CN112521113B - Low-temperature hydration hardening gel material and preparation method and application thereof - Google Patents
Low-temperature hydration hardening gel material and preparation method and application thereof Download PDFInfo
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- CN112521113B CN112521113B CN202011415299.9A CN202011415299A CN112521113B CN 112521113 B CN112521113 B CN 112521113B CN 202011415299 A CN202011415299 A CN 202011415299A CN 112521113 B CN112521113 B CN 112521113B
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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
- C04B28/06—Aluminous cements
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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
- 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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Abstract
The invention relates to the technical field of building materials, and provides a low-temperature hydration hardening gel material, and a preparation method and application thereof. The gel material provided by the invention comprises the following components: modified aluminate cement, ultrafine powder active admixture, sand, coagulant, retarder, antifreezing agent and water; the modified aluminate cement is obtained by mixing aluminate cement and alkaline oxide. The invention can lead the obtained gel material to be hydrated smoothly and generate enough strength in the environment as low as minus 10 ℃ by modifying aluminate cement and regulating and controlling the component ratio of the material, and simultaneously can control the temperature peak value of mortar not to exceed 0 ℃ during hydration, avoid the disturbance of heat emitted in the hydration process to the temperature field of surrounding frozen soil in pile foundation engineering, avoid the problems of unstable foundation pit support, inclined pile foundation and the like caused by the thawing of the frozen soil, meet the construction requirement of the pile foundation in the frozen soil area, and lead the engineering of the frozen soil area in plateau to be safer and more reliable.
Description
Technical Field
The invention relates to the technical field of building materials, in particular to a low-temperature hydration hardening gel material and a preparation method and application thereof.
Background
Concrete is the building material with the largest use amount and the widest application range in modern buildings. The concrete is formed by mixing a gel material, aggregate and the like and then curing and hardening, wherein the hydration and hardening processes of the gel material directly influence the mechanical property and durability of the concrete.
At present, gel materials commonly used in the field such as portland cement, aluminate cement and the like have good hydration hardening effect only at normal temperature, are slowly hydrated in a low-temperature environment of a plateau frozen soil area, have low strength after hardening, and generate hydration heat which can generate adverse effect on the thermal stability of the frozen soil, so that the disturbance of a surrounding frozen soil temperature field in pile foundation engineering is caused, and the problems of unstable foundation pit support, pile foundation inclination and the like caused by the thawing of the frozen soil are easily generated.
Disclosure of Invention
In view of the above, the present invention aims to provide a low temperature hydration hardening gel material and a preparation method thereof. The gel material provided by the invention can be smoothly hydrated in an environment as low as 15 ℃ and generate enough strength, and the hydrothermal heat release temperature is controllable, so that the plateau frozen soil area engineering is safer and more reliable, and the requirements of pile foundation construction in the frozen soil area are met.
In order to achieve the above object, the present invention provides the following technical solutions:
a low-temperature hydration hardening gel material comprises the following components in parts by mass:
10-20 parts of modified aluminate cement, 0-10 parts of ultrafine powder active admixture, 60-70 parts of sand, 0.15-0.3 part of coagulant, 0.5-0.7 part of retarder, 1-2 parts of anti-freezing agent and 8-12 parts of water;
the modified aluminate cement is obtained by mixing aluminate cement and alkaline oxide.
Preferably, the alkaline oxide is one or more of magnesium oxide, calcium oxide and potassium oxide; the mass of the alkaline oxide is 1-3% of that of the aluminate cement.
Preferably, Al in the aluminate cement2O3The mass fraction is more than or equal to 68 percent, and the specific surface area of the aluminate cement is more than or equal to 300m2/kg。
Preferably, the ultrafine powder active blending material comprises at least one of silica fume, fly ash, blast furnace slag powder and metakaolin; the particle size of the ultrafine powder active admixture is 2-3 mu m.
Preferably, the sand is natural river sand and/or machine-made sand; the grain size of the sand is less than or equal to 2 mm.
