CN107473622A - Graphene oxide/polycarboxylate water-reducer and preparation method thereof - Google Patents
Graphene oxide/polycarboxylate water-reducer and preparation method thereof Download PDFInfo
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- CN107473622A CN107473622A CN201710887726.5A CN201710887726A CN107473622A CN 107473622 A CN107473622 A CN 107473622A CN 201710887726 A CN201710887726 A CN 201710887726A CN 107473622 A CN107473622 A CN 107473622A
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- graphene oxide
- reducer
- polycarboxylate water
- water
- mass fraction
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The present invention relates to Material Field, in particular to a kind of graphene oxide/polycarboxylate water-reducer and preparation method thereof.The APEO aqueous solution that mass fraction is 30 40% and the graphene oxide water solution that mass fraction is 1 3% are well mixed at 20 30 DEG C substrate liquid is made；Mixing quality ratio is 28:25‑30:2000 ascorbic acid, TGA and water obtains mixed solution.21 34% hydrogen peroxide and stabilizer that mixed solution, the acrylic acid aqueous solution that mass fraction is 27 34%, mass fraction are are added in basad liquid；It is well mixed.Graphene oxide/polycarboxylate water-reducer that the present invention is prepared can influence the microstructure of hydrated product in concrete from microcosmic point, the polycarboxylic acids finally given is interspersed in the interlayer structure of graphene oxide, the problem of improving distress in concrete and porosity, the compactness for improving cement-based material improve the seepage-resistant grade of concrete.
Description
Technical field
The present invention relates to Material Field, in particular to a kind of graphene oxide/polycarboxylate water-reducer and its preparation side
Method.
Background technology
The cementing integral engineered composite material of aggregate is referred to as concrete by binder materials, in concreting process
Or gap and stomata can be formed after casting process；Gap and stomata can decline the service life of concrete；And it can lead
The steel construction of inside concrete is caused to be damaged.
In underground cushion construction region, it is necessary to using polymer concrete, to improve the impervious effect of concrete integral anti-freezing.
It is bituminous concrete currently for the most popular polymer concrete of this problem, its freeze proof impervious effect is good, and price
Suitably.But the drawbacks of bituminous concrete maximum is that its viscosity is excessive, it can not mix and stir and pump well, it is more difficult to accomplish
The effect of self-compaction.
So inventor invents a kind of inside density that can improve concrete, the coagulation of space and stomata is reduced
Soil additive.
The content of the invention
It is an object of the invention to provide a kind of graphene oxide/polycarboxylate water-reducer and preparation method thereof, it is intended to change
Kind scattering problem of the graphene oxide in cement-based material, while concrete pore and microcrack are reduced, improve compactness.
The present invention provides a kind of technical scheme：
A kind of preparation method of graphene oxide/polycarboxylate water-reducer, it includes：
The graphene oxide water for being 1-3% with mass fraction by the APEO aqueous solution that mass fraction is 30-40%
Solution is in 20-30 DEG C of well mixed obtained substrate liquid；Wherein the mass ratio of APEO and graphene oxide is 70:2-6.
Mixing quality ratio is 2-8:25-30:2000 ascorbic acid, TGA and water obtains mixed solution.
Mixed solution, the acrylic acid aqueous solution that mass fraction is 27-34%, mass fraction are added in basad liquid
21-34% hydrogen peroxide and stabilizer；It is well mixed.
In other embodiments of the invention, it is above-mentioned that mixed solution, acrylic acid aqueous solution are slowly added in substrate liquid,
Hydrogen peroxide and stabilizer are added while dropwise addition.
In other embodiments of the invention, the volume ratio of above-mentioned mixed solution, acrylic acid aqueous solution and substrate liquid is
1-3.5:1-3.5:13。
In other embodiments of the invention, the mass fraction of the above-mentioned APEO aqueous solution is 35%.
In other embodiments of the invention, the mass fraction of above-mentioned graphene oxide water solution is 1%.
In other embodiments of the invention, in above-mentioned mixed solution ascorbic acid, TGA and water mass ratio
For 3:27:2000.
