CN108585587B - Normal-temperature synthesized early-strength liquid alkali-free accelerator and preparation method thereof - Google Patents
Normal-temperature synthesized early-strength liquid alkali-free accelerator and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
- C04B40/0046—Premixtures of ingredients characterised by their processing, e.g. sequence of mixing the ingredients when preparing the premixtures
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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
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Abstract
The invention relates to a normal-temperature synthesized early-strength liquid alkali-free accelerator and a preparation method thereof, wherein the accelerator comprises the following components in percentage by mass: 60-80% of modified polyaluminium sulfate solution, 1-3% of graphene oxide, 1-5% of stabilizer, 1-5% of performance regulator and the balance of water. The normal-temperature synthesized early-strength liquid alkali-free accelerator provided by the invention is added into concrete, so that the early strength of the concrete is rapidly developed, the final strength is not influenced, and the possibility of generating alkali-aggregate reaction can be greatly reduced. And the Portland cement of different brands meets the requirements of the sprayed concrete construction; it also has the advantages of low temperature resistance, high quick setting, low mixing amount, no (low) corrosion, stable long-term storage performance, reasonable price and the like, and has excellent comprehensive performance and good economic benefit.
Description
Technical Field
The invention belongs to the technical field of cement concrete additives, and particularly relates to a normal-temperature synthesized early-strength liquid alkali-free accelerator and a preparation method thereof.
Background
The accelerating agent is an additive for quickly hardening and coagulating concrete, and is mainly used for construction of sprayed concrete. The traditional accelerator generally has strong alkalinity, and can meet the use requirement of sprayed concrete, but also brings many problems: the retention rate of the later strength of sprayed concrete is low, the health of constructors is damaged, the probability of alkali aggregate reaction of the concrete is increased, and the later strength and durability of the concrete are reduced.
In order to overcome the defects, the alkali-free liquid accelerator is a main direction for the development of accelerators internationally, and the research on the accelerator is relatively late in China, particularly the research on the alkali-free liquid accelerator is not mature. Accelerators having a base content of less than 1% are referred to as alkali-free accelerators according to international standards. From the patents disclosed so far, some patents are named alkali-free setting accelerators, but the alkali introduced into the formula of the accelerator is often more than 1%. The Shanxi Kaiwei science and technology Limited company published patent (patent application number: 201710101577.5) is named as alkali-free accelerator, and the alkali content in the actual formula can reach 13.3 percent at most. The Longyi scientific and technological development limited company (patent application number: 201610708544.2) in Tangshan City is named as alkali-free accelerator, and the alkali content in the actual formula can reach as high as 2.95 percent. The setting accelerator disclosed in Jiangsu Orlette New Material Co., Ltd. (patent application No. 201410742161.8) has a large space for increasing the setting time and a large loss of strength in the later period. The Xuzhou jiulong synthetic material factory published patent (patent application number: 201310700044.0) has large late strength loss of an accelerator, and magnesium fluosilicate used in the accelerator is toxic and is not beneficial to large-scale popularization and application. Therefore, the development of the alkali-free liquid accelerator with low temperature resistance, high quick setting, low mixing amount, no (low) corrosion, high strength, excellent comprehensive performance and reasonable price has great significance.
Disclosure of Invention
The invention aims to solve the technical problem of the prior art and provides a normal-temperature synthesized early-strength liquid alkali-free accelerator and a preparation method thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the early strength type liquid alkali-free setting accelerator synthesized at normal temperature is composed of the following components in percentage by mass: 60-80% of modified polyaluminium sulfate solution, 1-3% of graphene oxide, 1-5% of stabilizer, 1-5% of performance regulator and the balance of water;
the modified polyaluminium sulfate solution comprises the following components in percentage by mass: 45-60% of polyaluminium sulfate, 5-15% of diethanolamine and 30-45% of water; the preparation method comprises the following steps: mixing and stirring polyaluminium sulfate, diethanolamine and water at normal temperature for 1h to obtain the product.
