CN110304872B - Nano modified cement-based underwater non-dispersible material and preparation method thereof - Google Patents

Nano modified cement-based underwater non-dispersible material and preparation method thereof Download PDF

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Publication number
CN110304872B
CN110304872B CN201910757767.1A CN201910757767A CN110304872B CN 110304872 B CN110304872 B CN 110304872B CN 201910757767 A CN201910757767 A CN 201910757767A CN 110304872 B CN110304872 B CN 110304872B
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underwater
nano
cement
dispersible
modified cement
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CN110304872A (en
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陈晓星
李东云
曾灶红
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Leap magnesium technology (Shenzhen) Co.,Ltd.
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陈晓星
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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
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • 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
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/74Underwater applications

Abstract

The invention is applied to the fields of hydraulic engineering, buildings, bridges, sea wall bank protection and the like, and particularly relates to a nano modified cement-based underwater non-dispersible material and a preparation method thereof2Or CaCO3And a preferable flocculating agent, the materials are uniformly mixed by using a stirrer, and quartz sand is added to obtain the nano modified cement-based non-dispersible material. The material has the fluidity of 260cm, can realize underwater self-leveling, has high fluidity and good anti-dispersion property, has the suspended matter content of less than 80mg/L, the 1d strength of nearly 20MPa, the 28d strength of more than 50MPa and has the micro-expansion effect. The material can be in the form of dry powder, wet-mixed mortar or concrete, can be made into dry powder material, can be directly constructed underwater by adding water and mixing on site, and is easy to realize large-scale production and application. Can meet the application requirements in the fields of hydraulic engineering, buildings, bridges and seawall bank protection.

