CN110723918A - Nano material for freeze-thaw resistant concrete and use method thereof - Google Patents
Nano material for freeze-thaw resistant concrete and use method thereof Download PDFInfo
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- CN110723918A CN110723918A CN201910980178.XA CN201910980178A CN110723918A CN 110723918 A CN110723918 A CN 110723918A CN 201910980178 A CN201910980178 A CN 201910980178A CN 110723918 A CN110723918 A CN 110723918A
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- resistant concrete
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/12—Nitrogen containing compounds organic derivatives of hydrazine
- C04B24/121—Amines, polyamines
-
- 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
-
- 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
- C04B40/0046—Premixtures of ingredients characterised by their processing, e.g. sequence of mixing the ingredients when preparing the premixtures
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
-
- 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
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses a nano material for freeze-thaw resistant concrete, which is a titanium dioxide-loaded reticular polyaniline nanosheet, adopts nontoxic sodium acetate as a dopant, and under the action of a proper temperature and a proper amount of initiator ammonium persulfate, aniline monomers are polymerized in deionized water to obtain a high-specific-surface-area flat-plate-shaped polyaniline nano material, and titanium dioxide is prepared by taking the high-specific-surface-area flat-plate-shaped polyaniline nano material as a template to obtain the titanium dioxide-modified polyaniline nano material. The material can improve the frost resistance of the concrete by resisting the volume shrinkage and expansion of the concrete, obviously reduce the quality loss of the concrete and improve the collapse resistance of the concrete on the premise of not influencing the mechanical property of the concrete.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a nano material for freeze-thaw resistant concrete and a using method thereof.
Background
With the rapid development of social economy, the requirement of buildings on the durability of concrete is continuously improved, and the freeze-thaw resistance is an important durability index of the concrete. At present, two main technical means for improving the freeze-thaw resistance of concrete are as follows: the freezing point of water is reduced by adding some salts into the additive, and the ice expansion stress generated by the solid-liquid phase change of the water is relieved by air entraining. The two measures have certain limitation, the freezing point of the salt to water is not greatly reduced, and the salt can not be frozen generally only at a few degrees below zero. However, the lowest temperature in winter in northeast China, especially in Heilongjiang, can reach below-40 ℃, and the traditional freeze-thaw resistant concrete can not meet the road requirement of the area at all due to seawater erosion and acid rain erosion, so that a nano material for the freeze-thaw resistant concrete needs to be researched, and the nano material added into the concrete can not only improve the freeze-thaw resistance of the concrete, but also has very good chloride ion corrosion resistance.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a nano material for freeze-thaw resistant concrete and a using method thereof.
The technical scheme of the invention is as follows:
a nano material for freeze-thaw resistant concrete is a reticular polyaniline nanosheet.
Further preferably, the nano material for the freeze-thaw resistant concrete is a titanium dioxide-loaded reticular polyaniline nanosheet.
Further preferably, the preparation method of the nanomaterial for freeze-thaw resistant concrete comprises the following steps:
A. dispersing sodium acetate in deionized water, adding aniline monomer after uniform dispersion, blending at the reaction temperature of 20-40 ℃, dropwise adding an ammonium persulfate aqueous solution, continuing to react for 5-20h after dropwise adding, and standing to obtain a template solution;
B. dripping titanate into glacial acetic acid, uniformly mixing, adding long-chain alkylamine, uniformly mixing with a template solution;
C. transferring the material obtained in the step B into a reaction kettle for reaction; and cooling, filtering, and spray drying after reaction.
The post-treatment method after the reaction of the nano material for the freeze-thaw resistant concrete has the advantages that although the purity of the obtained nano material is not high, the application effect of the material in the concrete is not influenced.
Preferably, in the step a, the mass ratio of sodium acetate, aniline and ammonium persulfate is 1: (1-5.1):(2.8-13.2).
Preferably, in the step A, the addition amount of the aniline monomer is 1.2-3.5 g/L.
Preferably, in the step B, the mass ratio of the titanate to the template solution is 1: (10-20).
Preferably, in the reaction process of the step C, the temperature is raised to 65-70 ℃ at the temperature raising rate of 5-10 ℃/min, and the temperature is kept for 30-60 min; then the temperature is raised to the maximum temperature of 250 ℃ and 280 ℃ at the same temperature raising rate, and the temperature is kept at the maximum temperature for 12 to 36 hours.
The nano material for the freeze-thaw resistant concrete is added into the freeze-thaw resistant concrete in an amount of 0.2-0.8% when in use.
Further preferably, the freeze-thaw resistant concrete comprises the following components in percentage by weight: 0.2-0.8% of reticular polyaniline nanosheet, 12-18% of portland cement, 18-25% of silica micropowder, 0.5-1% of water reducing agent, 0.2-0.5% of calcium formate, 3-8% of latex powder, 3-6% of aluminum sulfate, 0.1-0.2% of methyl hydroxypropyl cellulose ether and the balance of fine sand.
