CN109400038A - A kind of high resistance to corrosion low-heat cement material and preparation method thereof containing graphene oxide - Google Patents

A kind of high resistance to corrosion low-heat cement material and preparation method thereof containing graphene oxide Download PDF

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CN109400038A
CN109400038A CN201811434594.1A CN201811434594A CN109400038A CN 109400038 A CN109400038 A CN 109400038A CN 201811434594 A CN201811434594 A CN 201811434594A CN 109400038 A CN109400038 A CN 109400038A
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graphene oxide
cement
heat
water
corrosion
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CN109400038B (en
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蒙坤林
黄小青
杨义
蒋杉平
邓玉莲
吴飚
黄丽霖
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Guangxi Green Cement Industry Engineering Institute Co Ltd
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Guangxi Green Cement Industry Engineering Institute Co Ltd
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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
    • C04B28/025—Belite cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B40/02—Selection of the hardening environment
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/2015—Sulfate resistance
    • 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
    • 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
    • C04B2201/52—High compression strength concretes, i.e. with a compression strength higher than about 55 N/mm2, e.g. reactive powder concrete [RPC]

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The present invention discloses a kind of high resistance to corrosion low-heat cement material and preparation method thereof containing graphene oxide, belongs to building material technical field.High resistance to corrosion low-heat cement material containing graphene oxide of the invention consists of the following components in percentage by weight: High-belite Cement 22.5-23.0%, normal sand 67.6-68.5%, polycarboxylate water-reducer 0.5-0.6%, graphene oxide dispersion 0.72-1.2%, surplus are water；Preparation method is to be stirred raw material, form and conserve, the obtained high resistance to corrosion low-heat cement material containing graphene oxide has the advantages that the heat of hydration is low, intensity is high, corrosion stability is good, it is applicable in the foundation engineerings such as mass concrete engineering and harbour by salt corrosions such as sulfate and water conservancy, underground, tunnel, diversion, road and bridge, preparation process is simple, cost is controllable, there is preferable development prospect, is suitble to promote and apply.

Description

A kind of high resistance to corrosion low-heat cement material and preparation method thereof containing graphene oxide
Technical field
The invention belongs to building material technical fields, and in particular to a kind of high resistance to corrosion low-heat cement material containing graphene oxide Material and preparation method thereof.
Background technique
There is low hydration heat, environmental protection by the High-belite Cement of China Building Materials Academy's research and development at present, it is durable The advantages that property is good.Compared with traditional portland, it, which is applied in mass concrete engineering, which can reduce alkali-bone, gathers materials instead Answer, temperature stress the problems such as caused concrete cracking risk.But due to the main component silicic acid two of High-belite Cement The reaction speed of calcium aquation is slower, and thermal discharge is low, and the hydrated calcium silicate gel of generation is less, therefore causes strength of cement lower, Make it in practical projects application be restricted.Therefore, the low water of High-belite Cement can be maintained by finding a kind of method Change heat, and can improve the performances such as its intensity, corrosion stability be it is vital, this will to its industrialization have facilitation.
Graphene oxide is a kind of carbon for forming and having two-dimensional surface honeycomb crystal lattice structure by carbon atom monolayer alignment Nano material, oxygen-containing functional group rich on basal plane, edge, such as the epoxy group and hydroxyl of basal plane, the carboxyl at edge and Carbonyl.These oxygen-containing functional groups make graphene oxide have good hydrophily and surface-active, that is to say, that graphene oxide It can be evenly dispersed in aqueous solution, and be incorporated into cement material in a manner of solution, effectively play its effect.Mesh Preceding research achievement shows that for ordinary portland cement material, its flexural strength 30%-110% can be improved in graphene oxide, Compression strength 35% or so.This illustrates that it has excellent toughening effect.And in terms of special cement, graphene oxide is to its property The research of energy aspect is less, since the mineral content accounting of High-belite Cement and portland cement has a certain difference, leads Performance, the purposes etc. for causing two kinds of cement would also vary from, therefore, it is also desirable to which further research graphene oxide is to high Baily The influence of special cement material performance, especially etch resistant properties, in the hope of preparing a kind of high and low heat of hydration of early strength, high resistance to corrosion The cement material of property.
