CN110981273A - Cement hydration hardening accelerator composition and preparation method thereof - Google Patents
Cement hydration hardening accelerator composition and preparation method thereof Download PDFInfo
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- CN110981273A CN110981273A CN201911411508.XA CN201911411508A CN110981273A CN 110981273 A CN110981273 A CN 110981273A CN 201911411508 A CN201911411508 A CN 201911411508A CN 110981273 A CN110981273 A CN 110981273A
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- dispersant
- water
- calcium
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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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/10—Accelerators; Activators
- C04B2103/12—Set accelerators
Abstract
The invention discloses a cement hydration hardening accelerator composition and a preparation method thereof, wherein the cement hydration hardening accelerator composition is prepared by reacting a water-soluble calcium solution and a water-soluble silicate solution in a solution containing a composite dispersant. The cement hydration hardening accelerant composition is widely applied to cement-based products with special requirements on early strength, such as pipe pieces, pipe piles, PC members, special mortar and the like, can greatly improve the development speed of the early strength, accelerate the turnover of a mould, improve the productivity, reduce the maintenance energy consumption and save the cost.
Description
Technical Field
The invention belongs to the technical field of building materials, and relates to an organic/inorganic hybrid hydrated calcium silicate suspension and a preparation method thereof, in particular to a cement hydration hardening accelerator.
Background
The strength increasing speed is improved in the production process of the prefabricated part, the turnover of the die can be accelerated, and the production efficiency is improved. The component factory usually adopts the method of high-temperature steam pressure curing and adding early strength agent to improve the turnover speed of the die. The high-temperature steam pressure curing has high energy consumption, and is not beneficial to energy conservation and emission reduction. Screening a proper early strength agent becomes a preferable technical way for improving the production efficiency of the prefabricated part and reducing the energy consumption.
Early strength agents mainly comprising inorganic and organic materials are commonly applied for years, but have a plurality of defects, the workability and durability of concrete are reduced, for example, the dosage of the triethanolamine early strength agent is not easy to control, and excessive mixing of the triethanolamine early strength agent is easy to cause ultra-retarding or rapid setting; the chlorine-containing early strength agent is easy to cause the corrosion of the steel bar; the sulfate early strength agent increases the content of macropores in the set cement, and reduces the impermeability and corrosion resistance of the concrete.
Disclosure of Invention
The invention aims to provide a cement hydration hardening accelerator and a preparation method thereof. As a novel crystal nucleus type early strength agent, the preparation method is simple and easy to operate, and the early strength performance is excellent.
The specific technical scheme for realizing the purpose of the invention is as follows:
a cement hydration hardening accelerator composition is characterized in that: the water-soluble calcium solution and the water-soluble silicate solution react in the solution containing the composite dispersant to generate organic/inorganic hybrid calcium silicate hydrate sol particles, namely the cement hydration hardening accelerator composition containing the composite dispersant.
The composite dispersant consists of a dispersant A and a dispersant B, wherein the chemical structural formula of the dispersant A is shown as (1),
wherein the value of n is 0-100; r is sodium atom, potassium atom, methyl, hydrogen atom or hydroxyl.
The dispersant B is a polycarboxylic acid polymer containing the following structural unit (2) derived from an unsaturated polyether monomer and the following structural unit (3) derived from an unsaturated carboxylic acid monomer, wherein:
the structural unit (2) is
Wherein: r5Represents hydrogen or methyl; r6Represents hydrogen, methyl or ethyl; r7Represents hydrogen or alkyl of 1 to 6 carbon atoms; x is a linking group of-O-),-CH2O-、CH2CH2O-、
or-O-CH2CH2CH2CH2O-; n represents an average molar number of addition of the oxyalkylene group and is an arbitrary integer of 1 to 300.
The structural unit (3) is
Wherein: r8Represents hydrogen, methyl or a COOM group, R9Represents hydrogen, methyl or CH2COOM group, M represents hydrogen, monovalent metal, 1/2 divalent metal, ammonium group or organic amine group.
The dispersant B is characterized by containing a polycarboxylic acid polymer having the following structural unit (4) derived from an unsaturated polyether monomer and the following structural unit (5) derived from an unsaturated carboxylic acid monomer, wherein the structural unit (4) is
Wherein: r10Represents hydrogen or methyl; r11O represents an oxyalkylene group of 2 to 8 carbon atoms and mixtures thereof; n represents an average molar number of addition of the oxyalkylene group and is an integer of 1 to 180; r12Represents hydrogen or an alkyl group of 1 to 6 carbon atoms.
