CN112745055A - Graphene suspension, and preparation method and application thereof - Google Patents
Graphene suspension, and preparation method and application thereof Download PDFInfo
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- CN112745055A CN112745055A CN202011605300.4A CN202011605300A CN112745055A CN 112745055 A CN112745055 A CN 112745055A CN 202011605300 A CN202011605300 A CN 202011605300A CN 112745055 A CN112745055 A CN 112745055A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 121
- 239000000725 suspension Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000004568 cement Substances 0.000 claims abstract description 38
- 239000002253 acid Substances 0.000 claims abstract description 25
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 19
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920005646 polycarboxylate Polymers 0.000 claims abstract description 8
- 239000008030 superplasticizer Substances 0.000 claims abstract description 8
- 238000005303 weighing Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 79
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 25
- 239000000178 monomer Substances 0.000 claims description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 17
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-isoascorbic acid Chemical compound OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 claims description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 8
- 235000010350 erythorbic acid Nutrition 0.000 claims description 8
- 229940026239 isoascorbic acid Drugs 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229920000570 polyether Polymers 0.000 claims description 8
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 8
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 6
- 238000007865 diluting Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- -1 polyoxypropylene Polymers 0.000 claims description 4
- WVYSWPBECUHBMJ-UHFFFAOYSA-N 2-methylprop-1-en-1-ol Chemical compound CC(C)=CO WVYSWPBECUHBMJ-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000036626 alertness Effects 0.000 abstract description 3
- 239000004567 concrete Substances 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 9
- 238000001132 ultrasonic dispersion Methods 0.000 description 8
- 239000002131 composite material Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 230000002572 peristaltic effect Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- WPKYZIPODULRBM-UHFFFAOYSA-N azane;prop-2-enoic acid Chemical compound N.OC(=O)C=C WPKYZIPODULRBM-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000011083 cement mortar Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004318 erythorbic acid Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 230000000051 modifying effect Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- 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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2641—Polyacrylates; Polymethacrylates
- C04B24/2647—Polyacrylates; Polymethacrylates containing polyether side chains
-
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- 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
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
Abstract
The invention discloses a graphene suspension and a preparation method and application thereof, belonging to the technical field of concrete admixtures, wherein the graphene suspension comprises 0.5-2.5 parts by weight of a polycarboxylic acid water reducing agent, 0.01-0.05 part by weight of graphene, 0.008-0.04 part by weight of graphene oxide and 170-200 parts by weight of water; the acid-ether molar ratio of the polycarboxylate superplasticizer is (2-6) to 1; the preparation method comprises the following steps: weighing a polycarboxylic acid water reducing agent, graphene oxide and water, and adding the graphene oxide into the water to obtain a graphene oxide solution; mixing graphene with a graphene oxide solution, adding the balance of water, performing ultrasonic treatment, adding a polycarboxylic acid water reducing agent, and performing ultrasonic treatment again to obtain a graphene suspension; the graphene suspension prepared by the invention has high dispersibility and good compatibility with cement, and can effectively improve the mechanical property, durability, conductivity and alertness of cement-based materials.
Description
Technical Field
The invention belongs to the technical field of concrete admixtures, and particularly relates to a graphene suspension and a preparation method and application thereof.
Background
Cement-based materials are widely used in the construction of important civil infrastructures, including bridges, dams, underground pipelines, skyscrapers and nuclear containment vessels. The carbon nano materials such as graphene, graphene oxide and carbon nano tubes have excellent mechanical, thermal and electrical properties, so that when the carbon nano materials are added into cement, the generation and the expansion of nano-scale cracks can be inhibited, the mechanical properties of the cement can be improved, and unique electromechanical response can be provided.
Due to the hydrophobicity of graphene and strong van der waals force among molecules, the graphene inevitably generates agglomeration problems such as winding, stacking and the like in an aqueous medium. Poorly dispersed graphene can cause a cement matrix to form a weak area or a potential area with concentrated stress, so that the reinforcing/modifying effect of the graphene material is limited, and the mechanical property and durability of the cement-based material are damaged. Therefore, a key problem in preparing high-performance and multifunctional graphene-cement-based composite materials is to uniformly disperse graphene in the cementitious material.