Description

Nano modified cement-based underwater non-dispersible material and preparation method thereof
Technical Field
The invention is applied to the fields of hydraulic engineering, buildings, bridges, sea wall bank protection and the like, and particularly relates to a nano modified cement-based underwater nondispersive material and a preparation method thereof.
Background
The underwater undispersed material is prepared by adding flocculant into cement-based material, so that it has anti-dispersion property when it is constructed in water, and when it is used, fine aggregate or coarse aggregate can be added according to the requirements. The non-dispersive material needs to have the characteristics of high fluidity, high early strength, no shrinkage and the like, so that the construction is convenient, the construction period is greatly shortened, and the engineering quality is ensured.
The patent CN106082849A in the prior art provides an underwater undispersed high-performance concrete which is composed of a cementing material, a flocculating agent, sand, stone and a water reducing agent, wherein the cementing material is composed of cement and mineral powder, the content of suspended substances in the undispersed concrete is 152mg/L, the underwater forming strength for 7 days is 41.6MPa, the 28d strength is 61.2MPa, and the 28d electric flux is 1192C.
Patent CN107298564A is composed of portland cement, aluminate cement, desulfurized gypsum, medium-activity magnesium oxide, high-activity magnesium oxide expanding agent, triethanolamine, polyacrylamide, ethylene oxide propylene oxide copolymer, etc., and has good fluidity, pourability and volume stability.
The underwater undispersed material is mainly characterized by that it utilizes the action of "bridge frame" of high-molecular long chain of flocculant to make the mixture form stable space network structure, raise cohesive force of fresh concrete, limit dispersion and segregation of fresh concrete and prevent cement loss. However, the presence of flocculants causes a large increase in water demand, poor flowability, and a slow hydration rate, resulting in low early strength, which severely affects the strength development of the material if the water is in a flowing state.
In the prior art, triethanolamine, epoxy organic substances and the like are used as flocculating agents, the substances are liquid and toxic, and the following problems are mainly caused when the substances are used on a large scale:
1. the use of a large amount of the water-saving agent can cause serious water pollution and is harmful to human bodies;
2. other materials are solid, the flocculating agent is viscous liquid, and the transportation, the field construction and the like are inconvenient;
3. the anti-dispersion effect is not good. In addition, the cementing material used in the prior art is single, poor in fluidity and anti-dispersion property, low in early strength and inconvenient to construct, the most important properties of the non-dispersible material are underwater fluidity and anti-dispersion property, the content of suspended solids measured in the prior art is 150mg/L, the requirements of the test procedure standard of underwater non-dispersible concrete are only marginally met, but the water quality around the actual construction is still very turbid.
The invention starts from gel materials, adds nano materials to improve the activity, preferentially selects flocculating agents, can realize underwater self-leveling without dispersing materials, has high early strength, has the suspended matter content lower than 80mg/L, is obviously superior to the prior art, and is more convenient for large-scale production and application.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a nano modified cement-based underwater non-dispersible material and a preparation method thereof, and the prepared non-dispersible material has good fluidity, can realize underwater self-leveling, has high early strength, good dispersibility resistance, high bonding strength with a base layer, good durability, can be directly constructed underwater, and greatly shortens the working hours.
The invention is realized by the following technical scheme:
a nano modified cement-based underwater non-dispersible material comprises a gelled material, an additive and water, wherein,
the mass ratio of each component in the gelled material to the common cement is as follows: silica fume: fly ash: mineral powder: metakaolin: 30-70% of superfine cement: 3-15%: 0-20%: 5% -20%: 0-10%: 5-25%, and the sum of the mass ratios of the components is 100%.
The composition of the gel material is obtained through a large number of experimental researches, and the material obtained by the composition and the proportion has high underwater early strength, good fluidity, compact slurry and good durability.
As a preferred technical scheme of the invention, the common cement is preferably 525 cement, the mineral powder is preferably ultrafine mineral powder, and the specific surface area is more than or equal to 500m2Per kg of ultra-fine cement D50≤8μm。
According to a preferable technical scheme, the mass ratio of each component in the additive to the cementing material is 5-15%, 5-20%, 0.25-1.5%, 6-25% and 0.05-0.2% respectively.
In a preferred embodiment of the present invention, the water reducing agent is a powder type polycarboxylic acid water reducing agent, the defoamer P803 is a polyacrylamide flocculant, and the non-dispersant is commercially available.
A large number of experimental researches show that the materials used according to the proportion have good early strength, fluidity and anti-dispersion property, are all powder type, are convenient to construct on site, and are non-toxic and harmless.
