CN112939542A - High-strength, quick-setting and expansion type multipurpose grouting material and preparation and application methods thereof - Google Patents

High-strength, quick-setting and expansion type multipurpose grouting material and preparation and application methods thereof Download PDF

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Publication number
CN112939542A
CN112939542A CN202110332413.XA CN202110332413A CN112939542A CN 112939542 A CN112939542 A CN 112939542A CN 202110332413 A CN202110332413 A CN 202110332413A CN 112939542 A CN112939542 A CN 112939542A
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quick
grouting material
agent
water
grouting
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CN112939542B (en
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罗卫东
蒋中承
唐勇
杨乘
任青山
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Guizhou Panjiang Coal Power Group Technology Research Institute Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02Compositions 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
    • C04B28/04Portland cements
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/70Grouts, e.g. injection mixtures for cables for prestressed concrete
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Soil Conditioners And Soil-Stabilizing Materials (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The invention discloses a high-strength, quick-setting and expansion type multipurpose grouting material, which comprises the following components: double-quick cement: 45% -60%; ordinary portland cement: 30% -45%; water-retaining agent: 0.05% -0.15%; water reducing agent: 0.10% -0.25%; modifying an air entraining agent: 0.01% -0.15%; compound dispersing agent: 0.05% -0.15%; industrial cellulose: 0.05% -0.15%; quick lime: 4% -6%; bentonite: 3.5% -6%; the grouting material and water are mixed according to the water-cement ratio of 0.6-1 to prepare slurry, and the slurry is used for consolidation of a broken surrounding rock body, grouting and plugging of gas and carbon monoxide toxic and harmful gas emission cracks, efficient sealing of gas extraction drill holes, gas pressure measurement drill holes and plugging of mine water leakage cracks. The invention has the advantages of high strength, large expansion, good fluidity, quick setting, compactness, low permeability and the like, and has low price and cost saving.

Description

High-strength, quick-setting and expansion type multipurpose grouting material and preparation and application methods thereof
Technical Field
The invention belongs to the technical field of mine safety production, and particularly relates to a high-strength, quick-setting and expansion type multipurpose grouting material, and preparation and application methods thereof.
Background
The grouting method is an essential construction method for controlling mine disasters in safe mining of mines, and is widely applied to multiple application fields of roadway surrounding rock reinforcement, gas control, water prevention and control of mines, fire prevention and extinguishing of goafs and the like. The quality of the grouting material in the field determines whether the mine can be safely and efficiently mined, and the quality of the grouting material is a key factor for determining the grouting construction quality, and the performance of the grouting material is particularly important.
The grouting materials applied to mine enterprises at present are mainly organic expansion materials and common cement materials. At present, large-scale mining enterprises in China stop or greatly reduce the use of polyurethane organic expansion materials during mining, and the reasons are that the organic expansion materials have the defects of toxicity, high reaction temperature, easy shrinkage after cooling, low compressive strength, high price and the like. The common cement material has no expansion capability, shrinks after solidification, has long solidification time and other inherent defects, so that the common cement material has no obvious advantages in the aspect of treating mine disasters, and aiming at the defects, an expanding agent is added into the common cement, the expansion rate of the obtained slurry is only 3-5 per mill, the expansion rate is too low, no obvious expansion effect is realized, and the high-efficiency plugging requirements such as grouting, filling and the like in mine safety production cannot be met.
The Chinese patent with publication number CN 109437771A discloses a mining flexible plugging grouting material, which comprises portland cement, gypsum, fly ash, an accelerator and a water reducing agent, wherein the raw materials in percentage by weight are as follows: 45-55% of Portland cement, 5-10% of gypsum, 30-40% of fly ash, 2-3% of an accelerating agent and 7-10% of an expanding agent. The grouting material has low cost and good fluidity, but has very low early strength and longer solidification time.
Chinese patent with publication number CN 111620657 a discloses a mine working face bottom suction roadway soft rock broken roof bead grouting material and a construction process thereof, wherein the grouting material comprises: a material slurry: 100 parts of sulphoaluminate clinker, 1-2 parts of naphthalene water reducer, 0.6-0.9 part of hydroxycarboxylic acid retarder, 1-5 parts of sulphoaluminate expanding agent and 150 parts of water; b, slurry of the material: 90 parts of dihydrate gypsum, 15 parts of lime, 15 parts of primary fly ash, 1-2 parts of a water reducing agent, 1-4 parts of an accelerating agent, 1-5 parts of a sodium metaaluminate early strength agent, 1-3 parts of a suspending agent sodium carboxymethyl cellulose and 150 parts of water, wherein the slurry A and the slurry B are mixed in a ratio of 1:1 when the mortar A and the slurry B are used. The grouting material produced by the formula has high early strength after being condensed, but the later strength is hardly increased basically, and the expansion rate is low, so that the plugging requirements of grouting, filling and the like in mine safety production cannot be met.
