CN105174773B - A kind of preparation method of corrosion inhibitors for reinforced concrete - Google Patents
A kind of preparation method of corrosion inhibitors for reinforced concrete Download PDFInfo
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- CN105174773B CN105174773B CN201510627188.7A CN201510627188A CN105174773B CN 105174773 B CN105174773 B CN 105174773B CN 201510627188 A CN201510627188 A CN 201510627188A CN 105174773 B CN105174773 B CN 105174773B
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Abstract
A kind of preparation method of corrosion inhibitors for reinforced concrete, is related to corrosion inhibitors for reinforced concrete.1) with layered double hydroxide as presoma, calcining；2) by step 1) calcining after product be placed in sodium hydroxide solution, stir, filtering, washing, obtain filtration product 1；3) filtration product 1 is placed in Potassium Hydrogen Phthalate solution, is stirred, filtering, washing obtains filtration product 2；4) after filtration product 2 is dried, powder is ground to form, obtains final product corrosion inhibitors for reinforced concrete.Various corrosion inhibiter ions are loaded in double-metal hydroxide layer structure using modified calcining recombination method and corrosion inhibitors for reinforced concrete is prepared; for in concrete structure; chloride ions concentration of concrete, release corrosion inhibiter ion, the high ph-values for maintaining concrete, raising concrete density can simultaneously be reduced; there is excellent comprehensive anticorrosive performance to reinforced concrete structure, the multiple effective protection to burying the reinforcing bar overlayed in concrete is capable of achieving.
Description
Technical field
The present invention relates to corrosion inhibitors for reinforced concrete, more particularly, to a kind of preparation method of corrosion inhibitors for reinforced concrete.
Background technology
Corrosion of the reinforcing bar in concrete is one of main reason of influence concrete structure durability and security.
Under environmental activity, the neutralisation of concrete and Cl-、SO4 2-Deng aggressive species erosion be cause reinforcement corrosion it is important because
Element.This is closely related with the particularity and complexity of concrete structure.Concrete structure is the complexity of gas, liquid, solid three-phase coexistence
There is nanometer to the uneven hole of micron order size in system, internal structure so that the O in air2、H2O、CO2Molecule and environment
Cl in medium-、SO4 2-Internally spread by the hole and crackle of concrete Deng aggressive species, until rebar surface is reached,
Cause reinforcement corrosion.After reinforcement corrosion occurs, its corrosion product is accumulated near rebar surface, and the stress that volumetric expansion causes is caused
Concrete is further ftractureed, for corrosive medium provides passage into concrete, cause more serious corrosion.Reinforced concrete
The corrosion of soil will trigger a series of serious consequences once occurring, and cause huge economic loss, or even trigger serious dashing forward
Hair accident.Develop various corrosion protection technologies, the service life and security of reinforced concrete structure are effectively improved, for resource
Save, economic development all has great importance.
The anticorrosive measure of reinforcement in concrete mainly have using stainless steel rebar, coated reinforcement, concrete surface treatment,
Use corrosion inhibiter, cathode current protection, electrochemical treatments technology etc..It is a kind of most economical, most widely used wherein using corrosion inhibiter
General corrosion protection technology.
In recent years, layered double hydroxide (LDHs) turns into a study hotspot in the application of corrosion-resistant field.LDHs
The characteristics of there is Yin Qite special layer structure and interlayer can accommodate each anionoid, corrosion-resistant field show it is huge should
Use prospect.M.L.Zeludkevich et al. (Corrosion Science 52 (2010) 602-611) has synthesized and has been loaded with vanadic acid root
The magnalium and zinc-aluminium layered double hydroxide of ion, and being scattered in organic coating, realize vanadic acid radical ion can
The release of control property, achieves good antiseptic effect.Wang Jun et al. (Progress in Organic Coatings 71 (2011)
302-309) synthesize the magnalium laminar double-metal hydroxide for being loaded with tungstate ion, not only may act as filling out for coating mesopore
Thing is filled, can also act as storing the carrier of corrosion inhibiter.S.K.Poznyak et al. (Applied materials＆interfaces 10
(2009) 1528-1535 of 2353-2362, Applied materials＆interfaces 5 (2010)) by various organic and nothing
Machine ion is embedded into LDHs interlayer structures, and is applied in organic coating, so that it is resistance to effectively improve raising AA2024 aluminium alloys
Rotten performance.The report for being presently used for the inhibiter technology of armored concrete is few.
