CN112551935A - Concrete hydration heat inhibiting material and preparation method thereof - Google Patents

Concrete hydration heat inhibiting material and preparation method thereof Download PDF

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CN112551935A
CN112551935A CN201910911862.2A CN201910911862A CN112551935A CN 112551935 A CN112551935 A CN 112551935A CN 201910911862 A CN201910911862 A CN 201910911862A CN 112551935 A CN112551935 A CN 112551935A
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concrete
hydration
cement phase
hydration heat
regulation
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张守祺
路振宝
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Zhonglu Hi Tech Transport Certification And Inspection Co ltd
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Zhonglu Hi Tech Transport Certification And Inspection Co ltd
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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
    • C04B40/00Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039Premixtures of ingredients

Abstract

The invention discloses a concrete hydration heat inhibiting material, which comprises the following components: the cement phase selective hydration regulation and control material comprises a cement phase selective hydration regulation and control material and a carrier material, wherein the cement phase selective hydration regulation and control material accounts for 30-80% of the total mass of the cement phase selective hydration regulation and control material and the carrier material accounts for 20-70%. The concrete hydration heat inhibiting material provided by the invention is designed based on the original innovative principle, namely a cement phase selective hydration regulation theory, can prolong the hydration heat release process of concrete, solves the problem of concentrated release of concrete hydration heat, and achieves the purpose of greatly reducing the structural temperature rise peak value of the concrete.

Description

Concrete hydration heat inhibiting material and preparation method thereof
Technical Field
The invention belongs to the technical field of concrete, and particularly relates to a concrete hydration heat inhibiting material and a preparation method thereof.
Background
Cement concrete hydration is an exothermic chemical reaction process, and the temperature difference inside the concrete structure caused by the hydration heat is one of the main reasons for concrete cracking. After the concrete is poured, the hydration heat is intensively released in a short time, so that the internal temperature of the concrete structure is rapidly increased and can reach 70-80 ℃. Because of the reasons such as long heat conduction path and low heat conduction rate, the heat in the concrete structure can not be conducted to the surface in time and released, so that the temperature rise in the structure is obviously higher than that of the surface layer, an uneven temperature field is formed, temperature stress is generated, and particularly the temperature difference between the interior of the large-volume concrete structure and the surface layer can reach more than 30 ℃. Temperature cracking occurs when the temperature stress of the concrete exceeds its tensile strength. The analysis of the concrete temperature crack cause shows that the concrete temperature crack cause is controlled to reduce the concrete structure temperature rise by controlling the hydration heat release quantity and the heat release rate of the concrete (including chemical additives, low-heat cement, large-dosage fly ash and the like) or assisting the internal heat energy release of the structure (including precooling raw materials, cooling water pipes and the like), and the method is an effective way for preventing and treating the concrete temperature crack, and the domestic and foreign prior art follows the technical route.
The chemical admixture is adopted to regulate and control the cement hydration process so as to reduce the temperature cracking risk of concrete, and is a key technology which is concerned in recent years. The patenting and disclosing situation up to now is as follows: patents JP3729340B2, EP1233008a1 and JP4905977B2 use dextrin, which has low solubility in cold water and is not modified, as a hydration heat inhibiting material, and can reduce the temperature rise of concrete by 1 ℃ and remarkably prolong the setting time. The hydration heat regulating and controlling material in patent CN103739722A is surface cross-linked modified dextrin prepared by cross-linking reaction, the preparation process comprises the processes of dispersion, cross-linking, separation, drying and the like, and the action effect is closely related to the surface cross-linking degree, the original size, the molecular weight and the like of the dextrin. Patent CN104592403A discloses a cement hydration regulating agent, which is prepared by polymerization and crosslinking reaction of dextrin and a crosslinking agent under the action of microwave radiation under the action of a redox initiator, and the preparation involves the process of heating, washing, concentrating, drying, sieving and the like. Patent CN1810703A discloses a preparation method of a concrete hydration heat reducing agent, which selects a copolymer of hydroxycarboxylic acid-starch graft, modified starch and the like, and carries out hydrolysis reaction at a specific temperature to prepare the concrete hydration heat reducing agent, and the preparation relates to the technical processes of solid-liquid separation, drying and the like.
