CN114195419B - Carbon-based composition, cement-based composite material, and preparation method and application thereof - Google Patents
Carbon-based composition, cement-based composite material, and preparation method and application thereof Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 57
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 54
- 239000004568 cement Substances 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 24
- 230000007797 corrosion Effects 0.000 claims abstract description 23
- 238000005260 corrosion Methods 0.000 claims abstract description 23
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 21
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011150 reinforced concrete Substances 0.000 claims abstract description 20
- 238000001179 sorption measurement Methods 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 11
- 239000011398 Portland cement Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 238000005536 corrosion prevention Methods 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 230000002265 prevention Effects 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- UJOHNXQDVUADCG-UHFFFAOYSA-L aluminum;magnesium;carbonate Chemical group [Mg+2].[Al+3].[O-]C([O-])=O UJOHNXQDVUADCG-UHFFFAOYSA-L 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000003125 aqueous solvent Substances 0.000 claims 1
- 239000004567 concrete Substances 0.000 abstract description 17
- 239000003112 inhibitor Substances 0.000 abstract description 13
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 230000002787 reinforcement Effects 0.000 abstract description 3
- 238000007596 consolidation process Methods 0.000 abstract description 2
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- 229910000831 Steel Inorganic materials 0.000 description 12
- 239000010959 steel Substances 0.000 description 12
- 239000006228 supernatant Substances 0.000 description 10
- 229910001294 Reinforcing steel Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
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- 238000002161 passivation Methods 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 206010063493 Premature ageing Diseases 0.000 description 1
- 208000032038 Premature aging Diseases 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
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- 239000010410 layer Substances 0.000 description 1
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- 238000003760 magnetic stirring Methods 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RAFRTSDUWORDLA-UHFFFAOYSA-N phenyl 3-chloropropanoate Chemical compound ClCCC(=O)OC1=CC=CC=C1 RAFRTSDUWORDLA-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Images
Classifications
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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
-
- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/60—Agents for protection against chemical, physical or biological attack
- C04B2103/61—Corrosion inhibitors
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
The invention provides a carbon-based composition, a cement-based composite material, and a preparation method and application thereof, and belongs to the field of corrosion protection. The carbon-based composition includes water-soluble carbon dots and a layered double hydroxide. The carbon-based composition and the cement-based composite material prepared by the invention are simple and easy to obtain, have low cost and are environment-friendly green materials; the material has strong chloride ion adsorption capacity, and can effectively protect the concrete reinforcement from corrosion; the problems of poor consolidation capability and low dispersing capability of the traditional rust inhibitor can be solved, and the rust inhibitor has the advantages of excellent rust inhibiting effect, environmental protection, high efficiency and the like; can be widely applied to reinforced concrete and has wide application prospect.
Description
Technical Field
The invention belongs to the field of corrosion protection, and relates to a carbon-based composition, a cement-based composite material, and preparation methods and applications thereof.
Background
The reinforced concrete structure combines the advantages of the steel bars and the concrete, has lower manufacturing cost, is a preferred form of engineering structure design, and is widely applied to building various infrastructures. Over time, while concrete structures have gained increasing popularity, there is also a growing recognition that concrete structures degrade under many environmental conditions to a point where they are difficult to design. For example, the steel bars in reinforced concrete are vulnerable to corrosion from the external environment, which causes premature aging of the reinforced concrete structure, and the corrosion of the steel bars in reinforced concrete is one of the main factors affecting the durability of the structure. The calcium hydroxide in the concrete can provide an alkaline environment, so that a layer of passivation protective film is formed on the surface of the reinforcing steel bar, and the stable protective film can well protect the reinforcing steel bar from corrosion. However, the pH value of the pore solution is reduced due to the invasion of chloride ions in the environment, and a steel bar passivation film is damaged, so that the service life of the reinforced concrete structure is greatly shortened. Compared with the reinforcing steel bar corrosion caused by carbonization of a concrete protective layer, the reinforcing steel bar corrosion caused by the invasion of chloride ions is faster (about 10 times of the reinforcing steel bar corrosion caused by carbonization), the loss is larger, and the wide attention of the engineering and academic circles is caused.
With the demand of economic development, some super ocean engineering is continuously emerging, more and more large reinforced concrete structures are put into use, and the total economic loss caused by corrosion damage is increased. According to the statistical result of the United states, more than 50% of nearly 60 ten thousand bridges in the United states have steel bar corrosion diseases, and the maintenance cost is 750 hundred million dollars each year. The repair costs for reinforced concrete facilities in japan currently far exceed their construction costs. In conclusion, the reinforced concrete structure is very seriously corroded by the influence of the marine environment, so that the method has important significance for the research of the reinforced concrete multiple corrosion prevention technology in the marine environment. The method effectively solves the problem of chloride ion corrosion in the reinforced concrete structure, and has very important significance for prolonging the service life of concrete, meeting social requirements and promoting economic development.
