shows Na
2PO
3F can significantly improve the effect of corrosion inhibition of reinforcing bar to chlorion.Ngala etc. have investigated Na
2PO
3F solution is as the effect of concrete surface penetration type rust inhibitor, and the result shows Na
2PO
3F can not well spread in concrete, thereby when repairing as the concrete result, and the inhibition of reinforcing bar is not had good effect.Magnifying congruent people passes through Na
2PO
3Na is thought in the corrosion inhibition properties research of F in concrete hole solution
2PO
3F is a kind of mixing rust inhibitor, and the anode and the cathodic process of corrosion electrochemistry all had retardation.He it can form the precipitation threshold protective membrane, under alkaline condition, can suppress the reinforcement corrosion that chlorion causes.
The world and the organic rust inhibitor of domestic research mainly comprise amine, aldehydes, alkynol class, Organophosphorous compounds, organic sulfide, carboxylic acid and salt, sulfonic acid and its esters, heterogeneous ring compound etc. at present.Main product all belongs to the type of mixing (MCI); migration-type reinforcing bar rust inhibitor is a kind of novel concept that proposes in recent years; it is directly to be coated on concrete surface, reaches the concrete reinforcement surface by spontaneous process of osmosis, finally in the protection of rebar surface film forming realization to reinforcing bar.Than mixing the shaped steel bar rust inhibitor, the migration rebar surface has plurality of advantages, is described as the new technology that concrete structure is repaired the tool prospect in field.The whole world also is in the starting stage to the research of migration-type reinforcing bar rust inhibitor at present.
The compound rust inhibitor that with the organism is component not only can be protected reinforcing bar effectively, the more important thing is to stop aqueous medium to enter inside concrete, has improved concrete impervious ability greatly.Can delay concrete weathering process own greatly like this, durability index such as concrete weathering resistance, erosion resistance, frost resistance all are improved.This admixture not only can be used as the reinforcing bar rust inhibitor, is again concrete sanitas simultaneously.
Summary of the invention
Organic composite Nano diameter sepiolite fibre antirust for reinforced concrete of the present invention, be composited by organic rust inhibitor and inorganic nanometer diameter sepiolite fibre, the mass ratio of organic rust inhibitor and inorganic nanometer diameter sepiolite fibre is 1-1.5: 2.0-2.5, described organic rust inhibitor is formed with organic compound resistance rust component and modified material, described compound resistance rust component is 1-2 by organic phospho acid salt and benzotriazole class by mass ratio: 0.8-1.3 forms, and described modified material is an anionic dispersing agents.
Described organic phospho acid salt is a kind of in Amino Trimethylene Phosphonic Acid (ATMP), the hydroxy ethylene diphosphonic acid (HEDP) or two kinds.Described benzotriazole class is a kind of or two or more combinations in benzotriazole (BTA), mercapto benzothiazole (MBT), the tolyltriazole (TTA).The content of described modified material is the 0.7-1% of nanometer diameter sepiolite fibre quality.Described nanometer diameter sepiolite fibre is a kind of nano-scale fiber, and its radial dimension is 50～60nm, and vertical scale is 1～3 μ m, is fibrous pilotaxitic texture.Described anionic dispersing agents is a fatty alcohol sulfate salt.Fatty alcohol sulfate salt is a kind of or two or more combinations in sodium lauryl sulphate, tridecyl sodium sulfate, the sodium stearyl sulfate.
Organic composite Nano diameter sepiolite fibre antirust for reinforced concrete of the present invention is to prepare by the following method: at first by the organic rust inhibitor of proportioning weighing, modified material and inorganic nanometer diameter sepiolite fibre, the three is put into homogenizer carry out the homogenizing processing promptly.Described homogenizing is handled and is adopted 4800 rev/mins stirring velocity, and churning time is 10-20 minute.
The organic composite Nano diameter of the present invention sepiolite fibre antirust for reinforced concrete hinders rust in Steel Concrete and the rot-resistant application is the organic composite Nano diameter sepiolite fibre antirust for reinforced concrete that adds cement quality 2%-3% in cement, presses the conventional stirring technique of concrete and mixes.
