CN105601154B - A kind of graphene reinforcing agent and preparation method thereof - Google Patents

A kind of graphene reinforcing agent and preparation method thereof Download PDF

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Publication number
CN105601154B
CN105601154B CN201510999208.3A CN201510999208A CN105601154B CN 105601154 B CN105601154 B CN 105601154B CN 201510999208 A CN201510999208 A CN 201510999208A CN 105601154 B CN105601154 B CN 105601154B
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component
graphene
reinforcing agent
percentage
weight
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CN105601154A (en
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丁立
张仲才
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Sichuan Carbon World Technology Co Ltd
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Sichuan Carbon World Technology Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039Premixtures of ingredients

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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 a kind of graphene reinforcing agent and preparation method thereof, wherein graphene reinforcing agent includes diminishing component 10~14%, protects collapse component 12~18%, sodium gluconate 3.2~3.6%, graphene oxide 8~12%, stabilizer 0.4~0.6%, deionized water 51~66%, by by diminishing component and guarantor collapse component add deionized water in, add sodium gluconate, pH value is adjusted to 7.0 using sodium hydroxide solution, is added graphene oxide and is made.The present invention solves the technological deficiency for causing concrete substrate defect to cause loss of strength using graphene oxide in existing concrete reinforcing agent, so as to the intensity for effectively improving concrete, impervious and durability, and the graphene synergist has efficient, extended storage stability good, it can improve with proportioning concrete strength 30%~46%.

