CN111704383A - Hydration heat inhibitor suitable for concrete construction in high-temperature environment and preparation method thereof - Google Patents
Hydration heat inhibitor suitable for concrete construction in high-temperature environment and preparation method thereof Download PDFInfo
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- CN111704383A CN111704383A CN202010505857.4A CN202010505857A CN111704383A CN 111704383 A CN111704383 A CN 111704383A CN 202010505857 A CN202010505857 A CN 202010505857A CN 111704383 A CN111704383 A CN 111704383A
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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
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Abstract
The invention discloses a hydration heat inhibitor suitable for high-temperature environment hydraulic concrete construction and a preparation method thereof. The hydration heat inhibitor comprises the following components in percentage by weight: 2 to 20 percent of organic phosphonic acid, 10 to 20 percent of polybasic weak acid, 1 to 5 percent of strong base weak acid salt, 0 to 1 percent of stabilizer, 0 to 1 percent of organic tackifier and the balance of water. The hydration heat inhibitor is a clear and uniform liquid, the pH value of the hydration heat inhibitor is 3.0-5.0, and the density of the hydration heat inhibitor is 1.40g/cm3～1.50g/cm3And the solid content is 10-30%. The hydration heat release of the cement 7d doped with 0.6 percent (cement weight) of the hydration heat inhibitor is 14.4 to 53.7 percent of that of a blank sample, and the time delay of the occurrence of the hydration heat peak is 108.4 to 113.3 hours. The hydration heat inhibitor has obvious hydration heat inhibition effect, and can be used for individually making preparation schemes according to the requirements of different projects. At 35 ℃, the retention rate of the cement setting time doped with the hydration heat inhibitor is 97.6-98.8%, and the hydration heat inhibitor is used in hot summer and high-temperature environmentThe hydration heat inhibition effect can be kept at 35 ℃, and the method is suitable for high-temperature environment hydraulic concrete construction.
Description
Technical Field
The invention belongs to the field of concrete admixtures. Relates to a preparation method of a hydration heat inhibitor based on organic phosphonic acid, which is suitable for high-temperature environment hydraulic concrete construction.
Background
The control of hydraulic concrete cracks has been a problem concerned by extensive scientific research and engineering personnel, and has gradually attracted the attention of the engineering world since the 30 s in the 20 th century. The generation of hydraulic concrete cracks is influenced by various factors, but mainly due to the action of temperature stress. The method is an important means for reducing the temperature crack generation of the hydraulic concrete by reducing the hydration heat release rate and the heat release quantity of a hydraulic concrete gelling system. From the concrete material perspective, mineral admixtures such as fly ash, phosphorus slag powder, volcanic ash or limestone powder and the like are usually added in large and medium-sized hydraulic and hydroelectric engineering, and the hydration heat release rate and the hydration heat release quantity of a hydraulic concrete cementing system are reduced by adopting medium and low heat portland cement and using additives such as hydration heat inhibitors, retarders and the like. And the hydration heat release and the heat release rate of a gelling system are reduced by adding the admixture with hydration heat inhibition, so that the engineering has better economical efficiency and operability.
The main components of the currently commonly used concrete hydration heat inhibiting materials are saccharides such as starch, dextrin and the like. The hydration heat inhibiting material has limited hydration heat inhibiting capacity, and the hydration heat inhibiting effect is greatly weakened when the environment temperature is higher (higher than 35 ℃). Therefore, it is difficult for the conventional hydration heat inhibitor to exhibit its hydration heat inhibiting effect in a high-temperature environment or hot summer work. Thereby being difficult to realize the purpose of avoiding and reducing the concrete cracks.
Disclosure of Invention
Aiming at the disadvantages and shortcomings of the hydration heat inhibiting materials commonly used at present. The organic phosphonic acid is used as a base material, has a remarkable hydration heat inhibition effect, and simultaneously still maintains a strong hydration heat inhibition effect in construction at a higher environmental temperature or in hot summer. Provides a hydration heat inhibitor based on organic phosphonic acid and suitable for high-temperature environment hydraulic concrete construction and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme.
A hydration heat inhibitor suitable for high-temperature environment hydraulic concrete construction comprises the following components in percentage by weight:
2 to 20 percent of organic phosphonic acid, 10 to 20 percent of polybasic weak acid, 1 to 5 percent of strong base weak acid salt, 0 to 1 percent of stabilizer, 0 to 1 percent of organic tackifier and the balance of water.