The content of the invention
It is an object of the invention to provide a kind of preparation method of corrosion inhibitors for reinforced concrete.
The present invention is comprised the following steps：
1) with layered double hydroxide as presoma, calcining；
2) by step 1) calcining after product be placed in sodium hydroxide solution, stir, filtering, washing, obtain filtration product 1；
3) filtration product 1 is placed in Potassium Hydrogen Phthalate solution, is stirred, filtering, washing obtains filtration product 2；
4) after filtration product 2 is dried, powder is ground to form, obtains final product corrosion inhibitors for reinforced concrete.
In step 1) in, layered double-metal hydroxide may be selected from MgAl-LDHs, or ZnAl-LDHs, or FeAl-
LDHs, or CaAl-LDHs, or its mixture；The temperature of the calcining can be 200~700 DEG C, and the time of calcining can be 1~7h.
In step 2) in, product and the proportioning of sodium hydroxide solution after the calcining can be (0.5~5) g: 100mL, institute
The molar concentration for stating sodium hydroxide solution can be 0.01~1mol/L；The temperature of the stirring can be 15~80 DEG C, stirring when
Between can be 2~48h.
In step 3) in, the addition of the Potassium Hydrogen Phthalate solution can be 100mL, Potassium Hydrogen Phthalate solution
Molar concentration can be 0.05~1mol/L, the Potassium Hydrogen Phthalate solution ph can be 7~12；The temperature of the stirring
It can be 15~80 DEG C, the time of stirring can be 2~48h.
In step 4) in, the dry condition can dry 12~60h at 60~75 DEG C.
Major function of the present invention is as follows：(1) particle size based on its micro/nano level, can fill concrete hole, raising
The compactness of concrete, slows down H2O、CO3 2-、Cl-Deng the immersion of erosion carbon dioxide；(2) releasable hydroxide ion, maintains coagulation
Soil pores liquid pH value, slows down the carbonization of concrete；(3) based on its ion exchange property, corrosion inhibiter in interlayer structure from
Erosion carbon dioxide such as Cl in son and environment-、SO4 2-Deng there is ion exchange, environmental etch species are reduced, and discharged
Go out corrosion inhibiter ion, improve the corrosive environment residing for reinforcing bar, the corrosion resistance of reinforcing steel bar.
Ion exchange property of the present invention based on layered double hydroxide, phthalic acid is loaded into its interlayer structure
Radical ion (PTL) and hydroxide ion etc., obtain various corrosion inhibitors for reinforced concrete.The invention belongs to protection of materials technology
Field.It is related to a kind of corrosion inhibiter of Steel Corrosion In Concrete Structures protection.Corrosion inhibiter proposed by the present invention, is forged using modified
Burn recombination method to load various corrosion inhibiter ions in double-metal hydroxide layer structure and prepare, for concrete structure
In, can simultaneously reduce chloride ions concentration of concrete, release corrosion inhibiter ion, the high ph-values for maintaining concrete, raising concrete
The multiple actions such as density, have excellent comprehensive anticorrosive performance to reinforced concrete structure, are capable of achieving to overlay on concrete to burying
In reinforcing bar multiple effective protection.
Brief description of the drawings
Fig. 1 is the SEM figures of corrosion inhibitors for reinforced concrete prepared by the embodiment of the present invention.
Fig. 2 is electrochemical impedance spectrogram of the reinforcing bar in concrete simulated solution.
Fig. 3 is the equivalent circuit diagram of electrochemical impedance spectroscopy.
Fig. 4 is the releasing curve diagram of PTL.
Fig. 5 is Cl-Concentration changes with time figure.
Fig. 6 changes with time figure for the pH value of test fluid.