In other embodiments of the invention, the volume ratio of above-mentioned mixed solution, acrylic acid aqueous solution and substrate liquid is
2:2:13。
In other embodiments of the invention, aforementioned stable agent is that mass ratio is 1:0.8-1.2 sodium ascorbate and chlorine
Change ferrous.
In other embodiments of the invention, aforementioned stable agent is that mass ratio is 1:1 sodium ascorbate and frerrous chloride.
The present invention also provides a kind of technical scheme：
A kind of graphene oxide/polycarboxylate water-reducer, it passes through the preparation of above-mentioned graphene oxide/polycarboxylate water-reducer
Method is made.
The beneficial effect of graphene oxide/polycarboxylate water-reducer provided in an embodiment of the present invention and preparation method thereof is：
The graphene oxide that the preparation method of graphene oxide/polycarboxylate water-reducer provided by the invention is prepared/poly-
Carboxylic acid water reducer can influence the microstructure of hydrated product in concrete from microcosmic point, and the polycarboxylic acids finally given is interspersed in oxygen
In the interlayer structure of graphite alkene, the problem of so as to improve the crack of concrete and porosity, the cause of cement-based material is improved
Close property improves the seepage-resistant grade of concrete.
Brief description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below by embodiment it is required use it is attached
Figure is briefly described, it will be appreciated that the following drawings illustrate only certain embodiments of the present invention, therefore be not construed as pair
The restriction of scope, for those of ordinary skill in the art, on the premise of not paying creative work, can also be according to this
A little accompanying drawings obtain other related accompanying drawings.
Fig. 1 is each glue sand test block pressure resistance intensity result figure in test example 3；
Fig. 2 is the scanning electron microscope (SEM) photograph of blank control group in test example 3；
Fig. 3 is that 1 group of scanning electron microscope (SEM) photograph is tested in test example 3；
Fig. 4 is that 2 groups of scanning electron microscope (SEM) photograph is tested in test example 3；
Fig. 5 is that 3 groups of scanning electron microscope (SEM) photograph is tested in test example 3.
Embodiment
, below will be in the embodiment of the present invention to make the purpose, technical scheme and advantage of the embodiment of the present invention clearer
Technical scheme be clearly and completely described.Unreceipted actual conditions person, builds according to normal condition or manufacturer in embodiment
The condition of view is carried out.Agents useful for same or the unreceipted production firm person of instrument, it is the conventional production that can be obtained by commercially available purchase
Product.
Graphene oxide/polycarboxylate water-reducer of the embodiment of the present invention and preparation method thereof is specifically described below.
A kind of preparation method of graphene oxide/polycarboxylate water-reducer, it includes：
The graphene oxide water for being 1-3% with mass fraction by the APEO aqueous solution that mass fraction is 30-40%
Solution is in 20-30 DEG C of well mixed obtained substrate liquid；Wherein, the mass ratio of APEO and graphene oxide is 70:2-6.
Mixing quality ratio is 2-8:25-30:2000 ascorbic acid, TGA and water obtains mixed solution.
Mixed solution, the acrylic acid aqueous solution that mass fraction is 27-34%, mass fraction are added in basad liquid
21-34% hydrogen peroxide and stabilizer；It is well mixed.
Graphene oxide (graphene oxide) is the oxide of graphene, and oxygen-containing functional group increases and makes property thereon
It is more active compared with graphene, nature can be improved via the various and reaction of oxygen-containing functional group.
Graphene oxide has the two-dimensional structure similar with graphene.Graphene oxide has the intensity of superelevation, super large
Specific surface area, superpower pliability and very strong ion-exchange capacity.Its surface has hydroxyl, carboxyl and epoxy radicals etc. living
Sexual function group, it is more likely that the microstructure of hydrated product in concrete is influenceed from microcosmic point, so as to improve concrete
Crack problem.Research finds graphene oxide with occurring " template effect " in cement base cohesive process, you can to cause cement
Hydrated product --- entringite concentrates growth, can effectively reduce needle-like entringite, so as to improve the compactness of cement-based material,
The presence of harmful hole and microcrack is reduced, improves the seepage-resistant grade of concrete.
APEO is also known as polyethylene glycol oxide or PEO, is a kind of new type water-solubility resin, is a kind of non-again
Ionic surface active agent.