Description

A kind of graphene reinforcing agent and preparation method thereof
Technical field
The present invention relates to cement intensifier, more particularly to a kind of graphene reinforcing agent and preparation method thereof.
Background technology
To improve one of approach of concrete strength from appropriate additive, in cement concrete industry, in order to The Developing Circulation Economy that country advocates, the Industrial Structure Policy phase of Accelerating The Construction resource-conserving and environment-friendly society Coordinate, additive has been widely used in cement concrete, for the purpose of one side Save Resource Protect Environment, is on the other hand used for Improve the chemical composition of cement matrix, improve the pore structure of Behavior of Hardened Cement Paste, regulate and control cement hydration process, make gel in cement more Uniform densification, reduces the generation of needle-like entringite so that water mudrock structure is finer and close, so as to effectively improve the strong of concrete Degree, impervious and durability.
The grain diameter of cement is mostly at 7~200 μm, but its most hydrated product C-S-H gel is nanometer Size, by filling nano material in binder materials, can not only play a part of filling pore, the high energy table of nano material Face can also play nucleation, and the surface of nano material can be bonded with C-S-H gel-formings, and induction entringite is in nano material Annex grows, and eventually forms using nano material as node, and C-S-H gels are the three-dimensional space network structure of network, so that significantly Improve the physical and mechanical property and durability of slurry after hardening of cement in ground.Shenghua Lv et al. utilize improved Hummers Method graphite oxide and ultrasound obtain oxygen content be 29.75% graphene oxide and be compounded in cement-based material, test As a result the resistance to compression, bending resistance and tensile strength of cement mortar can be significantly improved by showing the graphene oxide of 0.03% mass volume, point It is indescribably high by 38.9%, 60.7% and 78.6%, graphene oxide can effectively regulate and control the microstructure of hydrolysis product of cement to improve The intensity and toughness of cement-based material, still, graphene oxide specific surface area is very big, is easily flocculated under alkaline environment, Therefore graphene oxide is directly incorporated into cement can produce flocculation, this for graphene oxide in cement-based material it is scattered very not Profit, can directly affect the enhancing effect of graphene oxide generation, or even can cause intensity due to generation cement matrix defect of reuniting Loss.
The content of the invention
It is an object of the invention to provide a kind of graphene reinforcing agent and preparation method thereof, to solve existing concrete reinforcing agent Middle use graphene oxide causes concrete substrate defect to cause the technological deficiency of loss of strength.
What the present invention was realized in:
A kind of graphene reinforcing agent, its component includes by weight percentage:Diminishing component 10~14%, guarantor are collapsed component 12 ~18%, sodium gluconate 3.2~3.6%, graphene oxide 8~12%, stabilizer 0.4~0.6%, deionized water 51~66%;
Wherein, diminishing component includes by weight percentage:30~35% methyl alkenyl APEOs, 3~4% propylene Acid, 61~67% deionized waters;
Wherein, protect component of collapsing includes by weight percentage:25~30% allyl polyethenoxy base ethers, 10~15% Malaysias Acid anhydrides, 1%~3% acrylic acid, 5~8% ethylene glycol diacrylates, 44~59% deionized waters;
Wherein, stabilizer is polyvinylpyrrolidone.
The graphene reinforcing agent that the present invention is provided, wherein, the percentage by weight preferably 12% of diminishing component, protect component of collapsing Percentage by weight preferably 16%, the percentage by weight preferably 3.4% of sodium gluconate, graphene oxide percentage by weight it is preferred 10%th, the percentage by weight of stabilizer preferably 0.5%, the percentage by weight preferably 58.1% of deionized water.
Wherein, diminishing component is by weight percentage:Methyl alkenyl APEO preferably 33%, acrylic acid preferably 3.5%, Deionized water preferably 63.5%, methyl alkenyl APEO and acrylic acid are synthetic copolymer.
Wherein, protect and collapse component by weight percentage:Allyl polyethenoxy base ether preferably 27%, maleic anhydride are preferred 12%th, acrylic acid preferably 2%, ethylene glycol diacrylate preferably 6%, deionized water preferably 53%, allyl polyethenoxy base ether, horse It is synthesis high-molecular copolymer to come acid anhydrides, acrylic acid and ethylene glycol diacrylate.
The present invention also provides a kind of preparation method for preparing above-mentioned graphene reinforcing agent, comprises the following steps:
Take diminishing component and guarantor collapse component add deionized water in, stir, then add sodium gluconate, continue to stir Mixing is mixed, adjusts pH value to 7.0 using sodium hydroxide solution, adds through the 20KHz graphene oxides of ultrasonically treated 2~5 hours, stir Mixing is mixed, stabilizer is finally slowly added to, produced after stirring.
Wherein, graphene oxide preferably ultrasonically treated 3 hours.
Beneficial effects of the present invention:
1st, the graphene reinforcing agent that the present invention is provided, is added in concrete mix, and graphene oxide can be achieved in water It is dispersed in mud, the hole inside Behavior of Hardened Cement Paste can be significantly reduced, improves the pore structure of Behavior of Hardened Cement Paste, while making solidifying in cement Glue is more uniform, can significantly reduce the generation of needle-like entringite so that water mudrock structure is finer and close, enables in cement CH grain refinements, so as to effectively improve the intensity of concrete, impervious and durability.
