CN108821690B - Preparation method of MOF high-performance concrete with high strength and small shrinkage - Google Patents

Preparation method of MOF high-performance concrete with high strength and small shrinkage Download PDF

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CN108821690B
CN108821690B CN201810805804.7A CN201810805804A CN108821690B CN 108821690 B CN108821690 B CN 108821690B CN 201810805804 A CN201810805804 A CN 201810805804A CN 108821690 B CN108821690 B CN 108821690B
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mof
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performance concrete
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CN108821690A (en
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金彩云
李洪文
李悦
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Beijing University of Technology
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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
    • C04B28/02Compositions 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
    • C04B28/04Portland 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
    • C04B2111/34Non-shrinking or non-cracking materials
    • C04B2111/343Crack resistant materials
    • 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
    • C04B2201/00Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50Mortars, 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

一种强度高收缩小的MOF高性能混凝土的制备方法,涉及建筑材料领域,按质量百分比计量如下:(1)水泥:15%‑20%;(2)矿物掺合料:5%‑10%;(3)粗集料:42%‑47%;(4)细集料:28%‑33%;(5)减水剂:胶凝材料质量的1%‑2%;(6)MOF:胶凝材料质量的1%‑3%;(7)表面活性剂:胶凝材料质量的1%‑3%。将组分(6)和(7)放入水中,然后超声分散120分钟后将组分(5)放入经超声分散后的分散液中,搅拌30分钟。将上述所得分散液与组分(1)、(2)、(3)和(4)放入混凝土搅拌机中搅拌均匀,得到高性能混凝土。本发明混凝土抗压、抗拉强度高,收缩小,可有效解决混凝土开裂问题,提高混凝土的耐久性。该混凝土无需特殊养护,易于现场施工。A preparation method of MOF high-performance concrete with high strength and low shrinkage, relates to the field of building materials, and is measured by mass percentage as follows: (1) cement: 15%-20%; (2) mineral admixture: 5%-10% ; (3) Coarse aggregate: 42%-47%; (4) Fine aggregate: 28%-33%; (5) Water reducing agent: 1%-2% of the mass of the cementitious material; (6) MOF: 1%-3% of the mass of the cementitious material; (7) Surfactant: 1%-3% of the mass of the cementitious material. The components (6) and (7) were put into water, and then ultrasonically dispersed for 120 minutes, and then the component (5) was put into the ultrasonically dispersed dispersion, and stirred for 30 minutes. The above-obtained dispersion liquid and components (1), (2), (3) and (4) are put into a concrete mixer and mixed evenly to obtain high performance concrete. The concrete of the invention has high compressive and tensile strength and small shrinkage, can effectively solve the problem of concrete cracking, and improve the durability of the concrete. The concrete requires no special maintenance and is easy to construct on site.

Description

Preparation method of MOF high-performance concrete with high strength and small shrinkage
Technical Field
The invention relates to a process for preparing MOF high-performance concrete with high strength and small shrinkage, belongs to the technical field of building materials, and can effectively solve the problem of early cracking of concrete.
Background
Metal-Organic frameworks (MOFs) are multi-dimensional periodic porous frameworks, which are mainly formed by coordination of Metal ions and Organic ligands (Organic linkers) containing N or O. In recent years, MOFs have been rapidly developed due to their excellent properties. The MOF has the advantages of high specific surface area, adjustable pore diameter and the like, so that the MOF can be applied to the field of gas and liquid adsorption. The MOF adsorption-desorption of water molecules is one of the material applications.
At present, high-performance concrete is widely applied to engineering. Compared with the common concrete, the high-performance concrete is prepared by adopting a lower water cement ratio, so that the self-drying phenomenon in the concrete is obvious, the self-shrinkage of the concrete caused by the self-drying phenomenon is larger, and even the self-shrinkage is a main shrinkage mode of the concrete. The large self-shrinkage of high-performance concrete can cause cracking, reduce the bearing capacity and durability of the concrete structure and cause great damage to the structure.