The corrosion products of the steel reinforcement have a large volume, resulting in the cracks of the concrete, thereby greatly accelerating the failure of the concrete structure. Therefore, the key to improving the corrosion resistance of the steel bar is to improve the service life of the reinforced concrete structure in the marine environment. The steel bar rust inhibitor is an additive for reducing and preventing steel bar corrosion, is added into concrete or smeared on the surface of the concrete to play a role, is increasingly becoming a means for preventing the steel bar corrosion at present, is one of effective measures for improving the durability of the steel bar concrete, and is widely applied to petrochemical, steel, machinery, transportation and other departments at present. The rust inhibitor can effectively delay the corrosion of chloride ions to reinforcing steel bars, but the traditional rust inhibitor has the defects of high price, poor rust inhibition effect, toxicity, harm, environmental friendliness and the like. For example, early rebar corrosion inhibitors comprised primarily sodium nitrite, chromate and sodium benzoate, nitrite being a typical anodic corrosion inhibitor that acted to form a passive film on the metal surface by reacting with the metal, protecting the rebar from corrosion. They have different negative effects on the setting time and early and late strength of concrete. The reinforcing steel bar rust inhibitor taking calcium nitrite as a main component has a long application history in engineering, but due to the harmful effect on human bodies and serious environmental pollution, a plurality of countries are forbidden gradually. Therefore, the development of a novel green corrosion inhibitor, the research of the reinforcing steel bar rust inhibitor which is low in price, good in rust resistance effect, non-toxic, harmless, environment-friendly and beneficial to popularization still has important significance in ensuring the long-term safe service of a reinforced concrete structure in the development direction of the existing rust inhibitor.
Disclosure of Invention
The invention provides a carbon-based composition, a cement-based composite material taking the carbon-based composition as an auxiliary agent, a preparation method of the cement-based composite material and application of the cement-based composite material in metal corrosion prevention and/or rust prevention, aiming at the problems of poor dispersibility, poor rust prevention performance and the like of the existing rust inhibitor material.
In one aspect, the present invention provides a carbon-based composition including water-soluble carbon dots and a layered double hydroxide. The carbon dots have small particle size and large specific surface area, and the surface contains rich oxygen-containing groups such as hydroxyl, carboxyl and the like, so that the dispersion performance of the layered double hydroxide can be greatly improved after the carbon dots are compounded with the layered double hydroxide, and meanwhile, a large number of active sites are provided, and the composite material is ensured to exert the maximum effect of adsorbing chloride ions.
Optionally, in the carbon-based composition, the mass ratio of the water-soluble carbon point to the layered double hydroxide is (0.01-1): 1, preferably 1: 3; the lower limit of the mass ratio of the carbon point to the layered double hydroxide is optionally from 0.01, 0.3; the upper limit is optionally selected from 0.3 and 1.
Optionally, the particle size of the water-soluble carbon dots is 2-10 nm.
Optionally, the water-soluble carbon dots are prepared by mixing a raw material containing citric acid and urea with water and performing a hydrothermal method; the mass ratio of the citric acid to the urea is 2-5: 1, preferably 3: 1; the lower limit of the mass ratio of the citric acid to the urea is selected from 2:1 and 3: 1; the upper limit is optionally selected from 3:1 and 5: 1; the ratio of citric acid to water is 1: 20-200 parts of; the temperature of the hydrothermal reaction is 160-220 ℃, and preferably 220 ℃; the lower limit is selected from 160 ℃ and 200 ℃; the upper limit is selected from 200 deg.C and 220 deg.C; the time is 1-3h, preferably 2 h; the lower limit is selected from 1h and 2 h; the upper limit is arbitrarily selected from 2h and 3 h.
Optionally, the layered double hydroxide is magnesium aluminum carbonate type layered double hydroxide.
Optionally, the composition further comprises a solvent, and the mass ratio of the solvent to the water-soluble carbon dots is 20-500: 1.
Optionally, the solvent is water.
Another aspect of the present invention provides a method for preparing the above carbon-based composition, the method comprising: step a, respectively obtaining water-soluble carbon dots and layered double hydroxides; and b, mixing the solvent with a raw material I containing the water-soluble carbon dots and the layered double hydroxide to obtain the carbon-based composition.