According to the scheme, the polyaluminium sulfate is industrial polyaluminium sulfate, wherein Al2O3The content is more than 17 percent. Polyaluminium sulfate is the main quick-setting component in the quick-setting agent, and the performance of the polyaluminium sulfate is influenced by Al2O3Influence of the content, Al2O3If the content is too low, the quick setting effect is poor.
According to the scheme, the graphene oxide is layered graphene oxide with less than 5 layers. The graphene oxide is used for improving the strength of the sprayed concrete.
According to the scheme, the stabilizer is one or more of ethylenediamine tetraacetic acid, citric acid, salicylic acid and phosphoric acid. The stabilizer serves to extend the shelf life of the present invention and maintain the dispersion for long periods of storage without significant settling.
According to the scheme, the performance regulator is prepared by mixing polyacrylamide (anionic type, the number average molecular weight is 300W) and silica sol according to the mass ratio of 1: 2 mixing and stirring the obtained stable transparent solution. The performance regulator is used as a cosolvent of polyaluminium sulfate to promote a system to form stable dispersion liquid, and can reduce the rebound rate of sprayed concrete.
According to the scheme, the silica sol is commercially available acidic silica sol, and the mass fraction of the silica sol is 30-40%. Because of the larger specific surface area, the cement has good dispersibility in cement, and can improve the strength of the cement and reduce the porosity of the cement.
The invention also comprises a preparation method of the normal-temperature synthesized early-strength liquid alkali-free accelerator, which comprises the following steps:
1) adding graphene oxide and water into a modified polyaluminium sulfate solution, and performing ultrasonic dispersion uniformly to obtain a stable transparent solution;
2) adding a performance regulator into the stable transparent solution obtained in the step 1), stirring for 1h at normal temperature, adding a stabilizer, and uniformly stirring to obtain the normal-temperature synthesized early-strength liquid alkali-free accelerator.
The use method of the early strength type liquid alkali-free setting accelerator synthesized at normal temperature comprises the following steps: in the process of spraying concrete by using a concrete sprayer, the early strength type liquid alkali-free accelerator synthesized at normal temperature is added into the concrete at the nozzle of the concrete sprayer to prepare the sprayed concrete.
Preferably, the doping amount of the normal-temperature synthesis early-strength liquid alkali-free accelerator is 5-7% (based on the weight of cement).
The invention firstly adopts diethanolamine to modify polyaluminium sulfate to lead polyaluminium sulfate and diethanolThe amine forms a stable complex to prevent Al in polyaluminium sulfate3+The early strength performance of the alkali-free setting accelerator is improved by adding graphene oxide, and a stabilizer in the setting accelerator can adjust the pH value of the solution and further inhibit Al3+The polyacrylamide in the finally added performance regulator forms a network structure in the solution due to the huge molecular weight of the polyacrylamide, so that the modified polyaluminium sulfate complex is not easy to settle.
The invention has the beneficial effects that: 1. the normal-temperature synthesized early-strength liquid alkali-free accelerator provided by the invention is added into concrete, so that the early strength of the concrete is rapidly developed, the final strength is not influenced, and the possibility of generating alkali-aggregate reaction can be greatly reduced. The normal-temperature synthesized early-strength liquid alkali-free accelerator provided by the invention has good adaptability with cement, meets the requirements of sprayed concrete construction on different brands of portland cement, and has the advantages that the later strength of concrete is obviously reduced by using the traditional strong-alkaline accelerator, and the higher the consumption is, the larger the reduction range is; 2. the normal-temperature synthesized early-strength liquid alkali-free accelerator also has the advantages of low temperature resistance, high acceleration, low mixing amount, no (low) corrosion, stable long-term storage performance, reasonable price and the like, has excellent comprehensive performance and good economic benefit; 3. the invention is synthesized at normal temperature, and has low energy consumption and simple operation.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the present invention is further described in detail with reference to the following examples.
The performance regulator used in the embodiment of the invention is prepared from polyacrylamide (anionic type, the number average molecular weight is 300W) and silica sol (commercially available acidic silica sol, the mass fraction is 30%) according to the mass ratio of 1: 2 mixing and stirring the obtained stable transparent solution.