The structural unit (5) is
Wherein: r13Represents hydrogen, methyl or a group, R14Represents hydrogen, methyl or a group, and M represents hydrogen, a monovalent metal, 1/2 a divalent metal, an ammonium group or an organic amine group.
The molar ratio of the water-soluble calcium salt to the water-soluble silicate is 1-3: 2-1.
The weight ratio of the dispersant A to the dispersant B is 0.005-0.5: 1.
The water-soluble calcium salt is one or a mixture of calcium chloride, calcium nitrate, calcium formate, calcium acetate, calcium citrate, calcium hydroxide and calcium oxide.
The water-soluble silicate is one or a mixture of sodium silicate, potassium silicate, sodium metasilicate, potassium metasilicate and water glass.
The preparation method of the cement hydration hardening accelerator composition containing the composite dispersant comprises the following steps:
(1) weighing water-soluble calcium salt and water-soluble silicate to respectively prepare solutions; and weighing the dispersant A and the dispersant B according to the mass ratio of 0.005-0.5:1 to prepare a composite dispersant solution.
(2) Controlling the temperature to be 10-90 ℃, dropwise adding the water-soluble calcium solution and the water-soluble silicate solution into the composite dispersant solution according to the molar ratio of 1-3:2-1, and simultaneously keeping stirring, wherein the dropwise adding time is set to be 1-8 hours; and after the dripping is finished, continuously stirring for 1-3 hours, and then slowly cooling to room temperature to prepare the cement hydration hardening accelerator composition containing the cation and anion composite dispersant.
The cement hydration hardening accelerant composition containing the composite dispersant has the solid content of 5-50%.
The particle size of calcium silicate hydrate sol particles contained in the cement hydration hardening accelerator composition containing the composite dispersant is 50-250 nm.
The cement hydration hardening accelerant composition containing the composite dispersant can greatly reduce the crystallization nucleation barrier of hydrated calcium silicate (C-S-H) gel, promote the hydration reaction rate of cement, and obviously improve the ultra-early strength of cement products within 12 hours. The adoption of the composite dispersing agent is beneficial to controlling the size of the calcium silicate hydrate sol particles in a suspension system and the stability of the suspension. The mortar can be widely applied to cement-based products with requirements on early strength, such as duct pieces, tubular piles, PC members, special mortar and the like, the strength development speed can be greatly increased, the turnover of a die is accelerated, the productivity is improved, the maintenance energy consumption can be reduced, and the cost is saved.
Detailed Description
The present invention is further illustrated below with reference to specific examples, which are intended to be illustrative only and not to limit the scope of the invention. Various equivalent modifications of the invention, which fall within the scope of the appended claims of this application, will occur to persons skilled in the art.
Example 1
38.25g of calcium chloride and 50.15g of water are weighed out to prepare a calcium chloride aqueous solution, 43.74g of potassium silicate and 44.26g of water are weighed out to prepare a potassium silicate solution, and 0.12g of dispersant A, 23.80g of dispersant B and 158.2g of water are weighed out to prepare a composite dispersant aqueous solution. The composite dispersant solution was introduced into a three-necked flask, the temperature was set at 15 ℃, and the dispersant solution was stirred uniformly. Simultaneously dripping the calcium chloride aqueous solution and the potassium silicate aqueous solution under the condition of keeping stirring, and adjusting the dripping speed to control the dripping time to be about 1 h. And continuously stirring for 1h after the dropwise addition is finished, and then slowly cooling to room temperature to obtain the hydration hardening accelerator HA-1.
Example 2
54.85g of calcium nitrate and 55.29g of water are weighed to prepare a calcium nitrate aqueous solution, 53.74g of water glass and 44.26g of water are weighed to prepare a water glass solution, and 0.15g of dispersant A, 22.72g of dispersant B and 141.5g of water are respectively weighed to prepare a composite dispersant aqueous solution. The composite dispersant solution was introduced into a three-necked flask, the temperature was set at 15 ℃, and the dispersant solution was stirred uniformly. Simultaneously dripping the calcium chloride aqueous solution and the potassium silicate aqueous solution under the condition of keeping stirring, and adjusting the dripping speed to control the dripping time to be about 2 hours. And continuously stirring for 4 hours after the dripping is finished, and then slowly cooling to room temperature to obtain the hydration hardening accelerator HA-2.