The graphene oxide water for being 1-3% with mass fraction by the APEO aqueous solution that mass fraction is 30-40%
Solution is in 20-30 DEG C of well mixed obtained substrate liquid；APEO is well-dispersed in graphene aqueous solution, make polyoxy second
Alkene ether is interspersed in graphene oxide layer.
Ascorbic acid has reproducibility, and antioxygenic property is strong, TGA (chemical formula：C2H4O2S), TGA conduct
A kind of chain-transferring agent.The mixed solution that TGA and ascorbic acid are mixed with to obtain can promote APEO to convert
As polycarboxylic acids.
During the course of the reaction, hydrogen peroxide and stabilizer are added, accelerates the reaction process entirely reacted；Stabilizer makes finally
Obtained graphene oxide/polycarboxylate water-reducer is more stable.
In detail, using peristaltic pump coutroi velocity, mixed solution, acrylic acid aqueous solution are slowly added in substrate liquid,
Hydrogen peroxide and stabilizer are added while dropwise addition.
In the present embodiment, stabilizer is that mass ratio is 1:0.8-1.2 sodium ascorbate and frerrous chloride.Further
Ground, stabilizer are that mass ratio is 1:1 sodium ascorbate and frerrous chloride.
In the present embodiment, the volume ratio of mixed solution, acrylic acid aqueous solution and substrate liquid is 1-3.5:1-3.5:13.
Further, the volume ratio of three is that volume ratio is 2:2:13.
Further, in the present embodiment, the mass fraction of the APEO aqueous solution is 35%.Graphene oxide is water-soluble
The mass fraction of liquid is 1%.The mass ratio of ascorbic acid, TGA and water is 3 in mixed solution:27:2000.
The present invention also provides a kind of technical scheme：
A kind of graphene oxide/polycarboxylate water-reducer, it passes through the preparation of above-mentioned graphene oxide/polycarboxylate water-reducer
Method is made.
The present invention also provides a kind of technical scheme：
Utilization of the above-mentioned graphene oxide/polycarboxylate water-reducer in concrete is prepared.
Inventor, which studies, to be found, graphene oxide/polycarboxylate water-reducer that the embodiment of the present invention is prepared makes concrete
It is uniformly dispersed in water, dispersion effect is good.
Pure polycarboxylate water-reducer is compared, and graphene oxide/polycarboxylate water-reducer that the embodiment of the present invention is prepared subtracts
Water is better.
In addition, graphene oxide/polycarboxylate water-reducer that the embodiment of the present invention is prepared is capable of the intensity of reinfored glue sand.
Further, when graphene oxide/polycarboxylate water-reducer is the 0.05wt% of cement, the maximum intensity of concrete.
The feature and performance of the present invention are described in further detail with reference to embodiments.
Embodiment 1
A kind of graphene oxide/polycarboxylate water-reducer is present embodiments provided, is mainly made by following steps：
The graphene oxide water solution that the APEO aqueous solution that mass fraction is 35% is 1% with mass fraction is existed
25 DEG C of well mixed obtained substrate liquid；Wherein, the mass ratio of APEO and graphene oxide is 70:3.
Mixing quality ratio is 6:27:2000 ascorbic acid, TGA and water obtains mixed solution.
Mixing quality ratio is 1:Stabilizer is prepared with frerrous chloride in 1 sodium ascorbate.
Mixed solution, the acrylic acid aqueous solution that mass fraction is 31% are slowly added in substrate liquid, while being added dropwise
Add 28% hydrogen peroxide and stabilizer that mass fraction is.
Wherein, the volume ratio of mixed solution, acrylic acid aqueous solution and substrate liquid is 2:2:13.
Embodiment 2
A kind of graphene oxide/polycarboxylate water-reducer is present embodiments provided, is mainly made by following steps：
The graphene oxide water solution that the APEO aqueous solution that mass fraction is 30% is 1% with mass fraction is existed
20 DEG C of well mixed obtained substrate liquid；Wherein, the mass ratio of APEO and graphene oxide is 70:2.
Mixing quality ratio is 2:25:2000 ascorbic acid, TGA and water obtains mixed solution.