Example 1
The preparation method of the normal-temperature synthesized early-strength liquid alkali-free setting accelerator comprises the following specific steps:
A. 30 parts of water and 10 parts of diethanolamine (purity)>99%) 60 parts of polyaluminium sulfate (Al) are added2O3Content 19%), at normal temperatureStirring until polyaluminium sulfate is dissolved to form a stable transparent solution, namely a modified polyaluminium sulfate solution;
B. weighing the following raw materials: 60% of modified polyaluminium sulfate solution, 3% of graphene oxide (layered graphene oxide below 5 layers), 1% of stabilizer (citric acid), 5% of performance regulator and 31% of water;
C. adding 3 parts of graphene oxide and 31 parts of water into 60 parts of modified polyaluminium sulfate solution, and performing ultrasonic dispersion for 20min to obtain a stable transparent solution;
D. and adding 5 parts of performance regulator into the stable and transparent solution, stirring for 1 hour at normal temperature to ensure full complexation, adding 1 part of citric acid, and stirring for 30min at normal temperature to obtain the normal-temperature synthesized early-strength liquid alkali-free accelerator.
Example 2
The preparation method of the normal-temperature synthesized early-strength liquid alkali-free setting accelerator comprises the following specific steps:
A. 30 parts of water and 15 parts of diethanolamine are added to 55 parts of polyaluminium sulfate (Al)2O3Content 18%), stirring at normal temperature until polyaluminium sulfate is dissolved to form a stable transparent solution, namely a modified polyaluminium sulfate solution;
B. weighing the following raw materials: 65% of modified polyaluminium sulfate solution, 2% of graphene oxide, 1% of stabilizer (ethylene diamine tetraacetic acid), 4% of performance regulator and 28% of water;
C. adding 2 parts of graphene oxide and 28 parts of water into 65 parts of modified polyaluminium sulfate solution, and performing ultrasonic dispersion for 20min to obtain a stable transparent solution;
D. and adding 4 parts of performance regulator into the stable transparent solution, stirring for 1 hour at normal temperature to ensure full complexation, adding 1 part of ethylene diamine tetraacetic acid, and stirring for 30min at normal temperature to obtain the stable liquid alkali-free accelerator.
Example 3
The preparation method of the normal-temperature synthesized early-strength liquid alkali-free setting accelerator comprises the following specific steps:
A. 40 parts of water and 10 parts of diethanolamine are added to 50 parts of polyaluminium sulfate (Al)2O3Content of 19%) at normal temperatureStirring the mixture until polyaluminium sulfate is dissolved to form a stable transparent solution, namely a modified polyaluminium sulfate solution;
B. weighing the following raw materials: 70% of modified polyaluminium sulfate solution, 1% of graphene oxide, 2% of stabilizer (citric acid), 3% of performance regulator and 24% of water;
C. adding 1 part of graphene oxide and 24 parts of water into 70 parts of modified polyaluminium sulfate solution, and performing ultrasonic dispersion for 20min to obtain a stable transparent solution;
D. and adding 3 parts of performance regulator into the stable transparent solution, stirring for 1 hour at normal temperature to ensure full complexation, adding 2 parts of citric acid, and stirring for 30min at normal temperature to obtain the stable liquid alkali-free accelerator.
Example 4
The preparation method of the normal-temperature synthesized early-strength liquid alkali-free setting accelerator comprises the following specific steps:
A. 45 parts of water and 10 parts of diethanolamine are added to 45 parts of polyaluminium sulfate (Al)2O3Content 19%) until polyaluminium sulfate is dissolved to form stable transparent solution, namely modified polyaluminium sulfate solution;
B. weighing the following raw materials: 72% of modified polyaluminium sulfate solution, 3% of graphene oxide, 3% of stabilizer (citric acid), 2% of performance regulator and 20% of water;
C. adding 3 parts of graphene oxide and 20 parts of water into 72 parts of modified polyaluminium sulfate solution, and performing ultrasonic dispersion for 20min to obtain a stable transparent solution;
D. adding 2 parts of performance regulator and 20 parts of water into 70 parts of modified polyaluminium sulfate solution, stirring at normal temperature for 1 hour to ensure full complexation, adding 3 parts of citric acid, and stirring at normal temperature for 30min to obtain the stable liquid alkali-free accelerator.