Specific embodiment
Following examples will the present invention is further illustrated with reference to accompanying drawing.
Embodiment 1：It is presoma from magnalium double-metal hydroxide (MgAl-LDHs).By MgAl-LDHs at 500 DEG C
Lower calcining 5h, naturally cools to room temperature, obtains magnesium aluminum oxide (MgAl-CLDHs).0.5g MgAl-CLDHs are taken to be scattered in
In the NaOH solution of 100mL 0.1mol/L, 24h is stirred vigorously at room temperature, the solid product after filtering is placed in 100mL0.5mol/
During L, pH are 11 Potassium Hydrogen Phthalate solution, 24h is stirred under greenhouse.After filtering, solids is dried in 70 DEG C of baking oven
Treatment 48h, dried product be ground in mortar it is powdered, labeled as corrosion inhibiter 1.
Embodiment 2：MgAl-CLDHs in embodiment 1 is changed into 1g, remaining condition is identical, labeled as corrosion inhibiter 2.
Embodiment 3：MgAl-CLDHs in embodiment 1 is changed into 3g, remaining condition is identical, labeled as corrosion inhibiter 3.
Embodiment 4：MgAl-CLDHs in embodiment 1 is changed into 5g, remaining condition is identical, labeled as corrosion inhibiter 4.
Gained corrosion inhibiter evaluates its corrosion inhibition using electrochemical method, and method of testing is as follows：
With pH be NaCl solution of the 11, concentration as 0.3mol/L as simulated concrete pore solution, the corrosion inhibiter of 20g/L is added
Enter in concrete simulated solution, stir process 0.5h obtains test solution.Electrochemical impedance is carried out in reinforcing bar electrode test solution
Tested with polarization curve.Test uses three-electrode system：Work area is 1.0cm2Q235 reinforcing bar electrodes as working electrode,
Pt electrodes are that, to electrode, calomel electrode is reference electrode, and tester is AUTOLAB electrochemical workstations.Electrochemical impedance is surveyed
Examination is completed under OCP, and frequency range is 105~10-2HZ, pumping signal is amplitude 10mV sine wave AC electric signals.Pole
Changing curve test condition is：With the sweep speed of 10mV/s to reinforcing bar electrode apply potential polarization, sweep limits be OCP-
120mV to polarization current be 150 μ A/cm2。
Cl in test fluid is tested using ion probe and ultraviolet specrophotometer-Concentration, pH value and phthalate
The situation of change of concentration.
It will be seen from figure 1 that corrosion inhibiter is presented sheet-like morphology, there is clustering phenomena, particle diameter is about at hundreds of nanometers to 1 micron
Between.
Figure it is seen that in the simulated concrete pore solution for being not added with corrosion inhibiter, the impedance of reinforcing bar is smaller, addition
After corrosion inhibiter, the impedance increase of reinforcing bar electrode, wherein the impedance arc of the reinforcing bar after addition corrosion inhibiter 2 is maximum, corrosion mitigating effect is best.
Electrochemical impedance spectroscopy obtains electrochemical parameter as shown in table 1 using the Equivalent Circuit Fitting treatment in Fig. 3.
Table 1
As it can be seen from table 1 after addition corrosion inhibiter, the impedance of reinforcing bar electrode is significantly improved compared with blank sample, wherein, addition is slow
The impedance for losing reinforcing bar in the test fluid of agent 2 is maximum, and inhibition efficiency highest can reach 93.73%.
As can be seen from Figure 4, after addition corrosion inhibiter 2, the concentration of PTL gradually rises in NaCl solution, in initial 20h concentration
Raise comparatively fast, reach 0.6mmol/L, concentration ramp-up rate slows down afterwards, and concentration reaches substantially to stationary value after 55h, about
0.65mmol/L, illustrates that the PTL in corrosion inhibiter can be discharged gradually.