Summary of the invention
In order to solve the above-mentioned technical problems, the present invention provides a kind of high resistance to corrosion low-heat cement material containing graphene oxide And preparation method thereof, the high resistance to corrosion low-heat cement material of the invention containing graphene oxide is by High-belite Cement, normal sand, poly- Carboxylic acid water reducer, graphene oxide dispersion and water composition, preparation method are to be stirred raw material, form and conserve, and are obtained The high resistance to corrosion low-heat cement material containing graphene oxide not only maintained High-belite Cement low hydration heat performance, but also overcome The defect of its intensity and corrosion resistance.
Technical scheme is as follows:
A kind of high resistance to corrosion low-heat cement material containing graphene oxide, the high resistance to corrosion low-heat cement containing graphene oxide Material consists of the following components in percentage by weight: High-belite Cement 22.5-23.0%, normal sand 67.6-68.5%, poly- carboxylic Sour water-reducing agent 0.5-0.6%, graphene oxide dispersion 0.72-1.2%, surplus are water；
The chemical constituent of the High-belite Cement are as follows: SiO2> 23%, CaO > 60%, Al2O3> 3.0%, Fe2O3> 4.5%, SO3> 2.3%, MgO > 3.4%.
As a preferred option of the technical scheme, the high resistance to corrosion low-heat cement material containing graphene oxide is by following weight percent The group of ratio is grouped as: High-belite Cement 22.7%, normal sand 68.0%, polycarboxylate water-reducer 0.55%, graphene oxide point Dispersion liquid 0.96%, surplus are water.
As a preferred option of the technical scheme, the normal sand is SiO2Content be not less than 98% natural rounded siliceous sand.
As a preferred option of the technical scheme, the solid content of the polycarboxylate water-reducer is 7.2-15.6%, water-reducing rate 15- 20%；As the further preferred of technical solution, the solid content of the polycarboxylate water-reducer is 8%, water-reducing rate 17%.
As a preferred option of the technical scheme, single layer rate > 90% of the graphene oxide dispersion, solid content 0.90- 0.98%, partial size is 2.2-2.8 μm；As the further preferred of technical solution, the solid content of the graphene oxide dispersion It is 0.94%, partial size is 2.56 μm.
A kind of preparation method such as the above-mentioned high resistance to corrosion low-heat cement material containing graphene oxide, at normal temperatures and pressures into Row, including following operating procedure:
(1) High-belite Cement, normal sand, polycarboxylate water-reducer, graphite oxide are weighed according to above-mentioned weight percent Alkene dispersion liquid and water；
(2) graphene oxide dispersion is dissolved in suitable quantity of water and graphene oxide solution is made；
(3) polycarboxylate water-reducer and graphene oxide solution are mixed and stirred for 5-10min, obtain mixed liquor；
(4) High-belite Cement, normal sand and remaining water are added in mixed liquor and stir 3-5min, obtain cement bonded sand Slurry, then forms cement mortar to obtain cement specimen, then conserve cement specimen, be obtained containing graphene oxide High resistance to corrosion low-heat cement material.
As a preferred option of the technical scheme, the molding specifically: cement mortar is poured into 40mm × 40mm × 160mm mould It is placed 1 day in tool；The maintenance specifically: cement specimen is conserved 25-30 days in clear water first, then takes out and is put by quality Score is calculated as 10% metabisulfite solution, 10% sodium chloride solution or 10% metabisulfite solution and 10% sodium chloride solution mixes in equal volume Maintenance 85-95 days is carried out in the composite solution of conjunction；The rate of the stirring is 135-295r/min.
The aquation thermal parameter of high resistance to corrosion low-heat cement material containing graphene oxide of the invention: the 3d heat of hydration≤176kJ/ Kg, the 7d heat of hydration≤233kJ/kg, the 28d heat of hydration≤285kJ/kg；Intensive parameter: 28d flexural strength >=9.0MPa；28d is anti- Compressive Strength >=63.0MPa；Parameter against corrosion: (1) resisting erosion of sulfate flexural strength is tested: flexural strength >=13.0MPa of 30d, Flexural strength >=14.0MPa of flexural strength >=14.3MPa of 90d, 180d；(2) resisting erosion of sulfate intensity test: Compression strength >=83.5Mpa of compression strength >=81.5Mpa of compression strength >=78.8MPa of 30d, 90d, 180d；(3) resist Chloride erosion flexural strength test: the anti-folding of flexural strength >=11.1MPa of flexural strength >=10.6MPa of 30d, 90d, 180d Intensity >=10.7MPa；(4) precenting chlorate corrosion intensity test: compression strength >=74.6MPa of 30d, the compression strength of 90d Compression strength >=81.0Mpa of >=78.3 Mpa, 180d；(5) anti-chlorine salt-sulfate attack flexural strength test: the anti-folding of 30d Intensity >=11.1 MPa, flexural strength >=12.5MPa of flexural strength >=12.2MPa of 90d, 180d；(6) anti-chlorine salt-sulfuric acid Salt corrosion intensity test: compression strength >=82.3Mpa of compression strength >=75.1MPa of 30d, 90d, the pressure resistance of 180d Degree >=83.4Mpa.