Example 5
The preparation method of the normal-temperature synthesized early-strength liquid alkali-free setting accelerator comprises the following specific steps:
A. 40 parts of water and 10 parts of diethanolamine are added to 50 parts of polyaluminium sulfate (Al)2O318 percent of the modified poly-aluminum sulfate is stirred at normal temperature until the polyaluminium sulfate is dissolved to form a stable transparent solution, namely the modified poly-aluminumSynthesizing aluminum sulfate solution;
B. weighing the following raw materials: 75% of modified polyaluminium sulfate solution, 1% of graphene oxide, 4% of stabilizer (citric acid), 1% of performance regulator and 19% of water;
C. adding 1 part of graphene oxide and 19 parts of water into 75 parts of modified polyaluminium sulfate solution, and performing ultrasonic dispersion for 20min to obtain a stable transparent solution;
D. and adding 1 part of performance regulator into the stable transparent solution, stirring for 1h at normal temperature to ensure full complexation, adding 4 parts of citric acid, and stirring for 30min at normal temperature to obtain the stable liquid alkali-free accelerator.
Example 6
The preparation method of the normal-temperature synthesized early-strength liquid alkali-free setting accelerator comprises the following specific steps:
A. 40 parts of water and 5 parts of diethanolamine are added to 55 parts of polyaluminium sulfate (Al)2O3Content 18%) until polyaluminium sulfate is dissolved to form a stable transparent solution, namely a modified polyaluminium sulfate solution;
B. weighing the following raw materials: 80% of modified polyaluminium sulfate solution, 2% of graphene oxide, 5% of stabilizer (citric acid), 1% of performance regulator and 12% of water;
C. adding 2 parts of graphene oxide and 13 parts of water into 80 parts of modified polyaluminium sulfate solution, and performing ultrasonic dispersion for 20min to obtain a stable transparent solution;
D. and adding 1 part of performance regulator into the stable transparent solution, stirring for 1h at normal temperature to ensure full complexation, adding 5 parts of citric acid, and stirring for 30min at normal temperature to obtain the stable liquid alkali-free accelerator.
Example 7
The preparation method of the normal-temperature synthesized early-strength liquid alkali-free setting accelerator comprises the following specific steps:
A. 40 parts of water and 5 parts of diethanolamine are added to 55 parts of polyaluminium sulfate (Al)2O3Content 18%) until polyaluminium sulfate is dissolved to form a stable transparent solution, namely a modified polyaluminium sulfate solution;
B. weighing the following raw materials: 80% of modified polyaluminium sulfate solution, 1% of graphene oxide, 1% of stabilizer (citric acid), 1% of performance regulator and 17% of water;
C. adding 1 part of graphene oxide and 17 parts of water into 80 parts of modified polyaluminium sulfate solution, and performing ultrasonic dispersion for 20min to obtain a stable transparent solution;
D. and adding 1 part of performance regulator into the stable transparent solution, stirring for 1h at normal temperature to ensure full complexation, adding 1 part of citric acid, and stirring for 30min at normal temperature to obtain the stable liquid alkali-free accelerator.
Examples 1-7 are shown in Table 1 for comparison of formulations.
TABLE 1
Example 8
The normal-temperature synthesized early-strength liquid alkali-free setting accelerators prepared in examples 1-7 have a storage stability period of more than six months at room temperature, and are tested for the performance after being blended with cement, and the test results are shown in Table 2.
