CN112374783B - A kind of multifunctional admixture for improving concrete strength, efficiently inhibiting chloride ion diffusion and steel corrosion, and preparation method thereof - Google Patents
A kind of multifunctional admixture for improving concrete strength, efficiently inhibiting chloride ion diffusion and steel corrosion, and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims abstract 11
- 238000005260 corrosion Methods 0.000 title claims abstract 11
- 230000007797 corrosion Effects 0.000 title claims abstract 11
- 238000009792 diffusion process Methods 0.000 title claims abstract 11
- 230000002401 inhibitory effect Effects 0.000 title claims abstract 10
- 229910000831 Steel Inorganic materials 0.000 title claims abstract 4
- 239000010959 steel Substances 0.000 title claims abstract 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract 18
- 239000000843 powder Substances 0.000 claims abstract 8
- 229910003023 Mg-Al Inorganic materials 0.000 claims abstract 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract 6
- 238000000593 microemulsion method Methods 0.000 claims abstract 4
- 239000000377 silicon dioxide Substances 0.000 claims abstract 3
- 239000000243 solution Substances 0.000 claims 20
- 235000012239 silicon dioxide Nutrition 0.000 claims 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 8
- 229910001294 Reinforcing steel Inorganic materials 0.000 claims 7
- 239000012153 distilled water Substances 0.000 claims 7
- 239000005543 nano-size silicon particle Substances 0.000 claims 7
- 238000003756 stirring Methods 0.000 claims 5
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims 4
- 239000000654 additive Substances 0.000 claims 4
- 230000000996 additive effect Effects 0.000 claims 4
- 230000002194 synthesizing effect Effects 0.000 claims 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims 3
- 238000009830 intercalation Methods 0.000 claims 3
- 230000002687 intercalation Effects 0.000 claims 3
- 239000002244 precipitate Substances 0.000 claims 3
- 235000019766 L-Lysine Nutrition 0.000 claims 2
- 239000004472 Lysine Substances 0.000 claims 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims 2
- 238000001914 filtration Methods 0.000 claims 2
- 239000012467 final product Substances 0.000 claims 2
- 238000000227 grinding Methods 0.000 claims 2
- 238000000034 method Methods 0.000 claims 2
- 239000011259 mixed solution Substances 0.000 claims 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims 2
- 238000009210 therapy by ultrasound Methods 0.000 claims 2
- 238000001291 vacuum drying Methods 0.000 claims 2
- 238000005406 washing Methods 0.000 claims 2
- 238000004140 cleaning Methods 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 150000004679 hydroxides Chemical class 0.000 claims 1
- 229910000000 metal hydroxide Inorganic materials 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 239000000047 product Substances 0.000 claims 1
- 229910004298 SiO 2 Inorganic materials 0.000 abstract 2
- 238000000151 deposition Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 239000000725 suspension Substances 0.000 abstract 1
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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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
- C01B33/186—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof from or via fluosilicic acid or salts thereof by a wet process
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
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- 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
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/06—Oxides, Hydroxides
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Abstract
本发明公开了一种提高混凝土强度、高效抑制氯离子扩散和钢筋腐蚀的多功能外加剂及制备方法，外加剂由二氧化硅纳米点修饰亚硝酸根插层层状双金属氢氧化物(nano‑SiO2@LDHs)组成；通过微乳液法合成纳米二氧化硅(nano‑SiO2)溶液，共沉积法合成亚硝酸根插层的层状Mg‑Al氢氧化物(LDHs)粉末；将制备的LDHs溶液加入纳米二氧化硅溶液，所得悬浊液经离心、洗涤、烘干，即得。本发明提供的混凝土外加剂可广泛应用于港口、跨海大桥、防汛堤坝等海工混凝土工程，可以同时提高混凝土强度、高效抑制氯离子扩散和钢筋腐蚀，且该外加剂制备工艺简单易于产业化和推广，应用前景十分广阔。
The invention discloses a multifunctional admixture for improving concrete strength and efficiently inhibiting chloride ion diffusion and steel corrosion, and a preparation method. SiO 2 @LDHs) composition; nano-silica (nano-SiO 2 ) solution was synthesized by microemulsion method, and nitrite-intercalated layered Mg-Al hydroxide (LDHs) powder was synthesized by co-deposition method; the prepared LDHs The solution is added to the nano-silica solution, and the obtained suspension is centrifuged, washed and dried to obtain. The concrete admixture provided by the invention can be widely used in marine concrete projects such as ports, cross-sea bridges, flood control dams, etc., can simultaneously improve concrete strength, effectively inhibit chloride ion diffusion and steel corrosion, and the preparation process of the admixture is simple and easy to industrialize. And promotion, the application prospect is very broad.