Common chemical dispersion methods are classified into covalent modification and non-covalent modification, and since the covalent modification changes the structure of graphene and affects the electrothermal performance of graphene, the non-covalent modification method is usually used to improve the dispersibility of graphene, and a common method is to mix a surfactant into a graphene suspension and then subject the suspension to ultrasonic treatment to obtain a graphene aqueous suspension with good dispersibility. However, the compatibility of the conventional surfactant with cement is poor, and the graphene modified by the conventional surfactant has low dispersibility in a complex ionic solution environment of cement, so that the function of the graphene in the cement-based material cannot be fully exerted.
Disclosure of Invention
In view of the above, the invention provides a graphene suspension, and a preparation method and an application thereof, and the graphene suspension is prepared by primarily dispersing graphene with a graphene oxide solution and further dispersing graphene with a polycarboxylic acid water reducing agent with a reasonable acid-ether ratio, so that the high-dispersibility graphene suspension with excellent dispersibility and suitable for cement-based materials is prepared, can be directly used for preparing cement-based materials, and has good practicability and engineering application prospects.
In order to achieve the above object, the present invention provides the following technical solutions.
One of the technical schemes of the invention is as follows: the graphene suspension comprises the following raw materials in parts by weight:
0.5-2.5 parts of a polycarboxylic acid water reducing agent, 0.01-0.05 part of graphene, 0.008-0.04 part of graphene oxide and 170-200 parts of water;
the acid-ether molar ratio of the polycarboxylate superplasticizer is (2-6) to 1.
Further, the thickness of a sheet layer of the graphene is 1-3 nm, and the sheet diameter is 0.5-5 mu m; the thickness of the graphene oxide sheet layer is 1-2 nm, and the sheet diameter is 0.5-1 μm.
The purity of the graphene is more than or equal to 99.4%.
Further, the preparation method of the polycarboxylate superplasticizer comprises the following steps: mixing a polyether monomer with water to obtain a solution A; mixing thioglycolic acid and mercaptopropionic acid to obtain a mixed solution, and mixing the mixed solution, an acrylic monomer and water to obtain a solution B; mixing isoascorbic acid and water to obtain solution C; and adding the solution B and the solution C into the solution A to react to obtain the polycarboxylate superplasticizer.
Further, the polyether monomer is selected from one or more of allyl alcohol polyoxyethylene ether, polyoxypropylene ether, prenol polyoxyethylene ether and isobutenol polyoxyethylene ether; the acrylic monomer is selected from one or more of methacrylic acid, acrylic acid or acrylate.
Still further, the acrylic acid salt is selected from a monovalent metal salt, an ammonium salt, or an organic amine salt of acrylic acid.
Still further, the acrylic monomer has a purity of > 99%.
Further, the mass ratio of the polyether monomer to the water in the solution A is (0.5-1.5) to 1, and the molar ratio of the acrylic monomer to the polyether monomer is (2-6) to 1; the mass ratio of the thioglycolic acid to the mercaptopropionic acid is 1: 1-1.2; the mass ratio of the acrylic monomer, the mixed liquid of thioglycolic acid and mercaptopropionic acid and water in the solution B is 1: 0.005-0.03: 0.2-0.8; the mass ratio of the isoascorbic acid to the water in the solution C is (0.005-0.2) to (0.5-2).
Furthermore, the mass ratio of the liquid A, the liquid B and the liquid C is (1.5-2.5): (1.205-9.83): (0.505-2.2).
Further, the liquid B and the liquid C are added into the liquid A in a dropwise manner at the same time.
Further, the reaction temperature is 25-65 ℃, the reaction time is 1-6 hours, and the method further comprises the steps of preserving heat for 1-3 hours after the reaction is finished, adjusting the pH value to 6.5-7.5, and diluting until the solid content is 18-22 wt%.
