CN111392721A - Graphene oxide dispersion liquid and preparation method and application thereof - Google Patents
Graphene oxide dispersion liquid and preparation method and application thereof Download PDFInfo
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- CN111392721A CN111392721A CN202010224248.1A CN202010224248A CN111392721A CN 111392721 A CN111392721 A CN 111392721A CN 202010224248 A CN202010224248 A CN 202010224248A CN 111392721 A CN111392721 A CN 111392721A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 165
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 164
- 239000006185 dispersion Substances 0.000 title claims abstract description 92
- 239000007788 liquid Substances 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 131
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000004021 humic acid Substances 0.000 claims abstract description 82
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 69
- 239000011083 cement mortar Substances 0.000 claims abstract description 32
- 229920005646 polycarboxylate Polymers 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 64
- 239000002253 acid Substances 0.000 claims description 63
- 238000002156 mixing Methods 0.000 claims description 41
- 239000002994 raw material Substances 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 17
- 238000010907 mechanical stirring Methods 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- 239000004570 mortar (masonry) Substances 0.000 abstract description 10
- 239000011575 calcium Substances 0.000 abstract description 9
- 229910052791 calcium Inorganic materials 0.000 abstract description 6
- 230000015271 coagulation Effects 0.000 abstract description 5
- 238000005345 coagulation Methods 0.000 abstract description 5
- 239000004568 cement Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 16
- 238000002835 absorbance Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 9
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000004576 sand Substances 0.000 description 6
- 238000006703 hydration reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 230000036571 hydration Effects 0.000 description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002500 ions Chemical group 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
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- 238000001514 detection method Methods 0.000 description 1
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- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
-
- 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
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/022—Carbon
- C04B14/024—Graphite
-
- 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
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/02—Treatment
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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
- 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
-
- 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
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- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
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Abstract
The invention provides a graphene oxide dispersion liquid, which comprises the following components: pure water, graphene oxide, a polycarboxylate water reducing agent and humic acid, wherein the mass of the pure water is greater than that of the polycarboxylate water reducing agent and the mass of the graphene oxide or the humic acid. The high-dispersity graphene oxide dispersion liquid provided by the application can obviously increase the stable dispersion of graphene oxide in a high-calcium and high-alkalinity environment, and can still ensure that the graphene oxide dispersion liquid has high dispersity; the mechanical property of the mortar can be obviously improved by using the dispersion liquid to blend cement mortar, and the flexural strength and the compressive strength of the mortar can be greatly improved by 28 days. The application also provides a preparation method of the graphene oxide dispersion liquid, which can prevent the graphene oxide from coagulation in advance, so that the graphene oxide dispersion liquid with higher dispersibility can be prepared.
Description
Technical Field
The invention relates to the technical field of building materials, in particular to a graphene oxide dispersion liquid, a preparation method thereof and application of the graphene oxide dispersion liquid in preparation of modified cement mortar.
Background
Graphene is a novel two-dimensional nano material, which is successfully separated from graphite in 2004 by scientists such as Novoseov and Geim, and not only has very high tensile strength and elastic modulus, but also has excellent electric conductivity, heat conductivity and super-large specific surface area. The graphene oxide is a product of graphene after oxidation treatment, inherits many excellent performances of graphene, such as high tensile strength, large specific surface area, better hydrophilicity and low price, and is non-conductive, so that the graphene oxide is more suitable for being compounded with a cement-based material than other nano materials, and the tensile strength, the flexural strength, the compressive strength and the like of the cement-based composite material (cement paste, cement mortar and concrete) are fundamentally improved. Meanwhile, the proper doping of the graphene oxide improves the micro-pore structure of the cement-based composite material, and improves the chloride ion permeation resistance, carbonization resistance, freezing resistance and the like of the cement-based composite material.