Description
Technical Field
The invention relates to a concrete admixture and a preparation method thereof, in particular to a multifunctional admixture for improving the strength of concrete and efficiently inhibiting chloride ion diffusion and reinforcing steel bar corrosion and a preparation method thereof.
Background
The reinforced concrete structure combines the advantages of steel bars and concrete, has low manufacturing cost, is the preferred form in the structural design of civil engineering at present, and has wide application. However, the reinforced concrete structure in the chlorine salt environment is very easy to be corroded by the chloride ions of the steel bars, so that the engineering structure fails in advance and the service life is shortened. The added steel bar rust-resisting material is a protection method with wide practical application due to the advantages of simplicity, convenience, high efficiency, relative low price and the like. However, the traditional steel bar rust-resisting material has single function, can not solidify chloride ions, has no obvious inhibition effect on the diffusion effect of the chloride ions, is often low in rust-resisting efficiency, is lost due to the exchange effect with the environment, and influences the long-term effect of the rust-resisting effect. Meanwhile, the existing rust inhibitor has no obvious effect of improving the strength of concrete.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a multifunctional concrete admixture which can simultaneously improve the strength of concrete and efficiently inhibit chloride ion diffusion and steel bar corrosion; the invention also provides a preparation method of the multifunctional concrete admixture.
The technical scheme is as follows: the invention relates to a multifunctional additive for improving concrete strength and efficiently inhibiting chloride ion diffusion and reinforcing steel bar corrosion, which is prepared by modifying nitrite intercalation layered double hydroxides (nano-SiO) by silicon dioxide nano dots2@ LDHs).
The invention also provides a preparation method of the multifunctional additive for improving the strength of concrete and efficiently inhibiting chloride ion diffusion and reinforcing steel bar corrosion, which comprises the following steps:
(1) synthesizing to obtain a nano silicon dioxide solution by adopting a micro-emulsion method;
(2) the layered Mg-Al double hydroxide of nitrite intercalation synthesized by codeposition method;
(3) dispersing the layered Mg-Al bimetal hydroxide prepared in the step (2) in a solvent, adding the solvent into a nano silicon dioxide solution, adjusting the pH value to 10-12, and stirring and reacting at the temperature of 30-60 ℃; centrifuging, filtering to obtain precipitate, cleaning the precipitate, and vacuum drying.
Wherein, in the step (1), the preparation method of the nano silicon dioxide solution comprises the following steps: dissolving octane and L-lysine in distilled water, and stirring for 1-3 hours at 50-60 ℃ to obtain a mixed solution; dissolving tetraethoxysilane in the solution, and stirring for 4-6 hours at 50-60 ℃ to obtain the nano silicon dioxide solution synthesized by the microemulsion method. Furthermore, the mass concentration of the added octane is 2-3g/mL, the mass concentration of the L-lysine is 0.04-0.06g/mL, and the mass concentration of the ethyl orthosilicate is 1-2 g/mL.
Wherein, in the step (2), the preparation method of LDHsThe method comprises the following steps: mixing Mg (NO)3)2·6H2O and Al (NO)3)3·9H2Dissolving O in distilled water to obtain solution A, and dissolving NaNO in the solution2Dissolving in distilled water to form solution B; dropwise adding the solution A into the solution B to obtain a mixed solution, and adjusting the pH value of the solution to 9-10; stirring, keeping the temperature of 60-80 ℃ in a water bath for 15-20 h, taking out the precipitate, cleaning, and drying in vacuum to obtain the product. Further, Mg (NO) is added to the solution A3)2·6H2The mass concentration of O is 15-20g/mL, and the Mg/Al molar ratio is kept at 2-3; NaNO is added into the solution B2The mass concentration of (A) is 3-4 g/mL.
In the step (3), the LDHs prepared in the step (2) is ground into powder, then the powder is dissolved in distilled water, ultrasonic treatment is carried out for 20-50 min, then the powder is dropwise added into the nano silicon dioxide solution synthesized in the step (1), the pH value of the solution is maintained at 10-12, and the solution is stirred for 2-4 h at the temperature of 30-60 ℃; after centrifugal filtration treatment, washing the precipitate with distilled water for 3-5 times, and vacuum drying for 12-48 h. Furthermore, the mass concentration of the LDHs powder added into the nano silicon dioxide solution is 3.5-4.5 g/mL.