Disclosure of Invention
The invention aims to provide a high-strength, quick-setting and expansion type multipurpose grouting material, and preparation and application methods thereof, wherein the grouting material has the advantages of high strength, expansion, good fluidity, quick setting and the like, is suitable for multiple mine safety mining fields such as consolidation of broken surrounding rock mass, grouting and plugging of toxic and harmful gas emission cracks, efficient sealing of gas drilling holes, plugging of mine water leakage cracks and the like, realizes low cost and high quality, and can effectively replace an organic grouting material to greatly save the production cost of mine enterprises.
The invention adopts the technical scheme that the high-strength, quick-setting and expansion type multipurpose grouting material comprises the following components:
double-quick cement: 45% -60%;
ordinary portland cement: 30% -45%;
water-retaining agent: 0.05% -0.15%;
water reducing agent: 0.10% -0.25%;
modifying an air entraining agent: 0.01% -0.15%;
compound dispersing agent: 0.05% -0.15%;
industrial cellulose: 0.05% -0.15%;
quick lime: 4% -6%;
bentonite: 3.5 to 6 percent.
Preferably, the modified air entraining agent is a mixture of a common metal powder air entraining agent and a sodium lauryl sulfate surfactant solution,
preferably, the preparation method of the modified air entraining agent comprises the following steps:
c1: fully stirring a common metal powder air entraining agent and a sodium lauryl sulfate surfactant solution for 1 hour according to the mass ratio of 1:1, and uniformly mixing to obtain a mixed material;
c2: placing the obtained mixed material into a vacuum drying oven for low-temperature drying at the drying temperature of not higher than 30 ℃ for more than 8 hours;
c3: and (3) putting the dried mixed material into a closed type crushing sampling machine, fully grinding and crushing to prepare the modified air-entraining agent, wherein the modified air-entraining agent is 400-1000 meshes.
Preferably, the dual-quick cement is 42.5 type.
Preferably, the water-retaining agent is powdered re-dispersible latex powder.
Preferably, the water reducing agent is a powdery polycarboxylic acid high-efficiency water reducing agent.
Preferably, the composite dispersing agent is obtained by mixing sodium hexametaphosphate and sodium polyphosphate according to the mass ratio of 1: 1.
Preferably, the industrial cellulose is hydroxypropyl methylcellulose.
Preferably, the bentonite is sodium bentonite.
Preferably, the preparation and application method of the high-strength, quick-setting and expansive type multipurpose grouting material is characterized in that the grouting material is uniformly mixed with water to prepare slurry, and the water-cement ratio of the slurry is 0.6-1; the slurry is used for consolidation of a broken surrounding rock body, grouting and plugging of gas and carbon monoxide poisonous and harmful gas emission cracks, efficient sealing of a gas extraction drill hole, a gas pressure measurement drill hole and plugging of mine water leakage cracks; when the modified air entraining agent is used for the solidification of a broken surrounding rock mass, the mass fraction of the modified air entraining agent is 0.01-0.05%, and when the modified air entraining agent is used for crack grouting plugging, drilling hole sealing or mine water leakage crack plugging, the mass fraction of the modified air entraining agent is 0.05-0.15%.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, the double-rapid cement is matched with the ordinary portland cement as a main raw material, so that the advantages of double-rapid cement rapid setting and early strength and the advantages of high-later strength and compactness of the ordinary portland cement are achieved, the modified air entraining agent is added to enable the material to have the characteristics of rapid setting, high strength, expansion and the like, and the three materials are compounded into a certain high-efficiency additive on the basis to further achieve the advantages of high strength, expansion, good fluidity, rapid setting, compactness and low permeability of the material; experiments prove that the grouting material has the advantages of quick setting, expansion and good fluidity in a slurry state, the setting time of the grouting material is 10-30min, the expansion coefficient is 3% -10%, the expansion effect can be seen by naked eyes, the grouting material has early strength and middle and later high strength after setting, the uniaxial compressive strength is more than 10Mpa after 1 day, and the grouting material has the advantages of compactness and strong adhesion, is suitable for multiple mine safety exploitation fields such as consolidation of broken surrounding rock mass, grouting and plugging of toxic and harmful gas emission cracks, efficient sealing of gas drilling, plugging of mine water leakage cracks and the like, and in addition, the raw material in the formula is low in price, and the production cost of an enterprise can be obviously saved after large-scale popularization and use;