Polycarboxylate water-reducer of the invention is bought from Guangxi Xin Guangjian Chemical Industry Science Co., Ltd, graphene oxide dispersion The SE3522 from Changzhou No.6 Element Material Technology Co., Ltd. is bought, High-belite Cement and normal sand are also market It is commercially available, without especially preparation.
Beneficial effects of the present invention:
1. the present invention uses graphene oxide dispersion made of novel nano-material graphene oxide for raw material, in poly- carboxylic Under sour water-reducing agent effect, the compactness of cement material internal structure is can be improved in it, and then can effectively improve high belite water The intensity of mud material reduces its heat of hydration, improves its etch resistant properties.
2. the fluidity of the high resistance to corrosion low-heat cement material of the invention containing graphene oxide is in 180mm or more, the heat of hydration Parameter: the 3d heat of hydration≤176kJ/kg, the 7d heat of hydration≤233kJ/kg, the 28d heat of hydration≤285kJ/kg；Intensive parameter: 28d Flexural strength >=9.0MPa；28d compression strength >=63.0MPa；Parameter against corrosion: (1) resisting erosion of sulfate flexural strength is tested: Flexural strength >=14.0MPa of flexural strength >=14.3MPa of flexural strength >=13.0MPa of 30d, 90d, 180d；(2) sulfur resistive Hydrochlorate corrodes intensity test: compression strength >=81.5Mpa of compression strength >=78.8MPa of 30d, 90d, the resistance to compression of 180d Intensity >=83.5Mpa；(3) precenting chlorate corrosion flexural strength is tested: flexural strength >=10.6MPa of 30d, the flexural strength of 90d Flexural strength >=10.7MPa of >=11.1 MPa, 180d；(4) precenting chlorate corrosion intensity test: the compression strength of 30d >= Compression strength >=81.0Mpa of compression strength >=78.3Mpa of 74.6MPa, 90d, 180d；(5) anti-chlorine salt-sulfate attack Flexural strength test: the flexural strength of flexural strength >=12.2MPa of flexural strength >=11.1MPa of 30d, 90d, 180d >= 12.5MPa；(6) anti-chlorine salt-sulfate attack intensity test: compression strength >=75.1MPa of 30d, the pressure resistance of 90d Degree >=82.3Mpa, compression strength >=83.4Mpa of 180d.High resistance to corrosion low-heat cement material containing graphene oxide of the invention Harbour and water conservancy, underground, tunnel, diversion, road and bridge suitable for mass concrete engineering and by sulphate corrosion etc. In foundation engineering.
3. preparation process of the invention is simple, at low cost, there is preferable development prospect, is suitble to promote and apply.
Detailed description of the invention
Fig. 1 is the SEM figure of the High-belite Cement material of comparative example 2；
Fig. 2 is the SEM figure of the high resistance to corrosion low-heat cement material containing graphene oxide of embodiment 2；
Fig. 3 is the SEM figure of the High-belite Cement material of comparative example 3；
Fig. 4 is the SEM figure of the high resistance to corrosion low-heat cement material containing graphene oxide of embodiment 3；
Fig. 5 is the SEM figure of the High-belite Cement material of comparative example 4；
Fig. 6 is the SEM figure of the high resistance to corrosion low-heat cement material containing graphene oxide of embodiment 4.
Specific embodiment
Below in conjunction with specific embodiment, the present invention is described in more detail, but is not limited to protection scope of the present invention.
One, raw material selection and pre-processing requirements
The chemical constituent of the High-belite Cement of selection are as follows: SiO2> 23%, CaO > 60%, Al2O3> 3.0%, Fe2O3> 4.5%, SO3> 2.3%, MgO > 3.4%.
