CN107651876B - Concrete thermal curing synergist and preparation method and application thereof - Google Patents
Concrete thermal curing synergist and preparation method and application thereof Download PDFInfo
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- CN107651876B CN107651876B CN201710977433.6A CN201710977433A CN107651876B CN 107651876 B CN107651876 B CN 107651876B CN 201710977433 A CN201710977433 A CN 201710977433A CN 107651876 B CN107651876 B CN 107651876B
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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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
- C04B40/0042—Powdery mixtures
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Abstract
The invention provides a concrete thermal curing synergist and a preparation method and application thereof. The preparation method comprises the steps of mixing maleic acid-triethanolamine ester, acrylic acid-alkylene polyoxyethylene ether-hydroxyethyl acrylate copolymer, cellulose ether and water. The synergist is used as a thermal curing synergist in a thermal cured concrete product, improves the microstructure of set cement by promoting the hydration of a cementing material, improves the compressive strength of the concrete by 40-70% after the thermal curing is finished, improves the compressive strength of the concrete by 20-35% after 28 days, shortens the production period, is suitable for the thermal curing synergism of cement products such as assembled building parts, concrete bricks and the like, and particularly has an obvious effect on improving the thermal curing efficiency of the concrete product with a large amount of mineral admixture.
Description
Technical Field
The invention belongs to the technical field of building materials, and particularly relates to a concrete thermal curing synergist and a preparation method and application thereof.
Background
Thermal curing is an indispensable process for concrete products such as concrete prefabricated parts, concrete bricks and the like. Generally, in order to prevent the cement hydration product ettringite from decomposing in the thermal curing process and the concrete product from forming secondary ettringite in the application process due to the overhigh thermal curing temperature, the normal pressure thermal curing temperature of the concrete is controlled below 80 ℃. In order to ensure that the concrete reaches the preset mechanical property after the thermal curing is finished, the thermal curing time adopted by the prior art is longer, so that the turnover time of a mould and a curing facility is correspondingly prolonged.
The normal-pressure thermal curing of the concrete comprises dry thermal curing, wet thermal curing and heat medium directional circulating curing, heat sources comprise boiler steam supply, solar energy utilization, air energy utilization and the like, but the thermal curing efficiency of the concrete cannot be improved no matter what curing form and energy utilization mode is adopted.
CN106003397A discloses a concrete precast member curing method and a concrete precast member curing system, which improve the thermal curing efficiency of the concrete precast member by introducing carbon dioxide into a curing chamber, accelerate the early strength development of the concrete precast member, but have the problems of complex process and unsuitability for large-scale popularization and application, particularly when the concrete contains a large amount of mineral admixture, calcium hydroxide required by volcanic ash reaction is consumed by carbonization, the alkalinity of a hydration system is reduced, and the corrosion of steel bars in the concrete is promoted.
CN105198264A discloses an efficient energy-saving concrete synergist and a preparation method thereof, wherein the synergist can reduce the consumption of concrete cement by promoting the hydration of cement in the middle and later periods, and the main preparation method is to mix 10-25 parts of UFD high-molecular copolymer (composed of urea, formaldehyde and sodium dodecyl benzene sulfonate), 10-15 parts of water reducer mother liquor, 3-5 parts of sodium tripolyphosphate, 2-7 parts of sodium gluconate, 10-15 parts of a stabilizer and 33-65 parts of water. However, the synergist contains a retarding component, is not suitable for thermal curing of concrete products, and contains harmful substances such as urea, formaldehyde and the like, so that the application of the synergist in building engineering is limited.
CN106116224A discloses a multifunctional concrete synergist, which can hydrate 20-30% of cement which can not play normal effect in concrete, and the formula is as follows: 26-42 parts of diisopropylethanolamine, 2-8 parts of pentaerythritol, 15-26 parts of sodium lignosulfonate, 8-16 parts of hexadecyl trimethyl ammonium hydroxide, 1-6 parts of xanthan gum, 5-13 parts of alkyl glycoside and 40-80 parts of water. The sodium lignosulfonate in the synergist has the effects of entraining air and delaying cement hydration, cannot promote early hydration of cement, and is unfavorable for strength development of heat-cured concrete.
Said invention can promote the development of cement hydration system strength by means of physical and chemical action, but does not consider the requirements of heat-cured concrete for synergist and the influence of synergist component on concrete microstructure.
Disclosure of Invention
Aiming at the defects of the existing concrete synergist, the invention aims to provide the concrete thermal curing synergist which is efficient and easy to obtain.
