CN115304305B - Organic-inorganic composite early strength agent and preparation method thereof - Google Patents
Organic-inorganic composite early strength agent and preparation method thereof Download PDFInfo
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- CN115304305B CN115304305B CN202211019317.0A CN202211019317A CN115304305B CN 115304305 B CN115304305 B CN 115304305B CN 202211019317 A CN202211019317 A CN 202211019317A CN 115304305 B CN115304305 B CN 115304305B
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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
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/08—Acids or salts thereof
- C04B22/085—Acids or salts thereof containing nitrogen in the anion, e.g. nitrites
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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
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/08—Acids or salts thereof
- C04B22/12—Acids or salts thereof containing halogen in the anion
- C04B22/126—Fluorine compounds, e.g. silico-fluorine compounds
-
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses an organic-inorganic composite early strength agent and a preparation method thereof, wherein the preparation raw materials comprise the following components in parts by weight: 70-210 parts of scandium fluoride, 10-30 parts of triethanolamine, 5-20 parts of soluble silicate, 2-6 parts of sodium nitrite, 5-10 parts of dispersing agent and 0.5-4 parts of surfactant. Scandium fluoride is added in the composite early strength agent, and by utilizing the special negative thermal expansion characteristic of scandium fluoride, the influence caused by the thermal expansion of cement mortar is reduced through self thermal shrinkage in the cement hydration heat production process, so that the cracking phenomenon of concrete is effectively avoided, and meanwhile, the final setting strength is improved. In addition, the composite early strength agent does not contain chloride ions, sulfate ions and the like, and sodium nitrite is added at the same time, so that the corrosion of reinforcing steel bars in concrete can be effectively avoided after the composite early strength agent is used.
Description
Technical Field
The invention relates to the technical field of concrete additives, in particular to an organic-inorganic composite early strength agent and a preparation method thereof.
Background
In the construction process of the concrete, a long time is needed from setting and hardening caused by hydration to the expected strength, and the early strength of the concrete can be obviously improved by adding the early strength agent, so that the curing time is shortened. The early strength agent is also called a strength accelerator, and can adjust the setting and hardening speed of concrete. In winter construction or in concrete engineering with early strength requirement, the early strength agent is generally required to be added so as to shorten demoulding and curing time and accelerate construction progress, thereby effectively improving construction quality and saving concrete construction cost.
The early strength agent can be divided into three types of strong electrolyte inorganic salts, water-soluble organic substances, organic substances and inorganic substance composite early strength agents according to chemical components. The composite early strength agent can achieve better modification effect than single early strength agent through the combination of various early strength agent components and the combination of the early strength agent component and the water reducing agent component, so that more applications are gradually obtained.
However, although the existing organic-inorganic composite early strength agent can accelerate the hydration speed of cement and improve the early strength of concrete, at the same time, the acceleration of the hydration speed means that the hydration heat generated in the same time is increased, if the hydration heat is not released, the concrete material is heated excessively and is expanded, particularly mortar is heated (the temperature is increased by 0-120 ℃), the expansion is obvious, the final setting strength is reduced, and even the concrete material is cracked, so that destructive consequences are caused for large-volume engineering such as a dam, a bridge and the like. Therefore, how to solve the problems of thermal expansion cracking and final setting strength reduction of mortar caused by the fact that the hydration heat is not released when the traditional organic-inorganic composite early strength agent is used is a difficult problem to be solved by people at present.
Disclosure of Invention
The invention aims to provide an organic-inorganic composite early strength agent and a preparation method thereof, which solve the problems of thermal expansion cracking and final setting strength reduction of concrete materials caused by insufficient release of hydration heat when the traditional organic-inorganic composite early strength agent is used.
The invention realizes the above purpose through the following technical scheme:
the organic-inorganic composite early strength agent comprises the following preparation raw materials in parts by weight: 70-210 parts of scandium fluoride, 10-30 parts of triethanolamine, 5-20 parts of soluble silicate, 2-6 parts of sodium nitrite, 5-10 parts of dispersing agent and 0.5-4 parts of surfactant.
The further improvement is that scandium fluoride is powder with the grain diameter of 0.1-100 mu m.
The further improvement is that the soluble silicate is one or more of sodium silicate, potassium silicate, sodium fluosilicate and magnesium fluosilicate.
A further improvement is that the dispersant is sodium lignosulfonate, sulfonated melamine, or a combination thereof.