Optionally, the step I of mixing adopts a stirring manner, and the stirring time is more than 0.5h, preferably 0.5h to 2 h; the stirring temperature is 20-30 ℃ room temperature, preferably room temperature. The carbon dots and layered double hydroxide are preferably dispersed in water using magnetic stirring.
Optionally, the method further comprises the step of subjecting the layered double hydroxide to calcination pretreatment before mixing I; the calcining temperature is 450-550 ℃, and preferably 500 ℃; the lower limit is optionally 450 ℃ and 500 ℃; the upper limit is optionally 500 deg.C and 550 deg.C; the time is 2-5 hours, preferably 3 hours; the lower limit is selected from 2h and 3 h; the upper limit is arbitrarily selected from 3h and 5 h; the atmosphere is air or nitrogen.
In a further aspect, the present invention provides the use of any one of the above carbon-based compositions or the carbon-based composition obtained by any one of the above preparation methods for corrosion prevention and/or rust prevention of metals.
Optionally, the carbon-based composition is used as an auxiliary agent for cement or reinforced concrete, and the content of the auxiliary agent is 0.01 wt% to 10 wt%.
Optionally, the carbon-based composition is used to adsorb chloride ions in cement or reinforced concrete.
Optionally, the adsorption amount of the carbon-based composition to chloride ions in cement or reinforced concrete is 20.8499-34.6695 mg/g.
In another aspect, the present invention provides a cement-based composite comprising a carbon-based composition and portland cement; the carbon-based composition is selected from any one of the carbon-based compositions or from the carbon-based composition obtained by any one of the preparation methods.
Optionally, in the cement-based composite material, the mass ratio of the carbon-based composition to the portland cement is (0.0001-0.1): 1, preferably 0.005: 1; the lower limit is optionally selected from 0.0001, 0.005; the upper limit is optionally 0.005, 0.1.
Optionally, the cement-based composite material further comprises a retarder and/or a water reducing agent; the addition amount of the retarder is 0.1-1 wt% of the cement-based composite material; the addition amount of the water reducing agent is 0.1-1 wt% of the cement-based composite material.
Optionally, the preparation method comprises:
dispersing a carbon-based composition into water to obtain a colloidal solution; the dispersion is carried out by stirring with a conventional glass rod at normal temperature.
Step two, mixing II the colloidal solution with a material containing portland cement; and preparing the cement-based composite material.
Optionally, the mass ratio of the portland cement, water, and the carbon-based composition is 1: (0.25-0.6): (0.0001-0.1).
The invention further provides an application of any one of the cement-based composite materials or the cement-based composite material obtained by any one of the preparation methods, which is used for corrosion prevention and/or rust prevention of metal, wherein the adsorption amount of the cement-based composite material to chloride ions is 20.8499-34.6695 mg/g.
The invention has the following beneficial effects:
(1) the carbon-based composition and the cement-based composite material prepared by the invention are simple and easy to obtain, have low cost and are environment-friendly green materials.
(2) The carbon-based composition and the cement-based composite material prepared by the invention have strong chloride ion adsorption capacity and can effectively protect the concrete reinforcement from corrosion.
(3) The carbon-based composition and the cement-based composite material prepared by the invention can overcome the problems of poor consolidation capability and low dispersing capability of the traditional rust inhibitor, and have the advantages of excellent rust inhibiting effect, environmental protection, high efficiency and the like.
(4) The carbon-based composition and the cement-based composite material prepared by the invention can be widely applied to reinforced concrete and have wide application prospects.
Drawings
FIG. 1 is a flow chart of the present invention for preparing a carbon-based composition and a cement-based composite.
Detailed Description
To further illustrate the technical means and effects adopted by the present invention to achieve the predetermined objects, the concrete embodiments, features and effects of the cement-based composite material with high chloride ion adsorption and the preparation method thereof according to the present invention are described in detail below.
Example 1 carbon-based composition
In the embodiment, the carbon dots are prepared by a hydrothermal method, namely citric acid and urea are mixed with deionized water according to the mass ratio of 3: 1; heating at 200 deg.C for 2 h; the concentration of citric acid in the deionized water is 0.01 g/ml.
The layered double hydroxide is magnesium aluminum carbonate type layered double hydroxide (Allison (Beijing) Technology Co. LTDMg-Al-CO) 3 LDH) was prepared after calcining in air at 500 c for 3 hours.