A concrete thermal curing synergist comprises the following raw materials in parts by weight: 2-3 parts of maleic acid-triethanolamine ester, 15-20 parts of acrylic acid-alkylene polyoxyethylene ether-hydroxyethyl acrylate copolymer, 1.5-2 parts of cellulose ether and 70-80 parts of water.
Preferably, the preparation method of the acrylic acid-alkylene polyoxyethylene ether-hydroxyethyl acrylate copolymer comprises the following steps:
step 1, adding 30 parts of water, 30 parts of alkylene polyoxyethylene ether and 5 parts of hydroxyethyl acrylate into a reaction kettle in parts by weight, and stirring until the alkylene polyoxyethylene ether and the hydroxyethyl acrylate are completely dissolved;
step 2, adding 0.35 part by weight of 27% hydrogen peroxide solution into a reaction kettle, and heating to 45-55 ℃;
step 3, dripping 8 parts by weight of 25% acrylic acid aqueous solution, 3 parts by weight of 5% sodium methallyl sulfonate aqueous solution and 4 parts by weight of 5% sodium thiosulfate aqueous solution into a reaction kettle, wherein the dripping time of the acrylic acid solution is 3-4 hours, the dripping time of the sodium methallyl sulfonate aqueous solution and the sodium thiosulfate aqueous solution is 4-5 hours, and carrying out heat preservation reaction at 45-55 ℃ for 1 hour;
and 4, adding 15.95 parts by weight of water and 3.7 parts by weight of a 30% sodium hydroxide aqueous solution into a reaction kettle, and adjusting the pH to 6 to obtain the acrylic acid-alkylene polyoxyethylene ether-hydroxyethyl acrylate copolymer.
Preferably, the cellulose ether is one or a mixture of two of hydroxypropyl methyl cellulose ether and hydroxyethyl methyl cellulose ether.
Preferably, the cellulose ether has a viscosity specification of 200000 as a 2% aqueous solution.
Preferably, the molecular weight of the alkylene alkenyl polyoxyethylene ether is 600-5000, preferably 1200-2400.
The preparation method of the concrete thermal curing synergist is to mix maleic acid-triethanolamine ester, acrylic acid-alkylene polyoxyethylene ether-hydroxyethyl acrylate copolymer, cellulose ether and water to prepare the concrete thermal curing synergist.
The concrete thermal curing synergist is applied to concrete as a thermal curing synergist.
The concrete thermal curing synergist can be directly used as a thermal curing synergist to be doped into concrete for use or prepared into powder for use; when in use, the concrete hot curing synergist is added according to the condition that the mass of the solid in the concrete hot curing synergist accounts for 0.1-0.2% of the mass of the cementing material.
The concrete thermal curing synergist is prepared by fully mixing maleic acid-triethanolamine ester, acrylic acid-alkylene polyoxyethylene ether-hydroxyethyl acrylate copolymer, cellulose ether and water according to a certain mass part. The synergistic principle is as follows: promotion of C in cement by maleic acid-triethanolamine ester3Hydration of A and aluminium glue and C2The method has the beneficial effects that the fractal dimension of the microstructure of the set cement is increased, so that the heat curing efficiency of the concrete is improved.
Has the advantages that:
1. the preparation process is simple, the adopted raw materials are non-toxic and harmless, the preparation is easy, and the whole reaction process is easy to control because the acrylic acid-alkylene polyoxyethylene ether-hydroxyethyl acrylate copolymer does not need to be heated during synthesis.
2. The invention has good hot curing synergistic capability under the condition of low mixing amount. Compared with the prior synergist, the dosage is reduced from 0.5-0.6% to 0.1-0.2%, the compressive strength at the end of thermal curing is improved by 30-40%, the compressive strength in 28 days is improved by 20-35%, and the production period can be shortened by more than 30% compared with the standard concrete material.
3. The invention improves the microstructure of the set cement, and compared with a standard concrete material, the cement-air ratio is increased by more than 15% after the steam curing is finished, thereby obviously improving the long-term performance and durability of the concrete.
Detailed Description
The concrete thermal curing synergist and the use thereof prepared according to the method of the present invention are described in more detail in the following examples, which are intended to enable one skilled in the art to understand the contents of the present invention and to practice the same, but do not limit the scope of the present invention in any way.