Preferably, the coagulant comprises at least one of calcium chloride, calcium nitrate, calcium nitrite, sodium sulfate and sodium carbonate.
Preferably, the retarder includes at least one of an alcohol retarder, a carboxylic acid retarder, a phosphate retarder, a borate retarder, and sodium fluorosilicate.
Preferably, the antifreeze agent comprises at least one of ethylene glycol, calcium chloride and calcium formate.
The invention also provides a preparation method of the low-temperature hydration hardening gel material, which comprises the following steps:
(1) dissolving an antifreeze in water to obtain an antifreeze solution;
(2) mixing the modified aluminate cement, the ultrafine powder active admixture, the coagulant and the retarder to obtain mixed powder;
(3) mixing the mixed powder with the antifreeze solution and sand to obtain a low-temperature hydration hardening gel material;
the step (1) and the step (2) are not limited in time sequence.
The invention also provides the application of the low-temperature hydration hardening gel material or the low-temperature hydration hardening gel material prepared by the preparation method in the scheme in the construction of the pile foundation in the frozen soil area, wherein the application temperature is more than or equal to-10 ℃.
The invention provides a low-temperature hydration hardening gel material which comprises the following components in parts by mass: 10-20 parts of modified aluminate cement, 0-10 parts of ultrafine powder active admixture, 60-70 parts of sand, 0.15-0.3 part of coagulant, 0.5-0.7 part of retarder, 1-2 parts of anti-freezing agent and 8-12 parts of water; the modified aluminate cement is obtained by mixing aluminate cement and alkaline oxide. According to the invention, the alkaline oxide is doped into the aluminate cement, and is a functional inducing material, so that a gel phase X-AFm is preferentially formed in an aluminate system during hydration, and the generation of metastable hydrated aluminate is reduced, thereby increasing the early strength and stability of the material; the invention controls the freezing point of the mixed aqueous solution by adding the antifreezing agent, controls the hydration heat release of the gel material in unit time by the synergistic action of the coagulant and the retarder, and prolongs the total time of the hydration heat release, thereby achieving the purpose of controlling the hydration heat release peak value. According to the invention, through the matching of the gel material components, smooth hydration can be realized in an environment as low as-10 ℃ and sufficient strength can be generated, the hydration heat release peak value can be controlled not to exceed 0 ℃, and the problems that the heat released in the hydration process disturbs the surrounding frozen soil temperature field in the pile foundation engineering, the frozen soil unfreezes to make the foundation pit support unstable, the pile foundation inclines and the like are avoided.
The invention also provides a preparation method of the low-temperature hydration hardening gel material, which is simple in steps and easy to operate.
The invention also provides application of the low-temperature hydration hardening gel material in the scheme in construction of a pile foundation in a frozen soil area. The low-temperature hydration hardening gel material provided by the invention has controllable hydration heat release temperature, can be smoothly hydrated and hardened at low temperature, does not need additional pile foundation protection measures when being applied, has reliable strength and low cost, meets the pile foundation construction requirements of a frozen soil area, and ensures that plateau frozen soil area engineering is safer and more reliable.
Detailed Description
The invention provides a low-temperature hydration hardening gel material which comprises the following components in parts by mass:
10-20 parts of modified aluminate cement, 0-10 parts of ultrafine powder active admixture, 60-70 parts of sand, 0.15-0.3 part of coagulant, 0.5-0.7 part of retarder, 1-2 parts of antifreeze and 8-12 parts of water.
Unless otherwise specified, the raw material components used in the low-temperature hydration-hardening gel material of the present invention are commercially available.
The low-temperature hydration hardening gel material comprises, by mass, 10-20 parts of modified aluminate cement, preferably 13-18 parts, and more preferably 15 parts. In the invention, the modified aluminate cement is obtained by mixing aluminate cement and alkaline oxide, wherein the alkaline oxide is preferably at least one of magnesium oxide, calcium oxide and potassium oxide; the mass of the alkaline oxide is preferably 1 to 3 percent of that of the aluminate cement, and is preferably 2 percent; the mixing mode of the aluminate cement and the alkaline oxide is not required in the invention, and the aluminate cement and the alkaline oxide can be uniformly mixed by adopting the mixing mode which is well known by the technical personnel in the field.