The second technical scheme of the invention is as follows: the preparation method of the graphene suspension comprises the following steps: weighing a polycarboxylic acid water reducing agent, graphene oxide and water according to parts by weight, and adding the graphene oxide into the water to obtain a graphene oxide solution; and mixing graphene with the graphene oxide solution, adding the balance of water, performing ultrasonic treatment, adding a polycarboxylic acid water reducing agent, and performing ultrasonic treatment again to obtain the graphene suspension.
Further, the concentration of the graphene oxide solution is 3.8-4.2 mg/mL.
Further, mixing graphene and graphene oxide solution, adding the balance of water, stirring for 1-10 min, and performing ultrasonic treatment at the power of 250-750W for 5-15 min.
Further, before secondary ultrasound, stirring for 1-5 min, wherein the power of the secondary ultrasound is 250-750W, and ultrasound is performed for 5-10 min.
The third technical scheme of the invention is as follows: an application of the graphene suspension in cement-based materials.
Compared with the prior art, the invention has the following beneficial effects:
(1) the graphene suspension prepared by the invention can be used as a special additive to be doped into a cement-based material, so that the mechanical property and durability of the cement-based material can be effectively improved, and meanwhile, due to the existence of the graphene, the cement-based material is endowed with certain alertness, so that the engineering requirements of real-time self-monitoring of cracks of a cement concrete structure and the like can be met.
(2) According to the invention, the graphene oxide and the graphene act together, the hydrophilicity of the graphene oxide and the pi-pi stacking interaction of the graphene oxide and the graphene are fully utilized, and the dispersibility of the graphene in water is improved.
(3) Prepared by the inventionThe polycarboxylate superplasticizer with a reasonable structure not only can effectively disperse cement particles and improve the workability of cement paste, but also can prevent Ca of graphene oxide in a cement pore solution2+The complexing action further ensures the stable dispersibility of the graphene oxide and the graphene in the cement paste, improves the adaptability of the graphene suspension liquid and the cement, has good compatibility of the high-dispersibility graphene suspension liquid and the cement, and can effectively improve the mechanical property, the conductivity and the alertness of the cement-based material.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
The "parts" referred to in the present invention are, unless otherwise specified, in parts by weight;
in the following embodiments, the thickness of the graphene sheet is 1-3 nm, the sheet diameter is 0.5-5 μm, and the purity is not less than 99.4%; the thickness of a sheet layer of the graphene oxide is 1-2 nm, and the sheet diameter is 0.5-1 mu m; the purity of the adopted acrylic monomer is more than 99 percent;
in the following examples, an ultrasonic disperser type SCIENTZ-750F was used for the ultrasound.
The description will not be repeated below.
Example 1
The preparation method of the graphene suspension comprises the following steps:
(1) preparation of polycarboxylic acid water reducing agent
Mixing prenyl polyoxyethylene ether with water according to the mass ratio of 1: 1 to obtain solution A, and adding the solution A into a four-mouth reaction bottle with a thermometer and a reflux condenser for later use;
taking corresponding mass of acrylic acid according to the acid ether molar ratio of 2, wherein the mass ratio of the acrylic acid to distilled water, thioglycolic acid and mercaptopropionic acid is 1: the mixed solution of 1 is put into a conical flask to prepare a solution B for standby, wherein the mass ratio of the mixed solution of acrylic acid, thioglycollic acid and mercaptopropionic acid to distilled water is 1: 0.01: 0.2; placing isoascorbic acid and distilled water in a mass ratio of 0.005: 0.5 in a conical flask to prepare solution C for later use;
and dropwise adding the solution B and the solution C into the solution A by using a peristaltic pump, reacting for 3h at 45 ℃ by using the mass ratio of the solution A to the solution B to the solution C of 1.5: 4: 1, preserving heat for 2.5h, neutralizing by using 30% sodium hydroxide solution until the pH value is 7, and diluting until the solid content is 20 wt% to obtain the polycarboxylic acid water reducer.