The invention has the advantages that: the nano material for freeze-thaw resistant concrete is titanium dioxide loaded reticular polyaniline nanosheets, adopts nontoxic sodium acetate as a dopant, and obtains the high-specific surface area flat-plate-shaped polyaniline nano material through polymerization of aniline monomers in deionized water under the action of a proper amount of initiator ammonium persulfate at a proper temperature. And preparing titanium dioxide by taking the high-specific surface area flat-plate-shaped polyaniline nano material as a template to obtain the titanium dioxide modified polyaniline nano material. The material can improve the frost resistance of the concrete by resisting the volume shrinkage and expansion of the concrete, obviously reduce the quality loss of the concrete and improve the collapse resistance of the concrete on the premise of not influencing the mechanical property of the concrete.
Detailed Description
Example 1
A nano material for freeze-thaw resistant concrete is a reticular polyaniline nanosheet; the nano material for the freeze-thaw resistant concrete is titanium dioxide loaded reticular polyaniline nanosheets.
The preparation method of the nano material for the freeze-thaw resistant concrete comprises the following steps:
A. dispersing sodium acetate in deionized water, adding aniline monomer after uniform dispersion, blending at the reaction temperature of 35 ℃, dropwise adding an ammonium persulfate aqueous solution, continuing to react for 12 hours after dropwise adding, and standing to obtain a template solution;
B. dripping titanate into glacial acetic acid, uniformly mixing, adding long-chain alkylamine, uniformly mixing with a template solution;
C. transferring the material obtained in the step B into a reaction kettle for reaction; and cooling, filtering, and spray drying after reaction.
In the step A, the mass ratio of the sodium acetate to the aniline to the ammonium persulfate is 1: 3.5:8.7.
In the step A, the adding amount of the aniline monomer is 2.8 g/L.
In the step B, the mass ratio of the titanate to the template solution is 1: 14.
in the reaction process of the step C, the temperature is raised to 68 ℃ at the heating rate of 7 ℃/min, and the temperature is kept for 45 min; subsequently, the temperature was raised to a maximum temperature of 275 ℃ at the same temperature rising rate, and the temperature was maintained at the maximum temperature for 24 hours.
Example 2
A nano material for freeze-thaw resistant concrete is a reticular polyaniline nanosheet; the nano material for the freeze-thaw resistant concrete is titanium dioxide loaded reticular polyaniline nanosheets.
The preparation method of the nano material for the freeze-thaw resistant concrete comprises the following steps:
A. dispersing sodium acetate in deionized water, adding aniline monomer after uniform dispersion, blending at the reaction temperature of 20 ℃, dropwise adding an ammonium persulfate aqueous solution, continuing to react for 20 hours after dropwise adding, and standing to obtain a template solution;
B. dripping titanate into glacial acetic acid, uniformly mixing, adding long-chain alkylamine, uniformly mixing with a template solution;
C. transferring the material obtained in the step B into a reaction kettle for reaction; and cooling, filtering, and spray drying after reaction.
In the step A, the mass ratio of the sodium acetate to the aniline to the ammonium persulfate is 1: 1:5.5.
In the step A, the adding amount of the aniline monomer is 1.2 g/L.
In the step B, the mass ratio of the titanate to the template solution is 1: 20.
in the reaction process of the step C, the temperature is raised to 70 ℃ at the temperature rise rate of 5 ℃/min, and the temperature is kept for 30 min; then, the temperature was raised to a maximum temperature of 280 ℃ at the same temperature raising rate, and the temperature was maintained at the maximum temperature for 12 hours.
Example 3
A nano material for freeze-thaw resistant concrete is a reticular polyaniline nanosheet; the nano material for the freeze-thaw resistant concrete is titanium dioxide loaded reticular polyaniline nanosheets.
The preparation method of the nano material for the freeze-thaw resistant concrete comprises the following steps:
A. dispersing sodium acetate in deionized water, adding aniline monomer after uniform dispersion, blending at the reaction temperature of 40 ℃, dropwise adding an ammonium persulfate aqueous solution, continuing to react for 5 hours after dropwise adding, and standing to obtain a template solution;
B. dripping titanate into glacial acetic acid, uniformly mixing, adding long-chain alkylamine, uniformly mixing with a template solution;
C. transferring the material obtained in the step B into a reaction kettle for reaction; and cooling, filtering, and spray drying after reaction.
In the step A, the mass ratio of the sodium acetate to the aniline to the ammonium persulfate is 1: 5.1:12.8.
In the step A, the adding amount of the aniline monomer is 3.5 g/L.
In the step B, the mass ratio of the titanate to the template solution is 1: 10.
in the reaction process of the step C, the temperature is raised to 65 ℃ at the heating rate of 10 ℃/min, and the temperature is kept for 60 min; then, the temperature was raised to a maximum temperature of 250 ℃ at the same temperature raising rate, and the temperature was maintained at the maximum temperature for 36 hours.