In summary, in the issued and published patents, the concrete hydration heat inhibiting material is mainly prepared by directly applying starch and dextrin raw materials or modifying the starch and dextrin raw materials by hydrolysis, high-temperature gelatinization and other methods. Unmodified starch and dextrin materials have limited effect on inhibiting the hydration heat of concrete, and easily cause the problems of prolonged coagulation, strength reduction and the like. The modified starch and dextrin materials have the problems of complex preparation process, difficult control of the homogeneity of the prepared product, high economic efficiency, environmental protection and the like.
Disclosure of Invention
The invention provides a concrete hydration heat inhibiting material and a preparation method thereof. The material is designed based on the original innovative principle, namely a cement phase selective hydration regulation theory, and can realize the selective hydration of cement phases in concrete, namely the separate hydration of tricalcium aluminate and tricalcium silicate, which are main biological products of cement hydration heat, so as to reduce the exothermic superposition of hydration reactions of the tricalcium aluminate and the tricalcium silicate. The concrete hydration heat release process can be prolonged, the problem of concentrated release of concrete hydration heat is solved, and the purpose of reducing the peak value of concrete structure temperature rise is achieved. Meanwhile, hydration heat release is uniformly distributed for a longer time, the total heat release of the concrete is not reduced, and the concrete has excellent performances of improving the hydration microstructure of the concrete and improving the strength of the concrete.
In one aspect, the present invention provides a concrete hydration heat inhibiting material comprising: the cement phase selective hydration regulation and control material comprises a cement phase selective hydration regulation and control material and a carrier material, wherein the cement phase selective hydration regulation and control material accounts for 30-80% of the total mass of the cement phase selective hydration regulation and control material and the carrier material accounts for 20-70%.
According to an embodiment of the present invention, the cement phase selective hydration control material is one or more of phosphate materials, hydroxycarboxylic acids, polyhydroxy sugars, fluorosilicate materials, and alcamines.
According to another embodiment of the present invention, the phosphate-based material includes sodium phosphate, sodium tripolyphosphate, sodium pyrophosphate; the hydroxycarboxylic acid materials comprise tartaric acid, citric acid and malic acid; the polyhydroxy saccharide material comprises glucose, sucrose and sugar alcohol; the fluorosilicate materials comprise sodium fluorosilicate, potassium fluorosilicate and zinc fluorosilicate; the alcamines materials comprise triethanolamine, triisopropanolamine and diethanolamine monoisopropanolamine.
According to another embodiment of the present invention, the carrier material is one or more of a polyvinyl alcohol material, a polyethylene glycol material, a chitosan material, a stearate material, and a palmitate material.
According to another embodiment of the present invention, the polyvinyl alcohol based material includes polyvinyl alcohol 1788, polyvinyl alcohol 0588, polyvinyl alcohol 2588; the polyethylene glycol material comprises polyethylene glycol 6000, polyethylene glycol 8000 and polyethylene glycol 10000; the chitosan material comprises chitosan 20000, chitosan 120000 and chitosan 200000; the stearate materials comprise glyceryl stearate, sucrose stearate and sorbitan stearate; the palmitate material comprises monopalmitin and ascorbyl palmitate.
According to another embodiment of the present invention, the particle size of the cement phase selective hydration control material and the carrier material is between 0.1mm and 2.0 mm.
In another aspect, the present invention provides a method for preparing a hydration heat inhibiting material for concrete, comprising: the method comprises the following steps of heating and mixing a cement phase selective hydration control material and a carrier material according to the proportion that the cement phase selective hydration control material accounts for 30-80% and the carrier material accounts for 20-70% of the total mass of the cement phase selective hydration control material and the carrier material, cooling to room temperature, crushing and screening.
According to an embodiment of the present invention, the temperature of the heating and mixing is controlled to 40 to 290 ℃, the mixing speed is 0.1 to 3000 revolutions per minute, and the mixing time is 5 to 90 minutes.
The concrete hydration heat inhibiting material provided by the invention is designed based on the original innovative principle, namely a cement phase selective hydration regulation theory, can prolong the hydration heat release process of concrete, solves the problem of concentrated release of concrete hydration heat, and achieves the purpose of greatly reducing the structural temperature rise peak value of the concrete. Secondly, the hydration heat release is uniformly distributed for a longer time, the total heat release of the concrete is not reduced, and the concrete has excellent performances of improving the hydration microstructure of the concrete and enhancing the strength of the concrete. Finally, the material of the invention has simple preparation process, low cost and easy control of homogeneity, and can reduce the environmental pollution problem in the modification process.