2nd, preparation method of the invention is simple, and the graphene synergist has the good spy of efficient, extended storage stability Point, the graphene oxide reinforcing agent prepared by the present invention can be improved with proportioning concrete strength 30%~46%..
Embodiment
Embodiment 1
Graphene reinforcing agent:
By weight percentage:10% diminishing component, 12% protect collapse component, 3.2% sodium gluconate, 8% graphene oxide, 0.4% stabilizer polyvinylpyrrolidone, 66% deionized water.
Wherein, diminishing component includes by weight percentage:30% methyl alkenyl APEO, 3% acrylic acid, 67% are gone Ionized water.
Wherein, protect component of collapsing includes by weight percentage:25% allyl polyethenoxy base ether, 10% maleic anhydride, 1% Acrylic acid, 5% ethylene glycol diacrylate, 59% deionized water.
The preparation method of graphene reinforcing agent, comprises the following steps:
Take above-mentioned diminishing component and guarantor collapse component add deionized water in, stir, then add sodium gluconate, after Continuous stirring mixing, adjusts pH value to 7.0, adds through the 20KHz graphite oxides of ultrasonically treated 2 hours using sodium hydroxide solution section Alkene, stirring mixing, is finally slowly added to stabilizer polyvinylpyrrolidone, is produced after stirring.
Embodiment 2
Graphene reinforcing agent:
By weight percentage:14% diminishing component, 18% protect collapse component, 3.6% sodium gluconate, 12% graphene oxide, 0.6% stabilizer polyvinylpyrrolidone, 51% deionized water.
Wherein, diminishing component includes by weight percentage:35% methyl alkenyl APEO, 4% acrylic acid, 61% are gone Ionized water.
Wherein, protect component of collapsing includes by weight percentage:30% allyl polyethenoxy base ether, 15% maleic anhydride, 3% Acrylic acid, 8% ethylene glycol diacrylate, 44% deionized water.
The preparation method of graphene reinforcing agent, comprises the following steps:
Take diminishing component and guarantor collapse component add deionized water in, stir, then add sodium gluconate, continue to stir Mixing is mixed, adjusts pH value to 7.0 using sodium hydroxide solution section, adds through the 20KHz graphene oxides of ultrasonically treated 5 hours, stir Mixing is mixed, stabilizer is finally slowly added to, produced after stirring.
Embodiment 3
Graphene reinforcing agent:
By weight percentage:12% diminishing component, 16% protect collapse component, 3.4% sodium gluconate, 10% graphene oxide, 0.5% stabilizer polyvinylpyrrolidone, 58.1% deionized water.
Wherein, diminishing component includes by weight percentage:33% methyl alkenyl APEO, 3.5% acrylic acid, 63.5% deionized water.
Wherein, protect component of collapsing includes by weight percentage:27% allyl polyethenoxy base ether, 12% maleic anhydride, 2% Acrylic acid, 6% ethylene glycol diacrylate, 53% deionized water.
The preparation method of graphene reinforcing agent, comprises the following steps:
Take diminishing component and guarantor collapse component add deionized water in, stir, then add sodium gluconate, continue to stir Mixing is mixed, adjusts pH value to 7.0 using sodium hydroxide solution section, adds through the 20KHz graphene oxides of ultrasonically treated 3 hours, stir Mixing is mixed, stabilizer is finally slowly added to, produced after stirring.
According to GB/T 17671-1999 detection method, using PO42.5 cement, the anti-folding of cement mortar has been carried out The compressive strength test of intensity and cement mortar, wherein graphene reinforcing agent prepare gained, graphene reinforcing agent using embodiment 3 Usage amount according to cement weight percentage calculate.
Cement mortar intensity test:Cement 450g, normal sand 1350g, water 225g.
The volume of graphene synergist is added in cement slurry for the 0.20% of cement weight, the result of the test such as He of table 1 Shown in table 2.
The rupture strength of the cement mortar of table 1
The compression strength of the cement mortar of table 2
Drawn a conclusion by Tables 1 and 2:
1st, the graphene synergist can be such that bending strength of cement improves significantly, and mid-term 7d rupture strength increase rates are larger.
Wherein:PO42.5 cement 3d rupture strengths be up to state standards 134%~158%, be the 106% of reference intensity ~125%;It is up to state standards the 72%~85% of 28d intensity, is the 59%~70% of 28d reference intensities.7d rupture strengths reach state The 103%~125% of family's standard 28d intensity, is that 110%~133%, the 28d rupture strengths of reference intensity are up to state standards 28d The 132%~157% of intensity, is the 108%~130% of reference intensity, rupture strength index is more than 62.5R national standards.
2nd, the development of cement mortar mid-term 7d compression strength is very fast, and later strength is higher, mid-term 7d compression strength increase rates It is larger.
Wherein:PO42.5 cement 3d compression strength be up to state standards 134%~169%, be the 117% of reference intensity ~147%;It is up to state standards the 54%~68% of 28d intensity, is the 49%~62% of 28d reference intensities;7d compression strength reaches It is the 147%~185% of reference intensity to the 102%~129% of national standard 28d compression strength;28d compression strength reaches country The 140%~172% of standard, is the 128%~157% of reference intensity, and compression strength index basically reaches 62.5 national standards.
3rd, quickly, absolute figure is larger for cement mid-term 7d strength developments, and anti-folding almost increases with resistance to compression with width, and the middle and later periods increases Width eases up, and rupture strength amplification is slow compared with compression strength amplification, and generally, the later strength of cement mortar remains in that higher Growth rate.