As a preferred technical scheme of the invention, the nano modified cement-based underwater non-dispersible material also contains nano SiO2Or CaCO3Wherein, the nano SiO2Or CaCO3Is 0.5 to 5 percent of the gelled material.
As a preferred technical scheme of the invention, the nano SiO2The grain diameter is 10nm-150nm,the specific surface area is more than 150m2/g。
As a preferable technical scheme of the invention, the material also contains quartz sand No. 6, quartz sand No. 7 and quartz sand No. 8 in a mass ratio of 5:3:2, and the mass ratio of the total amount of the quartz sand to the cementing material is 0.5-2: 1.
A large number of experimental researches show that the early strength can be improved and more compact slurry can be obtained by adopting the nano material.
As a preferred technical scheme of the invention, the water addition amount is 15-60% of the mass of the cementing material.
The invention further provides a preparation method of the nano modified cement-based underwater non-dispersible material, which comprises the following steps:
uniformly mixing the gel adhesive material and the additive, adding water, uniformly mixing by using a stirrer, and adding quartz sand to obtain the nano modified cement-based non-dispersible material.
As a preferred technical scheme of the invention, the invention provides non-dispersible concrete, which adopts a (nano modified cement-based underwater non-dispersible material) cementing material: sand: stone: the water is prepared according to the mixing ratio of 10:14:21: 4.
The nano modified cement-based underwater non-dispersible material is prepared by firstly starting from a cementing material, compounding 525 cement, superfine mineral powder, silica fume, a high-efficiency water reducing agent, a defoaming agent and the like, and adding a certain amount of nano SiO2Or CaCO3And the preferable flocculating agent is prepared by uniformly mixing the materials by using a stirrer, adding quartz sand No. 6, 7 and 8 to obtain the nano modified cement-based non-dispersible material, and directly adding water for mixing according to engineering requirements or adding crushed stone for mixing.
The beneficial effects of the invention compared with the prior art comprise:
the invention provides a nano modified cement-based underwater undispersed material and a preparation method thereof, which are characterized in that a nano material is doped for modification on the basis of optimizing the prior art by adopting a single cementing material, and a preferable flocculating agent is adopted, so that the problem that the prior art cannot simultaneously achieve good fluidity and high early strength is solved, the underwater anti-dispersion property is greatly improved, and the nano modified cement-based underwater undispersed material is safe, environment-friendly and high in practical value. The product job site of this patent only needs to add water and mixes and can carry out direct construction under water. The preparation process is simple and easy to operate, and the product belongs to an inorganic system, and has high fluidity, good construction performance and good durability.
The non-dispersed material has a fluidity of 260cm, no bleeding, can realize underwater self-leveling, has high fluidity and good dispersibility resistance, has a suspended matter content of less than 80mg/L, a cement loss of only 0.5 percent, a 1d strength of more than 15MPa, a 28d strength of more than 50MPa, a strength ratio of 98 percent, a bonding strength with a matrix of more than 2.5MPa, and has a micro-expansion effect.
The invention has the advantages that the raw materials are all solid, can be made into dry powder materials, can be directly constructed underwater by adding water and mixing on site, and is easy to realize large-scale production and application. Can meet the application requirements in the fields of hydraulic engineering, buildings, bridges and seawall bank protection.
Drawings
Fig. 1 is a schematic view of a fluidity test, wherein (1a) the fluidity test in air is a schematic view, and (1b) the fluidity test in water is a schematic view.
FIG. 2 is a schematic diagram of the adhesion strength test with the substrate.
Fig. 3, schematic view of underwater casting of non-dispersed material.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the invention are not limited thereto.
Example 1
525 cement: 50%, silica fume: 7%, fly ash: 10%, limestone powder: 9% of mineral powder: 10%, metakaolin: 5% of superfine cement: 9 percent of the components form a gelled material, the gelled material is 1000g, and then aluminum sulfate accounting for the mass fraction of the gelled material is added: 10%, sodium metasilicate: 15%, no dispersant: 0.52%, water reducing agent 16%, defoaming agent: 0.1 percent of water reducing agent, wherein the water reducing agent is powder polycarboxylic acid water reducing agent, the P803 type defoaming agent, the non-dispersing agent is polyacrylamide flocculant, quartz sand No. 6, quartz sand No. 7 and quartz sand No. 8 are added according to the mass ratio of 5:3:2, the mass ratio of the total amount of the quartz sand to the cementing material is 1:1, and the added water amount is 540 g. The tests were carried out with reference to FIGS. 1, 2 and 3, and the freshly stirred non-dispersible material had a fluidity of 260mm (in air), a suspended solids content of 85mg/L, a 1d flexural strength of 2.1MPa, a compressive strength of 7.1MPa, a 3d flexural strength of 5.5MPa, a compressive strength of 19.6MPa, a 28d flexural strength of 7.4MPa and a compressive strength of 46.5 MPa.