A further improvement is that the surfactant is an alkyl polyoxyethylene phosphate, an alkyl phenol polyoxyethylene phosphate, or a combination thereof.
The invention also provides a preparation method of the organic-inorganic composite early strength agent, which comprises the following steps: adding deionized water into a mixing stirrer, adding scandium fluoride, soluble silicate and sodium nitrite according to the weight ratio, mixing and stirring for 30-60min, spraying and adding triethanolamine, mixing and stirring for 10-40min, adding a dispersing agent and a surfactant, and carrying out ultrasonic oscillation treatment for 50-80min while stirring to obtain the organic-inorganic composite early strength agent.
The further improvement is that the addition amount of the deionized water is 30-60% of the total weight of other raw materials.
The further improvement is that the stirring conditions are 25-35 ℃ and 600-1000r/min.
The further improvement is that the condition of the ultrasonic oscillation treatment is as follows: ultrasonic frequency is 20-50kHz, and ultrasonic power is 300-600W.
The invention has the beneficial effects that:
(1) Scandium fluoride is added in the composite early strength agent, and by utilizing the special negative thermal expansion characteristic of scandium fluoride, the influence caused by the thermal expansion of cement mortar is reduced through self thermal shrinkage in the cement hydration heat production process, so that the cracking phenomenon of concrete is effectively avoided, and meanwhile, the final setting strength is improved.
(2) The composite early strength agent does not contain chloride ions, sulfate ions and the like, and sodium nitrite is added at the same time, so that the corrosion of reinforcing steel bars inside the concrete can be effectively avoided after the composite early strength agent is used.
Detailed Description
The following examples are set forth in order to provide a further understanding of the present application and are not intended to limit the scope of the present application since it is believed that the present application is susceptible to numerous insubstantial modifications and variations by those skilled in the art in light of the foregoing disclosure.
Example 1
The organic-inorganic composite early strength agent comprises the following preparation raw materials in parts by weight: 70 parts of scandium fluoride, 10 parts of triethanolamine, 5 parts of soluble silicate, 2 parts of sodium nitrite, 5 parts of dispersing agent and 0.5 part of surfactant,
wherein scandium fluoride is powder with the particle size of 0.1-10 mu m, soluble silicate is sodium silicate, dispersing agent is sodium lignin sulfonate, and surfactant is alkyl polyoxyethylene phosphate.
The preparation method of the organic-inorganic composite early strength agent comprises the following steps: adding deionized water into a mixing stirrer, adding scandium fluoride, soluble silicate and sodium nitrite according to the weight ratio, mixing and stirring for 30min, spraying and adding triethanolamine, mixing and stirring for 10min, adding a dispersing agent and a surfactant, and carrying out ultrasonic oscillation treatment for 50min while stirring to obtain the organic-inorganic composite early strength agent.
Wherein, the addition amount of deionized water is 30 percent of the total weight of other raw materials, the stirring conditions are 25 ℃ and 600r/min, and the ultrasonic vibration treatment conditions are as follows: ultrasonic frequency 20kHz, ultrasonic power 300W.
Example 2
The organic-inorganic composite early strength agent comprises the following preparation raw materials in parts by weight: 150 parts of scandium fluoride, 20 parts of triethanolamine, 12 parts of soluble silicate, 4 parts of sodium nitrite, 8 parts of dispersing agent and 1.5 parts of surfactant,
wherein scandium fluoride is powder with the grain diameter of 40-60 mu m, soluble silicate is a mixture of sodium fluosilicate and magnesium fluosilicate, the mixing weight ratio is 1:1, the dispersing agent is sulfonated melamine, and the surfactant is alkylphenol polyoxyethylene phosphate.
The preparation method of the organic-inorganic composite early strength agent comprises the following steps: adding deionized water into a mixing stirrer, adding scandium fluoride, soluble silicate and sodium nitrite according to the weight ratio, mixing and stirring for 45min, spraying and adding triethanolamine, mixing and stirring for 25min, adding a dispersing agent and a surfactant, and carrying out ultrasonic oscillation treatment for 60min while stirring to obtain the organic-inorganic composite early strength agent.
Wherein, the addition amount of deionized water is 45 percent of the total weight of other raw materials, the stirring conditions are 30 ℃ and 800r/min, and the ultrasonic vibration treatment conditions are as follows: ultrasonic frequency 35kHz, ultrasonic power 500W.