2. according to the invention, through the modified air entraining agent, the common metal powder air entraining agent is dispersed in the grouting material after being wrapped by the sodium lauryl sulfate surfactant, and is stably attached to the surfaces of other raw materials, so that a matrix is provided for later reaction, bleeding and segregation of concrete are reduced, the homogeneity of the concrete is improved, the raw materials in the grouting material slurry are favorably reacted to generate bubbles, and the expansion coefficient is improved;
3. the invention adopts 42.5 type double-rapid cement, the final setting time is 10 minutes, and the setting rate of the grouting material is accelerated;
4. the water-retaining agent adopts powdery re-dispersible latex powder which is an organic material, so that uniform bubble micro-cracks of the slurry are facilitated, and the permeability of the slurry is improved;
5. the suspension performance of the slurry is improved and the stability of the slurry is improved through industrial cellulose and bentonite;
6. according to the invention, quicklime is used as a calcium increasing agent, so that the later strength of the grouting material can be enhanced, the alkalinity of the slurry is increased, the modified air entraining agent is favorably reacted to generate bubbles, the bubbles are uniformly dispersed, and the expansion of the slurry during coagulation is promoted;
7. according to the invention, sodium hexametaphosphate and sodium polyphosphate are adopted, so that the dispersion of the grouting material is better, the raw material components are uniformly and stably distributed, the large blocks in the slurry are avoided, and the fluidity is improved;
8. the fluidity of the slurry is enhanced by the powdery polycarboxylic acid high-efficiency water reducing agent, and the net slurry fluidity is tested to be between 210 and 300mm by adopting the net slurry fluidity of the cement, so that the flowing of the slurry to the inside of a drilled hole is facilitated.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further explained with reference to the following embodiments.
A high-strength, quick-setting and intumescent multipurpose grouting material comprises the following components: double-quick cement: 45% -60%; ordinary portland cement: 30% -45%; water-retaining agent: 0.05% -0.15%; water reducing agent: 0.10% -0.25%; modifying an air entraining agent: 0.01% -0.15%; compound dispersing agent: 0.05% -0.15%; industrial cellulose: 0.05% -0.15%; quick lime: 4% -6%; bentonite: 3.5 to 6 percent. The sum of the total amount of the components is 100 percent.
Preferably, the modified air-entraining agent is a mixture of a common metal powder air-entraining agent and a sodium lauryl sulfate surfactant solution, and the sodium lauryl sulfate surfactant coats the common metal powder air-entraining agent, disperses in the grouting material, and stably adheres to the surface of other raw materials, so that the raw materials in the grouting material slurry react to generate bubbles, and the expansion coefficient is improved.
The preparation method of the modified air entraining agent comprises the following steps:
c1: fully stirring a common metal powder air entraining agent and a sodium lauryl sulfate surfactant solution for 1 hour according to the mass ratio of 1:1, and uniformly mixing to obtain a mixed material;
c2: placing the obtained mixed material into a vacuum drying oven for low-temperature drying at the drying temperature of not higher than 30 ℃ for more than 8 hours;
c3: and (3) putting the dried mixed material into a closed type crushing sampling machine, fully grinding and crushing to prepare the modified air-entraining agent, wherein the modified air-entraining agent is 400-1000 meshes.
Preferably, the dual-rapid cement is 42.5 type, the final setting time is 10min, the setting time of a grouting material is reduced, and the type of the common Portland cement is 425# or 525 #.
Preferably, the water-retaining agent is powdered re-dispersible latex powder or an organic material, so that the permeability of the slurry is effectively improved.
Preferably, the water reducing agent is a powdery polycarboxylic acid high-efficiency water reducing agent, and the fluidity of the grouting material in the drilled hole is enhanced.
Preferably, the composite dispersing agent is prepared by mixing sodium hexametaphosphate and sodium polyphosphate according to the mass ratio of 1:1, so that the grouting material has better dispersibility, and the raw material components are uniformly and stably distributed to prevent sedimentation.
Preferably, the industrial cellulose is hydroxypropyl methyl cellulose, which is beneficial to improving the stability of the pulp.
Preferably, the bentonite is sodium bentonite, has certain expansibility and adsorptivity, and increases the suspension property of the slurry.
A preparation and application method of a high-strength, quick-setting and expansion type multipurpose grouting material comprises the following steps: and uniformly mixing the grouting material and water to prepare slurry for use, wherein the water-cement ratio of the slurry is 0.6-1, and the slurry is directly injected into the drilling hole plugging section or the crack through a grouting machine.