In order to solve the problems, the invention provides a preparation method of MOF high-performance concrete with high strength and small shrinkage. The invention adopts the internal curing principle to achieve the purpose of reducing self-shrinkage. In the previous research of reducing the shrinkage of high-performance concrete by adopting an internal curing principle, researchers mostly add porous water-saturated materials such as ceramsite and expanded shale, and although the shrinkage can be reduced, the strength of the concrete is often reduced. The invention uses the nano material MOF, so that the self-shrinkage of the concrete is obviously reduced, the strength of the concrete is not reduced, even the strength of the concrete is improved to a certain extent, the bearing capacity and the durability of a concrete structure can be effectively improved, and the maintenance cost is reduced.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: a preparation method of MOF high-performance concrete with high strength and small shrinkage is disclosed for solving the problems of high self-shrinkage, easy cracking and the like of the high-performance concrete.
The invention can be realized by the following technical scheme: a preparation method of MOF high-performance concrete with high strength and small shrinkage comprises the following components in percentage by mass:
(1) cement: 15% -20%;
(2) mineral admixture: 5% -10%;
(3) coarse aggregate: 42% -47%;
(4) fine aggregate: 28% -33%;
the above four are collectively referred to as gelling materials, and add up to 100%;
(5) water reducing agent: 1% -2% of the mass of the cementing material;
(6) MOF type Cr-MIL-101: 1% -3% of the mass of the cementing material;
(7) surfactant (b): 1-3% of the mass of the cementing material.
The cement is ordinary portland cement P.O.42.5.
The mineral admixture has a specific surface area of 0.4-0.6m2The specific surface area of the I-grade or II-grade fly ash is 20-28m2Per gram of silica fume.
The coarse aggregate is crushed stone with a particle size range of 5-16 mm.
The fine aggregate is medium sand.
The water reducing agent is a polycarboxylic acid water reducing agent with the solid content of more than 20 percent.
The specific surface area of the Cr-MIL-101 is 5000-6000m2The mesoporous aperture is 3-3.4 nm.
The surfactant is Sodium Dodecyl Sulfate (SDS).
The preparation method of the MOF high-performance concrete with high strength and small shrinkage comprises the following preparation steps:
adsorption: putting MOF accurately weighed according to the proportion into a closed container with the relative humidity of 100%, and applying 1.2-1.5 atmospheric pressures to enable the MOF to adsorb water vapor until the MOF is saturated;
dispersing: accurately weighing water, a surfactant and a water reducing agent according to a mass ratio, putting the MOF and the surfactant obtained in the step I into the water, performing ultrasonic dispersion for 120 minutes to obtain an MOF dispersion liquid, dissolving the water reducing agent into the dispersion liquid, and stirring for 30 minutes;
③ weighing the materials: accurately weighing cement, mineral admixture, coarse aggregate and fine aggregate according to the mass ratio of the rest components;
stirring: and (3) sequentially putting the materials obtained in the step (iii) into a concrete mixer, then putting 2/3 of the dispersion liquid obtained in the step (ii) into the mixer, mixing for 3 minutes, then putting the rest 1/3 dispersion liquid into the mixer, and mixing for 5 minutes to obtain the MOF high-performance concrete with high strength and small shrinkage.
A preparation process of MOF high-performance concrete with high strength and small shrinkage mainly has the technical innovation points that: the purposes of reducing the concrete shrinkage and improving the strength of the concrete are achieved by utilizing the excellent adsorption-desorption and structure stability of the MOF. The Cr-MIL-101 has excellent water stability, and can keep stable structure in water for a long time, so that the structure of the Cr-MIL-101 is not damaged when the Cr-MIL-101 is dispersed in the water; meanwhile, the structure of Cr-MIL-101 is not damaged under high pressure, so that it can stably exist in concrete. When the self-drying phenomenon is caused in concrete by mixing water consumed by cement hydration, the capillary stress in the partial saturated capillary pores is larger, so that self-shrinkage is generated. And after the saturated Cr-MIL-101 for adsorbing water molecules is added, when the capillary stress is increased, the Cr-MIL-101 is desorbed under the action of pressure, so that water is released from the Cr-MIL-101, the water loss of cement hydration is compensated, the self-drying phenomenon is relieved, the self-shrinkage is reduced, and the risk of concrete cracking is reduced. In addition, water released by Cr-MIL-101 can promote hydration reaction, increase the generation amount of C-S-H gel and improve the strength of concrete; and the Cr-MIL-101 has very high bearing capacity, so that the strength of the concrete is further improved.