Preferably, the multifunctional admixture is prepared by the following steps:
a. dissolving 7.3g of octane and 0.146g of L-lysine in 280ml of distilled water, and stirring for 1-3 h at 60 ℃; dissolving 4g of tetraethoxysilane in the solution, and stirring at 60 ℃ for 4-6 h to obtain nano silicon dioxide (nano-SiO) synthesized by a microemulsion method2) A solution;
b. 6.83g NaNO2Dissolving in 200ml distilled water to form solution B; 34.18g of Mg (NO)3)2·6H2O、25gAl(NO3)3·9H2Dissolving O (Mg/Al molar ratio is 2) in 200ml of distilled water to form solution A; dropwise adding the solution A into the solution B, and adding 2mol/L sodium hydroxide solution into the solution A to keep the pH value of the solution at about 10; stirring for 1h-3h at 25 ℃, keeping the temperature of 60-80 ℃ in a water bath kettle for 15h-20h, washing with distilled water for 3-5 times, and drying in vacuum for 18h-24h to obtain nitrite intercalated layered Mg-Al double hydroxides (LDHs) synthesized by a codeposition method;
c. weighing 1.12g of nitrite obtained in step 2Layered Mg-Al double metal hydroxides (LDHs) of the layers are ground into powder and dissolved in 280ml of distilled water for ultrasonic treatment for 20min to 50 min; it was added dropwise to the nano-silica (nano-SiO) synthesized in step 12) In the solution, 1mol/L sodium hydroxide is used for maintaining the pH value at 10-12, and the solution is stirred for 2-4 h at the temperature of 30-60 ℃; after centrifugal filtration treatment, washing the precipitate with distilled water for 3-5 times, and vacuum drying for 12-48 h to obtain nano silicon dioxide point modified nitrite intercalation layered Mg-Al double metal hydroxide (nano-SiO)2@ LDHs) powder.
Although double metal hydroxides (LDHs) have a typical layered structure, anions between the sheets are bonded to the sheets by weak electrostatic force and hydrogen bonding, and such weak force makes the anions between the sheets highly susceptible to replacement by new ion exchange, thereby adsorbing chlorine ions. When the interlayer anions have the rust inhibiting anions, the LDHs can adsorb chloride ions and inhibit rust through the rust inhibiting anions released by anion exchange, so that the reinforcement is protected together, and the long-acting, intelligent and multifunctional rust inhibiting material is promising. However, the LDHs nano-scale laminate has charged surface and high surface energy, so that the LDHs rust-resisting material has the advantages of easy accumulation of a large number of lamellar layers, high particle agglomeration degree, small effective surface area, incapability of being fully contacted with chloride ions in concrete for solidification, ineffective utilization of a large amount of space and ions between layers and lower functional utilization rate of the actual LDHs rust-resisting material.
The invention provides a concrete admixture for efficiently inhibiting chloride ion diffusion and reinforcing steel bar corrosion, and nano-silicon dioxide (nano-SiO) is prepared by adsorbing the negatively charged nano-silicon dioxide on a positively charged laminate through electrostatic force on the basis of fully utilizing the excellent performance of a rust-resisting anion intercalation LDHs material2) The LDHs material is point-modified, and the electrostatic repulsion and the steric hindrance effect of the nano-silica are utilized to improve the dispersibility of LDHs particles, so that the performances of inhibiting chloride ion diffusion and reinforcing steel bar corrosion are greatly improved. In addition, the nano silicon dioxide can have secondary hydration reaction in cement concrete to generate C-S-H gel, thereby enhancing the combination level of LDHs and cement hydration products, simultaneously densifying the concrete, improving the concrete strength and further increasing the mixing amountDurability of the concrete.
Has the advantages that: aiming at the problems that the existing rust inhibitor has single function and poor protection effect on chloride ion corrosion, the invention uses silicon dioxide (nano-SiO) on the basis of fully utilizing the excellent performance of the rust-inhibiting anion intercalation LDHs2) The LDHs material modified by the nanodots solves the problem of low utilization rate caused by serious agglomeration of single LDHs, and greatly improves the performance of inhibiting chloride ion diffusion and reinforcing steel bar corrosion.
Synthesizing nano silicon dioxide by a microemulsion method, preparing LDHs materials by utilizing a codeposition method, and performing point modification on the nano silicon dioxide on a layered double-metal hydroxide laminate by virtue of electrostatic action to obtain the multifunctional rust resisting material of the layered hydroxide modified by the nano silicon dioxide points. According to the invention, through the electrostatic repulsion and the steric hindrance effect of the modified nano silicon dioxide points, the problem of low functional utilization rate caused by serious agglomeration of single LDHs is solved, and highly dispersed nitrite intercalation LDHs is used for efficiently curing chloride ions, so that the diffusion of the chloride ions in concrete is effectively inhibited, and meanwhile nitrite rust-resisting ions are intelligently and targetedly released, thereby inhibiting the corrosion of steel bars in the concrete.
In addition, the nano-silica has secondary hydration reaction in the cement concrete to generate C-S-H gel, so that the bonding level of LDHs and cement hydration products is improved, the concrete is densified, the strength of the concrete is improved, and the durability of the concrete is further improved.