TABLE 2
Measurement of coagulation time: according to the regulation in (JT/T1088-: selecting the mixing amount of the water reducing agent under the conditions that the water-cement ratio is 0.35 and the net expansion degree of cement reaches (280 +/-10) mm as the mixing amount of the water reducing agent for detecting the alkali-free setting accelerator. The cement paste setting time is tested to be 0.35 of water cement ratio, wherein 400g of cement is used, and water in the liquid accelerator is deducted from the water consumption. And (3) putting the weighed water, cement and water reducing agent into a stirring pot, starting the stirrer, and stirring at a low speed for 30 s. Quickly adding weighed liquid accelerator (the mixing amount is based on the weight of cement) by an injector at one time, slowly stirring for 5s, quickly stirring for 15s, immediately filling into a circular cutting die after stirring is finished, inserting and smashing by a knife, slightly vibrating for a plurality of times, scraping redundant clear paste, and leveling the surface. The total operating time should not exceed 50s from the addition of the liquid accelerator. The setting time is measured by a concrete neat paste standard consistency and setting time measuring instrument, and the setting time is measured once every 10 seconds in the measuring process from the time of adding the liquid setting accelerator until the initial setting and the final setting. The initial setting time is determined when the test needle is inserted into the slurry and is 4mm +/-1 mm away from the bottom plate, and the final setting time is determined when the test needle is inserted into the slurry and is less than 0.5 mm.
Determination of compressive strength: according to the stipulations in (JT/T1088) -2016 alkali-free setting accelerator for sprayed concrete in highway engineering, the proportion of water in a mortar strength test is as follows: cement: the mass ratio of the standard sand is 1: 2: and 4, deducting water contained in the water reducing agent and the alkali-free accelerator by using the water consumption. The weighed water and cement are sequentially put into a stirring pot, the stirrer is started immediately to stir for 30s at a slow speed, then the standard sand is uniformly added in the second 30s slow stirring process, and then the mixture is stirred for 30s at a high speed. Stopping stirring for 90s, and scraping mortar on the blades and the pot wall into the stirring pot by using a rubber scraper in the first 15s during the stopping stirring. The high speed stirring was continued for another 30 seconds. And immediately adding the liquid accelerator with the recommended mixing amount by using a syringe, slowly stirring for 5s, quickly stirring for 15s, and finishing stirring. And (3) filling the mixed mortar into a cement mortar test mold as soon as possible. And (3) putting the mortar into a standard environment curing box for curing, demolding after 24 hours, and measuring the compressive strength of the mortar at 1d, 28d and 90d, wherein the total operation time from the addition of the liquid accelerator to the mold filling of the mortar is not more than 50 s.
The cement used in the test is Huaxin P.O42.5 ordinary portland cement, and the setting time of the cement paste and the cement mortar strength can meet the requirements of the first-class products in JT/T1088 and 2016 (alkali-free accelerator for road engineering shotcrete) by adopting the accelerators prepared in example 4, example 5, example 6 and example 7 when the addition amount is 5%.
Example 9
The samples of the room temperature synthesis early strength type liquid alkali-free setting accelerator prepared in examples 1 to 7 were tested for suitability to cement brands, and the test results are shown in table 3.
TABLE 3
As shown in Table 3, when the sea snail brand, Jiahua brand, Huarun brand and red lion brand P.O42.5 ordinary portland cement are respectively adopted and the addition of the accelerator prepared in example 6 is carried out, the setting time of the cement paste and the strength of the cement mortar can both meet the requirements of the first-class products in JT/T1088-fold 2016 alkali-free accelerator for road engineering shotcrete.
Before the sample provided by the invention is used, an adaptability test needs to be carried out on materials such as ordinary portland cement and other additives used in construction, and the influence of construction temperature, water-cement ratio and cement freshness is considered, so that the optimal mixing amount is determined. Note that the water cement ratio should be strictly controlled in the construction, if the water cement ratio is too large, the solidification time will be prolonged, and the use effect will be affected.
The normal-temperature synthesized liquid alkali-free accelerator provided by the invention is light yellow uniform liquid in appearance, has the advantages of no alkali, no chlorine, no pungent smell, low doping amount, quick condensation, no corrosion to human bodies, no corrosion to steel bars, good adaptability to various cements, overcomes the defects of strong corrosion and poor workability, slow condensation time, large later strength loss and the like of the traditional alkali accelerator, and is simple in production process, low in raw material cost and suitable for large-scale production. The method can be widely applied to the projects of shotcrete construction and leaking stoppage, ground cement concrete rapid construction, concrete emergency rescue, rush repair reinforcement and the like of the projects of mine engineering, roadway engineering, traffic tunnel engineering, urban construction, water conservancy and the like.
