CN105776991A - Modified ecological cementing nano-material and preparation method therefor - Google Patents

Modified ecological cementing nano-material and preparation method therefor Download PDF

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Publication number
CN105776991A
CN105776991A CN201510975172.5A CN201510975172A CN105776991A CN 105776991 A CN105776991 A CN 105776991A CN 201510975172 A CN201510975172 A CN 201510975172A CN 105776991 A CN105776991 A CN 105776991A
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ecological
ecological nano
cement
modified
nano
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CN105776991B (en
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郭丽萍
雷东移
曹园章
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Southeast University
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Southeast University
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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
    • C04B28/04—Portland 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
    • 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
    • C04B20/10—Coating or impregnating
    • C04B20/1055—Coating or impregnating with inorganic materials
    • C04B20/1066—Oxides, Hydroxides
    • 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
    • C04B2111/00008—Obtaining or using nanotechnology related materials
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Road Paving Structures (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The invention relates to a modified ecological cementing nano-material and a preparation method therefor. According to the modified ecological cementing nano-material, the water cement ratio is 0.15 to 0.35; and the modified ecological cementing nano-material contains other ingredients in percentage by mass: 35% to 55% of cement, 3% to 11% of modified silica fume, 10% to 20% of limestone flour, 30% to 40% of high-quality I-class low-calcium fly ash and 0.2% to 2% of efficient water reducing agent. Through carrying out predispersing treatment on the silica fume of the ecological nano-material, the dispersity of the ecological nano-material in a cement-based material is greatly improved, so that the micro-aggregate effect, filler effect and volcanic ash effect of the ecological nano-material are more sufficiently exerted. By adding the high-quality limestone flour, the grain size distribution is further optimized, the cohesiveness of cementing material blended slurry is effectively improved, the compactness of a hardened cementing material is improved, and the microstructure of the cementing material is improved. Meanwhile, by adding the fly ash, the fluidity and later strength of cement slurry are improved, and the microstructure of the cementing material is improved.