In the invention, Al in the aluminate cement2O3The mass fraction of the aluminate cement is more than or equal to 68 percent, preferably 70 to 80 percent, and the specific surface area of the aluminate cement is more than or equal to 300m2/kg, preferably 350 to 450m2In terms of/kg. The invention adds the alkaline oxide to modify the aluminate cement,can promote the formation of early ettringite in the hydration process and improve the early strength of the cement.
Based on the mass part of the modified aluminate cement, the low-temperature hydration hardening gel material provided by the invention comprises 0-10 parts of ultrafine powder active admixture, preferably 2-8 parts, and more preferably 3-5 parts. In the present invention, the ultrafine powder active admixture preferably includes at least one of silica fume, fly ash, blast furnace slag powder and metakaolin; the particle size of the superfine powder active admixture is preferably 2-3 mu m. The invention can generate active effect by adding the ultrafine powder active admixture, and the active admixture reacts with the added alkaline oxide hydration product to generate a small amount of gel which is filled between cement hydrates, thereby being beneficial to increasing the compactness of cement mortar and improving the later strength.
The low-temperature hydration hardening gel material comprises, by mass, 60-70 parts of sand, preferably 63-68 parts of sand, and more preferably 64-65 parts of sand. In the present invention, the sand preferably includes natural river sand and/or machine-made sand; the grain size of the sand is preferably less than or equal to 2mm, and more preferably 0.5-1.5 mm. In the invention, the sand can play a skeleton role, and the cement paste wraps the surface of the sand aggregate and fills the gap of the sand aggregate, so that the cement is cemented into a solid whole after being hardened.
The low-temperature hydration hardening gel material provided by the invention comprises 0.15-0.3 part of coagulant, preferably 0.2-0.25 part of coagulant by mass. In the present invention, the coagulant preferably includes at least one of calcium chloride, calcium nitrate, calcium nitrite, sodium sulfate, and sodium carbonate.
Based on the mass parts of the modified aluminate cement, the low-temperature hydration hardening gel material provided by the invention comprises 0.5-0.7 part of retarder, preferably 0.6 part. In the present invention, the retarder preferably includes at least one of an alcohol retarder, a carboxylic acid retarder, a phosphate retarder, a borate retarder, and sodium fluorosilicate; the alcohol retarder is preferably ethylene glycol, the carboxylic acid retarder is preferably tartaric acid, the phosphate retarder is preferably sodium hexametaphosphate, and the borate retarder is preferably borax and/or sodium fluorosilicate. The invention controls the hydration heat release amount of the gel material in unit time, prolongs the total time of the hydration heat release and controls the heat release peak value of the cement hydration not to exceed 0 ℃ through the synergistic action of the coagulant and the retarder, thereby avoiding the disturbance of the hydration heat release on the frozen soil temperature field.
Based on the mass part of the modified aluminate cement, the low-temperature hydration hardening gel material provided by the invention comprises 1-2 parts of an antifreezing agent, and preferably 1.3-1.5 parts. In the present invention, the antifreeze preferably includes at least one of ethylene glycol, calcium chloride, and calcium formate. The invention controls the freezing point of water by adding the antifreezing agent, so that the water cannot be frozen at low temperature, thereby providing conditions for the hydration of the gel material.
Based on the mass parts of the modified aluminate cement, the low-temperature hydration hardening gel material provided by the invention comprises 8-12 parts of water, and preferably 9-11 parts of water. The water is not particularly required in the present invention, and water known to those skilled in the art may be used.