The step S1 in FIG. 1 is adopted to prepare the carbon-based composition, namely adding the carbon dots and the layered double hydroxide into deionized water according to the mass ratio of 1:3, wherein the ratio of water to the carbon dots is 200:1, and stirring at room temperature for 0.5h to disperse to prepare the carbon-based composition.
EXAMPLE 2 preparation of Cement-based composite Material
The step S2 in FIG. 1 is adopted, namely the preparation method of the cement-based composite material with high chloride ion adsorption is as follows:
step one, 2.5g of the carbon-based composition prepared in example 1 and 250g of water are taken, and stirred and dispersed uniformly by a glass rod at normal temperature to obtain a colloidal solution.
And step two, uniformly stirring 500g of 42.5R-grade ordinary portland cement and the colloidal solution obtained in the step one to prepare the cement-based composite material (1#) with high chloride ion adsorption.
Comparative example 1
The step S2 in FIG. 1 is adopted, namely the preparation method of the cement-based composite material with high chloride ion adsorption is as follows:
step one, 2.5g of pure layered double hydroxide (magnesium aluminum carbonate based layered double hydroxide (Alison (Beijing)) Technology Co. LTDMg-Al-CO is taken 3 LDH)) and 250g of water, and was uniformly dispersed at normal temperature with a glass rod to obtain a colloidal solution.
And step two, uniformly stirring 500g of 42.5R-grade ordinary portland cement and the colloidal solution obtained in the step one to prepare the cement-based composite material (2#) with high chloride ion adsorption.
Test example 1
The cement-based composite material 1# obtained in example 2 was poured into a 1.5cm × 1.5cm × 1.5cm silica gel mold, covered with a plastic film, placed in a curing room for 24 hours, and then released from the mold, and the sample obtained by releasing the mold was placed in the curing room and cured for 28 days. And grinding and sieving the test block which is cured for 28 days for 0.15 mm, and placing the powder obtained by sieving in a vacuum drying oven for 7 days to obtain a powder sample No. 1.
And dissolving the NaCl particles in deionized water to prepare a NaCl solution with the concentration of 3 mol/L. And putting 5g of the dried powder sample No. 11 and 50ml of prepared NaCl solution into a closed container, fully stirring uniformly, and standing for 14 days to obtain a solid-liquid mixture No. 1.
Placing the solid-liquid mixture 1# in a high-speed centrifuge, centrifuging for 5min at 3500rpm to obtain a supernatant 1#, taking out the supernatant 1#, preparing 0.01mol/L silver nitrate solution according to the national standard JGJT 322-2013 & lt technical Specification for detecting chloride ion content in concrete, titrating the supernatant by using an automatic point titration instrument to obtain the residual chloride ion content in the supernatant 1#, and obtaining the residual chloride ion content in the supernatant by using a formula C b ＝35.453*(Ci-Ce)*V SCHS /m total Calculation) to obtain the content of chloride ions absorbed by the cement-based composite material 1#, wherein 35.453 in the formula is the molar mass of the chloride ions, and Ci is the initial chloride ion concentration (mol/L) in the formula shown in Table 1;ce is the concentration (mol/L) of free chloride ions; v SCHS Volume (ml) of saturated calcium hydroxide solution; m is total Is the sample mass (g).
Test example 2
The cement-based composite material No. 2 prepared in comparative example 1 was poured into a 1.5 cm. times.1.5 cm silica gel mold, covered with a plastic film, placed in a curing room for 24 hours, and then released from the mold, and the sample obtained by releasing the mold was placed in the curing room for curing for 28 days. And grinding and sieving the test block which is cured for 28 days for 0.15 mm, and placing the powder obtained by sieving in a vacuum drying oven for 7 days to obtain a powder sample No. 2.
And dissolving the NaCl particles in deionized water to prepare a NaCl solution with the concentration of 3 mol/L. And (3) putting 5g of the dried powder sample No. 2 and 50ml of prepared NaCl solution into a closed container, fully stirring uniformly, and standing for 14 days to obtain a solid-liquid mixture No. 2.
Placing the solid-liquid mixture 2# in a high-speed centrifuge, centrifuging for 5min at 3500rpm to obtain a supernatant 2#, taking out the supernatant 2#, preparing 0.01mol/L silver nitrate solution according to the national standard JGJT 322-2013 technical specification for detecting the content of chloride ions in concrete, titrating the supernatant by using an automatic point titration instrument to obtain the content of residual chloride ions in the supernatant 2#, and obtaining the content of the residual chloride ions in the supernatant by using a formula C b ＝35.453*(Ci-Ce)*V SCHS /m total Calculation) to obtain the content of chloride ions absorbed by the cement-based composite material 2#, wherein 35.453 in the formula is the molar mass of the chloride ions, and Ci is the initial chloride ion concentration (mol/L) in the table 1; ce is free chloride ion concentration (mol/L); v SCHS Volume (ml) of saturated calcium hydroxide solution; m is total Is the sample mass (g).
