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CN113087459A - High-ductility cement-based material in ultralow temperature environment, and preparation method and application thereof - Google Patents

High-ductility cement-based material in ultralow temperature environment, and preparation method and application thereof Download PDF

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Publication number
CN113087459A
CN113087459A CN202110276884.3A CN202110276884A CN113087459A CN 113087459 A CN113087459 A CN 113087459A CN 202110276884 A CN202110276884 A CN 202110276884A CN 113087459 A CN113087459 A CN 113087459A
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cement
composite material
based composite
temperature environment
ductility cement
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苏骏
钱维民
赵家玉
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Hubei University of Technology
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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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/34—Non-shrinking or non-cracking materials
    • C04B2111/343—Crack resistant 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/76—Use at unusual temperatures, e.g. sub-zero
    • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The invention discloses a high-ductility cement-based material in an ultralow temperature environment, and a preparation method and application thereof. The cement, fly ash, silica fume, river sand, water, PVA fiber, high efficiency water reducing agent and the like are used as raw materials for preparation. The preparation method comprises the following steps: 1) the gelled material is dispersed in a dry mixing way; 2) adding fine aggregate and dry-mixing; 3) adding water and mixing; 4) adding a water reducing agent; 5) adding PVA fiber; 6) preparing a high-ductility cement-based composite material; 7) the axial compression test, the bending test and the toughness evaluation test are carried out on the high-toughness cement-based material, the problem that various mechanical properties of the traditional material in low-temperature storage equipment are degraded is solved, the problem that the common concrete material is easy to crack at ultralow temperature is solved, the LNG liquefied storage tank is ensured to have good working performance and crack control capability in an extreme environment of-196 ℃, and the technical problem of the LNG liquefied natural gas low-temperature storage tank is met.