Rust inhibitor of the present invention is the compound rust inhibitor of component with the organism and mixes with the nanometer diameter sepiolite fibre; grinding homogenizing through high-speed stirring handles; form evengranular powder; mix by a certain percentage in the concrete and not only can protect reinforcing bar effectively; the more important thing is and stop the water-based hazardous medium to enter inside concrete; improved concrete impervious ability greatly, the nanometer diameter sepiolite fibre helps compound rust inhibitor and implements protection to the rebar surface diffusion.Can delay concrete weathering process own greatly like this, durability index such as concrete weathering resistance, erosion resistance, frost resistance all are improved.This compound rust inhibitor not only can be used as the reinforcing bar rust inhibitor, is again concrete sanitas simultaneously.Proportioning raw materials of the present invention is to obtain optimum proportioning through a large amount of experiments, adopt the rust inhibitor anticorrosion performance of this proportioning more excellent, has good resistance rust effect, concrete is had no adverse effects, performance index meet the regulation of " reinforcing bar rust inhibitor use technology rules " YB/T 9231, wherein spontaneous potential be-170mv～-210mv, have excellent resistance rust effect, can significantly improve the reinforcing bar corrosion resisting property.
The technique effect of rust inhibitor of the present invention is as follows:
(1) at various Cl
-Concentration and CO
2Under the environment reinforcing bar is implemented corrosionproof protection;
(2) can in concrete, disperse, permeate, spread;
(3) suppress the corrosion of the anode and the negative electrode of reinforcing bar simultaneously;
(4) nontoxic, environmental safety good.
Embodiment
Embodiment one: the present invention is used for skeleton construction at various Cl
-Concentration and CO
2Under the environment reinforcing bar is implemented the compound rust inhibitor of resistance rust, corrosionproof protection; organic rust inhibitor and inorganic nanometer diameter sepiolite fibre carry out composite; its mass ratio is 1.0: 2.0; wherein organic components and mass ratio are: organic phosphate (ATMP): benzotriazole class (BTA)=1.0: 0.8, the content of anionic dispersing agents are the 0.7-1% of nanometer diameter sepiolite fibre quality.Concrete preparation method is as follows: at first by the organic rust inhibitor of proportioning weighing, modified material and inorganic nanometer diameter sepiolite fibre, the three is put into homogenizer carry out the homogenizing processing promptly.Described homogenizing is handled and is adopted 4800 rev/mins stirring velocity, and churning time is 10-20 minute.
Embodiment two: adopt the BTA in the TTA replacement embodiment one.
Embodiment three: adopt the BTA in the MBT replacement embodiment one.
Embodiment four: what present embodiment and embodiment one were different is to be used for the reinforcing bar structure at various Cl
-Under the concentration environment reinforcing bar is implemented the compound rust inhibitor of resistance rust, corrosionproof protection, suppressed the corrosion of the anode and the negative electrode of reinforcing bar simultaneously.Organic rust inhibitor and inorganic nanometer diameter sepiolite fibre carry out composite, its mass ratio is 1.3: 2.0, wherein organic components and mass ratio are: organic phosphate (HEDP): benzotriazole class (BTA)=1.0: 0.8, the content of anionic dispersing agents are the 0.7-1% of nanometer diameter sepiolite fibre quality.
Embodiment five: adopt the BTA in the MBT replacement embodiment one.
Embodiment six: what present embodiment and embodiment one were different is to be used for the reinforcing bar structure at various Cl
-Concentration and CO
2Under the environment reinforcing bar is implemented the compound rust inhibitor of resistance rust, corrosionproof protection; organic rust inhibitor and inorganic nanometer diameter sepiolite fibre carry out composite; its mass ratio is 1.3: 2.5; wherein organic components and mass ratio are: organic phosphate (HEDP): benzotriazole class (TTA)=1.0: 0.8, the content of anionic dispersing agents are the 0.7-1% of nanometer diameter sepiolite fibre quality.