The invention also provides a preparation method of the low-temperature hydration hardening gel material, which comprises the following steps:
(1) dissolving an antifreeze in water to obtain an antifreeze solution;
(2) mixing the modified aluminate cement, the ultrafine powder active admixture, the coagulant and the retarder to obtain mixed powder;
(3) mixing the mixed powder with the antifreeze solution and sand to obtain a low-temperature hydration hardening gel material;
the step (1) and the step (2) are not limited in time sequence.
The invention dissolves the antifreeze in water to obtain the antifreeze solution. The invention has no special requirements on the dissolving conditions, and can completely dissolve the antifreezing agent.
The invention mixes modified aluminate cement, ultrafine powder active admixture, coagulant and retarder to obtain mixed powder. The invention preferably mixes the modified aluminate cement and the ultrafine powder active admixture, then adds the coagulant and the retarder, and evenly stirs to obtain the mixed powder.
After the antifreeze solution and the mixed powder are obtained, the mixed powder, the antifreeze solution and the sand are mixed to obtain the low-temperature hydration hardening gel material. The invention preferably pours the mixed powder into the antifreeze solution, adds sand after stirring evenly, continues stirring evenly, and the obtained slurry is the low-temperature hydration hardening gel material of the invention.
The invention also provides the application of the low-temperature hydration hardening gel material or the low-temperature hydration hardening gel material prepared by the preparation method in the scheme in the construction of pile foundations in the frozen soil area. In the present invention, the temperature of the application is preferably ≥ 10 deg.C, more preferably-10-8 deg.C. In a specific embodiment of the invention, the slurry obtained by stirring in the step (3) (i.e. the low-temperature hydration hardening gel material of the invention) is poured in an environment at a temperature of not less than-10 ℃, and no additional pile foundation protection measures are needed.
The method has no special requirement on the maintenance measure after pouring, and the maintenance can be carried out in the environment of more than or equal to-10 ℃ according to the method well known by the technical personnel in the field.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
Example 1
The low-temperature hydration hardening gel material is prepared from the following components in parts by mass:
10 parts of modified aluminate cement, 3 parts of fly ash (the particle size is 2-3 mu m), 60 parts of natural river sand (the particle size is less than or equal to 2mm), 0.15 part of calcium chloride (coagulant), 0.5 part of ethylene glycol (retarder), 1 part of calcium formate (anti-freezing agent) and 10 parts of water;
wherein the modified aluminate cement is prepared from aluminate cement and calcium oxide according to the proportion of 100: 1 in a weight ratio of Al aluminate cement2O3Is 68 percent by mass, and the specific surface area of the aluminate cement is 300m2/kg。
The preparation method comprises the following steps:
(1) dissolving an antifreeze in water to obtain an antifreeze solution;
(2) adding the fly ash into the modified aluminate cement, adding the calcium chloride and the ethylene glycol into the fly ash, and uniformly stirring to obtain mixed powder.
(3) Pouring the mixed powder into an antifreezing agent solution, uniformly stirring, adding natural river sand, and uniformly stirring to obtain slurry, namely the low-temperature hydration hardening gel material;
example 2
Other conditions were the same as in example 1, except that the components of the low-temperature hydration-hardening gel material were changed to: 15 parts of modified aluminate cement, 5 parts of silica fume (the particle size is 2-3 mu m), 65 parts of machine-made sand (the particle size is less than or equal to 2mm), 0.2 part of calcium nitrate (coagulant), 0.6 part of tartaric acid (retarder), 1.5 parts of calcium chloride (anti-freezing agent) and 12 parts of water.
Wherein the modified aluminate cement is prepared from aluminate cement and magnesium oxide according to the weight ratio of 100: 3, and aluminate cement Al2O3Is 68 percent by mass, and the specific surface area of the aluminate cement is 300m2/kg。
Example 3
Other conditions were the same as in example 1, except that the components of the low-temperature hydration-hardening gel material were changed to:
20 parts of modified aluminate cement, 10 parts of fly ash (the particle size is 2-3 mu m), 70 parts of machine-made sand (the particle size is less than or equal to 2mm), 0.3 part of calcium nitrite (coagulant), 0.7 part of sodium hexametaphosphate (retarder), 2 parts of calcium formate (antifreeze) and 8 parts of water.