Description

High-ductility cement-based material in ultralow temperature environment, and preparation method and application thereof
Technical Field
The invention relates to a building material, in particular to a high-ductility cement-based material in an ultralow temperature environment, and a preparation method and application thereof.
Background
Liquefied natural gas as a novel energy-saving clean energy source, and at present, China is dedicated to environmental protection andreducing greenhouse gases such as carbon dioxide and the like, and promoting the supply and demand of natural gas to be greatly increased. The exploration of rich natural gas resources in China still belongs to the starting stage, the domestic natural gas yield still cannot meet the rapidly increasing demand, and the demand of natural gas in China, serving as an LNG import country, 2020 China reaches 4500 multiplied by 108m3It is predicted that 8000X 10 will be reached in 20308m3. The demand of LNG storage tanks is exacerbated by the huge demand of LNG, which is currently composed of an inner tank and an outer tank, but due to its complex process and cost, the concept of building a full concrete LNG storage tank with prestressed concrete is proposed in the FIP conference held in london to save cost and shorten construction period.
When the traditional concrete material is applied to the construction of a full-concrete LNG storage tank, the risk of natural gas leakage exists; because the traditional concrete material has the defects of low tensile strength, poor toughness, easiness in cracking, difficulty in controlling the width of a crack after cracking and the like, the concrete has the problems that a small amount of natural gas leaks to generate larger expansion force in a high-pressure and ultralow-temperature (-196 ℃) environment, the mechanical property of the concrete is deteriorated due to water-to-ice transition in the material under the action of ultralow temperature and the like, and the residual strain generated inside the LNG liquefied storage tank is accelerated to cause the generation and expansion of the crack of an aggregate and slurry interface.
Aiming at the problem of mechanical property degradation of the existing concrete material at ultralow temperature, the LNG storage tank construction material is provided, wherein the LNG storage tank construction material is a novel high-ductility cement-based composite material and meets the working requirement under the ultralow temperature environment. The material still has extremely high mechanical property, durability and crack control capability under the action of ultralow temperature.
Disclosure of Invention
The invention aims to provide a preparation technology and a test method of a high-ductility cement-based composite material, wherein the high-ductility cement-based composite material still has extremely high toughness and mechanical property and excellent crack control capability under the action of ultralow temperature.
The technical scheme adopted by the invention for solving the technical problems is as follows:
in a first aspect, the invention provides a high-ductility cement composite material applied to an LNG storage tank at ultralow temperature, wherein the composite material comprises the following components in percentage by mass: 28.26% of cement, 39.42% of fly ash, 13.16% of river sand, 1.33% of PVA fiber and 0.82% of water reducing agent, wherein the total volume of all the components after being uniformly mixed is taken as a base number.
Preferably, the cement is ordinary portland cement with the reference number of 42.5. As a main cementing material, the portland cement has the advantages of quick setting and hardening, higher early strength, strong freezing resistance, large hydration heat, strong carbonization resistance and the like, is suitable for structures which are easy to suffer from low temperature action in winter construction and severe cold areas, is a key component for hardening and forming strength of the novel composite material, and has large influence on the mechanical property of the composite material.
Further, the fly ash is F-class I-class fly ash collected from flue gas of a pulverized coal fired boiler, wherein the chemical component of the fly ash is SiO240.28% of Al2O318.19 percent of CaO, 18.08 percent of CaO, and active SiO in the fly ash2、Al2O3And CaO is an active beneficial component, and can greatly improve the ductility and workability of the composite material.
Furthermore, the sand adopts refined river sand with fineness modulus of 2.3-3.0.
Further, the PVA fiber was a Cola K-II fiber having a length of 12mm, a diameter of 0.04mm, an elastic modulus of 120MPa, a tensile strength of 526MPa and an elongation of 6%, which was manufactured by Kuraray of Japan. The PVA fiber is used as a toughening agent of the composite material, and can effectively improve the mechanical property, the crack resistance and the tensile ductility of the composite material.
Furthermore, the water reducing agent adopts a polyhydroxy acid water reducing agent, so that the workability of the composite material is remarkably improved, and the uniform distribution of fibers in the composite material is facilitated.
In a second aspect, the present invention provides a method for preparing a high-ductility cement-based composite material for an LNG liquefied natural gas storage tank, comprising the steps of:
s1: dry-mixing and dispersing the cementing material;
s2: adding fine aggregate and dry-mixing;
s3: adding water and mixing;
s4: adding a water reducing agent;
s5: adding PVA fiber;