Description

A kind of ecological nano modified adhesive gel material and preparation method thereof
Technical field
The present invention relates to building material technical field, the preparation method particularly relating to a kind of ecological nano modified adhesive gel material.
Background technology
In the research that cement-based material is modified, there is the mineral admixture of different grain size size or superfine powder is often used to optimize the grain composition of cement-based material, to hope the most close particle packing of formation, thus improving the microstructure of hardening cement base material, and then the physical and mechanical property of improvement cement and durability etc., the admixture such as silicon ash commonly used, flyash, ground blast furnace slag, ground steel slag, agstone etc..
Silicon ash is a kind of ecological nano material being referred to as and having micro-nano granules, it has good volcano ash effect and microgranule filling effect, internal pore structure and the density of cement-based material can be significantly improved, significantly improve the performance such as its intensity, impervious, freeze proof, resist chemical.Why silicon ash has significantly high mineral active, has benefited from the SiO that silicon ash is high on the one hand2Active component, it is possible to the Ca (OH) produced in cement hydration process2Reaction generates C-S-H gel；Then have benefited from the micro-nano granules that it has on the other hand, the granule of this size have the nano materials such as quantum size effect, skin effect and macro quanta tunnel effect the physics of peculiar a series of excellences, chemistry and surface and interface performance, the use of cement-based material can obtain extraordinary result of use.But owing to silicon ash particle is superfine, surface can be significantly high, when existing with individual particle form, being in thermodynamic instability state, can automatically attract each other near and be transformed into steady statue between granule, this phenomenon very easily causes micro-nano granules to reunite, its surface activity is made to decline, the characteristic causing the micro/nano level silicon many excellences of ash completely loses, and practical effect is not good, therefore, about the reuniting effect how eliminated between silicon ash particle, it is always up emphasis and the focus of research.A kind of new silicon ash dispersion method of modifying is provided for this this research, mainly there is hydroxyl by silicon gray surface in the method, with containing certain density aqua calcis, silicon ash is carried out pretreatment, its surface elecrtonegativity is modified as electropositive in advance, put in the configuration use of cement-based material then in conjunction with anionic dispersing agents, thus realizing better dispersion effect.
In combination with there is varigrained flyash and the grain composition of cement-based material is optimized by limestone powder mineral admixture further, to forming the most close particle packing, thus improving the mobility of cement-based material, improve the performances such as the microstructure of hardening cement base material, physical and mechanical property and durability.
Summary of the invention
It is an object of the invention to provide a kind of ecological nano modified adhesive gel material and preparation method thereof, preparation technology is simple, cost is low, good fluidity, intensity high, good endurance.
The preparation method that the technical scheme is that a kind of ecological nano modified adhesive gel material, the ratio of mud is 0.15～0.35, other component is counted as follows with weight/mass percentage composition: cement is 35%～55%, ecological nano material is 3%～11%, agstone 10%～20%, high-quality I level Class F fly ash is 30%～40%, and water reducer is 0.2%～2%；Described ecological nano material is modified silicon ash, SiO2Content is more than 92%wt；The preparation method of described ecological nano material is: by saturated Ca (OH)2With volume ratio preparation Ca (OH) that water presses 1:32Aqueous solution, then by by the load weighted silicon ash of preset blending ratio and the Ca (OH) configured2Aqueous solution configures silicon ash slurry by the mass ratio of 1:10 and stirs, and is then standing and soak for after fully, carries out sucking filtration, be placed on electronic scale by bottle,suction while sucking filtration, as sucking filtration to silicon ash and Ca (OH)2When the mass ratio of solution is 1:1, stops sucking filtration, obtain ecological nano material.
Cement of the present invention is for being numbered common 42.5 grades of portland cements.
Ecological nano material of the present invention is commercially available ordinary silicon ash, SiO2Content is more than 92%wt.
The calcium carbonate content of agstone of the present invention is more than 95%wt, mean diameter 5～20 μm.
Flyash of the present invention is high-quality F class I level Class F fly ash, free CaO content < 1%.
Water reducer of the present invention is polycarboxylic acid series high efficiency water reducing agent, solid content >=40%, water-reducing rate >=40%.
The preparation method of ecological nano modified adhesive gel material of the present invention, comprises the steps:
(1) ecological nano material modification: by saturated Ca (OH)2With volume ratio preparation Ca (OH) that water presses 1:32Aqueous solution, then by by the load weighted silicon ash of preset blending ratio and the Ca (OH) configured2Aqueous solution configures silicon ash slurry by the mass ratio of 1:10 and stirs, and is then standing and soak for after fully, it is carried out sucking filtration, is placed on electronic scale by bottle,suction while sucking filtration, as sucking filtration to silicon ash and Ca (OH)2When the mass ratio of solution is 1:1, stopping sucking filtration, now ecological nano material is modified successfully with standby；
(2) successful ecological nano material modified in step (1) is poured in agitator for cement mortar, water consumption is added by the predetermined ratio of mud, wherein water consumption includes and modifiies the water comprised in the ecological nano material after successfully in step (1), it is subsequently adding according to the load weighted water reducer of preset blending ratio, stirring, then it is sequentially added into by the load weighted cement of preset blending ratio, agstone, flyash, stirring, then the compound stirred being poured into vibration moulding in mould, namely 20 DEG C of standard curings obtain ecological nano modified adhesive gel material for 28 days.
Beneficial effect:
(1) by ecological nano material silicon ash is carried out pre-dispersed process, ecological nano material dispersibility in cement-based material is substantially increased so that the micro aggregate effect of ecological nano material, filling effect and volcano ash effect obtain and play more fully.(2) addition of fat lime stone powder not only considerably reduces cost, the more important thing is and optimize grain composition further, it is effectively increased the cohesiveness of Binder Materials mix slurry, improves the compactness of hardened cement, improve the microstructure of Binder Materials.(3) flyash is introduced, it is possible to reduce further the cost of Binder Materials, the volcano ash effect of prior flyash can be effectively improved later strength, improves the microstructure of Binder Materials；And due to " the ball effect " of fly ash grain, it is possible to increase substantially the mobility of cement slurry.Comprehensive function, is effectively improved the performances such as the microstructure of gel material, physical and mechanical property and durability.
Accompanying drawing explanation
Fig. 1 is the surface potential comparison diagram of the grey and unmodified silicon ash of modified silicon in example 1,
Fig. 2 be in example 1 grey the and unmodified silicon ash of modified silicon in conjunction with the microscopic appearance comparison diagram after water reducer,
Fig. 3 is the microscopic appearance comparison diagram with corresponding reference of hardening ecological nano modified adhesive gel material in embodiment 1.
Detailed description of the invention
Further illustrate the present invention by the examples below.
Fluidity test is undertaken by " 13. flowing degree of net paste of cement " in " Methods for testing uniformity of concrete admixture " GBT8077-2012.
Anti-folding, intensity test are undertaken by " Test method for strength of hydraulic cement mortar (ISO method) " GB/T17671-1999.
All raw material is commercially available finished product.Described cement is for being numbered common 42.5 grades of portland cements.Described ecological nano material is commercially available ordinary silicon ash, SiO2Content is more than 92%wt.The calcium carbonate content of described agstone is more than 95%wt, mean diameter 5～20 μm.Described flyash is high-quality F class I level Class F fly ash, free CaO content < 1%.Described water reducer is polycarboxylic acid series high efficiency water reducing agent, solid content >=40%, water-reducing rate >=40%.
Embodiment 1
A kind of ecological nano modified adhesive gel material, by weight, the ratio of mud is 0.15, other component and weight/mass percentage composition are as follows: cement is 35%, and ecological nano material is 3%, agstone 20%, high-quality I level Class F fly ash is 40%, and high-efficiency water-reducing agent of poly-carboxylic acid is 2%.
After before modified, the surface electrical bitmap of silicon ash particle is as it is shown in figure 1, picture display modified silicon ash granule current potential is transformed into positive potential；Silicon ash particle after before modified in conjunction with water reducer microscopic appearance comparison diagram as in figure 2 it is shown, picture show modified silicon ash dispersibility significantly improve；Hardening ecological nano modified adhesive gel material with the microscopic appearance figure of corresponding reference as shown in Figure 3, in picture display hardening ecological nano modified adhesive gel material, the surface of silicon ash is almost all wrapped up by C-S-H gel, and silicon ash dispersibility is not only worse in reference hardening sample, and a lot of silicon gray surface is still the smooth surface of primary granule.
Embodiment 2
A kind of ecological nano modified adhesive gel material, by weight, the ratio of mud is 0.20, other component and weight/mass percentage composition are as follows: cement is 38.5%, and ecological nano material is 5%, agstone 17%, high-quality I level Class F fly ash is 38%, and high efficiency water reducing agent is 1.5%.
Embodiment 3
A kind of ecological nano modified adhesive gel material, by weight, the ratio of mud is 0.25, other component and weight/mass percentage composition are as follows: cement is 42%, and ecological nano material is 7%, agstone 15%, high-quality I level Class F fly ash is 35%, and high efficiency water reducing agent is 1.0%.
Embodiment 4
A kind of ecological nano modified adhesive gel material, by weight, the ratio of mud is 0.30, other component and weight/mass percentage composition are as follows: cement is 56%, and ecological nano material is 3.5%, agstone 10%, high-quality I level Class F fly ash is 30%, and high efficiency water reducing agent is 0.5%.
Embodiment 5
A kind of ecological nano modified adhesive gel material, by weight, the ratio of mud is 0.35, other component and weight/mass percentage composition are as follows: cement is 36%, and ecological nano material is 3.8%, agstone 20%, high-quality I level Class F fly ash is 40%, and high efficiency water reducing agent is 0.2%.
The preparation method of the nano modification cement described in embodiment 1-embodiment 5, comprises the following steps:
(1) ecological nano material modification: be pre-configured with saturated Ca (OH)2Saturated solution, then by saturated Ca (OH)2With volume ratio preparation Ca (OH) that water presses 1:32Aqueous solution, then by by the load weighted silicon ash of preset blending ratio and the Ca (OH) configured2Aqueous solution is pressed the mass ratio configuration silicon ash slurry of 1:10 and stirs 30 minutes with the rotating speed of 1000r/min with magnetic stirrer, then after being standing and soak for 24h, it is carried out sucking filtration, while sucking filtration, bottle,suction is placed on electronic scale, as sucking filtration to silicon ash and Ca (OH)2When the mass ratio of solution is 1:1, stopping sucking filtration, now ecological nano material is modified successfully with standby.
(2) successful ecological nano material modified in step (1) is poured in agitator for cement mortar, water consumption is added by the predetermined ratio of mud, wherein water consumption includes and modifiies the water comprised in the ecological nano material after successfully in step (1), it is subsequently adding according to the load weighted water reducer of preset blending ratio, stirs slowly 1-2 minute.Then being sequentially added into by the load weighted cement of preset blending ratio, agstone, flyash, stir slowly 1-2 minute, stir soon 2-4 minute, then the compound stirred is poured into vibration moulding in mould, namely 20 DEG C of standard curings obtain ecological nano modified adhesive gel material for 28 days.
Relevant parameter test result is as shown in table 1.
Table 1
Note: the embodiment reference in table 1 is identical with the match ratio of corresponding embodiment, the difference is that the silicon ash that silicon ash therein is unmodified mistake.
The above; it is only the specific embodiment of the present invention; but protection scope of the present invention is not limited thereto; any those of ordinary skill in the art are in the technical scope that disclosed herein; the change can expected without creative work or replacement, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with claims protection defined.