Example 2
525 cement: 50%, silica fume: 7%, fly ash: 10%, limestone powder: 9% of mineral powder: 10%, metakaolin: 5% of superfine cement: 9 percent of the components form a gelled material, the gelled material is 1000g, and then aluminum sulfate accounting for the mass fraction of the gelled material is added: 10%, sodium metasilicate: 15%, nano-silica: 10%, no dispersant: 0.52%, water reducing agent 16%, defoaming agent: 0.1 percent of water reducing agent, wherein the water reducing agent is powder polycarboxylic acid water reducing agent, the P803 type defoaming agent, the non-dispersing agent is polyacrylamide flocculant, quartz sand No. 6, quartz sand No. 7 and quartz sand No. 8 are added according to the mass ratio of 5:3:2, the mass ratio of the total amount of the quartz sand to the cementing material is 1:1, and the added water amount is 540 g. The test is carried out by referring to the figures 1, 2 and 3, the fluidity of the fresh non-dispersed material is 255mm (in air), the suspended matter content is 79mg/L, the 1d flexural strength is 3.3MPa, the compressive strength is 9.8MPa, the 3d flexural strength is 6.5MPa, the compressive strength is 27.8MPa, the 28d flexural strength is 9.6MPa, the compressive strength is 50.2MPa, and the micro-expansion effect is achieved.
Example 3
525 cement: 55%, silica fume: 7%, fly ash: 5% of mineral powder: 6%, metakaolin: 5% of superfine cement: 17%, limestone powder: 5 percent of the components form a gelled material, the gelled material is 1000g, and then aluminum sulfate accounting for the mass fraction of the gelled material is added: 10%, sodium metasilicate: 14%, nano-silica: 10%, no dispersant: 0.5%, water reducing agent 12%, defoaming agent: 0.1 percent of water reducing agent, wherein the water reducing agent is powder polycarboxylic acid water reducing agent, the P803 type defoaming agent, the non-dispersing agent is polyacrylamide flocculant, quartz sand No. 6, quartz sand No. 7 and quartz sand No. 8 are added according to the mass ratio of 5:3:2, the mass ratio of the total amount of the quartz sand to the cementing material is 1:1, and 491g of water is added. The test is carried out by referring to the figures 1, 2 and 3, the fluidity of the fresh non-dispersed material is 240mm (in air), the suspended matter content is 56mg/L, the 1d flexural strength is 3.6MPa, the compressive strength is 15.2MPa, the 3d flexural strength is 7.8MPa, the compressive strength is 35.4MPa, the 28d flexural strength is 10.5MPa, the compressive strength is 53.6MPa, and the micro-expansion effect is achieved.
Example 4
525 cement: 55%, silica fume: 7%, fly ash: 5% of mineral powder: 6%, metakaolin: 5% of superfine cement: 17%, limestone powder: 5 percent of the components form a gelled material, the gelled material is 1000g, and then aluminum sulfate accounting for the mass fraction of the gelled material is added: 10%, sodium metasilicate: 14% of nano CaCO3: 10%, no dispersant: 0.5%, water reducing agent 12%, defoaming agent: 0.1 percent of water reducing agent, wherein the water reducing agent is powder polycarboxylic acid water reducing agent, the P803 type defoaming agent, the non-dispersing agent is polyacrylamide flocculant, and then quartz sand with the mass ratio of 1:1 to the cementing material is added, wherein the quartz sand is 6#, 7# and 8# quartz sand with the mass ratio of 5:3:2, and 491g of water is added. The test is carried out by referring to the figures 1, 2 and 3, the fluidity of the fresh non-dispersed material is 250mm (in air), the suspended matter content is 61mg/L, the 1d flexural strength is 3.5MPa, the compressive strength is 13.8MPa, the 3d flexural strength is 7.3MPa, the compressive strength is 33.6MPa, the 28d flexural strength is 9.7MPa, the compressive strength is 50.2MPa, and the micro-expansion effect is achieved.
Example 5
Preparing a cementing material according to example 3, wherein the cementing material comprises the following components in percentage by mass: sand: stone: the non-dispersible concrete is prepared by the concrete mixing ratio of 10:14:21:4 of water, and tests are carried out by referring to figures 1, 2 and 3, the fluidity of fresh concrete is 260mm (in air), the expansion degree is 595mm, the cement loss is 1%, the suspended solid content is 82mg/L, the final setting time is 5.5h, the 1d underwater compressive strength is 12MPa, the 3d underwater compressive strength is 30.4MPa, the 28d underwater compressive strength is 54MPa, the strength ratio is 85%, and the micro-expansion effect is achieved.
Comparative example 1
Ordinary silica cement: 60 percent of mineral powder, 35 percent of silica fume and 5 percent of silica fume, wherein the cementing material is 1000g, 1 percent of a commercially available UWB-III type flocculating agent accounting for the mass fraction of the cementing material is added, 1 percent of a water reducing agent is added, and quartz sand accounting for 1:1 of the mass fraction of the cementing material is added, wherein the quartz sand is quartz sand No. 6, 7 and 8 according to the mass fraction of the cementing material and is 5:3:2, and the water addition amount is 450g, the test is carried out by referring to FIGS. 1, 2 and 3, the fluidity of a newly stirred non-dispersible material is 250mm (in air), the suspended matter content is 145mg/L, the final setting time is 10.5h, the 1d flexural strength is 1.9MPa, the compressive strength is 5.4MPa, the 3d flexural strength is 5.3MPa, the compressive strength is 25.4MPa, the 28d flexural strength is 8.5MPa, and the compressive strength is 33.2MPa, and the micro-expansion effect is achieved.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (8)