(2) Preparation of graphene suspension
Weighing 0.02 part of graphene oxide, 0.5 part of the polycarboxylic acid water reducing agent prepared in the step (1), 0.01 part of graphene and 200 parts of deionized water, adding deionized water into the graphene oxide to prepare a solution with the concentration of 4mg/mL, adding 0.02 part of graphene into the solution, adding the rest of deionized water, stirring for 5min by using a glass rod, adding 0.5 part of polycarboxylic acid water reducing agent after performing ultrasonic treatment for 10min by using a 300W ultrasonic dispersion instrument, stirring for 2min, and performing ultrasonic treatment for 5min by using the 300W ultrasonic dispersion instrument again to obtain the stable high-dispersity graphene suspension.
Example 2
Preparing a graphene suspension:
(1) preparation of polycarboxylic acid water reducing agent
Mixing the polyoxyethylene methacrylate and water according to the mass ratio of 1.5: 1 to obtain solution A, and adding the solution A into a four-mouth reaction bottle with a thermometer and a reflux condenser for later use;
placing the mixed solution of methacrylic acid with the corresponding mass and distilled water and the mixed solution of thioglycolic acid and mercaptopropionic acid with the mass ratio of 1: 1.2 in a conical flask according to the acid ether molar ratio of 6 to prepare a solution B for later use, wherein the mass ratio of the mixed solution of methacrylic acid, thioglycolic acid and mercaptopropionic acid to the distilled water is 1: 0.003: 0.8; placing isoascorbic acid and distilled water in a mass ratio of 0.2: 2 in a conical flask to prepare solution C for later use;
and dropwise adding the solution B and the solution C into the solution A by using a peristaltic pump, reacting for 6h at 25 ℃ with the mass ratio of the solution A to the solution B to the solution C being 2.5: 9.83: 2.2, preserving heat for 3h, neutralizing with 30% sodium hydroxide solution until the pH value is 6.5, and diluting until the solid content is 22 wt%, thus obtaining the polycarboxylic acid water reducer.
(2) Preparation of graphene suspension
Weighing 0.008 part of graphene oxide, 0.75 part of the polycarboxylic acid water reducing agent prepared in the step (1), 0.03 part of graphene and 170 parts of deionized water, adding deionized water into the graphene oxide to prepare a solution with the concentration of 3.8mg/mL, adding 0.03 part of graphene into the solution, adding the rest deionized water, stirring for 10min by using a glass rod, adding 0.75 part of polycarboxylic acid water reducing agent after performing ultrasonic treatment for 15min by using a 750W ultrasonic dispersion instrument, stirring for 1min, and performing ultrasonic treatment for 10min by using the 750W ultrasonic dispersion instrument again to obtain the stable high-dispersity graphene suspension.
Example 3
The preparation method of the graphene suspension comprises the following steps:
(1) preparation of polycarboxylic acid water reducing agent
Mixing allyl alcohol polyoxyethylene ether and water according to the mass ratio of 0.5: 1 to obtain solution A, and adding the solution A into a four-mouth reaction bottle with a thermometer and a reflux condenser for later use;
taking the corresponding mass of ammonium acrylate, distilled water and the mixed solution of thioglycolic acid and mercaptopropionic acid with the mass ratio of 1: 1 according to the molar ratio of acid ether to 4, and placing the mixed solution into a conical flask to prepare a solution B for later use, wherein the mass ratio of the mixed solution of ammonium acrylate, thioglycolic acid and mercaptopropionic acid to the distilled water is 1: 0.005: 0.5; placing isoascorbic acid and distilled water in a mass ratio of 0.1: 1.2 in a conical flask to prepare solution C for later use;
and dropwise adding the solution B and the solution C into the solution A by using a peristaltic pump, reacting for 1h at 65 ℃ with the mass ratio of the solution A to the solution B to the solution C being 2: 1.205: 0.505, preserving the temperature for 1h, neutralizing with 30% sodium hydroxide solution until the pH value is 7.5, and diluting until the solid content is 18 wt%, thus obtaining the polycarboxylic acid water reducer.