When graphene oxide is in a high-concentration calcium ion and a strong alkaline environment (high-calcium and high-alkaline environment), a serious coagulation phenomenon may occur. This is because the graphene oxide colloid structure can be destroyed in both calcium ions and strong alkaline environment, and the cement hydration medium is a typical high-calcium and high-alkaline environment. When graphene oxide is added into cement paste, carboxyl groups on the surface of the graphene oxide and a large amount of Ca generated in the hydration process of the cement2+A cross-linking reaction occurs, which destroys the stability between graphene oxide nanosheets and leads to coagulation. In order to exert the excellent reinforcing and toughening effects of the graphene oxide on the cement-based material, the stable dispersing capacity of the graphene oxide in a cement hydration medium must be improved.
At present, a polycarboxylic acid water reducing agent is mainly used for research on blending of graphene oxide with a cement-based material as a dispersing agent of the graphene oxide (such as CN201711373540.4, a low-cost graphene oxide mortar and a preparation method thereof, CN201711373555.0, a high-breaking-strength graphene oxide mortar and a preparation method thereof) and a method for blending fly ash (such as CN201711390304.3, a fly ash-blended graphene oxide concrete and a preparation method thereof). However, the polycarboxylic acid water reducing agent or the fly ash has no structural similarity with the graphene oxide, so that the excellent performance of the graphene oxide cannot be fully exerted in the high-calcium and high-alkalinity environment. Therefore, it is necessary to research a graphene oxide dispersion liquid which can significantly increase the stable dispersion capability of graphene oxide and retain the excellent performance of graphene oxide.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a graphene oxide dispersion liquid, which remarkably increases the dispersion performance of graphene oxide on the basis of keeping the game performance of graphene oxide. Meanwhile, the application also provides a preparation method of the graphene oxide dispersion liquid and application of the graphene oxide dispersion liquid in preparation of modified cement mortar.
In order to solve the technical problem, the invention provides the following scheme: a graphene oxide dispersion comprising: pure water, graphene oxide, a polycarboxylate water reducing agent and humic acid, wherein the mass of the pure water is greater than that of the polycarboxylate water reducing agent and the mass of the graphene oxide or the humic acid.
Further, the mass ratio of the humic acid to the graphene oxide is 1.5: 1.
Further, the coating comprises the following components in parts by mass: 1000 parts of pure water, 0.5 part of graphene oxide, 1 part of polycarboxylic acid water reducing agent and 0.25-1.25 parts of humic acid.
Further, the coating comprises the following components in parts by mass: 1000 parts of pure water, 0.5 part of graphene oxide, 1 part of polycarboxylic acid water reducing agent and 0.75 part of humic acid.
Further, the coating comprises the following components in parts by mass: 110.3-156.5 parts of pure water, 0.047-0.23 part of graphene oxide, 1.8 parts of polycarboxylic acid water reducing agent and 0.07-0.34 part of humic acid.
Further, the coating comprises the following components in parts by mass: 156.5 parts of pure water, 0.047 part of graphene oxide, 1.8 parts of polycarboxylic acid water reducing agent and 0.07 part of humic acid.
The application further provides a method for preparing the graphene oxide dispersion liquid, which comprises the following steps:
s1: preparing raw materials in parts by weight: 1000 parts of pure water, 0.5 part of graphene oxide, 1 part of polycarboxylic acid water reducing agent and 0.25-1.25 parts of humic acid;
s2: adding the polycarboxylic acid water reducing agent and humic acid in S1 into pure water, mixing and stirring in a mechanical stirring mode, wherein the stirring speed is 2000-3000 r/min;
s3: and adding the rest raw material graphene oxide in the S1 into the product obtained in the S2, and uniformly mixing to obtain the finished product dispersion liquid.
Meanwhile, the application further provides a method for preparing the graphene oxide dispersion liquid, which comprises the following steps:
s1: preparing raw materials in parts by weight: 1.8 parts of polycarboxylic acid water reducing agent, 0.07-0.34 part of humic acid, 110.3-156.5 parts of pure water and 0.047-0.23 part of graphene oxide,
s2: adding the polycarboxylic acid water reducing agent in S1 and humic acid into pure water, mixing and stirring;
s3: and adding the rest raw material graphene oxide in the S1 into the product obtained in the S2, mixing and uniformly stirring, wherein the mass ratio of humic acid to graphene oxide is 1.5:1, and thus obtaining the finished dispersion liquid.