The slurry can be used for consolidation of broken surrounding rock mass, grouting and plugging of gas and carbon monoxide poisonous and harmful gas emission cracks, efficient sealing of gas extraction drill holes, gas pressure measurement drill holes and plugging of mine water leakage cracks. When the grouting material is used for the consolidation of the broken surrounding rock mass, the mass fraction of the modified air entraining agent is 0.01-0.05%, so that the strength of the grouting material after solidification is effectively increased; when the grouting material is used for grouting and plugging cracks, sealing drill holes or plugging water leakage cracks of mines, the mass fraction of the modified air entraining agent is 0.05-0.15%, the modified air entraining agent is more in use amount, the expansion coefficient is increased, and the grouting material is favorable for expanding and plugging cracks in the condensation process.
Example 1
A high-strength, quick-setting and expansion type multipurpose grouting material is prepared, and comprises the following components: double-quick cement: 60 percent; ordinary portland cement: 30 percent; water-retaining agent: 0.1 percent; water reducing agent: 0.15 percent; modifying an air entraining agent: 0.15 percent; compound dispersing agent: 0.05 percent; industrial cellulose: 0.05 percent; quick lime: 4.5 percent; bentonite: 5 percent.
The preparation method and the application are as follows: the raw materials and water are uniformly mixed according to the weight ratio of 0.7:1, and the obtained slurry is used for grouting and plugging cracks caused by toxic and harmful gas such as gas and carbon monoxide.
Example 2
A high-strength, quick-setting and expansion type multipurpose grouting material is prepared, and comprises the following components: double-quick cement: 55 percent; ordinary portland cement: 45 percent; water-retaining agent: 0.1 percent; water reducing agent: 0.15 percent; modifying an air entraining agent: 0.1 percent; compound dispersing agent: 0.05 percent; industrial cellulose: 0.1 percent; quick lime: 5 percent; bentonite: 4.5 percent.
The preparation method and the application are as follows: the raw materials and water are uniformly mixed according to the weight ratio of 0.8:1, and the obtained slurry is used for efficient sealing of gas extraction drill holes and gas pressure measurement drill holes.
Example 3
A high-strength, quick-setting and expansion type multipurpose grouting material is prepared, and comprises the following components: double-quick cement: 50 percent; ordinary portland cement: 40 percent; water-retaining agent: 0.1 percent; water reducing agent: 0.2 percent; modifying an air entraining agent: 0.05 percent; compound dispersing agent: 0.1 percent; industrial cellulose: 0.05 percent; quick lime: 4 percent; bentonite: 5.5 percent.
The preparation method and the application are as follows: the raw materials and water are uniformly mixed according to the weight ratio of 0.85:1, and the obtained slurry is used for plugging mine water seepage cracks.
Example 4
A high-strength, quick-setting and expansion type multipurpose grouting material is prepared, and comprises the following components: double-quick cement: 45 percent; ordinary portland cement: 45 percent; water-retaining agent: 0.1 percent; water reducing agent: 0.15 percent; modifying an air entraining agent: 0.05 percent; compound dispersing agent: 0.1 percent; industrial cellulose: 0.1 percent; quick lime: 4.5 percent; bentonite: 5 percent.
The preparation method and the application are as follows: the raw materials and water are uniformly mixed according to the weight ratio of 1:1, and the obtained slurry is used for grouting reinforcement of the crushed rock mass.
The results of the performance tests on a high strength, quick setting, intumescent multipurpose grouting material prepared in examples 1-4 above are shown in the following table:
Figure BDA0002996700510000091
the test results show that the grouting material produced by the formula of the invention has the advantages of quick setting, good expansion and good fluidity in a slurry state, has the advantages of early strength, middle and later high strength after solidification, is compact and strong in adhesion, can be effectively combined with the wall surface of a drilled hole and the wall surface of a broken shelter in a seamless manner, and has excellent sealing and plugging effects.
The material is used for carrying out a sealing experiment for plugging a gas extraction drill hole on the underground site in a forward layer drill hole of No. 22 coal seam one-mining area 132204 transportation lane of Jinjia coal mine of Guizhou Panjiang clean coal, Inc. By detecting the gas extraction concentration of 20 random drilled holes in the drilling fluid at the observation time of 1 month, the average gas extraction concentration is 61.3%, which is improved by about 24.9% compared with the average gas extraction concentration of 36.4% of the drilled holes sealed by the common cement material under the same condition, the improvement ratio is 68.4%, and the sealing effect of the gas extraction drilled holes is greatly improved.