Claims (6)

1. an ecological nano modified adhesive gel material, it is characterised in that the ratio of mud is 0.15 ~ 0.35, other component is counted as follows with weight/mass percentage composition: cement is 35% ~ 55%, and ecological nano material is 3% ~ 11%, agstone 10% ~ 20%, high-quality I level Class F fly ash is 30% ~ 40%, and water reducer is 0.2% ~ 2%；Described ecological nano material is modified silicon ash, SiO2Content is more than 92%wt；The preparation method of described ecological nano material is: by saturated Ca (OH)2With volume ratio preparation Ca (OH) that water presses 1:32Aqueous solution, then by by the load weighted silicon ash of preset blending ratio and the Ca (OH) configured2Aqueous solution configures silicon ash slurry by the mass ratio of 1:10 and stirs, and is then standing and soak for after fully, carries out sucking filtration, be placed on electronic scale by bottle,suction while sucking filtration, as sucking filtration to silicon ash and Ca (OH)2When the mass ratio of solution is 1:1, stops sucking filtration, obtain ecological nano material.
2. ecological nano modified adhesive gel material according to claim 1, it is characterised in that: described cement is for being numbered common 42.5 grades of portland cements.
3. ecological nano modified adhesive gel material according to claim 1, it is characterised in that: the calcium carbonate content of described limestone powder is more than 95%wt, mean diameter 5 ~ 20 μm.
4. ecological nano modified adhesive gel material according to claim 1, it is characterised in that: described flyash is high-quality F class I level Class F fly ash, free CaO content < 1%.
5. ecological nano modified adhesive gel material according to claim 1, it is characterised in that: described water reducer is polycarboxylic acid series high efficiency water reducing agent, solid content >=40%, water-reducing rate >=40%.
6. one kind prepare as arbitrary in claim 1 ~ 5 described in the method for ecological nano modified adhesive gel material, it is characterised in that specifically comprise the following steps that
(1) ecological nano material modification: by saturated Ca (OH)2With volume ratio preparation Ca (OH) that water presses 1:32Aqueous solution, then by by the load weighted silicon ash of preset blending ratio and the Ca (OH) configured2Aqueous solution configures silicon ash slurry by the mass ratio of 1:10 and stirs, and is then standing and soak for after fully, carries out sucking filtration, be placed on electronic scale by bottle,suction while sucking filtration, as sucking filtration to silicon ash and Ca (OH)2When the mass ratio of solution is 1:1, stopping sucking filtration, now ecological nano material is modified successfully with standby；
(2) successful ecological nano material modified in step (1) is poured in agitator for cement mortar, water consumption is added by the predetermined ratio of mud, wherein water consumption includes and modifiies the water comprised in the ecological nano material after successfully in step (1), it is subsequently adding according to the load weighted water reducer of preset blending ratio, stirring, then it is sequentially added into by the load weighted cement of preset blending ratio, agstone, flyash, stirring, then the compound stirred being poured into vibration moulding in mould, namely 20 DEG C of standard curings obtain ecological nano modified adhesive gel material for 28 days.
CN201510975172.5A 2015-12-23 2015-12-23 A kind of ecological nano is modified binder materials and preparation method thereof Active CN105776991B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109384433A (en) * 2018-12-04 2019-02-26 湖北工业大学 Low-heat damages use in concrete member cementitious material
CN109626939A (en) * 2019-01-15 2019-04-16 北京化工大学 It is a kind of modified to enhance water-fast white lime cementitious material and preparation
CN110642550A (en) * 2019-10-10 2020-01-03 中国铁道科学研究院集团有限公司铁道建筑研究所 Composite microsphere for improving early performance of cement-based material

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102452805A (en) * 2010-10-20 2012-05-16 新疆研科节能科技有限公司 Mineral admixture for high durable concrete
CN103193420A (en) * 2012-01-10 2013-07-10 平湖市法而特建筑保温科技有限公司 Nano-material-containing high-strength high-heat insulation exterior wall inorganic heat-retaining face brick
KR20150014026A (en) * 2013-07-26 2015-02-06 동양시멘트 주식회사 Concrete-polymer composite using black polymer dispersion
CN105036659A (en) * 2015-07-31 2015-11-11 武汉理工大学 Nanometer and micrometer modified gel material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102452805A (en) * 2010-10-20 2012-05-16 新疆研科节能科技有限公司 Mineral admixture for high durable concrete
CN103193420A (en) * 2012-01-10 2013-07-10 平湖市法而特建筑保温科技有限公司 Nano-material-containing high-strength high-heat insulation exterior wall inorganic heat-retaining face brick
KR20150014026A (en) * 2013-07-26 2015-02-06 동양시멘트 주식회사 Concrete-polymer composite using black polymer dispersion
CN105036659A (en) * 2015-07-31 2015-11-11 武汉理工大学 Nanometer and micrometer modified gel material

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109384433A (en) * 2018-12-04 2019-02-26 湖北工业大学 Low-heat damages use in concrete member cementitious material
CN109384433B (en) * 2018-12-04 2021-08-17 湖北工业大学 Cementing material for low-heat-damage concrete member
CN109626939A (en) * 2019-01-15 2019-04-16 北京化工大学 It is a kind of modified to enhance water-fast white lime cementitious material and preparation
CN110642550A (en) * 2019-10-10 2020-01-03 中国铁道科学研究院集团有限公司铁道建筑研究所 Composite microsphere for improving early performance of cement-based material

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