Further, in step S3, the stirring manner is ultrasonic dispersion.
The application further provides an application of the graphene oxide dispersion liquid in preparation of modified cement mortar.
Humic acid is a natural substance in nature, the basic molecular structure of the humic acid is aromatic ring and alicyclic ring, the ring is connected with functional groups such as carboxyl, hydroxyl, carbonyl, quinonyl, methoxyl and the like, and the hydroxyl can be matched with Ca in cement2+The ions form unstable complex, and Ca in liquid phase is controlled at the initial stage of cement hydration2+The concentration of ions generates a retarding effect, so that the stability among graphene oxide nanosheets cannot be damaged to cause coagulation; as the benzene ring structure unit in the humic acid molecule can form a conjugation effect with the graphene oxide, the graphene oxide is adsorbed on the surface of the graphene oxide, so that the electronegativity of the graphene oxide is enhanced, the graphene oxide is prevented from agglomerating, and the prepared graphene oxide solution has high dispersibility.
The invention has the beneficial effects that: the high-dispersity graphene oxide dispersion liquid provided by the application can obviously increase the stable dispersion of graphene oxide in a high-calcium and high-alkalinity environment, and can still ensure that the graphene oxide dispersion liquid has high dispersity; the mechanical property of the mortar can be obviously improved by using the dispersion liquid to blend cement mortar, and the flexural strength and the compressive strength of the mortar can be greatly improved by 28 days. The application also provides a preparation method of the graphene oxide dispersion liquid, which can prevent the graphene oxide from coagulation in advance, so that the graphene oxide dispersion liquid with higher dispersibility can be prepared.
Drawings
FIG. 1 is an absorbance test chart of examples one to five of the present application and comparative example one;
Detailed Description
The present invention is further described below in conjunction with specific examples so that those skilled in the art may better understand the present invention and practice it. The following discloses many different embodiments or examples for implementing the subject technology described. Specific examples of one or more arrangements of features presented below are set forth to simplify the disclosure, but are not intended to limit the invention.
Example one
A graphene oxide dispersion liquid comprises the following components in parts by mass: 1000 parts of pure water, 0.5 part of graphene oxide, 1 part of polycarboxylic acid water reducing agent and 0.25 part of humic acid.
The method for preparing the graphene hair dispersion liquid comprises the following steps:
s1: preparing raw materials in parts by weight: 1000 parts of pure water, 0.5 part of graphene oxide, 1 part of polycarboxylic acid water reducing agent and 0.25 part of humic acid;
s2: adding the polycarboxylic acid water reducing agent and humic acid in S1 into pure water at room temperature, mixing and stirring in a mechanical stirring mode at the stirring speed of 2000 r/min;
s3: and adding the rest raw material graphene oxide in the S1 into the product obtained in the S2, and uniformly mixing to obtain the finished product dispersion liquid.
Example two
A graphene oxide dispersion liquid comprises the following components in parts by mass: 1000 parts of pure water, 0.5 part of graphene oxide, 1 part of polycarboxylic acid water reducing agent and 0.5 part of humic acid.
The method for preparing the graphene hair dispersion liquid comprises the following steps:
s1: preparing raw materials in parts by weight: 1000 parts of pure water, 0.5 part of graphene oxide, 1 part of polycarboxylic acid water reducing agent and 0.5 part of humic acid;
s2: adding the polycarboxylic acid water reducing agent and humic acid in S1 into pure water at room temperature, mixing and stirring in a mechanical stirring mode at the stirring speed of 3000 r/min;
s3: and adding the rest raw material graphene oxide in the S1 into the product obtained in the S2, and uniformly mixing to obtain the finished product dispersion liquid.