Embodiment four: present embodiment is different its volume difference of strength grade of concrete, and embodiment embodiment four, five, six is adapted to strength grade of concrete C40-C80, and compound rust inhibitor volume is 3% of a cement consumption; Embodiment one, two, three is adapted to strength grade of concrete C20-C30, and compound rust inhibitor volume is 2% of a cement consumption.
Resistance rust effect evaluation method
Electrochemical method is one of method of estimating, and it generally includes test reinforcing bar parameters such as corrosion potential, polarization resistance, corrosion current and alternating-current impedance in the Steel Concrete of blank and interpolation rust inhibitor.By test, can kind, the consumption of rust inhibitor be screened and optimize, grade estimation and resistance rust mechanism are inquired into.
The electrochemical impedance spectroscopy test
In the test of electrochemical impedance shop, add compound rust inhibitor, the charge transfer resistance Rct of concrete space resistance R c and reinforcing bar electrode all is significantly improved.Electrolyte concentration in concrete space resistance and the concrete space liquid, concrete pore structure factors such as (aperture and pore distributions) are relevant.When NaCl concentration was higher in the liquid of space, concrete space resistance will obviously descend.After in concrete mix, mixing compound rust inhibitor, just can obviously improve concrete space resistance, show that the electrolyte concentration in concrete space liquid this moment is lower than the blank test specimen that does not add, promptly Na+ and the Cl-infiltration rate in concrete is slack-off in the surrounding medium.Therefore, the blank test specimen of Cl-concentration ratio that is diffused into rebar surface by concrete is much lower, and this moment, the corrosion tendency and the corrosion current of reinforcing bar were more much smaller than blank test specimen.On the other hand, the compound rust inhibitor that is dissolved near the concrete space liquid reinforcing bar also will inevitably be on rebar surface and the Cl-competitive adsorption, can reduce the Cl-concentration of rebar surface equally.These two kinds of coefficient results of factor just make the charge transfer resistance Rct (being equivalent to the equational polarization resistance Rp of Stern-Geary) of reinforcing bar electrode become big.After corrosion potential is stablized in immersion arrival, measure, mix compound rust inhibitor impedance arc ring radius maximum, illustrate and mixing the most stable densification of passive film that compound rust inhibitor forms, compare with blank test specimen and suppressed the chlorion corrosion to a certain extent.
This experiment measures polarization resistance Rp, corrosion current Icorr by the linear time base sweep method and spontaneous potential comes evaluating combined type rust inhibitor type rust inhibitor effect.Rebar passivation film is thick more fine and close more, and Rp is big more, and Icorr is more little, and erosion rate is just more little, and the effectiveness of inhibiter is just good more, thus estimate its quality, can be by measuring relatively polarization resistance Rp value.The compound rust inhibitor of HEDP+TTA is a kind of mixing rust inhibitor, and it can form the precipitation threshold protective membrane, can suppress the reinforcement corrosion that chlorion causes under alkaline condition.The Rp value is more than 19000 ohm, and resistance rust effect is remarkable.
Claims (10)
1. organic composite Nano diameter sepiolite fibre antirust for reinforced concrete, it is characterized in that being composited by organic rust inhibitor and inorganic nanometer diameter sepiolite fibre, the mass ratio of organic rust inhibitor and inorganic nanometer diameter sepiolite fibre is 1-1.5: 2.0-2.5, described organic rust inhibitor is made up of organic compound resistance rust component and modified material, described compound resistance rust component is 1-2 by organic phospho acid salt and benzotriazole class by mass ratio: 0.8-1.3 forms, and described modified material is an anionic dispersing agents.
2. organic composite Nano diameter sepiolite fibre antirust for reinforced concrete as claimed in claim 1 is characterized in that described organic phospho acid salt is a kind of in Amino Trimethylene Phosphonic Acid (ATMP), the hydroxy ethylene diphosphonic acid (HEDP) or two kinds.
3. organic composite Nano diameter sepiolite fibre antirust for reinforced concrete as claimed in claim 1 or 2 is characterized in that described benzotriazole class is a kind of in benzotriazole (BTA), mercapto benzothiazole (MBT), the tolyltriazole (TTA) or more than one.