Preferably, the components are as follows according to the weight percentage:
5 to 15 percent of organic phosphonic acid, 12 to 18 percent of polybasic weak acid, 2 to 4 percent of strong base weak acid salt, 0 to 1 percent of stabilizer, 0 to 1 percent of organic tackifier and the balance of water.
The organic phosphonic acid is industrial organic phosphonic acid, and is amino trimethylene phosphonic Acid (ATMP), hydroxyethylidene diphosphonic acid (HEDP), ethylene diamine tetra methylene phosphonic acid sodium (EDTMP), 2-phosphonic acid butane-1, 2, 4-tricarboxylic acid (PBTC) or diethylenetriamine pentamethylene methylene phosphonic acid (DTPMPA). The weak polybasic acid is phosphoric acid, boric acid or carbonic acid. The strong alkali weak acid salt is borax or sodium tripolyphosphate. The stabilizer is Ethylene Diamine Tetraacetic Acid (EDTA), salicylic acid or citric acid, preferably EDTA; the organic tackifier may be polyacrylamide or acrylamide.
The hydration heat inhibitor is a clear and uniform liquid, the pH value of the hydration heat inhibitor is 3.0-5.0, and the density of the hydration heat inhibitor is 1.40g/cm3～1.50g/cm3And the solid content is 10-30%.
A preparation method of a hydration heat inhibitor suitable for high-temperature environment hydraulic concrete construction. The method is characterized in that the preparation method of the hydration heat inhibitor based on organic phosphonic acid and suitable for the high-temperature environment hydraulic concrete construction comprises the following steps:
weighing the components according to the weight percentage, wherein the component ratio is 2-20% of organic phosphonic acid, 10-20% of polybasic weak acid, 1-5% of strong base weak acid salt, 0-1% of stabilizing agent, 0-1% of organic tackifier and the balance of water;
adding a certain amount of organic phosphonic acid and water into a four-neck flask provided with a stirrer, a dropping funnel and a thermometer, heating to 30-40 ℃, and stirring at a speed of not less than 80 revolutions per minute;
adding weak polybasic acid with stirring speed not lower than 120 rpm while stirring continuously, and adding strong base and weak acid salt after the weak polybasic acid is dissolved to form stable solution;
preserving the temperature for 30-40 min, finally adding a stabilizer and an organic tackifier, and adjusting the pH of the solution to 3.0-5.0 to obtain a clear uniform solution.
Compared with the prior art, the invention has the beneficial effects that: the hydration heat inhibitor can still keep remarkable hydration heat inhibition effect in hot summer and under high temperature environment (35 ℃), and is suitable for high temperature environment hydraulic concrete construction.
Drawings
FIG. 1 is a heat release diagram for hydration of cement incorporating a hydration heat inhibitor according to the present invention at 20 ℃;
FIG. 2 is a graph of the heat release rate of hydration of a cement incorporating a hydration heat inhibitor of the present invention at 20 ℃;
FIG. 3 is the setting time of the cement of example 1 doped with a hydration heat inhibitor at 20 ℃ according to the invention;
FIG. 4 is the setting time of the cement of example 2 doped with a hydration heat inhibitor at 20 ℃ according to the invention;
FIG. 5 is the setting time of the cement of example 3 doped with a hydration heat inhibitor at 20 ℃ according to the invention;
FIG. 6 is a graph showing the retention of setting time of cement doped with a hydration heat inhibitor of example 1 at 35 ℃ in accordance with the present invention;
FIG. 7 is a graph showing the retention of setting time of cement blended with a hydration heat inhibitor of example 2 at 35 ℃ in accordance with the present invention;
FIG. 8 is a graph showing the retention time of cement set time of example 3 doped with a hydration heat inhibitor at 35 ℃ in accordance with the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The technical scheme provided by the invention.
A hydration heat inhibitor based on organic phosphonic acid and suitable for high-temperature environment hydraulic concrete construction. The components are as follows according to the weight percentage:
5 to 15 percent of organic phosphonic acid, 12 to 18 percent of polybasic weak acid, 2 to 4 percent of strong base weak acid salt, 0 to 1 percent of stabilizer, 0 to 1 percent of organic tackifier and the balance of water.