The result proves that the adsorption effect is obviously improved, the chloride ion adsorption capacity of the group 1 is 34.6695mg/g, the chloride ion adsorption capacity of the group 2 is 20.8499mg/g, and the chloride ion adsorption capacity is improved by 13.8196 mg/g.
TABLE 1 chloride ion content test
Claims (14)
1. A carbon-based composition, characterized in that the carbon-based composition comprises water-soluble carbon dots, layered double hydroxide and an aqueous solvent; the water-soluble carbon dots are compounded with the layered double hydroxide through hydroxyl and/or carboxyl on the surface to improve the dispersibility of the layered double hydroxide, and the mass ratio of the water-soluble carbon dots to the layered double hydroxide is (0.01-1): 1, the mass ratio of the water solvent to the water-soluble carbon dots is 20-500: 1; the carbon-based composition is used as a cementitious material in combination with cement.
2. The carbon-based composition according to claim 1,
the water-soluble carbon dots are prepared by mixing raw materials containing citric acid and urea with water and performing a hydrothermal method; the mass ratio of the citric acid to the urea is 2-5: 1;
the ratio of citric acid to water is 1: (20-200);
the temperature of the hydrothermal reaction is 160-220 ℃; the time is 1 h-3 h.
3. The carbon-based composition according to claim 1, wherein the water-soluble carbon dots have a particle size of 2 to 10 nm;
the layered double hydroxide is magnesium aluminum carbonate layered double hydroxide.
4. A process for the preparation of the carbon-based composition according to any one of claims 1 to 3, characterized in that it comprises: respectively obtaining water-soluble carbon dots and layered double hydroxides; and (3) mixing the water solvent with a raw material containing the water-soluble carbon dots and the layered double hydroxide to obtain the carbon-based composition.
5. A method of preparing a carbon-based composition according to claim 4,
the mixing I adopts a stirring mode, and the stirring time is 0.5-2 h; the temperature is 20-30 ℃;
the preparation method also comprises the step of calcining the layered double hydroxide before the step I of mixing; the calcining temperature is 450-550 ℃; the time is 2-5 h; the atmosphere is air or nitrogen.
6. Use of any carbon-based composition according to any one of claims 1-3, or obtained by the preparation process according to any one of claims 4-5, for corrosion protection and/or rust protection of metals.
7. Use according to claim 6,
the carbon-based composition is used as an auxiliary agent for cement or reinforced concrete, and the content of the auxiliary agent is 0.01-10 wt%.
8. The use according to claim 6,
the carbon-based composition is used for adsorbing chloride ions in cement or reinforced concrete.
9. The use according to claim 6,
the carbon-based composition has the adsorption capacity of 20.8499-34.6695 mg/g to chloride ions in cement or reinforced concrete.
10. A cement-based composite material characterized in that,
comprising a carbon-based composition and portland cement;
the carbon-based composition is selected from the carbon-based compositions according to any one of claims 1 to 3 or the carbon-based compositions obtainable by the process according to any one of claims 4 to 5.
11. The cement-based composite material as recited in claim 10,
in the cement-based composite material, the mass ratio of the carbon-based composition to the portland cement is (0.0001-0.6): 1.
12. the cement-based composite material as recited in claim 10,
the cement-based composite material also contains a retarder and/or a water reducing agent;
the addition amount of the retarder is 0.1-1 wt% of the cement-based composite material;
the addition amount of the water reducing agent is 0.1-1 wt% of the cement-based composite material.
13. A method of preparing a cementitious composite as claimed in any one of claims 10 to 12, characterised in that the method of preparation comprises:
dispersing the carbon-based composition into water to obtain a colloidal solution;
mixing II the colloidal solution with a material containing portland cement; preparing the cement-based composite material;
the mass ratio of the Portland cement to the water to the carbon-based composition is 1: (0.25-0.6): (0.0001-0.1).
14. Use of the cement-based composite material according to any one of claims 10 to 12 or the cement-based composite material obtained by the production method according to claim 13, for corrosion prevention and/or rust prevention of a metal, wherein the cement-based composite material has an adsorption amount of chloride ions of 20.8499 to 34.6695 mg/g.
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