The normal sand of selection is SiO2Content be not less than 98% natural rounded siliceous sand.
Polycarboxylate water-reducer is selected to buy from Guangxi Xin Guangjian Chemical Industry Science Co., Ltd, solid content 7.2-15.6%, Water-reducing rate is 15-20%.
The graphene oxide dispersion of selection buys the SE3522 from Changzhou No.6 Element Material Technology Co., Ltd., Single layer rate > 90%, solid content 0.90-0.98%, partial size are 2.2-2.8 μm.
Two, the preparation method of high resistance to corrosion low-heat cement material
Comparative example 1
(1) High-belite Cement 450g, normal sand 1350g, water 225g are weighed；
(2) High-belite Cement and normal sand are added to the water and 4min is stirred with the rate of 200r/min, obtain cement Mortar, then cement mortar poured into place 1 day in 40mm × 40mm × 160mm mold form, and obtains cement specimen, Cement specimen is conserved 28 days in clear water again, then takes out and is put into as mass fraction to be supported in 10% sodium chloride solution Shield 90 days, obtains High-belite Cement material.
Comparative example 2
(1) High-belite Cement 450g, normal sand 1350g, polycarboxylate water-reducer 11.7g, water 174.8g are weighed；
(2) High-belite Cement, normal sand and polycarboxylate water-reducer are added to the water and are stirred with the rate of 230r/min 4min obtains cement mortar, then pours into place 1 day in 40mm × 40mm × 160mm mold by cement mortar and forms, Cement specimen is obtained, then cement specimen is conserved 28 days in clear water, then takes out and is put into as mass fraction as 10% sulfuric acid Maintenance 90 days is carried out in sodium solution, obtains High-belite Cement material.
Comparative example 3
(1) High-belite Cement 450g, normal sand 1350g, polycarboxylate water-reducer 11.7g, water 174.8g are weighed；
(2) High-belite Cement, normal sand and polycarboxylate water-reducer are added to the water and are stirred with the rate of 230r/min 4min obtains cement mortar, then pours into place 1 day in 40mm × 40mm × 160mm mold by cement mortar and forms, Cement specimen is obtained, then cement specimen is conserved 28 days in clear water, then takes out and is put into as mass fraction as 10% chlorination Maintenance 90 days is carried out in sodium solution, obtains High-belite Cement material.
Comparative example 4
(1) High-belite Cement 450g, normal sand 1350g, polycarboxylate water-reducer 11.7g, water 174.8g are weighed；
(2) High-belite Cement, normal sand and polycarboxylate water-reducer are added to the water and are stirred with the rate of 230r/min 4min obtains cement mortar, then pours into place 1 day in 40mm × 40mm × 160mm mold by cement mortar and forms, Cement specimen is obtained, then cement specimen is conserved 28 days in clear water, then takes out and is put into as mass fraction as 10% sulfuric acid Maintenance 90 days is carried out in the composite solution that sodium solution and 10% sodium chloride solution mix in equal volume, obtains High-belite Cement material Material.
Embodiment 1
A kind of preparation method of the high resistance to corrosion low-heat cement material containing graphene oxide, carries out at normal temperatures and pressures, including Following operating procedure:
(1) High-belite Cement 450g, normal sand 1350g, polycarboxylate water-reducer 11.7g, graphene oxide dispersion are weighed Liquid 14.36g, water 160.5g；
(2) graphene oxide dispersion is dissolved in 50g water and graphene oxide solution is made；
(3) polycarboxylate water-reducer and graphene oxide solution are mixed and 8min is stirred with the rate of 135r/min, obtained Mixed liquor；
(4) High-belite Cement, normal sand and remaining water are added in mixed liquor and are stirred with the rate of 275r/min 4min obtains cement mortar, then pours into place 1 day in 40mm × 40mm × 160mm mold by cement mortar and forms, Cement specimen is obtained, then cement specimen is conserved 28 days in clear water, then takes out and is put into as mass fraction as 10% sulfuric acid Maintenance 90 days is carried out in sodium solution, obtains the high resistance to corrosion low-heat cement material containing graphene oxide.