s6: pouring the prepared mixture into a mold, demolding and molding after 1d, and curing in a standard curing room (20 +/-2 ℃ and 95% relative humidity) for 28 d;
s7: the method is applied to the preparation of the high-ductility cement-based composite material under the ultralow temperature environment;
s8: and carrying out axial compression test on the high-ductility cement-based composite material and evaluating the toughness.
In a third aspect, the invention provides an application of the high-ductility cement-based composite material in the preparation of an LNG storage tank in an ultralow temperature environment.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the high-ductility cement-based composite material provided by the invention has excellent mechanical properties, durability and crack control capability, and can effectively solve the problems of insufficient structural bearing capacity and durability caused by overlarge macroscopic cracks due to performance degradation of the traditional concrete material in an ultralow temperature environment after being applied to an LNG liquefied natural gas storage tank.
Drawings
FIG. 1 is a schematic diagram of a four-point bend test;
FIG. 2 is a load-deformation curve of a high ductility cement-based composite at different temperatures.
In the figure: 1. a load sensor; 2. a laser displacement meter.
Detailed Description
The preparation and testing methods of the high ductility cement-based composite material provided by the present invention are further described below with reference to examples.
Example 1:
s1: stirring dry materials such as cement, fly ash and river sand according to a proportion to obtain mixed powder;
s2: adding water into the mixed powder, stirring, adding a high-efficiency water reducing agent, and stirring to form viscous slurry;
s3: and adding PVA fiber into the slurry and uniformly stirring to obtain the high-ductility cement-based composite material applied to the ultralow temperature environment.
S4: and filling the prepared cement-based mixture into a mold, demolding and molding after 1d, and placing the mold into a standard curing room (20 +/-2 ℃ and 95% relative humidity) for standard curing for 28 d.
S5: and placing the cube and prism test blocks after the maintenance is finished into an independently researched and developed ultralow temperature test box of Hubei industry university for temperature reduction test.
S6: and (3) carrying out uniaxial compression test on the cubic and prismatic test blocks of the high-ductility cement-based composite material under the action of ultralow temperature by adopting an electrohydraulic servo press.
A high ductility cement-based composite material C1 prepared by the above example procedure and applied in an ultra-low temperature environment.
(1) The high-ductility cement-based composite material 28d prepared by the steps is a cube of 100mm multiplied by 100mm, the loading is carried out by adopting an electro-hydraulic servo pressure tester according to a load control mode, the loading rate is set to be 0.5MPa/s, the average value of the compressive strength at normal temperature is 38MPa, and the test result shows that: under the action of ultralow temperature, the cubic compressive strength of the high-ductility cement-based composite material is improved along with the reduction of the temperature, and when the temperature is reduced to-196 ℃, the compressive strength reaches 53.19MPa and is improved by 40.2 percent compared with the normal temperature state.
TABLE 1 cube compressive strength values (MPa) for high ductility cement-based composites at different temperatures
Figure BDA0002977012180000041
(2) The high-ductility cement-based composite material 28d prepared by the steps is loaded in a load control mode by adopting an electrohydraulic servo pressure tester, the loading rate is set to be 0.5MPa/s, the average value of the compressive strength at normal temperature is 30MPa, and the test result shows that: under the action of ultralow temperature, the compressive strength of the prism of the high-ductility cement-based composite material is improved along with the reduction of the temperature, when the temperature is reduced to-196 ℃, the compressive strength reaches 42.55MPa, and is improved by 40.2 percent compared with the normal temperature state, and the test block shows obvious compressive toughness in the process of destruction.
TABLE 2 high ductility cement-based composite prismatic compressive Strength values (MPa) at different temperatures
Figure BDA0002977012180000042
The test results show that the novel high-ductility cement-based composite material has good compression resistance under the action of ultralow temperature, and compared with common concrete materials, brittle failure but ductile failure can not occur after the ultralow temperature action, and the cement-based material has high ductility.
Example 2:
s1: stirring dry materials such as cement, fly ash and river sand according to a proportion to obtain mixed powder;
s2: adding water into the mixed powder, stirring, adding a high-efficiency water reducing agent, and stirring to form viscous slurry;
s3: and adding PVA fiber into the slurry and uniformly stirring to obtain the high-ductility cement-based composite material applied to the ultralow temperature environment.
S4: and filling the prepared cement-based mixture into a mold, demolding and molding after 1d, and placing the mold into a standard curing room (20 +/-2 ℃ and 95% relative humidity) for standard curing for 28 d.
S5: and placing the cube and prism test blocks after the maintenance is finished into an independently researched and developed ultralow temperature test box of Hubei industry university for temperature reduction test.