Drawings
The above and other features and advantages of the present invention will become more apparent by describing in detail exemplary embodiments thereof with reference to the attached drawings.
Figure 1 is a tricalcium aluminate + gypsum hydration microcalorimetry curve.
Fig. 2 is a tricalcium silicate hydration microcalorimetry curve.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The described embodiments are only some embodiments of the invention, not all embodiments. All other embodiments obtained by others without inventive step are within the scope of the invention, based on the claims and the examples of the invention.
FIG. 1 and FIG. 2 show the hydration law of the hydration heat inhibiting material of the present invention (obtained by TAM AIR isothermal microcalorimeter test) on cement hydration heat key phases tricalcium aluminate and tricalcium silicate, the test temperature is 20 ℃, the test sample is pure slurry, and the water-to-gel ratio is 0.45. Wherein, the mass ratio of the tricalcium aluminate to the dihydrate gypsum in the tricalcium aluminate test sample is 3: 1. As can be seen from the graphs in FIGS. 1 and 2, the hydration heat inhibiting material of the invention accelerates the hydration rate of tricalcium aluminate, obviously delays the hydration rate of tricalcium silicate, realizes the selective hydration of cement phases, can reduce the hydration heat superposition of the tricalcium aluminate and the tricalcium silicate, and reduces the peak value of temperature rise. Based on the original innovative principle, a concrete hydration heat inhibiting material and a preparation method thereof are designed.
The concrete hydration heat inhibiting material of the present invention comprises: the cement phase selective hydration regulation and control material and the carrier material, wherein the cement phase selective hydration regulation and control material accounts for 30-80% and the carrier material accounts for 20-70% of the total mass of the cement phase selective hydration regulation and control material and the carrier material.
The cement phase selective hydration regulating and controlling material can realize the selective hydration of the cement phase in the concrete, namely the separate hydration of tricalcium aluminate and tricalcium silicate which are main biological products of cement hydration heat. The cement phase selective hydration regulation material can be one or more of phosphate materials, hydroxycarboxylic acid materials, polyhydroxy carbohydrate materials, fluorosilicate materials and alcohol amine materials. Specifically, the phosphate material includes sodium phosphate, sodium tripolyphosphate, and sodium pyrophosphate. Hydroxycarboxylic acid materials include tartaric acid, citric acid, malic acid; the polyhydroxy saccharide material comprises glucose, sucrose, and sugar alcohol. The fluorosilicate materials comprise sodium fluorosilicate, potassium fluorosilicate and zinc fluorosilicate; the alcamines include triethanolamine, triisopropanolamine, and diethanolamine monoisopropanolamine.
The carrier material assists in adjusting the selective hydration process of the cement phase selective hydration control material, and simultaneously adjusts the effective concentration of the cement phase selective hydration control material. The carrier material is one or more of polyvinyl alcohol material, polyethylene glycol material, chitosan material, stearate material and palmitate material. Specifically, the polyvinyl alcohol-based material includes polyvinyl alcohol 1788, polyvinyl alcohol 0588, and polyvinyl alcohol 2588. The polyethylene glycol material includes polyethylene glycol 6000, polyethylene glycol 8000, and polyethylene glycol 10000. The chitosan material comprises chitosan 20000, chitosan 120000 and chitosan 200000. The stearate materials include glyceryl stearate, sucrose stearate, and sorbitan stearate. Palmitate materials include monopalmitin and ascorbyl palmitate.
Preferably, the particle diameters of the cement phase selective hydration control material and the carrier material are 0.1 mm-2.0 mm.
The preparation method of the concrete hydration heat inhibiting material comprises the following steps: the cement phase selective hydration regulating material and the carrier material are heated, mixed, cooled to room temperature, crushed and screened according to the proportion that the cement phase selective hydration regulating material accounts for 30-80% and the carrier material accounts for 20-70% of the total mass of the cement phase selective hydration regulating material and the carrier material.
The temperature of heating and mixing is controlled to be 40-290 ℃, the mixing speed is 0.1-3000 r/min, and the mixing time is 5-90 minutes
The present invention is explained in detail below with reference to examples. In the examples, the equipment and materials used were commercially available, unless otherwise specified; the methods used, unless otherwise specified, are conventional in the art.