The MOF high-performance concrete with high strength and small shrinkage obtained by the method has high strength and small shrinkage, can effectively reduce the cracking risk and improve the durability of a concrete structure, is easy to construct and has wide practical value. Compared with the prior art, the invention has the following advantages:
(1) the self-contraction of the MOF high-performance concrete with high strength and small contraction is small, and compared with the existing high-performance concrete, the MOF high-performance concrete with high strength and small contraction can greatly reduce the cracking risk and reduce the maintenance cost.
(2) The MOF high-performance concrete with high strength and small shrinkage provided by the invention has high compressive strength, and the later strength is still improved because Cr-MIL-101 gradually releases water.
(3) The preparation method of the MOF high-performance concrete with high strength and small shrinkage is different from the existing technology for changing the performance of the concrete, and the invention changes the shrinkage and strength of the concrete from the nanoscale, thereby providing a new method for improving the performance of the concrete.
Detailed Description
In order to further embody the efficacy of the present invention, the present invention is further described in detail with reference to specific application cases.
Examples of mineral admixtures having a specific surface area of 0.4 to 0.6m2A/g class I or II fly ash, and a specific surface area of 20-28m2Silica fume per gram. The coarse aggregate is crushed stone with a particle size range of 5-16 mm.
The fine aggregate is medium sand. The specific surface area of the Cr-MIL-101 is 5000-6000m2The mesoporous aperture is 3-3.4 nm.
Example 1:
a preparation method of MOF high-performance concrete with high strength and small shrinkage comprises the following components in percentage by mass:
(1) ordinary portland cement p.o.42.5: 15 percent;
(2) class I fly ash: 6 percent of
(3) Silica fume: 4 percent;
(4) crushing stone: 42%;
(5) river sand: 33%;
(6) 22% solid content DH-4004 type polycarboxylate water reducer: 2% of the mass of the cementing material;
(7) Cr-MIL-101: 1% of the mass of the cementing material;
(8) sodium lauryl sulfate: 1% of the mass of the cementing material;
the preparation method of the MOF high-performance concrete with the water-to-gel ratio of 0.28 and high strength and small shrinkage comprises the following steps:
adsorption: putting Cr-MIL-101 accurately weighed according to the proportion into a closed container with the relative humidity of 100%, and applying 1.2 atmospheric pressures to enable the container to absorb water vapor until the container is saturated;
dispersing: accurately weighing drinking water, sodium dodecyl sulfate and a polycarboxylate superplasticizer according to a designed water-to-gel ratio of 0.28, putting Cr-MIL-101 and sodium dodecyl sulfate obtained in the step I into water, ultrasonically dispersing for 120 minutes to obtain Cr-MIL-101 dispersion liquid, then dissolving the polycarboxylate superplasticizer into the dispersion liquid, and stirring for 30 minutes;
③ weighing the materials: accurately weighing cement, fly ash, silica fume, broken stone and river sand according to the mass ratio of the rest components;
stirring: and (3) sequentially putting the materials obtained in the step (iii) into a concrete mixer, then putting 2/3 of the dispersion liquid obtained in the step (ii) into the mixer, mixing for 3 minutes, then putting the rest 1/3 dispersion liquid into the mixer, and mixing for 5 minutes to obtain the MOF high-performance concrete with high strength and small shrinkage.