EXAMPLE III
A graphene oxide dispersion liquid comprises the following components in parts by mass: 1000 parts of pure water, 0.5 part of graphene oxide, 1 part of polycarboxylic acid water reducing agent and 0.75 part of humic acid.
The method for preparing the graphene hair dispersion liquid comprises the following steps:
s1: preparing raw materials in parts by weight: 1000 parts of pure water, 0.5 part of graphene oxide, 1 part of polycarboxylic acid water reducing agent and 0.75 part of humic acid;
s2: adding the polycarboxylic acid water reducing agent and humic acid in S1 into pure water at room temperature, mixing and stirring in a mechanical stirring mode at the stirring speed of 2500 r/min;
s3: and adding the rest raw material graphene oxide in the S1 into the product obtained in the S2, and uniformly mixing to obtain the finished product dispersion liquid.
Example four
A graphene oxide dispersion liquid comprises the following components in parts by mass: 1000 parts of pure water, 0.5 part of graphene oxide, 1 part of polycarboxylic acid water reducing agent and 1 part of humic acid.
The method for preparing the graphene hair dispersion liquid comprises the following steps:
s1: preparing raw materials in parts by weight: 1000 parts of pure water, 0.5 part of graphene oxide, 1 part of polycarboxylic acid water reducing agent and 1 part of humic acid;
s2: adding the polycarboxylic acid water reducing agent and humic acid in S1 into pure water at room temperature, mixing and stirring in a mechanical stirring mode at the stirring speed of 2000 r/min;
s3: and adding the rest raw material graphene oxide in the S1 into the product obtained in the S2, and uniformly mixing to obtain the finished product dispersion liquid.
EXAMPLE five
A graphene oxide dispersion liquid comprises the following components in parts by mass: 1000 parts of pure water, 0.5 part of graphene oxide, 1 part of polycarboxylic acid water reducing agent and 1.25 parts of humic acid.
The method for preparing the graphene hair dispersion liquid comprises the following steps:
s1: preparing raw materials in parts by weight: 1000 parts of pure water, 0.5 part of graphene oxide, 1 part of polycarboxylic acid water reducing agent and 1.25 parts of humic acid;
s2: adding the polycarboxylic acid water reducing agent and humic acid in S1 into pure water at room temperature, mixing and stirring in a mechanical stirring mode at the stirring speed of 3000 r/min;
s3: and adding the rest raw material graphene oxide in the S1 into the product obtained in the S2, and uniformly mixing to obtain the finished product dispersion liquid.
In order to prove that the dispersion effect of the humic acid on the graphene oxide is increased, namely that the graphene oxide can be better dispersed by increasing the humic acid, a comparative example is arranged for comparison.
Comparative example 1
A graphene oxide dispersion liquid comprises the following components in parts by mass: 1000 parts of pure water, 0.5 part of graphene oxide and 1 part of polycarboxylic acid water reducing agent.
The method for preparing the graphene hair dispersion liquid comprises the following steps:
s1: preparing raw materials in parts by weight: 1000 parts of pure water, 0.5 part of graphene oxide and 1 part of polycarboxylic acid water reducing agent;
s2: at room temperature, adding the polycarboxylic acid water reducing agent in S1 into pure water, mixing and stirring in a mechanical stirring mode at the stirring speed of 2000 r/min;
s3: and adding the rest raw material graphene oxide in the S1 into the product obtained in the S2, and uniformly mixing to obtain the finished product dispersion liquid.
Meanwhile, background liquids corresponding to examples one to five were prepared as comparative examples, in which the quality of humic acid added was kept in agreement with the dispersions prepared in examples one to five. The purpose of the test is not to be used, in order to ensure the accuracy of the tests of the first to fifth examples and the first comparative example, when the absorbance is tested, the zero point needs to be corrected by using the background liquid, and then the test is carried out.