Claims (6)

1. a kind of graphene reinforcing agent, it is characterised in that component includes by weight percentage:
Diminishing component 10~14%
Guarantor is collapsed component 12~18%
Sodium gluconate 3.2~3.6%
Graphene oxide 8~12%
Stabilizer 0.4~0.6%
Deionized water 58.1~66%
Wherein, the diminishing component includes by weight percentage:30~35% methyl alkenyl APEOs, 3~4% propylene Acid, 61~67% deionized waters;
Wherein, the component of collapsing of protecting includes by weight percentage:25~30% allyl polyethenoxy base ethers, 10~15% Malaysias Acid anhydrides, 1%~3% acrylic acid, 5~8% ethylene glycol diacrylates, 44~59% deionized waters;
Wherein, the stabilizer is polyvinylpyrrolidone.
2. graphene reinforcing agent according to claim 1, it is characterised in that:The percentage by weight of the diminishing component is 12%th, the percentage by weight for protecting component of collapsing is that the 16%, percentage by weight of the sodium gluconate is 3.4%, the oxidation stone The percentage by weight of black alkene is that the 10%, percentage by weight of the stabilizer is that the 0.5%, percentage by weight of the deionized water is 58.1%。
3. graphene reinforcing agent according to claim 1, it is characterised in that the diminishing component is wrapped by weight percentage Include:33% methyl alkenyl APEO, 3.5% acrylic acid, 63.5% deionized water.
4. graphene reinforcing agent according to claim 1, it is characterised in that guarantor component of collapsing is wrapped by weight percentage Include:27% allyl polyethenoxy base ether, 12% maleic anhydride, 2% acrylic acid, 6% ethylene glycol diacrylate, 53% deionized water.
5. a kind of method of the graphene reinforcing agent prepared any one of Claims 1-4, it is characterised in that including as follows Step:
Take diminishing component and guarantor component of collapsing to add in deionized water, stir, then add sodium gluconate, continue to stir mixed Close, pH value is adjusted to 7.0 using sodium hydroxide solution, add through the 20KHz graphene oxides of ultrasonically treated 2~5 hours, stirring is mixed Close, be finally slowly added to stabilizer, produced after stirring.
6. preparation method according to claim 5, it is characterised in that:Ultrasonically treated 3 hours of the graphene oxide.
CN201510999208.3A 2015-12-28 2015-12-28 A kind of graphene reinforcing agent and preparation method thereof Active CN105601154B (en)

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CN106673574A (en) * 2016-12-05 2017-05-17 同济大学 Non-calcined desulfurized gypsum hydraulic composite gel system
CN107337363B (en) * 2016-12-30 2019-12-27 江苏苏博特新材料股份有限公司 Cement concrete durability enhancing additive
CN110256109A (en) * 2019-06-18 2019-09-20 宁波墨西科技有限公司 A kind of graphene antistatic lithium based concrete sealing solidifying agent and preparation method thereof
CN114436560B (en) * 2022-02-22 2022-11-01 四川圣吉鸿博建筑材料有限公司 Concrete synergist and preparation method thereof

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CN102417643B (en) * 2011-10-17 2013-01-16 佛山市日丰企业有限公司 Grapheme-containing reinforced wear-resistant material composition, reinforced wear-resistant material and preparation method thereof
CN103738944B (en) * 2013-11-14 2016-07-06 盐城增材科技有限公司 A kind of method preparing three-dimensional grapheme by nanoparticle doped
CN104058676B (en) * 2014-07-15 2015-09-09 宏峰集团(福建)有限公司 A kind of high tenacity concrete and preparation method thereof
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