The preparation method of the acrylic acid-alkylene polyoxyethylene ether-hydroxyethyl acrylate copolymer comprises the following steps:
step 1, adding 30 parts of water, 30 parts of alkylene polyoxyethylene ether and 5 parts of hydroxyethyl acrylate into a reaction kettle in parts by weight, and stirring until the alkylene polyoxyethylene ether and the hydroxyethyl acrylate are completely dissolved;
step 2, adding 0.35 part by weight of 27% hydrogen peroxide solution into a reaction kettle, and heating to 45-55 ℃;
step 3, dripping 8 parts by weight of 25% acrylic acid aqueous solution, 3 parts by weight of 5% sodium methallyl sulfonate aqueous solution and 4 parts by weight of 5% sodium thiosulfate aqueous solution into a reaction kettle, wherein the dripping time of the acrylic acid solution is 3-4 hours, the dripping time of the sodium methallyl sulfonate aqueous solution and the sodium thiosulfate aqueous solution is 4-5 hours, and carrying out heat preservation reaction at 45-55 ℃ for 1 hour;
and 4, adding 15.95 parts by weight of water and 3.7 parts by weight of a 30% sodium hydroxide aqueous solution into a reaction kettle, and adjusting the pH to 6 to obtain the acrylic acid-alkylene polyoxyethylene ether-hydroxyethyl acrylate copolymer.
Example 1
According to the weight parts, 3 parts of maleic acid-triethanolamine ester, 20 parts of acrylic acid-alkylene polyoxyethylene ether 1200-hydroxyethyl acrylate copolymer, 2 parts of hydroxyethyl methyl cellulose ether and 75 parts of water are stirred in a reaction kettle for 30 minutes until the components are uniformly mixed, and the concrete thermal curing synergist H1 is obtained.
Example 2
According to the parts by weight, 2.5 parts of maleic acid-triethanolamine ester, 18 parts of acrylic acid-alkylene polyoxyethylene ether 2400-hydroxyethyl acrylate copolymer, 1.5 parts of hydroxyethyl methyl cellulose ether and 78 parts of water are stirred in a reaction kettle for 35 minutes to be uniformly mixed, and the concrete thermal curing synergist H2 is obtained.
Example 3
According to the weight parts, 3 parts of maleic acid-triethanolamine ester, 15 parts of acrylic acid-alkylene polyoxyethylene ether 1200-hydroxyethyl acrylate copolymer, 2 parts of hydroxypropyl methyl cellulose ether and 80 parts of water are stirred in a reaction kettle for 40 minutes until the components are uniformly mixed, and the concrete thermal curing synergist H3 is obtained.
Example 4
According to the weight parts, 2 parts of maleic acid-triethanolamine ester, 19 parts of acrylic acid-alkylene polyoxyethylene ether 2400-hydroxyethyl acrylate copolymer, 2 parts of hydroxypropyl methyl cellulose ether and 77 parts of water are stirred in a reaction kettle for 30 minutes to be uniformly mixed, and the concrete thermal curing synergist H4 is obtained.
Example 5
According to the weight parts, 2.5 parts of maleic acid-triethanolamine ester, 16 parts of acrylic acid-alkylene polyoxyethylene ether 2400-hydroxyethyl acrylate copolymer, 1 part of hydroxyethyl methyl cellulose ether, 1 part of hydroxypropyl methyl cellulose ether and 79.5 parts of water are stirred in a reaction kettle for 30 minutes to be uniformly mixed, and the concrete thermal curing synergist H5 is obtained.
According to the standard of GB 25779-.
According to the standard of GB/T24492-3And the strength of the load-bearing concrete brick with the strength grade MU7.5 is increased and the compressive strength of the load-bearing concrete brick is 28d compared with the concrete brick with the heat curing synergist, wherein the concrete brick is subjected to heat curing at 60 ℃ for 5-9 hours and at 60 ℃ for 9 hours.
According to JGJ 1-2014 technical Specification of prefabricated concrete structures, C35 concrete with the slump of 16-18 cm for producing reinforced concrete prefabricated parts is prepared, and the concrete strength increase and 28d compressive strength are compared with those of concrete subjected to thermal curing for 6-10 hours at 70 ℃ and 10 hours at 70 ℃.
According to JGJ 1-2014 technical Specification of prefabricated concrete structures, C50 concrete with the slump of 16-18 cm for producing the prestressed concrete prefabricated part is prepared, and the concrete strength increase and 28d compressive strength are compared with those of concrete subjected to thermal curing for 6-10 hours at 70 ℃ and 10 hours at 70 ℃.