EXAMPLE six
The method for preparing the background liquid comprises the following steps:
s1: preparing raw materials in parts by weight: 1000 parts of pure water, 1 part of polycarboxylic acid water reducing agent and 0.25 part of humic acid;
s2: adding the polycarboxylic acid water reducing agent in S1 and humic acid into pure water at room temperature, mixing and stirring to obtain a first background liquid.
EXAMPLE seven
The method for preparing the background liquid comprises the following steps:
s1: preparing raw materials in parts by weight: 1000 parts of pure water, 1 part of polycarboxylic acid water reducing agent and 0.5 part of humic acid;
s2: and adding the polycarboxylic acid water reducing agent in the S1 and the humic acid into pure water at room temperature, mixing and stirring to obtain a second background liquid.
Example eight
The method for preparing the background liquid comprises the following steps:
s1: preparing raw materials in parts by weight: 1000 parts of pure water, 1 part of polycarboxylic acid water reducing agent and 0.75 part of humic acid;
s2: and adding the polycarboxylic acid water reducing agent in the S1 and the humic acid into pure water at room temperature, mixing and stirring to obtain a third background liquid.
Example nine
The method for preparing the background liquid comprises the following steps:
s1: preparing raw materials in parts by weight: 1000 parts of pure water, 1 part of polycarboxylic acid water reducing agent and 1 part of humic acid;
s2: and adding the polycarboxylic acid water reducing agent in the S1 and the humic acid into pure water at room temperature, mixing and stirring to obtain a background liquid IV.
Example ten
The method for preparing the background liquid comprises the following steps:
s1: preparing raw materials in parts by weight: 1000 parts of pure water, 1 part of polycarboxylic acid water reducing agent and 1.25 parts of humic acid;
s2: and adding the polycarboxylic acid water reducing agent in the S1 and the humic acid into pure water at room temperature, mixing and stirring to obtain a background liquid V.
And (3) carrying out an absorbance experiment on the first to fifth examples and the first comparative example, adding 1.6 parts by mass of calcium hydroxide into the dispersions prepared in the first to fifth examples and the first comparative example, continuously stirring for 3min at room temperature, standing for 10min, and testing the absorbance. Similarly, 1.6 parts by weight of calcium hydroxide is added to the background liquid prepared in the sixth to tenth examples, and the mixture is stirred at room temperature for 3min and then kept stand for 10min for detection.
The specific compositions of the test solution and the background solution for absorbance are shown in table 1.
TABLE 1 Absorbance test substance ratios
A saturated calcium hydroxide solution is used for simulating a high-calcium and high-alkalinity cement hydration environment, and a purple light visible light spectrometry method is adopted to test the absorbance of the graphene oxide under the wavelength of 230nm so as to represent the dispersion capacity of the graphene oxide.
As for the absorbance of the graphene oxide dispersion liquid in saturated calcium hydroxide, referring to fig. 1, the absorbance of a6-a10 was greater than that of a0 among the absorbance of 6 samples at 1h, and it was found that the ratio of humic acid: the mass ratio of the graphene oxide is 0.5:1, 1:1, 1.5:1, 2:1 and 2.5:1, and the absorbance of the graphene oxide dispersion liquid in a saturated calcium hydroxide solution can be improved. This shows that the dispersion liquid mixed by additionally adding humic acid can improve the stable dispersing ability of graphene oxide in the saturated calcium hydroxide solution. Specifically, the absorbance values were arranged in the order of A8 > A9 > A10 > A7 > A6 > A0. Therefore, the absorbance of the A0 dispersion liquid not doped with humic acid is lowest, and the absorbance of the graphene oxide in the saturated calcium hydroxide solution is increased after the humic acid is added, which shows that the dispersion liquid formed by additionally adding the humic acid and mixing the humic acid can improve the stable dispersing capacity of the graphene oxide in the saturated calcium hydroxide solution, wherein when the mass ratio of the humic acid to the graphene oxide is 1.5:1, the absorbance is highest, the dispersion of the graphene oxide is optimal, and the dispersion effect of the graphene oxide is the best.