Comparative example 1
And D, directly cooling, separating, washing and drying the template solution obtained in the step A to obtain the reticular polyaniline nanosheet.
The nano-materials for the freeze-thaw resistant concrete of examples 1 to 3 and comparative example 1 were applied to the freeze-thaw resistant concrete, and the freeze-thaw resistant concrete was composed of the following components in percentage by weight: 0.5% of reticular polyaniline nanosheet, 13.5% of Portland cement, 19.5% of silica micropowder, 0.8% of water reducing agent, 0.3% of calcium formate, 4.5% of latex powder, 5.2% of aluminum sulfate, 0.15% of methyl hydroxypropyl cellulose ether and the balance of fine sand.
After the freeze-thaw resistant concrete in examples 1-3 and comparative example 1 and the comparative example (removing the reticular polyaniline nanosheets) is subjected to standard curing for 28d, a freeze-thaw cycle comparison test is performed, the mass loss rate of the concrete is detected after 180 times of freeze-thaw cycles by referring to a quick-freeze method in GB/T50082-2009 Standard test method for Long-term Performance and durability of ordinary concrete, and the mechanical property of the concrete is detected by referring to GB/T50081 and 2002 Standard test method for mechanical Properties of ordinary concrete. The specific test data obtained (the test data are the average of 5 test data) are shown in table 1.
Table 1: test data for examples 1-3, comparative example 1, and control;
| example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example | |
| Mass loss rate% | 0.816 | 0.836 | 0.842 | 2.126 | 6.729 |
| 28d flexural strength MPa | 6.7 | 6.5 | 6.5 | 6.7 | 6.4 |
| 28d compressive strength MPa | 43.6 | 42.3 | 42.5 | 42.5 | 42.1 |
According to the test data, the reticular polyaniline nanosheet disclosed by the invention is applied to freeze-thaw resistant concrete, so that the quality loss of the concrete can be obviously reduced, and the anti-damage strength of the concrete is improved.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (9)
1. The nano material for the freeze-thaw resistant concrete is characterized by being a reticular polyaniline nano sheet.
2. The nanomaterial for freeze-thaw resistant concrete according to claim 1, wherein the nanomaterial for freeze-thaw resistant concrete is a titanium dioxide-supported reticulated polyaniline nanosheet.
3. The nanomaterial for freeze-thaw resistant concrete according to claim 1 or 2, wherein the method for preparing the nanomaterial for freeze-thaw resistant concrete comprises the steps of:
A. dispersing sodium acetate in deionized water, adding aniline monomer after uniform dispersion, blending at the reaction temperature of 20-40 ℃, dropwise adding an ammonium persulfate aqueous solution, continuing to react for 5-20h after dropwise adding, and standing to obtain a template solution;
B. dripping titanate into glacial acetic acid, uniformly mixing, adding long-chain alkylamine, uniformly mixing with a template solution;
C. transferring the material obtained in the step B into a reaction kettle for reaction; and cooling, filtering, and spray drying after reaction.
4. The nanomaterial for freeze-thaw resistant concrete according to claim 3, wherein in the step A, the mass ratio of the sodium acetate to the aniline to the ammonium persulfate is 1: (1-5.1):(2.8-13.2).
5. The nanomaterial for freeze-thaw resistant concrete according to claim 3, wherein in the step A, the aniline monomer is added in an amount of 1.2 to 3.5 g/L.
6. The nanomaterial for freeze-thaw resistant concrete according to claim 3, wherein in the step B, the mass ratio of the titanate to the template solution is 1: (10-20).
7. The nanomaterial for freeze-thaw resistant concrete according to claim 3, wherein in the reaction process of the step C, the temperature is raised to 65-70 ℃ at a heating rate of 5-10 ℃/min, and the temperature is kept for 30-60 min; then the temperature is raised to the maximum temperature of 250 ℃ and 280 ℃ at the same temperature raising rate, and the temperature is kept at the maximum temperature for 12 to 36 hours.
8. A nanomaterial for freeze-thaw resistant concrete according to any one of claims 1 to 7, wherein the nanomaterial is added to the freeze-thaw resistant concrete in an amount of 0.2 to 0.8% when used.
9. The nanomaterial for freeze-thaw resistant concrete according to claim 8, wherein the freeze-thaw resistant concrete comprises the following components in percentage by weight: 0.2-0.8% of reticular polyaniline nanosheet, 12-18% of portland cement, 18-25% of silica micropowder, 0.5-1% of water reducing agent, 0.2-0.5% of calcium formate, 3-8% of latex powder, 3-6% of aluminum sulfate, 0.1-0.2% of methyl hydroxypropyl cellulose ether and the balance of fine sand.
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Application publication date: 20200124 |