Example 2
A preparation method of MOF high-performance concrete with high strength and small shrinkage comprises the following components in percentage by mass:
(1) ordinary portland cement p.o.42.5: 17 percent;
(2) class I fly ash: 5 percent of
(3) Silica fume: 3 percent;
(4) crushing stone: 45 percent;
(5) river sand: 30 percent;
(6) 24% solid content type DH-4004 polycarboxylic acid water reducing agent: 1.5% of the mass of the cementing material;
(7) Cr-MIL-101: 2% of the mass of the cementing material;
(8) sodium lauryl sulfate: 2% of the mass of the cementing material;
the preparation method of the MOF high-performance concrete with the water-to-gel ratio of 0.28 and high strength and small shrinkage comprises the following steps:
adsorption: putting Cr-MIL-101 accurately weighed according to the proportion into a closed container with the relative humidity of 100%, and applying 1.5 atmospheric pressures to enable the container to absorb water vapor until the container is saturated;
dispersing: accurately weighing drinking water, sodium dodecyl sulfate and a polycarboxylate superplasticizer according to a designed water-to-gel ratio of 0.28, putting Cr-MIL-101 and sodium dodecyl sulfate obtained in the step I into water, ultrasonically dispersing for 120 minutes to obtain Cr-MIL-101 dispersion liquid, then dissolving the polycarboxylate superplasticizer into the dispersion liquid, and stirring for 30 minutes;
③ weighing the materials: accurately weighing cement, fly ash, silica fume, broken stone and river sand according to the mass ratio of the rest components;
stirring: and (3) sequentially putting the materials obtained in the step (iii) into a concrete mixer, then putting 2/3 of the dispersion liquid obtained in the step (ii) into the mixer, mixing for 3 minutes, then putting the rest 1/3 dispersion liquid into the mixer, and mixing for 5 minutes to obtain the MOF high-performance concrete with high strength and small shrinkage.
Example 3
A preparation method of MOF high-performance concrete with high strength and small shrinkage comprises the following components in percentage by mass:
(1) ordinary portland cement p.o.42.5: 20 percent;
(2) class I fly ash: 3 percent of
(3) Silica fume: 2 percent;
(4) crushing stone: 47%;
(5) river sand: 28%;
(6) 20% solid content type DH-4004 polycarboxylic acid water reducing agent: 1% of the mass of the cementing material;
(7) Cr-MIL-101: 3% of the mass of the cementing material;
(8) sodium lauryl sulfate: 3% of the mass of the cementing material;
the preparation method of the MOF high-performance concrete with the water-to-gel ratio of 0.28 and high strength and small shrinkage comprises the following steps:
adsorption: putting Cr-MIL-101 accurately weighed according to the proportion into a closed container with the relative humidity of 100%, and applying 1.3 atmospheric pressures to enable the container to absorb water vapor until the container is saturated;
dispersing: accurately weighing drinking water, sodium dodecyl sulfate and a polycarboxylate superplasticizer according to a designed water-to-gel ratio of 0.28, putting Cr-MIL-101 and sodium dodecyl sulfate obtained in the step I into water, ultrasonically dispersing for 120 minutes to obtain Cr-MIL-101 dispersion liquid, then dissolving the polycarboxylate superplasticizer into the dispersion liquid, and stirring for 30 minutes;
③ weighing the materials: accurately weighing cement, fly ash, silica fume, broken stone and river sand according to the mass ratio of the rest components;
stirring: and (3) sequentially putting the materials obtained in the step (iii) into a concrete mixer, then putting 2/3 of the dispersion liquid obtained in the step (ii) into the mixer, mixing for 3 minutes, then putting the rest 1/3 dispersion liquid into the mixer, and mixing for 5 minutes to obtain the MOF high-performance concrete with high strength and small shrinkage.
Results of the experiment
The above experimental groups were subjected to tests for 28d compressive strength and 28d self-shrinkage according to the specifications. At the same time, 3 control groups (control group 1, control group 2 and control group 3) were set. The control groups 1, 2 and 3 were tested for 28d compressive strength and 28d self-contraction under the same conditions as the experimental groups 1, 2 and 3, respectively, except that they did not contain MOF and surfactant. The test results are shown in table 1.