1. A nano-modified cement-based underwater non-dispersible material is characterized by comprising a gelled rubber material, an additive and water, wherein:
the mass ratio of each component in the gelled material to the common cement is as follows: silica fume: fly ash: mineral powder: metakaolin: 30-70% of superfine cement: 3-15%: 0-20%: 5% -20%: 0-10%: 5-25%, wherein the ordinary cement is 525% cement, and the superfine cement is D50≤8μm;
The mass ratio of each component in the additive to the cementing material is 5-15%, 5-20%, 0.25-1.5%, 6-25% and 0.05-0.2% respectively;
the water reducing agent is a powder type polycarboxylic acid water reducing agent, the defoaming agent is a P803 type defoaming agent, and the non-dispersing agent is a polyacrylamide flocculating agent;
the sum of the mass ratios of the components is 100 percent.
2. The nano-modified cement-based underwater nondispersive material as claimed in claim 1, wherein the mineral powder is ultrafine mineral powder with a specific surface area of 500m or more2/kg。
3. The nano-modified cement-based underwater non-dispersible material of claim 1, wherein the nano-modified cement-based underwater non-dispersible material further comprises nano SiO2Or CaCO3Wherein, the nano SiO2Or CaCO3Is 0.5 to 5 percent of the mass of the gelled material.
4. The nano modified cement-based underwater non-dispersible material as claimed in claim 3, wherein the material further comprises quartz sand No. 6, quartz sand No. 7 and quartz sand No. 8 in a mass ratio of 5:3:2, and the mass ratio of the total amount of the quartz sand to the cementing material is 0.5-2: 1.
5. The nano-modified cement-based underwater non-dispersible material of claim 3, wherein the nano-SiO is2The particle diameter is 10nm-150nm, and the specific surface area is more than 150m2/g。
6. The nano-modified cement-based underwater non-dispersible material according to any one of claims 1 to 5, wherein the amount of added water is 15 to 60% by mass of the cementitious material.
7. The method for preparing a nano modified cement-based underwater nondispersive material according to any one of claims 1-6, comprising:
uniformly mixing the gel adhesive material and the additive, adding water, uniformly mixing by using a stirrer, and adding quartz sand to obtain the nano modified cement-based non-dispersible material.
8. A non-dispersing concrete, characterized in that a nano-modified cement-based underwater non-dispersing material according to any one of claims 1 to 7 is used: sand: stone: and (3) preparing by matching water.
CN201910757767.1A 2019-08-16 2019-08-16 Nano modified cement-based underwater non-dispersible material and preparation method thereof Active CN110304872B (en)

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CN111635497B (en) * 2020-05-26 2021-07-20 北京建筑材料科学研究总院有限公司 Underwater concrete anti-dispersant and preparation method thereof
CN113004003A (en) * 2021-03-05 2021-06-22 上海建工建材科技集团股份有限公司 Underwater anti-dispersion mortar and preparation method thereof

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