Example 3
44.85g of calcium formate and 53.57g of water are weighed out to prepare a calcium formate aqueous solution, 48.36g of potassium metasilicate and 43.78g of water are weighed out to prepare a potassium metasilicate solution, and 0.15g of dispersant A, 24.18g of dispersant B and 133.5g of water are respectively weighed out to prepare a composite dispersant aqueous solution. The composite dispersant solution was introduced into a three-necked flask, the temperature was set at 15 ℃, and the dispersant solution was stirred uniformly. Simultaneously dripping the calcium chloride aqueous solution and the potassium silicate aqueous solution under the condition of keeping stirring, and adjusting the dripping speed to control the dripping time to be about 7 hours. And continuously stirring for 3 hours after the dripping is finished, and then slowly cooling to room temperature to prepare the hydration hardening accelerator HA-3.
Example 4
44.85g of calcium formate and 53.57g of water are weighed out to prepare an aqueous calcium formate solution, 48.36g of potassium metasilicate and 43.78g of water are weighed out to prepare a potassium metasilicate solution, and 1.28g of dispersant A, 24.18g of dispersant B and 133.5g of water are respectively weighed out to prepare an aqueous composite dispersant solution. The composite dispersant solution was introduced into a three-necked flask, the temperature was set at 15 ℃, and the dispersant solution was stirred uniformly. Simultaneously dripping the calcium chloride aqueous solution and the potassium silicate aqueous solution under the condition of keeping stirring, and adjusting the dripping speed to control the dripping time to be about 7 hours. And continuously stirring for 3 hours after the dripping is finished, and then slowly cooling to room temperature to obtain the hydration hardening accelerator HA-4.
Example 5
39.64g of calcium nitrate and 54.20g of water are weighed to prepare a calcium nitrate aqueous solution, 54.37g of sodium metasilicate and 52.68g of water are weighed to prepare a sodium metasilicate solution, and 7.75g of dispersant A, 19.36g of dispersant B and 145.62g of water are weighed to prepare a composite dispersant aqueous solution. The composite dispersant solution was introduced into a three-necked flask, the temperature was set at 15 ℃, and the dispersant solution was stirred uniformly. Simultaneously dripping the calcium chloride aqueous solution and the potassium silicate aqueous solution under the condition of keeping stirring, and adjusting the dripping speed to control the dripping time to be about 2 hours. And (4) continuing stirring after the dropwise addition is finished, and then slowly cooling to room temperature to obtain the hydration hardening accelerator HA-5.
Application example
The early strength of the resulting hydration hardening accelerator was evaluated using the mortar mixing ratios shown in Table 1, and the test materials were standard cement P.O 42.5, standard sand, and a polycarboxylic acid water reducing agent (VIVID-500(D), commercially available).
TABLE 1 mortar mixing ratio
| Cement | Standard sand | Hydration hardening accelerator | VIVID-500(D) | Water (W) | Maintenance conditions |
| 600g | 1350g | 1.0-5.0％ | 2.5g | 210g | Standard culture |
TABLE 2 mortar Strength test results
As can be seen from the data in Table 2, the strength of the mortar sample blocks added with the hydration hardening accelerator in examples 1-5 is remarkably improved, particularly the 7h compressive strength can reach 969% (example 4), while the 7h compressive strength ratio is only 261% by adopting the conventional anhydrous sodium sulfite. Meanwhile, in the aspect of 28d compressive strength, the phenomenon of shrinkage is avoided by adding the hydration hardening accelerator, which is a great advantage different from the traditional early strength agent.