Mixing quality ratio is 1:Stabilizer is prepared with frerrous chloride in 0.8 sodium ascorbate.
It is water-soluble for 34% acrylic acid that mixed solution, mass fraction are added using peristaltic pump coutroi velocity, in basad liquid
21% hydrogen peroxide and stabilizer that liquid, mass fraction are；It is well mixed.
Wherein, the volume ratio of mixed solution, acrylic acid aqueous solution and substrate liquid is 1:1:13.
Embodiment 3
A kind of graphene oxide/polycarboxylate water-reducer is present embodiments provided, is mainly made by following steps：
The graphene oxide water solution that the APEO aqueous solution that mass fraction is 40% is 3% with mass fraction is existed
30 DEG C of well mixed obtained substrate liquid；Wherein, the mass ratio of APEO and graphene oxide is 70:2.
Mixing quality ratio is 8:30:2000 ascorbic acid, TGA and water obtains mixed solution.
Mixing quality ratio is 1:Stabilizer is prepared with frerrous chloride in 1.1 sodium ascorbate.
It is water-soluble for 29% acrylic acid that mixed solution, mass fraction are added using peristaltic pump coutroi velocity, in basad liquid
34% hydrogen peroxide and stabilizer that liquid, mass fraction are；It is well mixed.
Wherein, the volume ratio of mixed solution, acrylic acid aqueous solution and substrate liquid is 3.5:3.5:13.
Embodiment 4
A kind of graphene oxide/polycarboxylate water-reducer is present embodiments provided, is mainly made by following steps：
The graphene oxide water solution that the APEO aqueous solution that mass fraction is 35% is 2% with mass fraction is existed
20 DEG C of well mixed obtained substrate liquid；Wherein, the mass ratio of APEO and graphene oxide is 70:6.
Mixing quality ratio is 6:29:2000 ascorbic acid, TGA and water obtains mixed solution.
Mixing quality ratio is 1:Stabilizer is prepared with frerrous chloride in 0.9 sodium ascorbate.
Mixed solution, the acrylic acid aqueous solution that mass fraction is 29%, mass fraction are 31% is added in basad liquid
Hydrogen peroxide and stabilizer；It is well mixed.
Wherein, the volume ratio of mixed solution, acrylic acid aqueous solution and substrate liquid is 2.1:2.2:13.
Embodiment 5
A kind of graphene oxide/polycarboxylate water-reducer is present embodiments provided, is mainly made by following steps：
The graphene oxide water solution that the APEO aqueous solution that mass fraction is 36% is 2% with mass fraction is existed
28 DEG C of well mixed obtained substrate liquid；Wherein, the mass ratio of APEO and graphene oxide is 70:4.
Mixing quality ratio is 5:28:2000 ascorbic acid, TGA and water obtains mixed solution.
Mixing quality ratio is 1:Stabilizer is prepared with frerrous chloride in 1 sodium ascorbate.
It is water-soluble for 31% acrylic acid that mixed solution, mass fraction are added using peristaltic pump coutroi velocity, in basad liquid
28% hydrogen peroxide and stabilizer that liquid, mass fraction are；It is well mixed.
Wherein, the volume ratio of mixed solution, acrylic acid aqueous solution and substrate liquid is 2.1:2.1:13.
Test example 1
Graphene oxide/polycarboxylate water-reducer that the embodiment of the present invention 1 is prepared carries out dispersion experiment with cement.
To three beakers of water for filling 50ml, 1g graphene oxides/polycarboxylate water-reducer is separately added into, the pure polycarboxylic acids of 1g subtracts
Aqua, 1g water；0.5g cement mixings are separately added into three beakers uniformly stand 15min afterwards again.Three beakers are seen
Examine.
It is in flocculence in beaker corresponding to graphene oxide/polycarboxylate water-reducer, and is uniformly dispersed, does not have coagulation phenomenon；
There is solidifying shape to precipitate in corresponding to pure polycarboxylate water-reducer, and have part coagulation to bottom of a cup.Burnt corresponding to 1g water (blank control group)
Solution compares clarification in cup, and concrete is settled down to bottom of a cup.