The concrete admixture provided by the invention can be widely applied to marine concrete projects such as ports, cross-sea bridges, flood control dams and the like, and can cure chloride ions and release NO through well-dispersed LDHs2 -The steel bar is protected by dual functions of rust resistance, the durability of the concrete is effectively improved, the secondary hydration reaction of the nano silicon dioxide in the cement concrete can be utilized, the combination level of LDHs and cement hydration products is improved, the concrete is densified, the strength of the concrete is improved, and the durability of the concrete is further improved; in addition, the additive disclosed by the invention is simple in preparation process, easy to industrialize and popularize and very wide in application prospect.
Drawings
FIG. 1 is an SEM picture of LDHs.
FIG. 2 shows a nano-SiO film according to the present invention2@ LDHs.
Detailed Description
The present invention will be described in further detail with reference to examples.
The starting materials and reagents used in the following examples are all commercially available.
In order to evaluate the inhibition effect of the prepared concrete admixture on chloride ion diffusion and steel bar corrosion, an alkaline simulated concrete pore solution chloride ion isothermal adsorption and steel bar corrosion test is carried out; in addition, concrete strength tests were performed, the specific test schedule being as follows:
(1) chloride ion isothermal adsorption test
Preparing 100ml (pH 13) of alkaline concrete simulated pore solution with chloride ion concentration of 0.002mol/l, 0.005mol/l, 0.01mol/l, 0.02mol/l, 0.04mol/l, 0.1mol/l, 0.16mol/l and 0.2mol/l, and respectively adding 1g of prepared nano-SiO2@ LDHs. Keeping the temperature at 25 ℃ for 48h, titrating the content of chloride ions in the solution by potentiometric method, and fitting and determining nano-SiO by using a Langmuir formula2@ LDHs, the adsorption amount of saturated chloride ions.
(2) Corrosion test of steel bar
Will be provided with
One side of the HPB235 steel bar with the length of 5mm is connected with a lead, the other side is reserved as a working surface, and the rest surfaces are sealed by epoxy resin. And (3) grinding the working surface step by using metallographic abrasive paper, polishing the working surface to a mirror surface, and then putting the mirror surface into a saturated calcium hydroxide solution for pre-passivation for 7 d. Preparing 100ml of saturated calcium hydroxide solution with the sodium chloride content of 0.6mol/L, and then respectively adding 1g of nano-SiO2@ LDHs, putting in the steel bar to be passivated, carrying out steel bar corrosion test by potentiodynamic polarization and electrochemical impedance spectroscopy, fitting out corrosion potential and polarization resistance, and calculating corrosion current by using a sternformula.
(3) Strength test of concrete
Preparing concrete with strength grade of C30 by using P.O.42.5 ordinary portland cement, and performing standard curing for 28dThe compression strength of the concrete is measured to be 31.5MPa, and 2 percent nano-SiO is added into the concrete2@ LDHs and single LDHs, standard maintenance 28d for compressive strength testing.
Example 1:
dissolving 7.3g of octane and 0.146g of L-lysine in 280ml of distilled water, and stirring for 1h at the temperature of 60 ℃; then adding 4g of ethyl orthosilicate, and stirring for 4 hours at 60 ℃ to obtain the nano silicon dioxide solution synthesized by the microemulsion method. 6.83g of NaNO2Dissolving in 200ml distilled water to obtain solution B, and adding 34.18g Mg (NO)3)2·6H2O、25g Al(NO3)3·9H2O (Mg/Al molar ratio equal to 2) was dissolved in 200ml of distilled water to form solution A. The solution A is added dropwise to the solution B, the pH value is maintained at about 10 by using 2mol/l NaOH, and the mixture is stirred for 1 hour at 25 ℃. Then keeping the temperature of 60 ℃ in a water bath for 15h, washing with distilled water for 3 times, and drying in vacuum for 15h to obtain the layered Mg-Al double metal hydroxide (LDHs) synthesized by the codeposition method. 1.12g of the prepared layered Mg-Al double hydroxide is ground into powder, dissolved in 280ml of distilled water and subjected to ultrasonic treatment for 20min, then the powder is dropwise added into the synthesized nano silicon dioxide solution, the pH value is maintained at 10 by using 1mol/l of sodium hydroxide, and the solution is stirred for 2h at 30 ℃. After centrifugal filtration treatment, washing the precipitate with distilled water for 3 times, and vacuum drying at 80 ℃ for 12h to obtain nano silicon dioxide dot modified LDHs powder (nano-SiO)2@ LDHs) material.