S6: and (3) carrying out uniaxial compression test on the cubic and prismatic test blocks of the high-ductility cement-based composite material under the action of ultralow temperature by adopting an electrohydraulic servo press.
The high-ductility cement-based composite material C2 applied to the ultralow temperature environment is prepared by the steps of the example.
The invention researches the bending performance of the high-ductility cement-based composite material 28d in the beam type test piece of 100mm multiplied by 400mm under the action of different temperatures.
The loading span of the test piece is 300mm, the distribution beam adopts a customized sliding steel support, the load sensor is placed in the beam span, the mid-span deflection is monitored by using a laser displacement meter, and the acquisition system adopts an IMC Germany data acquisition system.
The beam type test piece with the thickness of 100mm multiplied by 400mm of the high-ductility cement-based composite material 28d prepared by the steps adopts an electro-hydraulic servo pressure tester, the loading mode adopts continuous and uniform loading, the loading rate before initial cracking is 0.05MPa/s, the displacement control loading is adopted after the initial cracking, and the loading rate is 0.1 mm/min. The average value of the bending strength at normal temperature is 26.06kN, which is increased by 160.03% compared with the common concrete and simultaneously shows good ductility. The data show that: under the action of ultralow temperature, the bending strength of the prism of the high-ductility cement-based composite material is reduced along with the reduction of the temperature, and the high-ductility cement-based composite material still shows good ductility after the ultralow temperature action.
TABLE 3 flexural Strength (kN) of high ductility Cement-based composites at different temperatures
Figure BDA0002977012180000051
The test results show that the novel high-ductility cement-based composite material has good bending resistance under the action of ultralow temperature, and compared with a common concrete material, the novel high-ductility cement-based composite material does not have brittle failure but ductile failure after the ultralow temperature action, and the cement-based material has high toughness.
Example 3:
s1: stirring dry materials such as cement, fly ash and river sand according to a proportion to obtain mixed powder;
s2: adding water into the mixed powder, stirring, adding a high-efficiency water reducing agent, and stirring to form viscous slurry;
s3: and adding PVA fiber into the slurry and uniformly stirring to obtain the high-ductility cement-based composite material applied to the ultralow temperature environment.
S4: and filling the prepared cement-based mixture into a mold, demolding and molding after 1d, and placing the mold into a standard curing room (20 +/-2 ℃ and 95% relative humidity) for standard curing for 28 d.
S5: and placing the cube and prism test blocks after the maintenance is finished into an independently researched and developed ultralow temperature test box of Hubei industry university for temperature reduction test.
S6: and (3) carrying out uniaxial compression test on the cubic and prismatic test blocks of the high-ductility cement-based composite material under the action of ultralow temperature by adopting an electrohydraulic servo press.
The high-ductility cement-based composite material C3 applied to the ultralow temperature environment is prepared by the steps of the example.
The high ductility cement-based composite material 28d prepared by the above steps is subjected to compressive toughness evaluation on a 100mm × 100mm × 300mm prism test piece.
And loading by adopting an electro-hydraulic servo pressure tester according to a load control mode, wherein the loading rate is set to be 0.5 MPa/s. And measuring a load-deformation curve under the condition that the shaft center is pressed.
Taking five times of the corresponding deformation of the peak load as a limit point of the residual toughness, calculating to obtain an area A under a curve corresponding to the limit point, and taking an area A under the corresponding curve when the load-deformation curve reaches the peak loadfz。
Defining the toughness coefficient R of the test piece after the peak valuecThe calculation formula is
Figure BDA0002977012180000061
And calculating the toughness coefficient of the high-ductility cement-based composite material under the action of ultralow temperature by the toughness evaluation mode.
TABLE 4 high ductility coefficient of toughness of cement-based composites at different temperatures
Figure BDA0002977012180000062
The test results show that the novel high-ductility cement-based composite material has good toughness under the action of ultralow temperature, and compared with a common concrete material, brittle failure but ductile failure does not occur after the ultralow temperature action, so that the cement-based material has the characteristic of high toughness.
The high-ductility cement-based composite material prepared by the method and applied to the ultralow temperature environment has good mechanical property, toughness and good crack control capability.
The foregoing is considered as illustrative only or illustrative only of the principles of the invention, and not in limitation thereof. Any modification, equivalent replacement and improvement made within the spirit and principle of the present invention, such as the type of fiber, diameter, length and the type and number of the related cement-based materials, etc., should be included in the protection scope of the present invention.