As can be seen from Table 1, the 28d compressive strength of the samples 1, 2 and 3 after being doped with Cr-MIL-101 is improved by about 20% compared with the control group; and the 28d self-contraction value is greatly reduced, and can be reduced by nearly 50 percent to the maximum. The results in Table 1 show that the Cr-MIL-101 MOF adsorbing water has obvious advantages in improving the strength of concrete and reducing the self-shrinkage of concrete, and lays a foundation for the research of changing the performance of concrete in a nanoscale.
TABLE 1 comparison of the results of examples 1-3 with those of controls 1-3
Test items Example 1 Control 1 Example 2 Control 2 Example 3 Control 3
28d compressive strength/MPa 87.4 72.6 92.3 74.4 91.8 77.5
28d self-contraction/. mu.epsilon 184 267 156 258 137 271

Claims (9)

1. A preparation method of MOF high-performance concrete with high strength and small shrinkage comprises the following main components in percentage by mass:
(1) cement: 15% -20%;
(2) mineral admixture: 5% -10%;
(3) coarse aggregate: 42% -47%;
(4) fine aggregate: 28% -33%;
the above four are collectively referred to as gelling materials, and add up to 100%;
(5) water reducing agent: 1% -2% of the mass of the cementing material;
(6) MOF type Cr-MIL-101: 1% -3% of the mass of the cementing material;
(7) surfactant (b): 1-3% of the mass of the cementing material.
2. The method for preparing the MOF high-performance concrete with high strength and small shrinkage according to claim 1, wherein the cement is Portland cement P.O.42.5.
3. The method for preparing the MOF high performance concrete with high strength and small shrinkage of claim 1, wherein the mineral admixture has a specific surface area of 0.4-0.6m2A/g class I or II fly ash, and a specific surface area of 20-28m2Silica fume per gram.
4. The method for preparing the MOF high-performance concrete with high strength and small shrinkage according to claim 1, wherein the coarse aggregate is crushed stone and has a particle size in a range of 5-16 mm.
5. The method for preparing the MOF high-performance concrete with high strength and small shrinkage according to claim 1, wherein the fine aggregate is medium sand.
6. The method for preparing the MOF high-performance concrete with high strength and small shrinkage according to claim 1, wherein the water reducing agent is a polycarboxylate water reducing agent with the solid content of more than 20%.
7. The method for preparing MOF high performance concrete with high strength and small shrinkage as claimed in claim 1, wherein the specific surface area of Cr-MIL-101 is 5000-6000m2The mesoporous aperture is 3-3.4 nm.
8. The method of claim 1, wherein the surfactant is sodium dodecyl sulfate.
9. The preparation method of the MOF high-performance concrete with high strength and small shrinkage, according to claim 1, comprises the following steps:
adsorption: putting MOF accurately weighed according to the proportion into a closed container with the relative humidity of 100%, and applying 1.2-1.5 atmospheric pressures to enable the MOF to adsorb water vapor until the MOF is saturated;
dispersing: accurately weighing water, a surfactant and a water reducing agent according to a designed water-to-gel ratio in a mass ratio, putting the MOF and the surfactant obtained in the step I into water, performing ultrasonic dispersion for 120 minutes to obtain an MOF dispersion liquid, dissolving the water reducing agent into the dispersion liquid, and stirring for 30 minutes;
③ weighing the materials: accurately weighing cement, mineral admixture, coarse aggregate and fine aggregate according to the mass ratio of the rest components;
stirring: and (3) sequentially putting the materials obtained in the step (iii) into a concrete mixer, then putting 2/3 of the dispersion liquid obtained in the step (ii) into the mixer, mixing for 3 minutes, then putting the rest 1/3 dispersion liquid into the mixer, and mixing for 5 minutes to obtain a product.
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