(2) Preparation of graphene suspension
Weighing 0.04 part of graphene oxide, 2.5 parts of the polycarboxylic acid water reducing agent prepared in the step (1), 0.05 part of graphene and 185 parts of deionized water, adding deionized water into the graphene oxide to prepare a solution with the concentration of 4.2mg/mL, adding 0.05 part of graphene into the solution, adding the rest of deionized water, stirring for 1min by using a glass rod, adding 1.25 parts of polycarboxylic acid water reducing agent after carrying out ultrasonic treatment for 5min by using a 250W ultrasonic dispersion instrument, stirring for 5min, and carrying out ultrasonic treatment for 10min by using the 250W ultrasonic dispersion instrument again to obtain the stable high-dispersity graphene suspension.
Comparative example 1
A graphene suspension is prepared by the following steps:
mixing 0.05 part of graphene and 0.05 part of sodium dodecyl benzene sulfonate (SDBS, purity of 88 percent, white powder), adding 200 parts of water, stirring for 5min, and carrying out ultrasonic treatment for 15min by using an ultrasonic dispersion instrument with the power of 300W.
Comparative example 2
A graphene suspension is prepared by the following steps:
adding 0.04 part of graphene oxide into deionized water to obtain a solution with the concentration of 4.2mg/mL, adding 0.05 part of graphene into the solution, adding 182 parts of deionized water, stirring for 5min by using a glass rod, and performing ultrasonic treatment for 15min by using a 300W ultrasonic dispersion instrument to obtain a stable graphene suspension.
Comparative example 3
The difference from example 1 is that erythorbic acid in step (1) was replaced with ascorbic acid.
Comparative example 4
The difference from example 1 is that no thioglycolic acid is added in step (1).
Comparative example 5
The difference from example 1 is that no mercaptopropionic acid was added in step (1).
Comparative example 6
The difference from example 1 is that in step (1), the solution B and the solution C are directly poured into the solution A.
Comparative example 7
The difference from example 1 is that in step (1) the pH is adjusted to 8.5 with 30% NaOH.
Comparative example 8
The preparation method of the graphene suspension comprises the following steps:
weighing 0.02 part of graphene oxide, 0.5 part of sodium dodecyl benzene sulfonate (SDBS, purity is greater than 88%, white powder), 0.01 part of graphene and 200 parts of deionized water, adding deionized water into the graphene oxide to prepare a solution with the concentration of 4mg/mL, adding 0.02 part of graphene into the solution, adding the rest of deionized water, stirring for 5min by using a glass rod, adding 0.5 part of sodium dodecyl benzene sulfonate after carrying out ultrasonic treatment for 10min by using a 300W ultrasonic disperser, stirring for 2min, and carrying out ultrasonic treatment for 5min by using the 300W ultrasonic disperser again to obtain the stable high-dispersity graphene suspension.
Example of Effect verification
(1) Testing of flexural and compressive strength of graphene-composite cement-based mortar
The tests are carried out according to GB/T17617-2007 method for testing cement mortar strength, the standard sand adopts Chinese ISO standard sand produced by Xiamen Aisi European standard sand Co., Ltd, the cement adopts standard cement produced by Fuzhou union cement Co., Ltd, and the strength grade is 42.5. The water-cement ratio was 0.35, the cement amount was 450g, the standard sand was 1350g, the admixture addition amount was 1.0% of the gelled material, and the admixtures were the graphene suspensions prepared in examples 1 to 3 and comparative examples 1 to 8, respectively, and the results are shown in table 1.
TABLE 1 data of 3d and 28d flexural and compressive strengths of graphene-composite cement-based mortar
(2) Graphene-cement hardened mortar conductivity test
Preparing a test block: putting 450g of cement into a stirring pot, and mixing the following materials in percentage by mass: cement 0.05: 100, taking a certain amount of the graphene suspensions of examples 1-3 and comparative examples 1-8, supplementing extra water (except water in the graphene suspension) according to a water-gel ratio of 0.4, slowly stirring uniformly by using a mortar stirrer, slowly adding 1350g of standard sand, continuously stirring uniformly, injecting into a mold, embedding 2 electrodes into a graphene cement-based composite material test block with the size of 160 x 40mm to obtain the pressure-sensitive sensor, wherein the 2 electrodes are sequentially distributed on the same surface of the test block from left to right and are symmetrically distributed by using a central axis of the surface of the test block, and the distance between the two electrodes is 80 mm. And curing for 28 days under the conditions that the temperature is 20 ℃ and the relative humidity is more than 95% to obtain the graphene cement-based composite material.