Claims (5)

1.一种超低温环境下高延性水泥基复合材料，其特征在于：按质量比计，包括以下组分：水泥:粉煤灰:河砂:高效减水剂:PVA纤维＝100:139:47:2.9:4.7；所述PVA纤维的体积掺量为1.5％。1. a high ductility cement-based composite material under an ultra-low temperature environment, is characterized in that: by mass ratio, comprising the following components: cement: fly ash: river sand: superplasticizer: PVA fiber=100:139:47 : 2.9: 4.7; the volume content of the PVA fibers is 1.5%. 2.根据权利要求1所述的超低温环境下高延性水泥基复合材料，其特征在于：2. high ductility cement-based composite material under ultra-low temperature environment according to claim 1, is characterized in that: 所述水泥采用P.O.42.5的普通硅酸盐水泥，作为主要胶凝材料；The cement adopts ordinary Portland cement of P.O.42.5 as the main cementitious material; 所述粉煤灰采用燃烧粉煤锅炉烟气中收集的F类I级粉煤灰，其中化学成分SiO2为40.28％，Al2O3为18.19％，CaO为18.08％，粉煤灰中的活性SiO2、Al2O3和CaO是活性有利成分，能极大提升复合材料的延性以及施工和易性；The fly ash adopts the F-class I grade fly ash collected from the flue gas of the coal-fired boiler, wherein the chemical composition of SiO 2 is 40.28%, Al 2 O 3 is 18.19%, CaO is 18.08%, and the fly ash is Active SiO 2 , Al 2 O 3 and CaO are active and favorable components, which can greatly improve the ductility and workability of composite materials; 所述河砂采用细度模数2.3-3.0的精制河砂；The river sand adopts the refined river sand with a fineness modulus of 2.3-3.0; 所述PVA纤维采用日本Kuraray公司生产的可乐纶K-Ⅱ型，其长度为12mm，弹性模量为120Mpa，伸长率为6％；所述PVA纤维作为复合材料的增韧剂，能够有效提升复合材料的力学性能、抗裂性能以及抗拉延性；The PVA fiber adopts the Kuralen K-II type produced by Kuraray Company of Japan, and its length is 12mm, the elastic modulus is 120Mpa, and the elongation is 6%. Mechanical properties, crack resistance and tensile properties of composite materials; 所述减水剂采用聚羟酸系减水剂，显著提升复合材料的和易性，有利于纤维在复合材料中均匀分布。The water-reducing agent adopts a polyhydroxy acid-based water-reducing agent, which significantly improves the workability of the composite material and is beneficial to the uniform distribution of fibers in the composite material. 3.根据权利要求2所述的超低温环境下高延性水泥基复合材料，其特征在于：所述减水剂采用三聚氰胺F10聚羟酸高效减水剂，减水率≥30％。3. The high-ductility cement-based composite material in an ultra-low temperature environment according to claim 2, characterized in that: the water-reducing agent is a melamine F10 polyhydroxy acid high-efficiency water-reducing agent, and the water reduction rate is greater than or equal to 30%. 4.一种制备如权利要求1-3中任一所述超低温环境下高延性水泥基复合材料的方法，其特征在于：包含如下步骤：4. a method for preparing high ductility cement-based composite material under ultra-low temperature environment as described in any one of claims 1-3, is characterized in that: comprise the steps: S1：胶凝材料的干拌分散；S1: Dry mixing and dispersion of cementitious materials; S2：加入细骨料干拌；S2: Add fine aggregate and dry mix; S3：加水进行拌和；S3: add water to mix; S4：减水剂的添加；S4: Addition of water reducing agent; S5：PVA纤维的添加；S5: Addition of PVA fiber; S6：配制后的拌合物倒入至模具中，1d后脱模成型，放入标准养护室中在20±2℃，95％相对湿度条件下，养护28d；S6: The prepared mixture is poured into the mold, demolded after 1 day, and put into a standard curing room for 28 days under the conditions of 20±2°C and 95% relative humidity; S7：运用于超低温环境下高延性水泥基复合材料的制成；S7: It is used in the manufacture of high ductility cement-based composite materials in ultra-low temperature environment; S8：对高延性水泥基复合材料进行轴压试验并进行韧性评价。S8: Axial compression test and toughness evaluation for high ductility cement-based composites. 5.一种如权利要求1-3中任一所述的超低温环境下高延性水泥基复合材料在LNG液化天然气储蓄罐制备中的应用。5. Application of the high ductility cement-based composite material in the ultra-low temperature environment according to any one of claims 1-3 in the preparation of LNG liquefied natural gas storage tanks.
CN202110276884.3A 2021-03-15 2021-03-15 High-ductility cement-based material in ultralow temperature environment, and preparation method and application thereof Pending CN113087459A (en)

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Citations (3)

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Publication number Priority date Publication date Assignee Title
CN103482927A (en) * 2013-09-02 2014-01-01 东南大学 High-crack-resistance low-shrinkage high-ductility mortar and preparation method thereof
CN107382183A (en) * 2017-06-29 2017-11-24 昆明理工大学 A kind of high tenacity cement-base composite material
CN108569873A (en) * 2018-05-07 2018-09-25 东南大学 A kind of ECC concrete of high impact-resistant toughness and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103482927A (en) * 2013-09-02 2014-01-01 东南大学 High-crack-resistance low-shrinkage high-ductility mortar and preparation method thereof
CN107382183A (en) * 2017-06-29 2017-11-24 昆明理工大学 A kind of high tenacity cement-base composite material
CN108569873A (en) * 2018-05-07 2018-09-25 东南大学 A kind of ECC concrete of high impact-resistant toughness and preparation method thereof

Non-Patent Citations (1)

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Title
苏骏等，: ""超低温对超高韧性水泥基复合材料抗压韧性影响试验"", 《复合材料学报》 *

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