Example 1
30 parts of one or two of a phosphate material (sodium tripolyphosphate and sodium pyrophosphate) and an alkanolamine material (triethanolamine and triisopropanolamine) as cement hydration regulation and control materials, 70 parts of one or two of a polyvinyl alcohol material (polyvinyl alcohol 1788 and polyvinyl alcohol 2588) and a polyethylene glycol material (polyethylene glycol with molecular weight 6000 and polyethylene glycol with molecular weight 10000) as carrier materials are placed in an electric mixer, the temperature in the mixer is kept at 40 ℃, the mixing speed is 0.1 r/min, and the mixture is cooled to room temperature after being mixed for 90 min. Mechanically crushing and sieving to prepare particles with the particle size of 0.1-1.0 mm.
Example 2
50 parts of a cement hydration regulation material, namely a hydroxycarboxylic acid material (tartaric acid and citric acid) and an alcamines material (one or two of triethanolamine and triisopropanolamine), 50 parts of a carrier material, namely a polyethylene glycol material (6000 molecular weight polyethylene glycol, 10000 molecular weight polyethylene glycol) and 50 parts of one or two of chitosan materials (20000 molecular weight chitosan and 200000 molecular weight chitosan), are placed in an electric mixer, the temperature in the mixer is kept at 100 ℃, the mixing speed is 190 r/min, and after mixing is carried out for 60 min, the mixture is cooled to the room temperature. Mechanically crushing and sieving to prepare particles with the particle size of 0.5-1.0 mm.
Example 3
70 parts of cement hydration regulation material polyhydroxy carbohydrate material (glucose, sucrose), 70 parts of alcamines material (one or two of triethanolamine and triisopropanolamine), 30 parts of carrier material chitosan material (molecular weight 20000 chitosan, molecular weight 200000 chitosan) and 30 parts of stearate material (glyceryl stearate and sucrose stearate) are placed in an electric mixer, the temperature in the mixer is kept at 190 ℃, the mixing speed is 1700 r/min, and after mixing is carried out for 35 min, the mixture is cooled to room temperature. Mechanically crushing and sieving to prepare particles with the particle size of 1.0-1.5 mm.
Example 4
80 parts of one or two of a cement hydration regulation material fluosilicate material (sodium fluosilicate and potassium fluosilicate) and an alkanolamine material (triethanolamine and triisopropanolamine), 20 parts of one or two of a carrier material stearate material (glyceryl stearate and sucrose stearate) and a palmitate material (monopalmitin and ascorbyl palmitate) are placed in an electric mixer, the temperature in the mixer is kept at 290 ℃, the mixing speed is 3000 r/min, and after mixing is carried out for 5 min, the mixture is cooled to the room temperature. Mechanically crushing and sieving to prepare particles with the particle size of 1.5-2.0 mm.
The concrete hydration heat inhibiting materials prepared in example 1, example 2, example 3 and example 4 were tested and evaluated for their effects on the hydration temperature rise and compressive strength of concrete according to the following methods.
The concrete hydration temperature rise is tested by adopting an embedded temperature sensor method, the concrete casting body is a cube with the side length of 1.0 meter, the template adopts a 16mm steel template and an externally attached 50mm extruded polystyrene insulation board, and the temperature sensor is embedded in the center point of the cube. The temperature sensor adopts a real-time data acquisition mode, and the data acquisition frequency is 1/second. The concrete compressive strength is executed according to standard of general concrete mechanical property test method (GB/T50081-2002).
The mixing ratio of the concrete for the test is shown in Table 1. The raw materials comprise P.I type portland cement, first-level fly ash, river sand (fine aggregate with the fineness modulus of 2.50), broken stone (coarse aggregate which is continuously prepared by 5-20 mm), mixing water and a polycarboxylic acid water reducing agent. The performance of the raw materials meets the requirements of the national current technical standard.