Embodiment 2
A kind of preparation method of the high resistance to corrosion low-heat cement material containing graphene oxide, carries out at normal temperatures and pressures, including Following operating procedure:
(1) High-belite Cement 450g, normal sand 1350g, polycarboxylate water-reducer 11.7g, graphene oxide dispersion are weighed Liquid 23.94g, water 150.9g；
(2) graphene oxide dispersion is dissolved in 50g water and graphene oxide solution is made；
(3) polycarboxylate water-reducer and graphene oxide solution are mixed and 8min is stirred with the rate of 140r/min, obtained Mixed liquor；
(4) High-belite Cement, normal sand and remaining water are added in mixed liquor and are stirred with the rate of 285r/min 4min obtains cement mortar, then pours into place 1 day in 40mm × 40mm × 160mm mold by cement mortar and forms, Cement specimen is obtained, then cement specimen is conserved 28 days in clear water, then takes out and is put into as mass fraction as 10% sulfuric acid Maintenance 90 days is carried out in sodium solution, obtains the high resistance to corrosion low-heat cement material containing graphene oxide.
Embodiment 3
A kind of preparation method of the high resistance to corrosion low-heat cement material containing graphene oxide, carries out at normal temperatures and pressures, including Following operating procedure:
(1) High-belite Cement 450.94g, normal sand 1350.82g, polycarboxylate water-reducer 10.93g, graphite oxide are weighed Alkene dispersion liquid 19.07g, water 154.74g；
(2) graphene oxide dispersion is dissolved in 50g water and graphene oxide solution is made；
(3) polycarboxylate water-reducer and graphene oxide solution are mixed and 7min is stirred with the rate of 145r/min, obtained Mixed liquor；
(4) High-belite Cement, normal sand and remaining water are added in mixed liquor and are stirred with the rate of 295r/min 4min obtains cement mortar, then pours into place 1 day in 40mm × 40mm × 160mm mold by cement mortar and forms, Cement specimen is obtained, then cement specimen is conserved 27 days in clear water, then takes out and is put into as mass fraction as 10% chlorination Maintenance 90 days is carried out in sodium solution, obtains the high resistance to corrosion low-heat cement material containing graphene oxide.
Embodiment 4
A kind of preparation method of the high resistance to corrosion low-heat cement material containing graphene oxide, carries out at normal temperatures and pressures, including Following operating procedure:
(1) High-belite Cement 446.96g, normal sand 1342.87g, polycarboxylate water-reducer 9.93g, graphite oxide are weighed Alkene dispersion liquid 14.30g, water 172.44g；
(2) graphene oxide dispersion is dissolved in 50g water and graphene oxide solution is made；
(3) polycarboxylate water-reducer and graphene oxide solution are mixed and 10min is stirred with the rate of 155r/min, obtained Mixed liquor；
(4) High-belite Cement, normal sand and remaining water are added in mixed liquor and are stirred with the rate of 265r/min 5min obtains cement mortar, then pours into place 1 day in 40mm × 40mm × 160mm mold by cement mortar and forms, Cement specimen is obtained, then cement specimen is conserved 30 days in clear water, then takes out and is put into as mass fraction as 10% sulfuric acid Maintenance 95 days is carried out in the composite solution that sodium solution and 10% sodium chloride solution mix in equal volume, obtains the height containing graphene oxide Low-heat cement material against corrosion.
Embodiment 5
A kind of preparation method of the high resistance to corrosion low-heat cement material containing graphene oxide, carries out at normal temperatures and pressures, including Following operating procedure:
(1) High-belite Cement 456.90g, normal sand 1360.75g, polycarboxylate water-reducer 11.92g, graphite oxide are weighed Alkene dispersion liquid 23.84g, water 133.09g；
(2) graphene oxide dispersion is dissolved in 50g water and graphene oxide solution is made；
(3) polycarboxylate water-reducer and graphene oxide solution are mixed and 5min is stirred with the rate of 165r/min, obtained Mixed liquor；
(4) High-belite Cement, normal sand and remaining water are added in mixed liquor and are stirred with the rate of 255r/min 3min obtains cement mortar, then pours into place 1 day in 40mm × 40mm × 160mm mold by cement mortar and forms, Cement specimen is obtained, then cement specimen is conserved 25 days in clear water, then takes out and is put into as mass fraction as 10% sulfuric acid Maintenance 85 days is carried out in the composite solution that sodium solution and 10% sodium chloride solution mix in equal volume, obtains the height containing graphene oxide Low-heat cement material against corrosion.