Claims (3)
1. The cement hydration hardening accelerant composition is characterized in that a water-soluble calcium solution and a water-soluble silicate solution react in a solution containing a composite dispersant to generate organic/inorganic hybrid calcium silicate hydrate sol particles, namely the cement hydration hardening accelerant composition containing the composite dispersant;
the composite dispersant consists of a dispersant A and a dispersant B, wherein the chemical structural formula of the dispersant A is shown as (1),
wherein the value of n is 0-100; r is sodium atom, potassium atom, methyl, hydrogen atom or hydroxyl;
the dispersant B is a polycarboxylic acid polymer containing the following structural unit (2) derived from an unsaturated polyether monomer and the following structural unit (3) derived from an unsaturated carboxylic acid monomer, wherein:
the structural unit (2) is
Wherein: r5Represents hydrogen or methyl; r6Represents hydrogen, methyl or ethyl; r7Represents hydrogen or alkyl of 1 to 6 carbon atoms; x is a linking group of-O-, -CH2O-、-CH2CH2O-、
or-O-CH2CH2CH2CH2O-; n represents an average molar number of addition of the oxyalkylene group and is an integer of 1 to 300;
the structural unit (3) is
Wherein: r8Represents hydrogen, methyl or a COOM group, R9Represents hydrogen, methyl or CH2COOM group, M represents hydrogen, monovalent metal, 1/2 divalent metal, ammonium group or organic amine group;
the dispersant B is a polycarboxylic acid polymer containing the following structural unit (4) derived from an unsaturated polyether monomer and the following structural unit (5) derived from an unsaturated carboxylic acid monomer, wherein:
the structural unit (4) is
Wherein: r10Represents hydrogen or methyl; r11O represents an oxyalkylene group of 2 to 8 carbon atoms and mixtures thereof; n represents an average molar number of addition of the oxyalkylene group and is an integer of 1 to 180; r12Represents hydrogen or alkyl of 1 to 6 carbon atoms;
the structural unit (5) is
Wherein: r13Represents hydrogen, methyl or a group, R14Represents hydrogen, methyl or a group, M represents hydrogen, a monovalent metal, 1/2 a divalent metal, an ammonium group or an organic amine group;
the molar ratio of the water-soluble calcium salt to the water-soluble silicate is 1-3: 2-1;
the weight ratio of the dispersant A to the dispersant B is 0.005-0.5: 1;
the water-soluble calcium salt is one or a mixture of calcium chloride, calcium nitrate, calcium formate, calcium acetate, calcium citrate, calcium hydroxide and calcium oxide;
the water-soluble silicate is one or a mixture of sodium silicate, potassium silicate, sodium metasilicate, potassium metasilicate and water glass;
the preparation method of the cement hydration hardening accelerator composition containing the composite dispersant specifically comprises the following steps:
(1) weighing water-soluble calcium salt and water-soluble silicate to respectively prepare solutions; weighing the dispersant A and the dispersant B according to the mass ratio of 0.005-0.5:1 to prepare a composite dispersant solution;
(2) controlling the temperature to be 10-90 ℃, dropwise adding the water-soluble calcium solution and the water-soluble silicate solution into the composite dispersant solution according to the molar ratio of 1-3:2-1, and simultaneously keeping stirring, wherein the dropwise adding time is set to be 1-8 hours; and (4) continuing stirring for 1-3 hours after the dripping is finished, and then slowly cooling to room temperature to prepare the cement hydration hardening accelerator composition.
2. The cement hydration hardening accelerator composition according to claim 1, wherein the cement hydration hardening accelerator composition has a solid content of 5% to 50%.
3. The cement hydration hardening accelerator composition according to claim 1, wherein the calcium silicate hydrate sol particles have a particle size of 50 to 250 nm.
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2019
- 2019-12-31 CN CN201911411508.XA patent/CN110981273A/en active Pending
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|---|---|---|---|---|
| ES2323723T3 (en) * | 2006-07-14 | 2009-07-23 | Construction Research And Technology Gmbh | STABLE DISPERSION OF ACCELERATOR FOR PROJECTED CONCRETE WITH HIGH CONTENT IN ACTIVE MATTERS. |
| CN102770390A (en) * | 2010-02-25 | 2012-11-07 | 建筑研究和技术有限公司 | Hardening accelerator composition containing dispersants |
| CN107235650A (en) * | 2017-07-03 | 2017-10-10 | 中建西部建设西南有限公司 | Strong additive of a kind of water nano compound morning and preparation method thereof |
| CN109095807A (en) * | 2018-10-17 | 2018-12-28 | 武汉三源特种建材有限责任公司 | A kind of concrete liquid super instant coagulant and preparation method thereof |
| CN109503017A (en) * | 2018-12-29 | 2019-03-22 | 上海三瑞高分子材料股份有限公司 | A kind of hydrated cementitious enhancer compositions and preparation method thereof |
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