Test example 2
Graphene oxide/polycarboxylate water-reducer that the embodiment of the present invention 1 is prepared does water-reducing effect experiment, and two parts mixed
Solidifying soil is separately added into graphene oxide/polycarboxylate water-reducer of phase homogenous quantities and pure polycarboxylate water-reducer.Detect water-reducing rate；Detection
As a result show, the water-reducing rate of pure polycarboxylate water-reducer is 28%；The water-reducing rate of graphene oxide/polycarboxylate water-reducer is 25%；
Illustrate that the water-reducing effect for graphene oxide/polycarboxylate water-reducer that the embodiment of the present invention 1 provides is preferable.
The graphene oxide provided embodiment 1-5/polycarboxylate water-reducer detection water-reducing rate, wherein, embodiment 1-5 is obtained
Graphene oxide/polycarboxylate water-reducer water-reducing rate be respectively：25%th, 24%, 24%, 25%, 23%.
Test example 3
Graphene oxide/polycarboxylate water-reducer that the embodiment of the present invention 1 is prepared carries out dispersion experiment with cement.
Do one group of blank control group, three groups of experimental groups (marked as testing 1 group, testing 2 groups, test 3 groups)；Take four parts it is identical
The cement of quality is respectively placed in experimental group and control group, and quality is added into three groups of experimental groups as the poly- of cement quality 2%
Carboxylic acid water reducer.Then a certain amount of graphene oxide/polycarboxylate water-reducer is added respectively into three groups of experimental groups；Wherein, oxygen
Graphite alkene accounts for 0.05%, 0.07%, the 0.09% of cement quality respectively.
Blank control group and three groups of experimental groups are prepared into glue sand test block；Test early age (7d) and standard curing age
(28d) compression strength；Test result is as shown in Figure 1.
As can be known from Fig. 1, compared with blank group, graphene oxide/polycarboxylic acids that the embodiment of the present invention 1 is prepared
The glue sand compression strength of water reducer is higher；In addition, graphene oxide accounts for the experimental group (experiment 1 of cement quality 0.05% respectively
Group) maximum intensity, 7 days compressive strength rate blank groups improve 15% or so, and it is left that 28 days compressive strength rate blank groups improve 20%
It is right.With the raising of graphene oxide volume, the intensity of test block will not again be continued to increase, there is the trend slightly reduced on the contrary.
The glue sand microscopic appearance that scanning electron microscopic observation blank control group, three groups of experimental groups obtain.The form of blank control group
As shown in Fig. 2 the glue sand microscopic appearance of 1 group of experiment is as shown in figure 3, test 2 groups of glue sand microscopic appearance as shown in figure 4, experiment 3
The glue sand microscopic appearance of group is as shown in Figure 5.
Fig. 2-Fig. 5 is referred to, the glue sand porosity that three groups of experimental groups obtain is relatively low, and aligned orderly, crystal are regular.Blank
The glue sand space that group obtains is big, and crystal arrangement is chaotic, irregular.
The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.Within the spirit and principles of the invention, that is made any repaiies
Change, equivalent substitution, improvement etc., should be included in the scope of the protection.
Claims (10)
- A kind of 1. preparation method of graphene oxide/polycarboxylate water-reducer, it is characterised in that including：The graphene oxide water solution for being 1-3% with mass fraction by the APEO aqueous solution that mass fraction is 30-40% In 20-30 DEG C of well mixed obtained substrate liquid；Wherein, the mass ratio of the APEO and the graphene oxide is 70: 2-6；Mixing quality ratio is 2-8:25-30:2000 ascorbic acid, TGA and water obtains mixed solution；The mixed solution is added into the substrate liquid, the acrylic acid aqueous solution that mass fraction is 27-34%, mass fraction are 21-34% hydrogen peroxide and stabilizer；It is well mixed.
- 2. the preparation method of graphene oxide/polycarboxylate water-reducer according to claim 1, it is characterised in that by described in Mixed solution, the acrylic acid aqueous solution are slowly added in the substrate liquid, be added dropwise while add the hydrogen peroxide and The stabilizer.