Example 3
The organic-inorganic composite early strength agent comprises the following preparation raw materials in parts by weight: 210 parts of scandium fluoride, 30 parts of triethanolamine, 20 parts of soluble silicate, 6 parts of sodium nitrite, 10 parts of dispersing agent and 4 parts of surfactant,
wherein scandium fluoride is powder with the grain diameter of 90-100 mu m, soluble silicate is sodium silicate, dispersing agent is sodium lignin sulfonate, surfactant is mixture of alkyl polyoxyethylene phosphate and alkylphenol polyoxyethylene phosphate, and the mixing weight ratio is 1:1.
The preparation method of the organic-inorganic composite early strength agent comprises the following steps: adding deionized water into a mixing stirrer, adding scandium fluoride, soluble silicate and sodium nitrite according to the weight ratio, mixing and stirring for 60min, spraying and adding triethanolamine, mixing and stirring for 40min, adding a dispersing agent and a surfactant, and carrying out ultrasonic oscillation treatment for 80min while stirring to obtain the organic-inorganic composite early strength agent.
Wherein, the addition amount of deionized water is 60 percent of the total weight of other raw materials, the stirring conditions are 35 ℃ and 1000r/min, and the ultrasonic vibration treatment conditions are as follows: ultrasonic frequency 50kHz, ultrasonic power 600W.
Comparative example 1
The organic-inorganic composite early strength agent comprises the following preparation raw materials in parts by weight: 210 parts of calcium fluoride, 30 parts of triethanolamine, 20 parts of soluble silicate, 6 parts of sodium nitrite, 10 parts of dispersing agent and 4 parts of surfactant.
Wherein, the calcium fluoride is powder with the grain diameter of 90-100 mu m, the soluble silicate is sodium silicate, the dispersing agent is sodium lignin sulfonate, the surfactant is a mixture of alkyl polyoxyethylene phosphate and alkylphenol polyoxyethylene phosphate, and the mixing weight ratio is 1:1.
The preparation method of the organic-inorganic composite early strength agent comprises the following steps: adding deionized water into a mixing stirrer, adding calcium fluoride, soluble silicate and sodium nitrite according to the weight ratio, mixing and stirring for 60min, spraying and adding triethanolamine, mixing and stirring for 40min, adding a dispersing agent and a surfactant, and carrying out ultrasonic oscillation treatment for 80min while stirring to obtain the organic-inorganic composite early strength agent.
Wherein, the addition amount of deionized water is 60 percent of the total weight of other raw materials, the stirring conditions are 35 ℃ and 1000r/min, and the ultrasonic vibration treatment conditions are as follows: ultrasonic frequency 50kHz, ultrasonic power 600W.
Performance test:
1. early strength effect
The early strength effect of the early strength agent is represented by the compressive strength of cement mortar for 10h, 1d, 7d and 28d, the cement for test is conch brand ordinary Portland cement, the sand for test is ISO standard sand, the cement material consumption is 600g, the sand consumption is 1350g and the water consumption is 228g. Taking early strength agent samples prepared in examples 1-3 and comparative example 1, and adding the early strength agent samples in the form of grinding aids in cement production, wherein the addition amounts are 3% of the weight of cement; meanwhile, a blank group is set, and no early strength agent is added for comparison. Five test groups were used, and the cement mortar strengths of examples 1-3, comparative example 1 and blank were tested with reference to GB/T17671-1999 to give Table 1:
from the table above, it can be seen that the compressive strength of the early strength agent prepared in examples 1 to 3 of the present invention reaches 12MPa or more at 10 hours, 21MPa or more at 1d, the early strength effect is good, and 45MPa or more at 28d, and the level of no early strength agent added in the blank is reached, and example 2 even exceeds the blank. In addition, in comparative example 1, the expansion adjusting effect is lost due to the replacement of scandium fluoride with the equivalent amount of calcium fluoride, so that the compression strength in 10 hours is reduced by 8.5% compared with that in example 3, the compression strength in 1d is reduced by 11.6%, the compression strength in 7d is reduced by 14.3%, the compression strength in 28d is reduced by 15.4%, and the compression strength is reduced more and more along with the coagulation, so that the final-set compression strength cannot meet the requirement. This demonstrates that the negative thermal expansion characteristics of scandium fluoride plays a critical role.