The organic phosphonic acid is industrial organic phosphonic acid, and can be amino trimethylene phosphonic Acid (ATMP), hydroxyethylidene diphosphonic acid (HEDP), ethylene diamine tetra methylene phosphonic acid sodium (EDTMP), 2-phosphonic acid butane-1, 2, 4-tricarboxylic acid (PBTC) or diethylenetriamine pentamethylene methylene phosphonic acid (DTPMPA). The weak polybasic acid may be phosphoric acid, boric acid or carbonic acid. The strong alkali and weak acid salt can be borax or sodium tripolyphosphate. The stabilizer can be ethylenediamine tetraacetic acid (EDTA), salicylic acid, citric acid, preferably EDTA; the organic tackifier may be polyacrylamide or acrylamide.
The hydration heat inhibitor is a clear and uniform liquid, the pH value of the hydration heat inhibitor is 3.0-5.0, and the density of the hydration heat inhibitor is 1.40g/cm3～1.50g/cm3The solid content is 10 to 30 percent;
a method for preparing a hydration heat inhibitor based on organic phosphonic acid and suitable for high-temperature environment hydraulic concrete construction. The preparation method of the hydration heat inhibitor based on organic phosphonic acid and suitable for the high-temperature environment hydraulic concrete construction comprises the following steps:
weighing the components according to the weight percentage, wherein the component ratio is 2-20% of organic phosphonic acid, 10-20% of polybasic weak acid, 1-5% of strong base weak acid salt, 0-1% of stabilizing agent, 0-1% of organic tackifier and the balance of water;
adding a certain amount of organic phosphonic acid and water into a four-neck flask provided with a stirrer, a dropping funnel and a thermometer, heating to 30-40 ℃, and stirring at a speed of not less than 80 revolutions per minute;
and adding the polybasic acid while continuously stirring, wherein the stirring speed is not lower than 120 revolutions per minute. After the polybasic and weak acids are dissolved, adding strong base and weak acid salt to form stable solution;
preserving the temperature for 30-40 min, finally adding a stabilizer and an organic tackifier, and adjusting the pH of the solution to 3.0-5.0 to obtain a clear uniform solution.
Compared with the commonly used carbohydrate substances such as the concrete hydration heat inhibiting materials, such as starch, dextrin and the like, the hydration heat inhibiting material provided by the method has the following characteristics: 1) can keep strong hydration heat inhibition effect when being constructed in hot summer and high temperature environment (35 ℃). 2) Has strong hydration heat inhibiting effect. The hydration heat suppression degree can be adjusted according to the actual engineering requirements. Thereby realizing the purpose of reducing and avoiding the concrete cracks.
Example 1
6 percent of organic phosphonic acid, 12 percent of polybasic weak acid, 2 percent of strong base weak acid salt, 0.5 percent of stabilizing agent, 0.2 percent of organic tackifier and the balance of water.
The organic phosphonic acid is ATMP, the polybasic weak acid is boric acid, the strong base weak acid salt is borax, the stabilizing agent is EDTA, and the organic tackifier is polyacrylamide.
Adding a certain amount of organic phosphonic acid and water into a four-neck flask provided with a stirrer, a dropping funnel and a thermometer, heating to 30-40 ℃, and stirring at a speed of not less than 80 revolutions per minute.
And adding the polybasic acid while continuously stirring, wherein the stirring speed is not lower than 120 revolutions per minute. After the polybasic and weak acids are dissolved, adding strong base and weak acid salt to form stable solution.
Preserving the temperature for 30-40 min, finally adding a stabilizer and an organic tackifier, and adjusting the pH of the solution to 3.0-5.0 to obtain a clear uniform solution.
Example 2
8 percent of organic phosphonic acid, 16 percent of polybasic weak acid, 3 percent of strong base weak acid salt, 0.5 percent of stabilizing agent, 0.2 percent of organic tackifier and the balance of water.
The organic phosphonic acid is HEDP, the polybasic weak acid is boric acid, the strong base weak acid salt is sodium tripolyphosphate, the stabilizing agent is EDTA, and the organic tackifier is polyacrylamide.
Adding a certain amount of organic phosphonic acid and water into a four-neck flask provided with a stirrer, a dropping funnel and a thermometer, heating to 30-40 ℃, and stirring at a speed of not less than 80 revolutions per minute.