TABLE 1 concrete base mix ratio (kg/m)3)
Cement Fly ash River sand Crushing stone Mixing water Water reducing agent
240 160 771 1065 165 4.0
The test results of the concrete hydration heat inhibiting material on the hydration temperature rise and the compressive strength of the concrete are shown in the table 2. Therefore, when the hydration heat inhibition materials prepared in the examples 1-4 are added, the temperature peak value of the concrete is obviously lower than that of a reference group, and the temperature rise time is obviously prolonged. Compared with the initial temperature of the mold, the temperature rise value of the cast body of the reference group is 19.3 ℃; when the materials of the embodiments 1 to 4 are added, the temperature rise value of the concrete is only 7.3 to 11.0 ℃, and the reduction range reaches 43.0 to 62.2 percent. Meanwhile, in the aspect of 28-day compressive strength, the compressive strength of a reference group is 38.0MPa, and when the materials of the examples 1-4 are added, the compressive strength of the concrete is 40.2-43.1 MPa, and the improvement range is 5.8-13.4%. In conclusion, the hydration heat inhibiting materials of examples 1 to 4 can significantly reduce the hydration heat temperature rise of the concrete cast and significantly improve the compressive strength of the concrete. The method is very beneficial to controlling the temperature crack of the concrete and improving the construction quality of the concrete engineering.
TABLE 2 test results of hydration temperature rise and compressive strength of concrete
Figure BDA0002214936520000071
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it should be understood that various changes and modifications can be effected therein by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (8)

1. A concrete hydration heat inhibiting material comprising: the cement phase selective hydration regulation and control material comprises a cement phase selective hydration regulation and control material and a carrier material, wherein the cement phase selective hydration regulation and control material accounts for 30-80% of the total mass of the cement phase selective hydration regulation and control material and the carrier material accounts for 20-70%.
2. The concrete hydration heat inhibition material according to claim 1, wherein the cement phase-selective hydration regulation material is one or more of a phosphate material, a hydroxycarboxylic acid material, a polyhydroxy saccharide material, a fluorosilicate material, and an alcohol amine material.
3. The concrete hydration heat inhibiting material of claim 2, wherein the phosphate-based material includes sodium phosphate, sodium tripolyphosphate, sodium pyrophosphate; the hydroxycarboxylic acid materials comprise tartaric acid, citric acid and malic acid; the polyhydroxy saccharide material comprises glucose, sucrose and sugar alcohol; the fluorosilicate materials comprise sodium fluorosilicate, potassium fluorosilicate and zinc fluorosilicate; the alcamines materials comprise triethanolamine, triisopropanolamine and diethanolamine monoisopropanolamine.
4. The concrete hydration heat inhibiting material of claim 1, wherein the carrier material is one or more of a polyvinyl alcohol based material, a polyethylene glycol based material, a chitosan based material, a stearate based material, and a palmitate based material.
5. The concrete hydration heat inhibiting material of claim 4, wherein the polyvinyl alcohol based material includes polyvinyl alcohol 1788, polyvinyl alcohol 0588, polyvinyl alcohol 2588; the polyethylene glycol material comprises polyethylene glycol 6000, polyethylene glycol 8000 and polyethylene glycol 10000; the chitosan material comprises chitosan 20000, chitosan 120000 and chitosan 200000; the stearate materials comprise glyceryl stearate, sucrose stearate and sorbitan stearate; the palmitate material comprises monopalmitin and ascorbyl palmitate.
6. The concrete hydration heat inhibiting material according to any one of claims 1 to 5, wherein the particle diameters of the cement phase-selective hydration controlling material and the carrier material are 0.1mm to 2.0 mm.
7. A method for preparing a concrete hydration heat inhibiting material comprises the following steps:
the method comprises the following steps of heating and mixing a cement phase selective hydration control material and a carrier material according to the proportion that the cement phase selective hydration control material accounts for 30-80% and the carrier material accounts for 20-70% of the total mass of the cement phase selective hydration control material and the carrier material, cooling to room temperature, crushing and screening.
8. The method for producing a concrete hydration heat inhibiting material according to claim 7, wherein the temperature of the heating and mixing is controlled to 40 to 290 ℃, the mixing speed is 0.1 to 3000 revolutions per minute, and the mixing time is 5 to 90 minutes.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115745452A (en) * 2021-09-02 2023-03-07 江苏苏博特新材料股份有限公司 Concrete anti-cracking material, preparation method and application thereof
CN115745452B (en) * 2021-09-02 2024-03-29 江苏苏博特新材料股份有限公司 Concrete anti-cracking material, preparation method and application thereof
CN115057654A (en) * 2022-05-16 2022-09-16 中国路桥工程有限责任公司 Concrete hydration temperature rise inhibition type mineral admixture and preparation and application thereof

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