The material carries out broken rock mass grouting reinforcement operation during the 59210 air tunnel bottom suction tunnel excavation of the Longfeng coal mine No. 9 coal seam of Guizhou Panjiang coal-electricity group Lindong company, and a plurality of drill holes with the diameter of 94mm are drilled into the rock mass in front of an excavation face, wherein the hole depth is 60 meters. The material is used for grouting into a drill hole, wherein a depression hole is grouted by a grouting method, and an elevation hole adopts a sealed orifice and is additionally provided with a grouting pipe and a full-drill-hole-length grout return pipe for grouting into the drill hole. The tunneling construction can be carried out 1 day after grouting is finished, effective cemented filling of grouting materials is obtained from visible rock body cracks of rock bodies exposed in the tunneling period, the surrounding rock pressure of the tunnel in the tunneling period is very stable, the tunneling efficiency is greatly improved, and the safety benefit in the tunneling period is effectively guaranteed.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and their concepts should be equivalent or changed within the technical scope of the present invention.

Claims (10)

1. A high-strength, quick-setting and expansion type multipurpose grouting material is characterized by comprising the following components:
double-quick cement: 45% -60%;
ordinary portland cement: 30% -45%;
water-retaining agent: 0.05% -0.15%;
water reducing agent: 0.10% -0.25%;
modifying an air entraining agent: 0.01% -0.15%;
compound dispersing agent: 0.05% -0.15%;
industrial cellulose: 0.05% -0.15%;
quick lime: 4% -6%;
bentonite: 3.5 to 6 percent.
2. A high strength, quick setting, intumescent multipurpose grouting material as claimed in claim 1, characterised in that: the modified air entraining agent is a mixture of a common metal powder air entraining agent and a sodium lauryl sulfate surfactant solution.
3. A high strength, quick setting, intumescent multipurpose grouting material as claimed in claim 2, characterised in that: the preparation method of the modified air entraining agent comprises the following steps:
c1: fully stirring a common metal powder air entraining agent and a sodium lauryl sulfate surfactant solution for 1 hour according to the mass ratio of 1:1, and uniformly mixing to obtain a mixed material;
c2: placing the obtained mixed material into a vacuum drying oven for low-temperature drying at the drying temperature of not higher than 30 ℃ for more than 8 hours;
c3: and (3) putting the dried mixed material into a closed type crushing sampling machine, fully grinding and crushing to prepare the modified air-entraining agent, wherein the modified air-entraining agent is 400-1000 meshes.
4. A high strength, quick setting, intumescent multipurpose grouting material as claimed in claim 1, characterised in that: the dual-quick cement adopts 42.5 type.
5. A high strength, quick setting, intumescent multipurpose grouting material as claimed in claim 1, characterised in that: the water-retaining agent is powdery redispersible latex powder.
6. A high strength, quick setting, intumescent multipurpose grouting material as claimed in claim 1, characterised in that: the water reducing agent is a powdery polycarboxylic acid high-efficiency water reducing agent.
7. A high strength, quick setting, intumescent multipurpose grouting material as claimed in claim 1, characterised in that: the composite dispersing agent is obtained by mixing sodium hexametaphosphate and sodium polyphosphate according to the mass ratio of 1: 1.
8. A high strength, quick setting, intumescent multipurpose grouting material as claimed in claim 1, characterised in that: the industrial cellulose is hydroxypropyl methyl cellulose.
9. A high strength, quick setting, intumescent multipurpose grouting material as claimed in claim 1, characterised in that: the bentonite is sodium bentonite.
10. A method for preparing and using a high strength, quick setting, intumescent multipurpose grouting material according to any one of claims 1-9, characterised in that: uniformly mixing the grouting material with water to prepare slurry, wherein the water-cement ratio of the slurry is 0.6-0.1; the slurry is used for consolidation of a broken surrounding rock body, grouting and plugging of gas and carbon monoxide poisonous and harmful gas emission cracks, efficient sealing of a gas extraction drill hole, a gas pressure measurement drill hole and plugging of mine water leakage cracks; when the modified air entraining agent is used for the solidification of a broken surrounding rock mass, the mass fraction of the modified air entraining agent is 0.01-0.05%, and when the modified air entraining agent is used for crack grouting plugging, drilling hole sealing or mine water leakage crack plugging, the mass fraction of the modified air entraining agent is 0.05-0.15%.
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CN116283163A (en) * 2023-03-09 2023-06-23 山西保海管业有限责任公司 Coal seam gas extraction hole sealing material, preparation method and construction method
CN116477908A (en) * 2023-03-01 2023-07-25 江苏苏博特新材料股份有限公司 Quick-hardening early-strength shotcrete for high-stress tunnel support and construction application method thereof

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