In order to verify that the dispersion capability of the graphene oxide can be improved and the cement-based material can be reinforced and toughened, the application of the graphene oxide dispersion liquid in the preparation of the modified cement mortar is continuously researched.
EXAMPLE eleven
A manufacturing method of modified cement mortar comprises the following steps:
s1: preparing raw materials in parts by weight: 1.8 parts of polycarboxylic acid water reducing agent, 0.07 part of humic acid, 156.5 parts of pure water and 0.047 part of graphene oxide, namely the mass ratio of the humic acid to the graphene oxide is 1.5: 1;
s2: adding the polycarboxylic acid water reducing agent in S1 and humic acid into pure water, mixing and stirring;
s3: adding the rest raw material graphene oxide in the S1 into the product obtained in the S2, mixing and uniformly stirring in an ultrasonic dispersion mode for 3-5min to obtain a finished dispersion liquid;
s4: and pouring the finished dispersion liquid in the step S3 into a stirring pot, adding 450 parts by mass of cement, adjusting a stirring machine to an automatic stirring mode, stirring for 30 seconds, and slowly adding 1350 parts by mass of standard sand to obtain the finished cement mortar.
Example twelve
A manufacturing method of modified cement mortar comprises the following steps:
s1: preparing raw materials in parts by weight: 1.8 parts of polycarboxylic acid water reducing agent, 0.20 part of humic acid, 133 parts of pure water and 0.13 part of graphene oxide, namely the mass ratio of the humic acid to the graphene oxide is 1.5: 1;
s2: adding the polycarboxylic acid water reducing agent in S1 and humic acid into pure water, mixing and stirring;
s3: adding the rest raw material graphene oxide in the S1 into the product obtained in the S2, mixing and uniformly stirring in an ultrasonic dispersion mode for 3-5min to obtain a finished dispersion liquid;
s4: and pouring the finished dispersion liquid in the step S3 into a stirring pot, adding 450 parts by mass of cement, adjusting a stirring machine to an automatic stirring mode, stirring for 30 seconds, and slowly adding 1350 parts by mass of standard sand to obtain the finished cement mortar.
EXAMPLE thirteen
A manufacturing method of modified cement mortar comprises the following steps:
s1: preparing raw materials in parts by weight: 1.8 parts of polycarboxylic acid water reducing agent, 0.34 part of humic acid, 110.3 parts of pure water and 0.23 part of graphene oxide, wherein the mass ratio of the humic acid to the graphene oxide is 1.5: 1;
s2: adding the polycarboxylic acid water reducing agent in S1 and humic acid into pure water, mixing and stirring;
s3: adding the rest raw material graphene oxide in the S1 into the product obtained in the S2, mixing and uniformly stirring in an ultrasonic dispersion mode for 3-5min to obtain a finished dispersion liquid;
s4: and pouring the finished dispersion liquid in the step S3 into a stirring pot, adding 450 parts by mass of cement, adjusting a stirring machine to an automatic stirring mode, stirring for 30 seconds, and slowly adding 1350 parts by mass of standard sand to obtain the finished cement mortar.
In order to prove that the cement-based material can be reinforced and toughened by adding humic acid, a comparative example is set for comparison.
Comparative example No. two
A manufacturing method of modified cement mortar comprises the following steps:
s1: preparing raw materials in parts by weight: 1.8 parts of a polycarboxylic acid water reducing agent, 156.5 parts of pure water and 0.047 part of graphene oxide;
s2: adding the polycarboxylic acid water reducing agent in the S1 into pure water, mixing and stirring;
s3: adding the rest raw material graphene oxide in the S1 into the product obtained in the S2, mixing and uniformly stirring in an ultrasonic dispersion mode for 3-5min to obtain a finished dispersion liquid;
s4: and pouring the finished dispersion liquid in the step S3 into a stirring pot, adding 450 parts by mass of cement, adjusting a stirring machine to an automatic stirring mode, stirring for 30 seconds, and slowly adding 1350 parts by mass of standard sand to obtain the finished cement mortar.