The test results are as follows: the saturated adsorption capacity of chloride ions relative to single LDHs is 2.03mmol/g, nano-SiO2The saturated chloride ion adsorption capacity of @ LDHs is 2.82mmol/g, which is obviously improved. The equilibrium corrosion potential of the steel bar in the solution without any additive is as follows: sce, corrosion current density of-625 mV vs: 17.31. mu.A/cm2(ii) a The steel bar added with the LDHs solution has the following equilibrium corrosion potential: SCE at 571mV vs. SCE, with a corrosion current density of: 8.3. mu.A/cm2(ii) a And nano-SiO is added2The equilibrium potential of the corrosion of the steel bar in the @ LDHs solution is as follows: sce at 473mV vs. corrosion current density: 1.72 μ A/cm2. The comparison shows that the corrosion potential of the steel bar is obviously shifted forwards, and the corrosion current density is obviously reduced. The compressive strength of the concrete doped with LDHs is not reduced, but is increased obviously,and 2% nano-SiO is added2The concrete strength of the @ LDHs is improved by 22 percent.
Example 2:
dissolving 7.3g of octane and 0.146g of L-lysine in 280ml of distilled water, and stirring for 3 hours at the temperature of 60 ℃; then adding 4g of ethyl orthosilicate, and stirring for 6 hours at 60 ℃ to obtain the nano silicon dioxide solution synthesized by the microemulsion method. 6.83g of NaNO2Dissolving in 200ml distilled water to obtain solution B, adding 34.18g Mg (NO)3)2·6H2O、16.69gAl(NO3)3·9H2O (Mg/Al molar ratio equal to 3) was dissolved in 200ml of distilled water to form solution A. The solution A is added dropwise to the solution B, the pH value is maintained at about 10 by using 2mol/l NaOH, and the mixture is stirred for 3 hours at the temperature of 25 ℃. Then keeping the temperature of 80 ℃ in a water bath kettle for 20h, washing with distilled water for 5 times, and drying in vacuum for 24h to obtain the layered Mg-Al double metal hydroxide (LDHs) synthesized by the codeposition method. 1.12g of the prepared layered Mg-Al double hydroxide is ground into powder, dissolved in 280ml of distilled water and subjected to ultrasonic treatment for 50min, then the powder is dropwise added into the synthesized nano silicon dioxide solution, the pH value is maintained at 12 by using 1mol/l of sodium hydroxide, and the solution is stirred for 4h at the temperature of 30 ℃. After centrifugal filtration treatment, washing the precipitate with distilled water for 5 times, and vacuum drying at 80 ℃ for 48h to obtain nano silicon dioxide dot modified LDHs powder (nano-SiO)2@ LDHs) material.
The test results are as follows: the saturated adsorption capacity of chloride ions relative to single LDHs is 2.03mmol/g, nano-SiO2The saturated chloride ion adsorption capacity of @ LDHs is 2.76mmol/g, which is obviously improved; the equilibrium corrosion potential of the steel bar in the solution without any additive is as follows: sce, corrosion current density of-625 mV vs: 17.31. mu.A/cm2(ii) a The steel bar added with the LDHs solution has the following equilibrium corrosion potential: SCE at 571mV vs. SCE, with a corrosion current density of: 8.3. mu.A/cm2(ii) a And nano-SiO is added2The equilibrium potential of the corrosion of the steel bar in the @ LDHs solution is as follows: sce at 498mV vs, corrosion current density: 1.69 μ A/cm2. The comparison shows that the corrosion potential of the steel bar is obviously shifted forwards, and the corrosion current density is obviously reduced. The compressive strength of the concrete doped with LDHs is not reduced, but is not obviously increased, and 2 percent nano-SiO is doped2The strength of the concrete of @ LDHs is improved by 25 percent.
Example 3
Dissolving 7.3g of octane and 0.146g of L-lysine in 280ml of distilled water, and stirring for 2 hours at the temperature of 60 ℃; then adding 4g of ethyl orthosilicate, and stirring for 5 hours at 60 ℃ to obtain the nano silicon dioxide solution synthesized by the microemulsion method. 6.83g of NaNO2Dissolving in 200ml distilled water to obtain solution B, adding 34.18g Mg (NO)3)2·6H2O、20.03g Al(NO3)3·9H2O (Mg/Al molar ratio equal to 2.5) was dissolved in 200ml of distilled water to form solution A. The solution A is added dropwise to the solution B, the pH value is maintained at about 10 by using 2mol/l NaOH, and the mixture is stirred for 2 hours at the temperature of 25 ℃. Then keeping the temperature of 70 ℃ in a water bath for 16h, washing with distilled water for 4 times, and drying in vacuum for 20h to obtain the layered Mg-Al double metal hydroxide (LDHs) synthesized by the codeposition method. 1.12g of the prepared layered Mg-Al double hydroxide is ground into powder, dissolved in 280ml of distilled water and subjected to ultrasonic treatment for 40min, then the powder is dropwise added into the synthesized nano silicon dioxide solution, the pH value is maintained at 11 by using 1mol/l of sodium hydroxide, and the solution is stirred for 3h at 50 ℃. After centrifugal filtration treatment, washing the precipitate with distilled water for 4 times, and vacuum drying at 80 ℃ for 36h to obtain nano silicon dioxide dot modified LDHs powder (nano-SiO)2@ LDHs) material.