Application example 1
In order to quantitatively analyze the influence of the concrete thermal curing synergist on the microstructure and the strength of the set cement, concrete samples with the water-cement ratio of 0.35 and 0.42 are prepared in the test, the mixing amount of the synergist is 0.1-0.2 percent of the mass of a cementing material (consisting of 60 parts of P, II 42.5 grade portland cement and 40 parts of low-calcium I grade fly ash) in terms of solid parts, and the concrete curing system is as follows: after standing at 20 ℃ for 5 hours, raising the temperature to 60 ℃ for 1 hour, and then carrying out constant-temperature heat curing for 8 hours, wherein the influences of H1, H3 and H5 in the examples on the microstructure and the strength of the concrete are evaluated respectively. The test results are summarized in Table 1.
TABLE 1 concrete microstructure and Strength of blended Hot curing synergists
As can be seen from Table 1, the addition of the thermal curing synergist accounting for 0.10-0.20% of the mass of the cementitious material in the concrete significantly improves the gel-to-air ratio and compressive strength of the cement stones in the concrete when the concrete is continuously cured to 28 days after thermal curing and after thermal curing. When the water-cement ratio is 0.35, the compressive strength ratio of the concrete doped with the heat curing synergist and the standard concrete after heat curing reaches more than 185%, the compressive strength of the concrete doped with the heat curing synergist is improved by about 30%, and the compressive strength of the concrete doped with the heat curing synergist after the heat curing is close to the compressive strength of the standard concrete 28 d; when the water-cement ratio is 0.42, the compressive strength ratio of the concrete at the end of thermal curing and 28d is respectively greater than 165% and 133%, and when the mixing amount of the synergist is higher, the compressive strength of the concrete at the end of thermal curing reaches the compressive strength of the reference concrete 28 d. The test result shows that the thermal curing synergist promotes the cement hydration and the volcanic ash reaction of the fly ash volcanic ash in the thermal curing process, thereby improving the density of the set cement and obtaining the double effects of early strength and enhancement.
Application example 2
Preparing concrete with 50 percent of fly ash doping amount, wherein the water-cement ratio is 0.42, the doping amount of the thermal curing synergist is 0.15 percent of the total weight of the cement and the fly ash in terms of solid parts, and respectively measuring the influence of the concrete thermal curing synergist on the strength of the concrete brick under the conditions that the concrete brick is stood at 20 ℃ for 5 hours, then heated to 60 ℃ for 1 hour, and then thermally cured at constant temperature for 5-9 hours. The test results are shown in table 2.
TABLE 2 influence of thermal curing agent and constant temperature time on compressive strength of MU20 concrete bricks
As can be seen from Table 2, compared with the standard concrete brick which is thermally cured at the constant temperature of 60 ℃ for 9 hours, the concrete brick doped with the concrete thermal curing synergist of 0.15 percent is thermally cured at the constant temperature of 60 ℃ for 5 to 9 hours, and the compressive strength of the concrete brick after the thermal curing is finished reaches the requirement of MU20, so the constant temperature time can be selected to be 5 to 6 hours. Therefore, the maintenance facility is changed from the original 2-day turnover to 3-day turnover, and the production efficiency can be improved by 50%.
The concrete with 60 percent of the blended fly ash is prepared on site, the water-cement ratio is 0.50, the blending amount of the thermal curing synergist is 0.20 percent of the total weight of the cement and the fly ash in terms of solid parts, the influence of the concrete thermal curing synergist on the strength of the concrete brick is respectively evaluated under the conditions that the non-bearing concrete brick is heated to 60 ℃ after being stood at 20 ℃ for 5 hours and then thermally cured at constant temperature for 5-9 hours, and the results are shown in Table 3.
TABLE 3 influence of thermal curing agent and constant temperature time on compressive strength of MU7.5 concrete brick
As shown in Table 3, the thermal curing synergist has a better effect on low-strength concrete bricks, and the compressive strength of the concrete bricks reaches 85% of the standard value after 5 hours of constant-temperature thermal curing at 60 ℃. Therefore, the constant-temperature thermal curing time is selected to be 5 hours, which can exceed the intensity index of the original curing process with the constant temperature of 9 hours, the thermal curing time is saved by 4 hours, and the turnover frequency of the curing facility per day is increased from the original 2 times to 3 times.
Application example 4
The concrete with the mixing amount of the prepared fly ash being 16% and the mixing amount of the S95 micro slag powder being 24% has the water-cement ratio being 0.42 and the mixing amount of the thermal curing synergist being 0.15% of the total weight of the cement, the fly ash and the micro slag powder in terms of solid parts, and the test shows that the concrete thermal curing synergist influences the strength of the concrete under the conditions that the concrete is statically stopped at 20 ℃ for 5 hours, then the concrete is heated to 70 ℃ for 1 hour and then thermally cured at constant temperature for 6-10 hours, and the results are shown in Table 4.