Wherein the modified aluminate cement is prepared from aluminate cement and potassium oxide according to the weight ratio of 100: 2 in a weight ratio of Al aluminate cement2O3Is 68 percent by mass, and the specific surface area of the aluminate cement is 300m2/kg。
Example 4
Other conditions were the same as in example 1, except that the components of the low-temperature hydration-hardening gel material were changed to:
15 parts of modified aluminate cement, 15 parts of metakaolin (with the particle size of 2-3 mu m), 62 parts of machine-made sand (with the particle size of less than or equal to 2mm), 0.25 part of sodium sulfate (coagulant), 0.65 part of borax (retarder), 1.5 parts of ethylene glycol (antifreeze) and 9 parts of water.
Wherein the modified aluminate cement is prepared from aluminate cement and calcium oxide according to the weight ratio of 100: 3, and aluminate cement Al2O3Is 68 percent by mass, and the specific surface area of the aluminate cement is 300m2/kg。
Example 5
Other conditions were the same as in example 1, except that the components of the low-temperature hydration-hardening gel material were changed to:
18 parts of modified aluminate cement, 63 parts of natural river sand (the particle size is less than or equal to 2mm), 0.15 part of sodium carbonate (coagulant), 0.65 part of sodium fluosilicate (retarder), 1 part of calcium chloride (antifreeze) and 10 parts of water.
Wherein the modified aluminate cement is prepared from aluminate cement and calcium oxide according to the weight ratio of 100: 1 in a weight ratio of Al aluminate cement2O3Is 68 percent by mass, and the specific surface area of the aluminate cement is 300m2/kg。
Comparative example 1
Other conditions were the same as in example 1 except that the modified aluminate cement was replaced with ordinary aluminate cement without blending an alkali oxide.
The modified aluminate cement and the ordinary aluminate cement of example 1 were tested for compressive strength under the same conditions, and the results are shown in table 1:
TABLE 1 compressive strengths of modified and ordinary aluminate cements
| Compressive strength (MPa) | Modified aluminate cement | Ordinary aluminate cement |
| 3d | 40.5MPa | 41.3MPa |
| 28d | 59.3MPa | 43.4MPa |
As can be seen from Table 1, the early strength and the late strength of the modified aluminate cement of the present invention are improved as compared with those of ordinary aluminate cement.
Comparative example 2
Other conditions were the same as in example 1, and only the retarder was omitted.
Comparative example 3
The other conditions were the same as in example 1, and only the accelerator was omitted.
The total amount of heat of hydration of the gel materials obtained in example 1 and comparative examples 2 to 3 was measured over 1 day, and the results are shown in Table 2:
TABLE 2 Total amount of heat of hydration of gel materials obtained in example 1 and comparative examples 2 to 3
| Total heat of hydration (j/g) | Example 1 | Comparative example 2 | Comparative example 3 |
| 4h | 22 | 30 | 0 |
| 12h | 53 | 100 | 0 |
| 1d | 98 | 250 | 10 |
| 2d | 220 | 323 | 31 |
| 3d | 312 | 342 | 98 |
As can be seen from Table 2, the retarder and the accelerator are used together, so that the heat release of hydration per day can be controlled, the purpose of uniform hydration is achieved, and the retarder or the accelerator are added separately, so that the hydration is too fast or too slow.
The low-temperature hydration hardening gel materials obtained in examples 1 to 5 and comparative examples 1 to 3 were directly poured at-10 ℃ to test the strength after hardening, and the pouring was performed under the same conditions with the conventional material (portland cement) as a comparison to test the strength after hardening, and the results are shown in table 1.
The peak mortar temperatures of the gel materials of examples 1 to 5 and comparative examples 1 to 3 and the conventional materials during hydration were measured by the TONI calorimetric method, and the results are shown in table 3.