The test result shows that: the saturated adsorption capacity of chloride ions relative to single LDHs is 2.03mmol/g, nano-SiO2The saturated chloride ion adsorption capacity of @ LDHs is 2.78mmol/g, which is obviously improved; the equilibrium corrosion potential of the steel bar in the solution without any additive is as follows: sce, corrosion current density of-625 mV vs: 17.31. mu.A/cm2(ii) a The steel bar added with the LDHs solution has the following equilibrium corrosion potential: SCE at 571mV vs. SCE, with a corrosion current density of: 8.3. mu.A/cm2(ii) a And nano-SiO is added2The equilibrium potential of the corrosion of the steel bar in the @ LDHs solution is as follows: sce, corrosion current density of-452 mV vs: 1.87 muA/cm2. The comparison shows that the corrosion potential of the steel bar is obviously shifted forwards, and the corrosion current density is obviously reduced.
The compressive strength of the concrete doped with LDHs is not reduced, but is not obviously increased, and 2 percent nano-SiO is doped2The strength of the concrete of @ LDHs is improved by 20 percent.
Example 4:
dissolving 7.3g of octane and 0.146g of L-lysine in 280ml of distilled water, and stirring at 60 ℃ for 1.5 h; then adding 4g of ethyl orthosilicate, and stirring for 5 hours at 60 ℃ to obtain the nano silicon dioxide solution synthesized by the microemulsion method. 6.83g of NaNO2Dissolving in 200ml distilled water to obtain solution B, adding 34.18g Mg (NO)3)2·6H2O、25gAl(NO3)3·9H2O (Mg/Al molar ratio equal to 2) was dissolved in 200ml of distilled water to form solution A. The solution A is added dropwise to the solution B, the pH value is maintained at about 10 by using 2mol/l NaOH, and the mixture is stirred for 2 hours at the temperature of 25 ℃. Then keeping the temperature of 50 ℃ in a water bath for 17h, washing with distilled water for 4 times, and drying in vacuum for 22h to obtain the layered Mg-Al double metal hydroxide (LDHs) synthesized by the codeposition method. 1.12g of the prepared layered Mg-Al double hydroxide is ground into powder, dissolved in 280ml of distilled water and subjected to ultrasonic treatment for 40min, then the powder is dropwise added into the synthesized nano silicon dioxide solution, the pH value is maintained at 11 by using 1mol/l of sodium hydroxide, and the solution is stirred for 3h at 50 ℃. After centrifugal filtration treatment, washing the precipitate with distilled water for 4 times, and vacuum drying at 80 ℃ for 36h to obtain nano silicon dioxide dot modified LDHs powder (nano-SiO)2@ LDHs) material.
The test result shows that: the saturated adsorption capacity of chloride ions relative to single LDHs is 2.03mmol/g, nano-SiO2The saturated chloride ion adsorption capacity of @ LDHs is 2.91mmol/g, which is obviously improved; the equilibrium corrosion potential of the steel bar in the solution without any additive is as follows: sce, corrosion current density of-625 mV vs: 17.31. mu.A/cm2(ii) a The steel bar added with the LDHs solution has the following equilibrium corrosion potential: SCE at 571mV vs. SCE, with a corrosion current density of: 8.3. mu.A/cm2(ii) a And nano-SiO is added2The equilibrium potential of the corrosion of the steel bar in the @ LDHs solution is as follows: sce, corrosion current density of-423 mV vs: 1.03 uA/cm2. The comparison shows that the corrosion potential of the steel bar is obviously shifted forwards, and the corrosion current density is obviously reduced. The compressive strength of the concrete doped with LDHs is not reduced, but is not obviously increased, and 2 percent nano-SiO is doped2The strength of the concrete of @ LDHs is improved by 28 percent.