Three, sem test
The high resistance to corrosion containing graphene oxide obtained to the obtained cement material of comparative example 2-4 and embodiment 2-4 is low Hot Cement material is scanned Electronic Speculum test, and obtained result is as shown in figures 1 to 6.
It can be seen from the figure that the internal structure gap of the High-belite Cement material of comparative example 2-4 is more, structure is dredged Pine, and the high resistance to corrosion low-heat cement material internal structure containing graphene oxide of embodiment 2-4 is closely knit, it is seen then that graphene oxide The addition of dispersion liquid improves the compactness of High-belite Cement material internal structure, thus can effectively improve high belite The intensity of cement material reduces the heat of hydration of High-belite Cement material, improves the etch resistant properties of High-belite Cement material.
Four, the performance parameter of the high resistance to corrosion low-heat cement material containing graphene oxide
To comparative example 1, the resulting High-belite Cement material of comparative example 2 and embodiment 1,2 gained of embodiment High resistance to corrosion low-heat cement material containing graphene oxide carry out aquation Thermal test (GB/T12959-2008) and strength test (GB/T17671-1999), as a result such as the following table 1.As it can be seen from table 1 the high resistance to corrosion low-heat water of the invention containing graphene oxide The heat of hydration of mud material is lower than comparative example.From the match ratio of raw material, incorporation polycarboxylate water-reducer can reduce water The heat of hydration of mud material.Therefore, by comparing four test numbers, it can be seen that graphene oxide has preferably on the heat of hydration Control, i.e. the holding lower heat of hydration of cement material and can improve intensity.
1 cement material aquation Thermal test of table and strength test results
To comparative example 1, the resulting High-belite Cement material of comparative example 2 and embodiment 1,2 gained of embodiment High resistance to corrosion low-heat cement material containing graphene oxide carry out resisting erosion of sulfate test (GB/T50082-2009), as a result such as The following table 2.
2 cement material resisting erosion of sulfate test result of table
To comparative example 1, the resulting High-belite Cement material of comparative example 2 and embodiment 1,2 gained of embodiment High resistance to corrosion low-heat cement material containing graphene oxide carry out precenting chlorate corrosion test, specific test method and sulfuric-resisting salt contamination Erosion test is consistent, as a result such as the following table 3.
3 cement material precenting chlorate corrosion test result of table
To comparative example 1, the resulting High-belite Cement material of comparative example 2 and embodiment 1,2 gained of embodiment High resistance to corrosion low-heat cement material containing graphene oxide carry out anti-chlorine salt/sulfate attack test, specific test method and anti- Sulfate attack test is consistent, as a result such as the following table 4.
4 cement material anti-chlorine salt of table/sulfate attack test result
From table 2 to table 4 as can be seen that compared with comparative example 1 and comparative example 2, with the growth for corroding age, High-belite Cement material can be improved under sulfate, villaumite and composite compaction technique in the incorporation of graphene oxide on the whole Flexural strength and compression strength.

Claims (10)

1. a kind of high resistance to corrosion low-heat cement material containing graphene oxide, which is characterized in that the highly resistance containing graphene oxide Erosion low-heat cement material consists of the following components in percentage by weight: High-belite Cement 22.5-23.0%, normal sand 67.6- 68.5%, polycarboxylate water-reducer 0.5-0.6%, graphene oxide dispersion 0.72-1.2%, surplus are water；
The chemical constituent of the High-belite Cement are as follows: SiO2> 23%, CaO > 60%, Al2O3> 3.0%, Fe2O3> 4.5%, SO3 > 2.3%, MgO > 3.4%.
2. the high resistance to corrosion low-heat cement material according to claim 1 containing graphene oxide, which is characterized in that described oxygen-containing The high resistance to corrosion low-heat cement material of graphite alkene consists of the following components in percentage by weight: High-belite Cement 22.7%, mark Quasi- sand 68.0%, polycarboxylate water-reducer 0.55%, graphene oxide dispersion 0.96%, surplus are water.
3. the high resistance to corrosion low-heat cement material according to claim 1 or 2 containing graphene oxide, which is characterized in that described Normal sand is SiO2Content be not less than 98% natural rounded siliceous sand.