And adding the polybasic acid while continuously stirring, wherein the stirring speed is not lower than 120 revolutions per minute. After the polybasic and weak acids are dissolved, adding strong base and weak acid salt to form stable solution.
Preserving the temperature for 30-40 min, finally adding a stabilizer and an organic tackifier, and adjusting the pH of the solution to 3.0-5.0 to obtain a clear uniform solution.
Example 3
9 percent of organic phosphonic acid, 18 percent of polybasic weak acid, 2 percent of strong base weak acid salt, 0.5 percent of stabilizing agent, 0.2 percent of organic tackifier and the balance of water.
The organic phosphonic acid is PBTC, the polybasic weak acid is boric acid, the strong base weak acid salt is borax, the stabilizing agent is salicylic acid, and the organic tackifier is acrylamide.
Adding a certain amount of organic phosphonic acid and water into a four-neck flask provided with a stirrer, a dropping funnel and a thermometer, heating to 30-40 ℃, and stirring at a speed of not less than 80 revolutions per minute.
And adding the polybasic acid while continuously stirring, wherein the stirring speed is not lower than 120 revolutions per minute. After the polybasic and weak acids are dissolved, adding strong base and weak acid salt to form stable solution.
Preserving the temperature for 30-40 min, finally adding a stabilizer and an organic tackifier, and adjusting the pH of the solution to 3.0-5.0 to obtain a clear uniform solution.
Tests were carried out using Huaxin brand 42.5 ordinary portland cement (P.O 42.5), and the basic chemical and physical properties thereof are shown in tables 1-2. The hydration heat release rate of the cement doped with 0.6 percent (cement mass fraction) hydration heat inhibitor at 20 ℃ is shown in figure 1, and the heat release is shown in figure 2. The characteristic parameters of the hydration heat release curve of the cement doped with the hydration heat inhibitor at 20 ℃ are shown in Table 3. The hydration heat release of the cement 7d doped with 0.6 percent of hydration heat inhibitor is 14.4 to 53.7 percent of that of the blank sample, and the time delay of the occurrence of the hydration heat peak is 108.4 to 113.3 hours. It can be seen that the hydration heat inhibitor prepared by the method has a very significant hydration heat inhibiting effect. Meanwhile, preparation schemes can be customized according to the requirements of different projects.
The setting time of the hydration heat inhibitor at 20 ℃ is shown in Table 4, and the tendency of the setting time of the three examples with the addition is shown in FIGS. 3 to 5. The hot summer and high temperature environment was simulated in the laboratory and the setting time of cement doped with hydration heat inhibitor at 35 c was measured. The setting times at 35 ℃ with the addition of the hydrated heat inhibitor are shown in Table 5. The adaptability of different hydration heat inhibitors to high temperatures is characterized by the retention rate of the setting time at 35 ℃ (the retention rate of the setting time is defined in formula 1). FIGS. 6 to 8 show the setting time retention rates of three examples of cement blended with a hydration heat inhibitor at 35 ℃.
Wherein Pr (%) is the retention rate of the coagulation time, T35And T20The setting times of the cement are 35 ℃ and 20 ℃ respectively.
It can be seen that the retention rate of the setting time of the cement doped with the hydration heat inhibitor is 97.6-98.8% under hot summer and high temperature environment (35 ℃). The cement mixed with the hydration heat inhibitor has less influence on the setting time by the temperature and can still keep strong hydration heat inhibition effect at high temperature. The retention rate of the condensation time of the dextrin which is a common hydration heat inhibitor at 35 ℃ is only 53.0-57.25% according to related literature reports. This shows that the hydration heat inhibitor prepared by the method can still maintain a remarkable hydration heat inhibition effect in hot summer and high temperature environment, compared with the conventional hydration heat inhibitor.
TABLE 1 basic physical Properties of Cement
TABLE 2 Cement chemistry (w/%)
TABLE 3 Cement hydration exotherm profile characteristic parameters (20 ℃ C.) with hydration heat inhibitor
TABLE 4 setting time of cement (20 ℃ C.) with hydration heat inhibitor
Cement setting time at 535 ℃ with the present hydration heat inhibitor
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (6)
1. The hydration heat inhibitor for the high-temperature environment hydraulic concrete construction is characterized by comprising the following components in percentage by weight:
2 to 20 percent of organic phosphonic acid, 10 to 20 percent of polybasic weak acid, 1 to 5 percent of strong base weak acid salt, 0 to 1 percent of stabilizer, 0 to 1 percent of organic tackifier and the balance of water.