Comparative example No. three
A manufacturing method of modified cement mortar comprises the following steps:
s1: preparing raw materials in parts by weight: 1.8 parts of a polycarboxylic acid water reducing agent, 133 parts of pure water and 0.13 part of graphene oxide;
s2: adding the polycarboxylic acid water reducing agent in the S1 into pure water, mixing and stirring;
s3: adding the rest raw material graphene oxide in the S1 into the product obtained in the S2, mixing and uniformly stirring in an ultrasonic dispersion mode for 3-5min to obtain a finished dispersion liquid;
s4: and pouring the finished dispersion liquid in the step S3 into a stirring pot, adding 450 parts by mass of cement, adjusting a stirring machine to an automatic stirring mode, stirring for 30 seconds, and slowly adding 1350 parts by mass of standard sand to obtain the finished cement mortar.
Comparative example No. four
A manufacturing method of modified cement mortar comprises the following steps:
s1: preparing raw materials in parts by weight: 1.8 parts of a polycarboxylic acid water reducing agent, 110.3 parts of pure water and 0.23 part of graphene oxide;
s2: adding the polycarboxylic acid water reducing agent in the S1 into pure water, mixing and stirring;
s3: adding the rest raw material graphene oxide in the S1 into the product obtained in the S2, mixing and uniformly stirring in an ultrasonic dispersion mode for 3-5min to obtain a finished dispersion liquid;
s4: and pouring the finished dispersion liquid in the step S3 into a stirring pot, adding 450 parts by mass of cement, adjusting a stirring machine to an automatic stirring mode, stirring for 30 seconds, and slowly adding 1350 parts by mass of standard sand to obtain the finished cement mortar.
The preparation of examples eleven to thirteen and of ratios two to four is carried out strictly in accordance with the requirements of the GB/T17671-1999 Specification; the finished cement mortars prepared in examples eleven to thirteen and comparative examples two to four were then subjected to mechanical strength tests strictly according to the requirements of GB/T17671-1999 specification, giving Table 2:
TABLE 2 Cement mortar mixing proportion and mechanical properties thereof
As shown in Table 2, the 28d compressive strength and the 28d flexural strength of the cement mortar (comparative example II) prepared by mixing 0.047 parts of graphene oxide with the polycarboxylic acid water reducer as the dispersing agent are respectively 8.23MPa and 49.43 MPa; after the relative humic acid is added for composite dispersion, the flexural strength and the compressive strength of the mortar (example eleven) are respectively improved by 32 percent and 25 percent and respectively reach 10.83Mpa and 61.96 Mpa;
similarly, only a polycarboxylic acid water reducing agent is used as a dispersion liquid of a dispersing agent, 0.013 part of graphene oxide cement mortar is mixed (comparative example three), and the 28d compression strength and the flexural strength of the cement mortar are respectively 8.97Mpa and 53.25 Mpa; after the relative humic acid is added for composite dispersion, the flexural strength and the compressive strength of the mortar (example twelve) are respectively improved by 9 percent and 12 percent and respectively reach 9.82Mpa and 59.82 Mpa;
similarly, only a polycarboxylic acid water reducing agent is used as a dispersion liquid of a dispersing agent, 0.023 part of graphene oxide cement mortar is mixed (comparative example four), and the 28d compressive strength and the 28d flexural strength of the cement mortar are respectively 8.51Mpa and 51.87 Mpa; after the relative humic acid is added for composite dispersion, the flexural strength and the compressive strength of the mortar (embodiment thirteen) are respectively improved by 13 percent and 8 percent and respectively reach 9.69Mpa and 56.28 Mpa.
The mass part unit in the examples and the comparative examples is g.