From fig. 5, it can be seen that after addition corrosion inhibiter 2, Cl- concentration reduction in test fluid, in initial 10h, Cl-Concentration is molten
Reduced rapidly in liquid, then declined slower.Illustrate that LDHs can effectively absorb the Cl in surrounding medium-。
From fig. 6, it can be seen that when not adding corrosion inhibiter 2, due to CO in air2Carbonization, test fluid pH value gradually drops
It is low.After addition corrosion inhibiter 2, test fluid pH value has in the initial period and rises to a certain degree, then slow to reduce, but is still significantly higher than
The pH value of blank solution.This is due to the OH of LDHs interlayers-It is releasable in simulated concrete pore solution, delayed the acid of solution
Change process.
Embodiment 5：It is presoma from magnalium double-metal hydroxide (MgAl-LDHs).By MgAl-LDHs at 200 DEG C
Lower calcining 7h, naturally cools to room temperature, obtains magnesium aluminum oxide (MgAl-CLDHs).Take 3g MgAl-CLDHs and be scattered in 100mL
In the NaOH solution of 1mol/L, 2h is stirred vigorously at 80 DEG C, it is 12 that the solid product after filtering is placed in 100mL1mol/L, pH
In Potassium Hydrogen Phthalate solution, 48h is stirred under greenhouse.After filtering, solids drying and processing 60h in 75 DEG C of baking oven does
Product after dry is ground to powdered in mortar.
Embodiment 6：It is presoma from magnalium double-metal hydroxide (MgAl-LDHs).By MgAl-LDHs at 700 DEG C
Lower calcining 1h, naturally cools to room temperature, obtains magnesium aluminum oxide (MgAl-CLDHs).Take 5g MgAl-CLDHs and be scattered in 100mL
In the NaOH solution of 0.01mol/L, 48h is stirred vigorously at 15 DEG C, the solid product after filtering is placed in 100mL 0.1mol/L, pH
In for 7 Potassium Hydrogen Phthalate solution, 2h is stirred under greenhouse.After filtering, solids drying and processing in 65 DEG C of baking oven
12h, dried product is ground to powdered in mortar.
Embodiment 6：It is presoma from magnalium double-metal hydroxide (MgAl-LDHs).By MgAl-LDHs at 600 DEG C
Lower calcining 3h, naturally cools to room temperature, obtains magnesium aluminum oxide (MgAl-CLDHs).Take 1g MgAl-CLDHs and be scattered in 100mL
In the NaOH solution of 0.05mol/L, 15h is stirred vigorously at 50 DEG C, the solid product after filtering is placed in 100mL0.5mol/L, pH
In for 10 Potassium Hydrogen Phthalate solution, 15h is stirred under greenhouse.After filtering, solids drying and processing in 70 DEG C of baking oven
30h, dried product is ground to powdered in mortar.
The present invention loads various rust inhibition ions using layered double hydroxide interlayer anion commutativity, and makees
It is a kind of novel reinforced concrete corrosion inhibiter.The corrosion inhibiter is used in concrete, the hole with fill concrete, raising coagulation
The multi-functionals such as density, absorption erosion carbon dioxide, release corrosion inhibiter ion and the hydroxide ion of soil, can be effectively improved coagulation
The chemical micro-environment of soil pores, significantly improves the corrosion resistance of reinforcing bar.The present invention is prepared using modified calcining recombination method and is embedded with simultaneously
Phthalate (PTL) and layered double hydroxide hydroxy.The present invention is with layered double hydroxide as preceding
Body, after being processed through high-temperature calcination, is stirred in liquid is recombinated, and filtering gained solid is corrosion inhibiter.
In sum, corrosion inhibiter ion, suction in the releasable interlayer structure of corrosion inhibitors for reinforced concrete that prepared by the present invention
Receive the Cl in medium-, improve environment pH value, improve reinforcing bar residing for corrosive environment, multiple is played to the reinforcing bar in concrete
Protective effect, can be used as the corrosion resistance that a kind of corrosion inhibitors for reinforced concrete effectively improves reinforcing bar, slow down the corrosion of reinforcing bar.Additionally,
Because corrosion inhibitors for reinforced concrete is in the powder of micro-nano-scale, in adding concrete system, can effectively fill concrete
Structure hole, improves concrete density, the permeability of concrete is reduced, so as to also enhance the decay resistance of concrete.