4. organic composite Nano diameter sepiolite fibre antirust for reinforced concrete as claimed in claim 1 or 2, the content that it is characterized in that described modified material is the 0.7-1% of nanometer diameter sepiolite fibre quality.
5. organic composite Nano diameter sepiolite fibre antirust for reinforced concrete as claimed in claim 1 or 2, it is characterized in that described nanometer diameter sepiolite fibre is a kind of nano-scale fiber, its radial dimension is 40～50nm, and vertical scale is 1～5 μ m, is fibrous pilotaxitic texture.
6. organic composite Nano diameter sepiolite fibre antirust for reinforced concrete as claimed in claim 1 or 2 is characterized in that described anionic dispersing agents is a fatty alcohol sulfate salt.
7. organic composite Nano diameter sepiolite fibre antirust for reinforced concrete as claimed in claim 6 is characterized in that described fatty alcohol sulfate salt is a kind of in sodium lauryl sulphate, tridecyl sodium sulfate, the sodium stearyl sulfate or more than one.
8. as the preparation method of organic composite Nano diameter sepiolite fibre antirust for reinforced concrete of one of claim 1-7, it is characterized in that:, the three is put into homogenizer carry out the homogenizing processing promptly at first by the organic rust inhibitor of proportioning weighing, modified material and inorganic nanometer diameter polygorskite fiber.
9. the preparation method of organic composite Nano diameter sepiolite fibre antirust for reinforced concrete as claimed in claim 8 is characterized in that: described homogenizing is handled and is adopted 4800 rev/mins stirring velocity, and churning time is 10-20 minute.
10. the organic composite Nano diameter sepiolite fibre antirust for reinforced concrete as one of claim 1-7 hinders rust and rot-resistant application in Steel Concrete, it is characterized in that: in cement, add organic composite Nano diameter polygorskite fiber steel reinforcing concrete rust inhibitor of cement quality 2%-3%, press the conventional stirring technique of concrete and mix.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105152559A (en) * | 2015-11-01 | 2015-12-16 | 刘应才 | Method for preparing corrosion inhibitor for reinforced concrete |
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|---|---|---|---|---|
| CN101007717A (en) * | 2007-01-25 | 2007-08-01 | 上海市建筑科学研究院(集团)有限公司 | Reinforced concrete anti-rusting agent |
| CN101407385A (en) * | 2008-11-04 | 2009-04-15 | 南京瑞迪高新技术公司 | Alkali-free non-nitrite concrete reinforcement antirust |
| CN101844890A (en) * | 2009-03-26 | 2010-09-29 | 北京冶建新技术有限公司 | Organic reinforcing steel bar rust inhibitor for reinforced concrete |
| CN101948264A (en) * | 2010-10-25 | 2011-01-19 | 上海电力学院 | Rust-resistant agent for concrete reinforcing bar and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101007717A (en) * | 2007-01-25 | 2007-08-01 | 上海市建筑科学研究院(集团)有限公司 | Reinforced concrete anti-rusting agent |
| CN101407385A (en) * | 2008-11-04 | 2009-04-15 | 南京瑞迪高新技术公司 | Alkali-free non-nitrite concrete reinforcement antirust |
| CN101844890A (en) * | 2009-03-26 | 2010-09-29 | 北京冶建新技术有限公司 | Organic reinforcing steel bar rust inhibitor for reinforced concrete |
| CN101948264A (en) * | 2010-10-25 | 2011-01-19 | 上海电力学院 | Rust-resistant agent for concrete reinforcing bar and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105152559A (en) * | 2015-11-01 | 2015-12-16 | 刘应才 | Method for preparing corrosion inhibitor for reinforced concrete |
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Address after: 730020 1188 Jiatan Road, Chengguan District, Lanzhou City, Gansu Province Patentee after: Gansu Academy of Civil Engineering Sciences Co., Ltd. Address before: 730020 1188 Jiatan Road, Chengguan District, Lanzhou City, Gansu Province Patentee before: Gansu Civil Engineering Research Institute |