Claims (8)
1. The normal-temperature synthesized early-strength liquid alkali-free setting accelerator is characterized by comprising the following components in percentage by mass: 60-80% of modified polyaluminium sulfate solution, 1-3% of graphene oxide, 1-5% of stabilizer, 1-5% of performance regulator and the balance of water;
the modified polyaluminium sulfate solution comprises the following components in percentage by mass: 45-60% of polyaluminium sulfate, 5-15% of diethanolamine and 30-45% of water; the preparation method comprises the following steps: mixing polyaluminium sulfate, diethanolamine and water at normal temperature and stirring for 1h to obtain;
the performance regulator is prepared from polyacrylamide and silica sol according to a mass ratio of 1: 2, mixing and stirring to obtain a stable and transparent solution, wherein the polyacrylamide is anionic and has the number average molecular weight of 300W.
2. The ambient-temperature synthesized early-strength liquid alkali-free accelerator as claimed in claim 1, wherein the polyaluminium sulfate is industrial polyaluminium sulfate, wherein Al is2O3The content is more than 17 percent.
3. The normal-temperature synthesis early-strength liquid alkali-free accelerator as claimed in claim 1, wherein the graphene oxide is layered graphene oxide with 5 layers or less.
4. The ambient-temperature-synthesized early-strength liquid alkali-free setting accelerator as claimed in claim 1, wherein the stabilizer is one or more of ethylenediamine tetraacetic acid, citric acid, salicylic acid and phosphoric acid.
5. The normal-temperature synthesized early-strength liquid alkali-free setting accelerator as claimed in claim 1, wherein the silica sol is a commercially available acidic silica sol, and the mass fraction of the silica sol is 30-40%.
6. A preparation method of an early strength type liquid alkali-free setting accelerator synthesized at normal temperature according to any one of claims 1 to 5 is characterized by comprising the following specific steps:
1) adding graphene oxide and water into a modified polyaluminium sulfate solution, and performing ultrasonic dispersion uniformly to obtain a stable transparent solution;
2) adding a performance regulator into the stable transparent solution obtained in the step 1), stirring for 1h at normal temperature, adding a stabilizer, and uniformly stirring to obtain the normal-temperature synthesized early-strength liquid alkali-free accelerator.
7. The use method of the normal-temperature synthesized early-strength liquid alkali-free setting accelerator as claimed in any one of claims 1 to 5 is characterized by comprising the following specific steps: in the process of spraying concrete by using a concrete sprayer, the early strength type liquid alkali-free accelerator synthesized at normal temperature is added into the concrete at the nozzle of the concrete sprayer to prepare the sprayed concrete.
8. The use method of claim 7, wherein the mixing amount of the normal-temperature synthesized early-strength liquid alkali-free accelerator is 5-7%.
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| CN110104987B (en) * | 2019-06-21 | 2021-09-24 | 广州市建筑科学研究院有限公司 | High early strength type alkali-free liquid accelerator and preparation method and application thereof |
| CN110510906B (en) * | 2019-09-30 | 2022-04-26 | 山东中岩建材科技有限公司 | Alkali-free liquid accelerator and preparation method thereof |
| CN113200704A (en) * | 2021-05-19 | 2021-08-03 | 湖南加美乐素新材料股份有限公司 | Environment-friendly stable alkali-free liquid accelerator and preparation method and application thereof |
| CN113845327A (en) * | 2021-10-27 | 2021-12-28 | 中国科学院过程工程研究所 | Graphene alkali-free liquid accelerator and preparation method and application thereof |
| CN115286279B (en) * | 2022-08-10 | 2023-08-25 | 庐江县新创新型材料有限公司 | Environment-friendly concrete liquid accelerator and preparation method and application thereof |
| CN115368051A (en) * | 2022-10-25 | 2022-11-22 | 石家庄市长安育才建材有限公司 | Antifreeze accelerator, preparation method thereof and sprayed concrete |
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