Claims (8)
1. a kind of preparation method of corrosion inhibitors for reinforced concrete, it is characterised in that comprise the following steps：
1) with layered double hydroxide as presoma, calcining；
2) by step 1) calcining after product be placed in sodium hydroxide solution, stir, filtering, washing, obtain filtration product 1；
Product and the proportioning of sodium hydroxide solution after the calcining are (0.5~5) g: 100mL, the sodium hydroxide solution
Molar concentration is 0.01~1mol/L；
3) filtration product 1 is placed in Potassium Hydrogen Phthalate solution, is stirred, filtering, washing obtains filtration product 2；
The molar concentration of the Potassium Hydrogen Phthalate solution is 0.05~1mol/L；
4) after filtration product 2 is dried, powder is ground to form, obtains final product corrosion inhibitors for reinforced concrete.
2. as claimed in claim 1 a kind of preparation method of corrosion inhibitors for reinforced concrete, it is characterised in that in step 1) in, it is described
Layered double hydroxide is selected from MgAl-LDHs, or ZnAl-LDHs, or FeAl-LDHs, or CaAl-LDHs, or its mixing
Thing.
3. as claimed in claim 1 a kind of preparation method of corrosion inhibitors for reinforced concrete, it is characterised in that in step 1) in, it is described
The temperature of calcining is 200~700 DEG C, and the time of calcining is 1~7h.
4. as claimed in claim 1 a kind of preparation method of corrosion inhibitors for reinforced concrete, it is characterised in that in step 2) in, it is described
The temperature of stirring is 15~80 DEG C, and the time of stirring is 2~48h.
5. as claimed in claim 1 a kind of preparation method of corrosion inhibitors for reinforced concrete, it is characterised in that in step 3) in, it is described
The addition of Potassium Hydrogen Phthalate solution is 100mL.
6. as claimed in claim 1 a kind of preparation method of corrosion inhibitors for reinforced concrete, it is characterised in that in step 3) in, it is described
Potassium Hydrogen Phthalate solution ph is 7~12.
7. as claimed in claim 1 a kind of preparation method of corrosion inhibitors for reinforced concrete, it is characterised in that in step 3) in, it is described
The temperature of stirring is 15~80 DEG C, and the time of stirring is 2~48h.
8. as claimed in claim 1 a kind of preparation method of corrosion inhibitors for reinforced concrete, it is characterised in that in step 4) in, it is described
Dry condition is that 12~60h is dried at 60~75 DEG C.
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| CN106854047A (en) * | 2016-12-21 | 2017-06-16 | 济南轨道交通集团有限公司 | A kind of method for controlling metro stray current corrosion armored concrete |
| CN108298845B (en) * | 2018-01-31 | 2020-09-04 | 青岛科技大学 | Anti-halogen-returning magnesium oxychloride cement and preparation method thereof |
| CN109879630A (en) * | 2019-03-14 | 2019-06-14 | 江苏力引建材科技股份有限公司 | A kind of High Performance Anticorrosion Concrete mixed with layered double-hydroxide corrosion inhibitor |
| CN112915960A (en) * | 2021-01-21 | 2021-06-08 | 中山大学 | Internal-doped marine reinforced concrete targeted adsorbent and preparation method and application thereof |
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Non-Patent Citations (4)
| Title |
|---|
| 层状双氢氧化物对混凝土抗碳化性能的影响;段平等;《硅酸盐学报》;20140831;第42卷(第8期);第10371041页 * |
| 层状双氢氧化物改善混凝土耐久性能的机理及其应用研究;段平;《中国博士学位论文全文数据库 工程科技Ⅱ辑》;20150415;C038-8 * |
| 缓释型萘系减水剂的合成;王素娟等;《硅酸盐学报》;20090731;第37卷(第7期);第1103-1109页 * |
| 锌铝层状双金属氢氧化物焙烧物对钢筋的缓蚀作用研究;张小娟等;《电化学》;20130630;第19卷(第3期);第256-261页 * |
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