In conclusion, the dispersion liquid additionally added with the humic acid can promote the stable dispersion of the graphene oxide in the cement mortar, so that the mechanical property of the mortar is improved, wherein when the mass of the graphene oxide is 0.047 parts, the mass of the polycarboxylic acid water reducing agent is 1.8 parts, and the mass of the humic acid is 0.07 parts, namely the mass of the humic acid and the graphene oxide is 1.5:1, the dispersion liquid has the best promotion effect on the cement mortar, and the mechanical property of the cement mortar can be remarkably promoted.
According to the invention, humic acid and polycarboxylic acid water reducing agent are adopted to prepare highly dispersed graphene oxide solution, and as the benzene ring structural unit in the humic acid molecule can form a conjugation effect with graphene oxide, the graphene oxide is adsorbed on the surface of the graphene oxide, so that the electronegativity of the graphene oxide is enhanced, the graphene oxide is prevented from agglomerating, and the prepared graphene oxide solution has high dispersibility. And tests show that the mechanical property of the cement mortar can be obviously improved by adding the dispersion liquid into the cement mortar.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (10)
1. A graphene oxide dispersion liquid, comprising: pure water, graphene oxide, a polycarboxylate water reducing agent and humic acid, wherein the mass of the pure water is greater than that of the polycarboxylate water reducing agent and the mass of the graphene oxide or the humic acid.
2. The graphene oxide dispersion liquid according to claim 1, wherein the mass ratio of the humic acid to the graphene oxide is 1.5: 1.
3. The graphene oxide dispersion liquid according to claim 1, comprising, in parts by mass: 1000 parts of pure water, 0.5 part of graphene oxide, 1 part of polycarboxylic acid water reducing agent and 0.25-1.25 parts of humic acid.
4. The graphene oxide dispersion liquid according to claim 3, comprising 1000 parts by mass of pure water, 0.5 part by mass of graphene oxide, 1 part by mass of a polycarboxylic acid water reducing agent, and 0.75 part by mass of humic acid.
5. The graphene oxide dispersion liquid according to claim 1, comprising, in parts by mass: 110.3-156.5 parts of pure water, 0.047-0.23 part of graphene oxide, 1.8 parts of polycarboxylic acid water reducing agent and 0.07-0.34 part of humic acid.
6. The graphene oxide dispersion liquid of claim 5, comprising, in parts by mass: 156.5 parts of pure water, 0.047 part of graphene oxide, 1.8 parts of polycarboxylic acid water reducing agent and 0.07 part of humic acid.
7. A preparation method of a graphene oxide dispersion liquid is characterized by comprising the following steps:
s1: preparing raw materials in parts by weight: 1000 parts of pure water, 0.5 part of graphene oxide, 1 part of polycarboxylic acid water reducing agent and 0.25-1.25 parts of humic acid;
s2: adding the polycarboxylic acid water reducing agent and humic acid in S1 into pure water, mixing and stirring in a mechanical stirring mode, wherein the stirring speed is 2000-3000 r/min;
s3: and adding the rest raw material graphene oxide in the S1 into the product obtained in the S2, and uniformly mixing to obtain the finished product dispersion liquid.
8. A preparation method of a graphene oxide dispersion liquid is characterized by comprising the following steps:
s1: preparing raw materials in parts by weight: 1.8 parts of polycarboxylic acid water reducing agent, 0.07-0.34 part of humic acid, 110.3-156.5 parts of pure water and 0.047-0.23 part of graphene oxide,
s2: adding the polycarboxylic acid water reducing agent in S1 and humic acid into pure water, mixing and stirring;
s3: and adding the rest raw material graphene oxide in the S1 into the product obtained in the S2, mixing and uniformly stirring, wherein the mass ratio of humic acid to graphene oxide is 1.5:1, and thus obtaining the finished dispersion liquid.
9. The method according to claim 8, wherein in step S3, the stirring is performed by ultrasonic dispersion.
10. Use of the graphene oxide dispersion liquid according to claim 5 or 6 in the preparation of modified cement mortar.
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