TABLE 4 influence of thermal curing agent and constant temperature time on compressive strength of C35 concrete
From table 4, it is found that the thermal curing synergist accelerates the strength development of the C35 concrete under the thermal curing condition, the compressive strength of the concrete with the thermal curing synergist in 6 hours is 25.4% higher than that of the concrete with the standard in 10 hours, and the compressive strength of the concrete with the thermal curing synergist in 28 days is 1 strength grade higher than that of the concrete with the standard in 10 hours. Therefore, the concrete is thermally cured for 6 hours at constant temperature, and the strength of the concrete meets the standard requirement.
Application example 5
The concrete with the mixing amount of the prepared fly ash being 16% and the mixing amount of the S95 slag micro powder being 24% has the water-cement ratio being 0.35 and the mixing amount of the thermal curing synergist being 0.20% of the total weight of the cement, the fly ash and the slag micro powder in terms of solid parts, and the test results are listed in Table 5, wherein the test shows that the thermal curing synergist influences the strength of the concrete under the conditions that the concrete is heated to 60 ℃ 1 hour after being statically stopped at 20 ℃ for 5 hours and then thermally cured at constant temperature for 6-10 hours.
TABLE 5 influence of thermal curing agent and constant temperature time on compressive strength of C50 concrete
As can be seen from Table 5, the thermal curing synergist has a remarkable reinforcing effect on the C50 concrete prepared by the invention, and the strength grade of the concrete basically reaches C70 after the thermal curing is carried out for 10 hours at constant temperature; and (5) carrying out constant-temperature heat curing for 6 hours, wherein the strength grade of the concrete reaches C60.
Claims (3)
1. A concrete thermal curing synergist is characterized in that: the raw materials comprise the following components in parts by weight: 2-3 parts of maleic acid-triethanolamine ester, 15-20 parts of acrylic acid-alkylene polyoxyethylene ether-hydroxyethyl acrylate copolymer, 1.5-2 parts of cellulose ether and 70-80 parts of water;
the preparation method of the acrylic acid-alkylene polyoxyethylene ether-hydroxyethyl acrylate copolymer comprises the following steps:
step 1, adding 30 parts of water, 30 parts of alkylene polyoxyethylene ether and 5 parts of hydroxyethyl acrylate into a reaction kettle in parts by weight, and stirring until the alkylene polyoxyethylene ether and the hydroxyethyl acrylate are completely dissolved;
step 2, adding 0.35 part by weight of 27% hydrogen peroxide solution into a reaction kettle, and heating to 45-55 ℃;
step 3, dripping 8 parts by weight of 25% acrylic acid aqueous solution, 3 parts by weight of 5% sodium methallyl sulfonate aqueous solution and 4 parts by weight of 5% sodium thiosulfate aqueous solution into a reaction kettle, wherein the dripping time of the acrylic acid solution is 3-4 hours, the dripping time of the sodium methallyl sulfonate aqueous solution and the sodium thiosulfate aqueous solution is 4-5 hours, and carrying out heat preservation reaction at 45-55 ℃ for 1 hour;
step 4, adding 15.95 parts by weight of water and 3.7 parts by weight of sodium hydroxide aqueous solution with the mass concentration of 30% into a reaction kettle, and adjusting the pH value to 6 to obtain an acrylic acid-alkylene polyoxyethylene ether-hydroxyethyl acrylate copolymer;
the synergist is applied to concrete as a thermal curing synergist.
2. The concrete thermal curing synergist of claim 1, wherein: the cellulose ether is one or a mixture of two of hydroxypropyl methyl cellulose ether and hydroxyethyl methyl cellulose ether.
3. The method for preparing the concrete thermal curing synergist of claim 1, wherein the concrete thermal curing synergist comprises the following steps: mixing maleic acid-triethanolamine ester, acrylic acid-alkylene polyoxyethylene ether-hydroxyethyl acrylate copolymer, cellulose ether and water.
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Effective date of registration: 20211018 Address after: 211124 Chunhua street chagang community, Jiangning District, Nanjing City, Jiangsu Province Patentee after: Nanjing pingda Green Building Materials Technology Co.,Ltd. Address before: 211316 No. 3 Gutan Avenue, economic development zone, Gaochun County, Nanjing City, Jiangsu Province Patentee before: NANJING JIANGAO NEW MATERIAL TECHNOLOGY Co.,Ltd. |