Example 5:
7.3g of octane and 0.146g of L-lysineDissolving in 280ml distilled water, and stirring at 60 deg.C for 1 h; then adding 4g of ethyl orthosilicate, and stirring for 4 hours at 60 ℃ to obtain the nano silicon dioxide solution synthesized by the microemulsion method. 6.83g of NaNO2Dissolving in 200ml distilled water to obtain solution B, adding 34.18g Mg (NO)3)2·6H2O、22.76gAl(NO3)3·9H2O (Mg/Al molar ratio equal to 2.2) was dissolved in 200ml of distilled water to form solution A. The solution A is added dropwise to the solution B, the pH value is maintained at about 10 by using 2mol/l NaOH, and the mixture is stirred for 1 hour at 25 ℃. Then keeping the temperature of 60 ℃ in a water bath for 15h, washing with distilled water for 3 times, and drying in vacuum for 15h to obtain the layered Mg-Al double metal hydroxide (LDHs) synthesized by the codeposition method. 1.12g of the prepared layered Mg-Al double hydroxide is ground into powder, dissolved in 280ml of distilled water and subjected to ultrasonic treatment for 20min, then the powder is dropwise added into the synthesized nano silicon dioxide solution, the pH value is maintained at 10 by using 1mol/l of sodium hydroxide, and the solution is stirred for 2h at 30 ℃. After centrifugal filtration treatment, washing the precipitate with distilled water for 3 times, and vacuum drying at 80 ℃ for 12h to obtain nano silicon dioxide dot modified LDHs powder (nano-SiO)2@ LDHs) material.
The test results are as follows: the saturated adsorption capacity of chloride ions relative to single LDHs is 2.03mmol/g, nano-SiO2The saturated chloride ion adsorption capacity of @ LDHs is 2.75mmol/g, which is obviously improved. The equilibrium corrosion potential of the steel bar in the solution without any additive is as follows: sce, corrosion current density of-625 mV vs: 17.31. mu.A/cm2(ii) a The steel bar added with the LDHs solution has the following equilibrium corrosion potential: SCE at 571mV vs. SCE, with a corrosion current density of: 8.3. mu.A/cm2(ii) a And nano-SiO is added2The equilibrium potential of the corrosion of the steel bar in the @ LDHs solution is as follows: sce at 482mV vs, corrosion current density: 1.95. mu.A/cm2. The comparison shows that the corrosion potential of the steel bar is obviously shifted forwards, and the corrosion current density is obviously reduced. The compressive strength of the concrete doped with LDHs is not reduced, but is not obviously increased, and 2 percent nano-SiO is doped2The strength of the concrete of @ LDHs is improved by 23 percent.
Example 6:
dissolving 7.3g of octane and 0.146g of L-lysine in 280ml of distilled water, and stirring for 1h at the temperature of 60 ℃; 4g of ethyl orthosilicate were then addedStirring for 4h at 60 ℃ to obtain the nano silicon dioxide solution synthesized by the microemulsion method. 6.83g of NaNO2Dissolving in 200ml distilled water to obtain solution B, and adding 34.18g Mg (NO)3)2·6H2O, 17.88g of Al (NO)3)3·9H2O (Mg/Al molar ratio equal to 2.8). The solution A is added dropwise to the solution B, the pH value is maintained at about 10 by using 2mol/l NaOH, and the mixture is stirred for 1 hour at 25 ℃. Then keeping the temperature of 60 ℃ in a water bath for 15h, washing with distilled water for 3 times, and drying in vacuum for 15h to obtain the layered Mg-Al double metal hydroxide (LDHs) synthesized by the codeposition method. 1.12g of the prepared layered Mg-Al double hydroxide is ground into powder, dissolved in 280ml of distilled water and subjected to ultrasonic treatment for 20min, then the powder is dropwise added into the synthesized nano silicon dioxide solution, the pH value is maintained at 10 by using 1mol/l of sodium hydroxide, and the solution is stirred for 2h at 30 ℃. After centrifugal filtration treatment, washing the precipitate with distilled water for 3 times, and vacuum drying at 80 ℃ for 12h to obtain nano silicon dioxide dot modified LDHs powder (nano-SiO)2@ LDHs) material.
The test results are as follows: the saturated adsorption capacity of chloride ions relative to single LDHs is 2.03mmol/g, nano-SiO2The saturated chloride ion adsorption capacity of @ LDHs is 2.75mmol/g, which is obviously improved. The equilibrium corrosion potential of the steel bar in the solution without any additive is as follows: sce, corrosion current density of-625 mV vs: 17.31. mu.A/cm2(ii) a The steel bar added with the LDHs solution has the following equilibrium corrosion potential: SCE at 571mV vs. SCE, with a corrosion current density of: 8.3. mu.A/cm2(ii) a And nano-SiO is added2The equilibrium potential of the corrosion of the steel bar in the @ LDHs solution is as follows: sce at 488mV vs, corrosion current density: 1.91 muA/cm2. The comparison shows that the corrosion potential of the steel bar is obviously shifted forwards, and the corrosion current density is obviously reduced. The compressive strength of the concrete doped with LDHs is not reduced, but is not obviously increased, and 2 percent nano-SiO is doped2The strength of the concrete of @ LDHs is improved by 25 percent.
As can be seen from the above embodiment, nano-SiO is prepared by the same preparation process2The @ LDHs is greatly improved in the aspects of chloride ion combination and corrosion protection compared with single LDHs, the compressive strength of concrete is also obviously improved, and a scanning electron microscope (shown in attached figures 1 and 2) also shows that nano-SiO2@ LDHs are more dispersible than LDHs alone.