2. The hydration heat inhibitor suitable for the high-temperature environment hydraulic concrete construction according to claim 1, wherein the hydration heat inhibitor comprises the following components in percentage by weight:
5 to 15 percent of organic phosphonic acid, 12 to 18 percent of polybasic weak acid, 2 to 4 percent of strong base weak acid salt, 0 to 1 percent of stabilizer, 0 to 1 percent of organic tackifier and the balance of water.
3. The hydration heat inhibitor for high-temperature environment hydraulic concrete construction according to claim 1, wherein the organic phosphonic acid is industrial grade organic phosphonic acid, and is amino trimethylene phosphonic acid, hydroxy ethylidene diphosphonic acid, sodium ethylene diamine tetra methylene phosphonic acid, 2-phosphonic butane-1, 2, 4-tricarboxylic acid or diethylenetriamine pentamethylene phosphonic acid; the polybasic weak acid is phosphoric acid, boric acid or carbonic acid; the strong base weak acid salt is borax or sodium tripolyphosphate; the stabilizer is ethylenediamine tetraacetic acid, salicylic acid or citric acid; the organic tackifier is polyacrylamide or acrylamide.
4. The hydration heat inhibitor for the high-temperature environment hydraulic concrete construction according to claim 1, wherein the hydration heat inhibitor is a clear and uniform liquid with a pH of 3.0-5.0 and a density of 1.40g/cm3～1.50g/cm3And the solid content is 10-30%.
5. A preparation method of a hydration heat inhibitor suitable for high-temperature environment hydraulic concrete construction is characterized in that the preparation method of the hydration heat inhibitor based on organic phosphonic acid and suitable for high-temperature environment hydraulic concrete construction comprises the following steps:
1) weighing the components according to the weight percentage, wherein the component ratio is 2-20% of organic phosphonic acid, 10-20% of polybasic weak acid, 1-5% of strong base weak acid salt, 0-1% of stabilizing agent, 0-1% of organic tackifier and the balance of water; adding organic phosphonic acid and water into a four-neck flask provided with a stirrer, a dropping funnel and a thermometer, heating to 30-40 ℃, and stirring at a speed of not less than 80 revolutions per minute;
2) adding weak polybasic acid with stirring speed not lower than 120 rpm while stirring continuously, and adding strong base and weak acid salt after the weak polybasic acid is dissolved to form stable solution;
3) preserving the temperature for 30-40 min, finally adding a stabilizer and an organic tackifier, and adjusting the pH of the solution to 3.0-5.0 to obtain a clear uniform solution.
6. The method for preparing hydration heat inhibitor for high temperature environment hydraulic concrete construction according to claim 5, wherein the organic phosphonic acid is industrial grade organic phosphonic acid, which is amino trimethylene phosphonic acid, hydroxy ethylidene diphosphonic acid, sodium ethylene diamine tetra methylene phosphonic acid, 2-phosphonic butane-1, 2, 4-tricarboxylic acid or diethylene triamine pentamethylene methylene phosphonic acid; the polybasic weak acid is phosphoric acid, boric acid or carbonic acid; the strong base weak acid salt is borax or sodium tripolyphosphate; the stabilizer is ethylenediamine tetraacetic acid, salicylic acid or citric acid; the organic tackifier is polyacrylamide or acrylamide.
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Cited By (2)
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| CN112979203A (en) * | 2021-03-04 | 2021-06-18 | 交通运输部公路科学研究所 | Cement concrete hydration heat inhibitor containing water-soluble cage-type inclusion compound and preparation method and application thereof |
| CN113121149A (en) * | 2021-03-01 | 2021-07-16 | 交通运输部公路科学研究所 | Cement-based hydration heat inhibitor and preparation method of cement hydration heat inhibiting concrete |
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| CN113121149A (en) * | 2021-03-01 | 2021-07-16 | 交通运输部公路科学研究所 | Cement-based hydration heat inhibitor and preparation method of cement hydration heat inhibiting concrete |
| CN112979203A (en) * | 2021-03-04 | 2021-06-18 | 交通运输部公路科学研究所 | Cement concrete hydration heat inhibitor containing water-soluble cage-type inclusion compound and preparation method and application thereof |
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