TABLE 3 compression Strength and hydration exotherm peaks for gel materials
According to the results in the table 1, the gel material prepared by the invention can be successfully hydrated at-10 ℃, and can generate enough strength, especially high early strength; the gel material has low heat release amount in the hydration process, the heat release peak value is not more than 0 ℃, and the gel material can not disturb the temperature field of surrounding frozen soil when being applied to the pile foundation construction in a frozen soil area; in addition, according to the results of the comparative example, it can be seen that when the aluminate cement is not modified (comparative example 1), the strength of the obtained gel material is low, when the retarder is not added (comparative example 2), the mortar temperature peak value of the obtained gel material is high, the strength is low, and when the accelerator is not added, the strength of the obtained gel material is greatly reduced in the same time, which indicates that the hydration speed is slow; in addition, the early strength of the traditional material is very low, the temperature peak value of mortar reaches 50 ℃, and during construction in a frozen soil area, the temperature field of frozen soil around the frozen soil can be disturbed, so that the construction requirement of the frozen soil area cannot be met.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. The low-temperature hydration hardening gel material is characterized by comprising the following components in parts by mass:
10-20 parts of modified aluminate cement, 0-10 parts of ultrafine powder active admixture, 60-70 parts of sand, 0.15-0.3 part of coagulant, 0.5-0.7 part of retarder, 1-2 parts of anti-freezing agent and 8-12 parts of water;
the modified aluminate cement is obtained by mixing aluminate cement and alkaline oxide;
the alkaline oxide is one or more of magnesium oxide, calcium oxide and potassium oxide; the mass of the alkaline oxide is 1% -3% of that of the aluminate cement.
2. According to claim1 the low-temperature hydration hardening gel material is characterized in that Al in the aluminate cement2O3The mass fraction is more than or equal to 68 percent, and the specific surface area of the aluminate cement is more than or equal to 300m2/kg。
3. The low temperature hydrohardened gel material of claim 1, wherein the ultrafine powder active blend comprises at least one of silica fume, fly ash, blast furnace slag powder, and metakaolin; the particle size of the ultrafine powder active admixture is 2-3 mu m.
4. The low temperature hydration hardened gel material of claim 1, wherein said sand is natural river sand and/or machine-made sand; the grain size of the sand is less than or equal to 2 mm.
5. The low temperature hydrohardened gelling material of claim 1, wherein the coagulant comprises at least one of calcium chloride, calcium nitrate, calcium nitrite, sodium sulfate, and sodium carbonate.
6. The low temperature hydration hardened gel material of claim 1, wherein the retarder comprises at least one of an alcohol retarder, a carboxylic acid retarder, a phosphate retarder, a borate retarder, and sodium fluorosilicate.
7. The low temperature, hydrohardened gelling material of claim 1, wherein the anti-freezing agent comprises at least one of ethylene glycol, calcium chloride and calcium formate.
8. The method for preparing the low-temperature hydration hardening gel material of any one of the claims 1 to 7, which is characterized by comprising the following steps:
(1) dissolving an antifreeze in water to obtain an antifreeze solution;
(2) mixing the modified aluminate cement, the ultrafine powder active admixture, the coagulant and the retarder to obtain mixed powder;
(3) mixing the mixed powder with the antifreeze solution and sand to obtain a low-temperature hydration hardening gel material;
the step (1) and the step (2) are not limited in time sequence.
9. The application of the low-temperature hydration hardening gel material according to any one of claims 1 to 7 or the low-temperature hydration hardening gel material prepared by the preparation method according to claim 8 in the construction of pile foundations in the frozen soil area is characterized in that the application temperature is not lower than-10 ℃.
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| CN115043615B (en) * | 2022-06-23 | 2023-11-17 | 中曼石油天然气集团股份有限公司 | Low-hydration heat low-density cement paste system for permafrost layer in extremely cold region and preparation method thereof |
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| CN103979914A (en) * | 2014-05-22 | 2014-08-13 | 同济大学 | Curing agent for reinforcing and treating soft soil foundation constructed at low temperature and preparation method thereof |
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