Claims (8)
1. The multifunctional additive for improving the strength of concrete and efficiently inhibiting chloride ion diffusion and reinforcing steel bar corrosion is characterized in that: the additive comprises layered double hydroxides of nitrite intercalation modified by silicon dioxide nanodots, and the preparation method of the multifunctional additive comprises the following steps:
(1) synthesizing a nano silicon dioxide solution by adopting a micro-emulsion method;
(2) synthesizing layered Mg-Al double hydroxide of nitrite intercalation by adopting a codeposition method;
(3) grinding the layered Mg-Al bimetal hydroxide prepared in the step (2) into powder, dissolving the powder in distilled water, performing ultrasonic treatment for 20-50 min, dropwise adding the powder into the nano silicon dioxide solution synthesized in the step (1), maintaining the pH value of the solution at 10-12, and stirring the solution at 30-60 ℃ for 2-4 h; after centrifugal filtration treatment, washing the precipitate with distilled water for 3-5 times, and vacuum drying for 12-48 h to obtain the final product.
2. A preparation method of a multifunctional additive for improving the strength of concrete and efficiently inhibiting chloride ion diffusion and steel bar corrosion is characterized by comprising the following steps:
(1) synthesizing a nano silicon dioxide solution by adopting a micro-emulsion method;
(2) synthesizing layered Mg-Al double hydroxide of nitrite intercalation by adopting a codeposition method;
(3) grinding the layered Mg-Al bimetal hydroxide prepared in the step (2) into powder, dissolving the powder in distilled water, performing ultrasonic treatment for 20-50 min, dropwise adding the powder into the nano silicon dioxide solution synthesized in the step (1), maintaining the pH value of the solution at 10-12, and stirring the solution at 30-60 ℃ for 2-4 h; after centrifugal filtration treatment, washing the precipitate with distilled water for 3-5 times, and vacuum drying for 12-48 h to obtain the final product.
3. The preparation method of the multifunctional admixture for improving the strength of concrete and efficiently inhibiting chloride ion diffusion and reinforcing steel bar corrosion according to claim 2, which is characterized by comprising the following steps: in the step (1), the preparation method of the nano silicon dioxide solution comprises the following steps: dissolving octane and L-lysine in distilled water, and stirring for 1-3 hours at 50-60 ℃ to obtain a mixed solution; dissolving tetraethoxysilane in the solution, and stirring for 4-6 hours at 50-60 ℃ to obtain the nano silicon dioxide solution synthesized by the microemulsion method.
4. The preparation method of the multifunctional admixture for improving the strength of concrete and efficiently inhibiting chloride ion diffusion and reinforcing steel bar corrosion according to claim 2, which is characterized by comprising the following steps: in the step (2), the preparation method of the layered Mg-Al bimetal hydroxide comprises the following steps: mixing Mg (NO)3)2·6H2O and Al (NO)3)3·9H2Dissolving O in distilled water to obtain solution A, and dissolving NaNO in the solution2Dissolving in distilled water to form solution B; dropwise adding the solution A into the solution B to obtain a mixed solution, and adjusting the pH value of the solution to 9-10; stirring, keeping the temperature of 60-80 ℃ in a water bath for 15-20 h, taking out the precipitate, cleaning, and drying in vacuum to obtain the product.
5. The preparation method of the multifunctional admixture for improving the strength of concrete and efficiently inhibiting chloride ion diffusion and reinforcing steel bar corrosion according to claim 3, which is characterized by comprising the following steps: the mass concentration of the added octane is 2-3g/mL, the mass concentration of the L-lysine is 0.04-0.06g/mL, and the mass concentration of the ethyl orthosilicate is 1-2 g/mL.
6. The preparation method of the multifunctional admixture for improving the strength of concrete and efficiently inhibiting chloride ion diffusion and reinforcing steel bar corrosion according to claim 4, which is characterized by comprising the following steps: mg (NO) added into the solution A3)2·6H2The mass concentration of O is 15-20g/mL, and the Mg/Al molar ratio is kept at 2-3.
7. The preparation method of the multifunctional admixture for improving the strength of concrete and efficiently inhibiting chloride ion diffusion and reinforcing steel bar corrosion according to claim 4, which is characterized by comprising the following steps: NaNO is added into the solution B2The mass concentration of (A) is 3-4 g/mL.
8. The preparation method of the multifunctional admixture for improving the strength of concrete and efficiently inhibiting chloride ion diffusion and reinforcing steel bar corrosion according to claim 2, which is characterized by comprising the following steps: the mass concentration of the layered Mg-Al double-metal hydroxide powder added into the nano silicon dioxide solution is 3.5-4.5 g/mL.
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