- 3. the preparation method of graphene oxide/polycarboxylate water-reducer according to claim 1, it is characterised in that described mixed The volume ratio for closing solution, the acrylic acid aqueous solution and the substrate liquid is 1-3.5:1-3.5:13.
- 4. the preparation method of graphene oxide/polycarboxylate water-reducer according to claim 1, it is characterised in that described poly- The mass fraction of the oxygen vinethene aqueous solution is 35%.
- 5. the preparation method of graphene oxide/polycarboxylate water-reducer according to claim 1, it is characterised in that the oxygen The mass fraction of graphite aqueous solution is 1%.
- 6. the preparation method of graphene oxide/polycarboxylate water-reducer according to claim 1, it is characterised in that described mixed The mass ratio for closing ascorbic acid, the TGA and water described in solution is 3:27:2000.
- 7. the preparation method of graphene oxide/polycarboxylate water-reducer according to claim 1, it is characterised in that described mixed The volume ratio for closing solution, the acrylic acid aqueous solution and the substrate liquid is 2:2:13.
- 8. the preparation method of graphene oxide/polycarboxylate water-reducer according to claim 1, it is characterised in that described steady It is that mass ratio is 1 to determine agent:0.8-1.2 sodium ascorbate and frerrous chloride.
- 9. the preparation method of graphene oxide/polycarboxylate water-reducer according to claim 1, it is characterised in that described steady It is that mass ratio is 1 to determine agent:1 sodium ascorbate and frerrous chloride.
- 10. a kind of graphene oxide/polycarboxylate water-reducer, it is characterised in that the graphene oxide/polycarboxylate water-reducer is by weighing Profit requires that the preparation method of graphene oxide/polycarboxylate water-reducer described in any one of 1-9 is made.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107915222A (en) * | 2017-12-29 | 2018-04-17 | 江苏苏博特新材料股份有限公司 | A kind of preparation method of poly ethyldiol modified graphene oxide |
| CN111410451A (en) * | 2020-03-30 | 2020-07-14 | 深圳港创建材股份有限公司 | Raw material formula of graphene polycarboxylate superplasticizer and preparation and use methods of water reducer |
| CN112708040A (en) * | 2019-11-14 | 2021-04-27 | 科之杰新材料集团(贵州)有限公司 | Concrete reinforcing and toughening additive and preparation method thereof |
| CN113896453A (en) * | 2021-10-27 | 2022-01-07 | 北京石墨烯技术研究院有限公司 | Modified graphene composite material and preparation method thereof, cement reinforcing agent and application thereof |
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| CN106478895A (en) * | 2016-10-09 | 2017-03-08 | 武汉工程大学 | Compound polycarboxylate water-reducer of a kind of graphene oxide and preparation method thereof |
| CN106496441A (en) * | 2016-10-27 | 2017-03-15 | 湖北工业大学 | A kind of lower valency appraises at the current rate cation-modified polycarboxylate water-reducer masterbatch and its low temperature preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106478895A (en) * | 2016-10-09 | 2017-03-08 | 武汉工程大学 | Compound polycarboxylate water-reducer of a kind of graphene oxide and preparation method thereof |
| CN106496441A (en) * | 2016-10-27 | 2017-03-15 | 湖北工业大学 | A kind of lower valency appraises at the current rate cation-modified polycarboxylate water-reducer masterbatch and its low temperature preparation method |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107915222A (en) * | 2017-12-29 | 2018-04-17 | 江苏苏博特新材料股份有限公司 | A kind of preparation method of poly ethyldiol modified graphene oxide |
| CN112708040A (en) * | 2019-11-14 | 2021-04-27 | 科之杰新材料集团(贵州)有限公司 | Concrete reinforcing and toughening additive and preparation method thereof |
| CN111410451A (en) * | 2020-03-30 | 2020-07-14 | 深圳港创建材股份有限公司 | Raw material formula of graphene polycarboxylate superplasticizer and preparation and use methods of water reducer |
| CN113896453A (en) * | 2021-10-27 | 2022-01-07 | 北京石墨烯技术研究院有限公司 | Modified graphene composite material and preparation method thereof, cement reinforcing agent and application thereof |
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