2. Concrete setting test
Concrete setting tests were performed according to the following recipe:
concrete matching table (Unit: kg)
Wherein, early strength agents prepared in examples 1-3 and comparative example 1 are respectively selected, a blank group is arranged at the same time, no early strength agent is added, and as a comparison, five groups are adopted, and each group adopts the same curing mode to observe whether the surface of the concrete has cracking phenomenon after final setting, and the following table is obtained by statistics of results:
| group of | Whether or not there is a cracking phenomenon |
| Example 1 | No obvious crack |
| Example 2 | No obvious crack |
| Example 3 | No obvious crack |
| Comparative example 1 | Has obvious crack |
| Blank group | No obvious crack |
As can be seen from the table above, the early strength agent prepared in examples 1 to 3 of the present invention does not cause obvious cracking of concrete after final setting, whereas comparative example 1, because scandium fluoride is replaced with an equivalent amount of calcium fluoride, loses the expansion adjusting effect, causes obvious cracking after final setting, and shows that the influence of cement hydration heat is great.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention.
Claims (8)
1. The organic-inorganic composite early strength agent is characterized by comprising the following preparation raw materials in parts by weight: 70-210 parts of scandium fluoride, 10-30 parts of triethanolamine, 5-20 parts of soluble silicate, 2-6 parts of sodium nitrite, 5-10 parts of dispersing agent and 0.5-4 parts of surfactant;
the preparation method of the organic-inorganic composite early strength agent comprises the following steps: adding deionized water into a mixing stirrer, adding scandium fluoride, soluble silicate and sodium nitrite according to the weight ratio, mixing and stirring for 30-60min, spraying and adding triethanolamine, mixing and stirring for 10-40min, adding a dispersing agent and a surfactant, and carrying out ultrasonic oscillation treatment for 50-80min while stirring to obtain the organic-inorganic composite early strength agent.
2. The organic-inorganic composite early strength agent according to claim 1, wherein scandium fluoride is powder with a particle size of 0.1-100 μm.
3. The organic-inorganic composite early strength agent according to claim 1, wherein the soluble silicate is one or more selected from sodium silicate, potassium silicate, sodium fluosilicate and magnesium fluosilicate.
4. The organic-inorganic composite early strength agent according to claim 1, wherein the dispersant is sodium lignin sulfonate, sulfonated melamine, or a combination thereof.
5. The organic-inorganic composite early strength agent according to claim 1, wherein the surfactant is an alkyl polyoxyethylene phosphate, an alkyl phenol polyoxyethylene phosphate, or a combination thereof.
6. The organic-inorganic composite early strength agent according to claim 1, wherein the addition amount of the deionized water is 30-60% of the total weight of other raw materials.
7. The organic-inorganic composite early strength agent according to claim 1, wherein the stirring conditions are 25-35 ℃ and 600-1000r/min.
8. The organic-inorganic composite early strength agent according to claim 1, wherein the ultrasonic vibration treatment conditions are as follows: ultrasonic frequency is 20-50kHz, and ultrasonic power is 300-600W.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211019317.0A CN115304305B (en) | 2022-08-24 | 2022-08-24 | Organic-inorganic composite early strength agent and preparation method thereof |
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| CN202211019317.0A CN115304305B (en) | 2022-08-24 | 2022-08-24 | Organic-inorganic composite early strength agent and preparation method thereof |
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| CN115304305B true CN115304305B (en) | 2023-07-25 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2004095532A2 (en) * | 2003-03-31 | 2004-11-04 | Tokyo Electron Limited | A barrier layer for a processing element and a method of forming the same |
| CN103224341B (en) * | 2013-05-13 | 2014-07-30 | 十九冶成都建设有限公司 | Early-strength antifreezing polycarboxylic acid composite water reducing agent and application thereof |
| CN104710128A (en) * | 2015-03-11 | 2015-06-17 | 东南大学 | Super early strength accelerator for portland cement concrete |
| CN108249845A (en) * | 2017-12-13 | 2018-07-06 | 镇江建科建设科技有限公司 | A kind of Organic-inorganic composite early strength agent and the self-compacting concrete prepared using the early strength agent |
| CN112028648A (en) * | 2020-08-28 | 2020-12-04 | 江苏苏嘉集团新材料有限公司 | Refractory brick with thermal shrinkage effect and preparation process thereof |
| CN112390581B (en) * | 2020-11-25 | 2022-06-28 | 北京城建九秋实混凝土有限公司 | Environment-friendly concrete and preparation method thereof |
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