And (3) conductivity test: after curing for 28 days, the water stain on the surface of the test block was wiped dry, the test was carried out for 120s using a TH2810d LCR bridge, and after the resistance was stabilized, the value was recorded and the conductivity was calculated, the results are shown in Table 2.
(3) Graphene-cement hardened mortar pressure sensitivity test
An electronic universal testing machine is adopted to load and unload cyclic pressure stress to the test block, a TH2810d LCR bridge is adopted to collect resistance data of the two electrodes, and the data is collected every 0.5 s. The loading and unloading speeds of the cyclic compressive stress are both 500N/s, the maximum compressive stress is 15MPa, the minimum compressive stress is 2.5MPa, and the resistance change rate obtained by calculation is shown in Table 2.
TABLE 2
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 able to cover the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.
Claims (9)
1. The graphene suspension is characterized by comprising the following raw materials in parts by weight:
0.5-2.5 parts of a polycarboxylic acid water reducing agent, 0.01-0.05 part of graphene, 0.008-0.04 part of graphene oxide and 170-200 parts of water;
the acid-ether molar ratio of the polycarboxylate superplasticizer is (2-6) to 1.
2. The graphene suspension according to claim 1, wherein the preparation method of the polycarboxylate superplasticizer comprises the following steps: mixing a polyether monomer with water to obtain a solution A; mixing thioglycolic acid and mercaptopropionic acid to obtain a mixed solution, and mixing the mixed solution, an acrylic monomer and water to obtain a solution B; mixing isoascorbic acid and water to obtain solution C; and adding the solution B and the solution C into the solution A to react to obtain the polycarboxylate superplasticizer.
3. The graphene suspension according to claim 2, wherein the polyether monomer is selected from one or more of allyl alcohol polyoxyethylene ether, polyoxypropylene ether, prenol polyoxyethylene ether and isobutenol polyoxyethylene ether; the acrylic monomer is selected from one or more of methacrylic acid, acrylic acid or acrylate.
4. The graphene suspension according to claim 2, wherein the mass ratio of the polyether monomer to water in the solution A is (0.5-1.5) to 1, and the molar ratio of the acrylic monomer to the polyether monomer is (2-6) to 1; the mass ratio of the thioglycolic acid to the mercaptopropionic acid is 1: 1-1.2; the mass ratio of the acrylic monomer, the mixed liquid of thioglycolic acid and mercaptopropionic acid and water in the solution B is 1: 0.005-0.03: 0.2-0.8; the mass ratio of the isoascorbic acid to the water in the solution C is (0.005-0.2) to (0.5-2).
5. The graphene suspension according to claim 2, wherein the mass ratio of the solution A, the solution B and the solution C is (1.5-2.5): (1.205-9.83): (0.505-2.2).
6. The graphene suspension according to claim 2, wherein the reaction temperature is 25-65 ℃, the reaction time is 1-6 h, and the method further comprises the steps of preserving heat for 1-3 h after the reaction is finished, adjusting the pH to 6.5-7.5, and diluting to a solid content of 18-22 wt%.
7. A preparation method of the graphene suspension liquid as claimed in any one of claims 1 to 6, characterized by comprising the following steps: weighing a polycarboxylic acid water reducing agent, graphene oxide and water according to parts by weight, and adding the graphene oxide into the water to obtain a graphene oxide solution; and mixing graphene with the graphene oxide solution, adding the balance of water, performing ultrasonic treatment, adding a polycarboxylic acid water reducing agent, and performing ultrasonic treatment again to obtain the graphene suspension.
8. The preparation method according to claim 7, wherein the concentration of the graphene oxide solution is 3.8-4.2 mg/mL.
9. Use of the graphene suspension according to any one of claims 1 to 6 in a cement-based material.
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