4. the high resistance to corrosion low-heat cement material according to claim 1 or 2 containing graphene oxide, which is characterized in that described The solid content of polycarboxylate water-reducer is 7.2-15.6%, water-reducing rate 15-20%.
5. the high resistance to corrosion low-heat cement material according to claim 4 containing graphene oxide, which is characterized in that the poly- carboxylic The solid content of sour water-reducing agent is 8%, water-reducing rate 17%.
6. the high resistance to corrosion low-heat cement material according to claim 1 or 2 containing graphene oxide, which is characterized in that described Single layer rate > 90% of graphene oxide dispersion, solid content 0.90-0.98%, partial size are 2.2-2.8 μm.
7. the high resistance to corrosion low-heat cement material according to claim 6 containing graphene oxide, which is characterized in that the oxidation The solid content of graphene dispersing solution is 0.94%, and partial size is 2.56 μm.
8. a kind of preparation method of the high resistance to corrosion low-heat cement material as claimed in claim 1 containing graphene oxide, It carries out at normal temperatures and pressures, which is characterized in that including following operating procedure:
(1) High-belite Cement, normal sand, polycarboxylate water-reducer, graphene oxide point are weighed according to above-mentioned weight percent Dispersion liquid and water；
(2) graphene oxide dispersion is dissolved in suitable quantity of water and graphene oxide solution is made；
(3) polycarboxylate water-reducer and graphene oxide solution are mixed and stirred for 5-10min, obtain mixed liquor；
(4) High-belite Cement, normal sand and remaining water are added in mixed liquor and stir 3-5min, obtain cement mortar, Then cement mortar is formed to obtain cement specimen, then cement specimen is conserved, obtain the height containing graphene oxide Low-heat cement material against corrosion.
9. the preparation method of the high resistance to corrosion low-heat cement material according to claim 8 containing graphene oxide, feature exist In the molding specifically: pour into 40mm × 40mm × 160mm mold cement mortar and place 1 day；The maintenance is specific Are as follows: first cement specimen is conserved 25-30 days in clear water, then take out be put into as mass fraction for 10% metabisulfite solution, It is conserved in the composite solution that 10% sodium chloride solution or 10% metabisulfite solution and 10% sodium chloride solution mix in equal volume 85-95 days；The rate of the stirring is 135-295r/min.
10. the high resistance to corrosion low-heat cement material containing graphene oxide that a kind of preparation method as described in claim 8 or 9 obtains Material, which is characterized in that the aquation thermal parameter of the high resistance to corrosion low-heat cement material containing graphene oxide: the 3d heat of hydration≤ 176kJ/kg, the 7d heat of hydration≤233kJ/kg, the 28d heat of hydration≤285kJ/kg；Intensive parameter: 28d flexural strength >=9.0MPa； 28d compression strength >=63.0MPa；Parameter against corrosion: (1) resisting erosion of sulfate flexural strength is tested: the flexural strength of 30d >= Flexural strength >=14.0MPa of flexural strength >=14.3MPa of 13.0MPa, 90d, 180d；(2) resisting erosion of sulfate pressure resistance Degree test: compression strength >=83.5Mpa of compression strength >=81.5Mpa of compression strength >=78.8MPa of 30d, 90d, 180d； (3) precenting chlorate corrosion flexural strength is tested: flexural strength >=11.1MPa of flexural strength >=10.6MPa of 30d, 90d, 180d Flexural strength >=10.7MPa；(4) precenting chlorate corrosion intensity test: compression strength >=74.6MPa's of 30d, 90d is anti- Compressive Strength >=78.3Mpa, compression strength >=81.0Mpa of 180d；(5) anti-chlorine salt-sulfate attack flexural strength test: 30d Flexural strength >=11.1MPa, flexural strength >=12.5MPa of flexural strength >=12.2MPa of 90d, 180d；(6) anti-chlorine salt- Sulfate attack intensity test: compression strength >=82.3Mpa's of compression strength >=75.1MPa of 30d, 90d, 180d is anti- Compressive Strength >=83.4Mpa.
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CN110183181A (en) * 2019-06-03 2019-08-30 南京工业大学 A kind of preparation method of modified cement-based composite material
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CN114573284A (en) * 2022-05-09 2022-06-03 太原理工大学 Graphene oxide magnetic oriented dispersion reinforced cement-based composite material and preparation method thereof
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