CN114644495B - Mining hole sealing curing expansion material and preparation method thereof - Google Patents

Mining hole sealing curing expansion material and preparation method thereof Download PDF

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CN114644495B
CN114644495B CN202210458411.XA CN202210458411A CN114644495B CN 114644495 B CN114644495 B CN 114644495B CN 202210458411 A CN202210458411 A CN 202210458411A CN 114644495 B CN114644495 B CN 114644495B
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parts
expansion
cement
hole sealing
aluminum powder
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CN114644495A (en
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包若羽
荆炜琛
程佳
宋宜猛
时宝
刘懿
邸帅
伦嘉云
庞博
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Henan Zhongyi Tendering Co ltd
Inner Mongolia Erdos Yongmei Mining Co ltd
Information Research Institute Of Emergency Management Department
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Henan Zhongyi Tendering Co ltd
Inner Mongolia Erdos Yongmei Mining Co ltd
Information Research Institute Of Emergency Management Department
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/04—Portland cements
    • 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
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/06—Combustion residues, e.g. purification products of smoke, fumes or exhaust gases
    • C04B18/08—Flue dust, i.e. fly ash
    • 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
    • C04B22/02—Elements
    • C04B22/04—Metals, e.g. aluminium used as blowing agent
    • 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
    • C04B22/14—Acids or salts thereof containing sulfur in the anion, e.g. sulfides
    • C04B22/142—Sulfates
    • C04B22/147—Alkali-metal sulfates; Ammonium sulfate
    • 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
    • C04B22/16—Acids or salts thereof containing phosphorus in the anion, e.g. phosphates
    • 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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/003—Phosphorus-containing 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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2641—Polyacrylates; Polymethacrylates
    • 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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
    • 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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/40—Compounds containing silicon, titanium or zirconium or other organo-metallic compounds; Organo-clays; Organo-inorganic complexes
    • 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
    • C04B2103/50—Defoamers, air detrainers
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00663—Uses not provided for elsewhere in C04B2111/00 as filling material for cavities or the like
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00724—Uses not provided for elsewhere in C04B2111/00 in mining operations, e.g. for backfilling; in making tunnels or galleries
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
    • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Environmental & Geological Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Civil Engineering (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The invention relates to the technical field of mining hole sealing materials, in particular to a mining hole sealing solidification expansion material and a preparation method thereof, wherein the raw materials comprise the following components in parts by mass: 97-118 parts of cement, 28-31 parts of fly ash, 56-66 parts of water, 2.9-3.9 parts of expanding agent and 3.8-4.7 parts of stabilizer; the stabilizer is acid or acid salt; the expanding agent is submicron aluminum powder with the particle size of 0.10-0.26 mu m, so that the expanding agent can enter into micro-gaps of drilling holes more easily to achieve a better blocking effect, and gaps between cement particles and fly ash particles and gaps between fly ash particles are filled; meanwhile, the retarder and the aluminum powder expansion system are cooperatively used, the initial setting time of the expansion material is longer than 80% of the final expansion rate, and no through air holes are formed in the surface of the material, so that the problems of overlong curing time and mismatching of curing and expansion time of the mining hole sealing material are avoided; the stabilizer can inhibit the retarder or water from reacting with the expanding agent too fast to generate gas, so that the expanding time and the curing time can be matched better, and the stability of the expanding agent in a high-humidity environment is improved greatly.

Description

Mining hole sealing curing expansion material and preparation method thereof
Technical Field
The invention relates to the technical field of mining hole sealing materials, in particular to a mining hole sealing solidification expansion material and a preparation method thereof.
Background
The gas extraction and most gas control measures are realized by implementing drilling, and the drilling hole sealing quality directly influences the exertion of drilling energy efficiency. In the gas extraction process of the drill hole, the quality of the hole sealing of the drill hole influences the extraction concentration, and the orifice extraction negative pressure is the key for determining the extraction. The current cement-based hole sealing material is the hole sealing material with the largest coal mine consumption and the most extensive application in China at present: cement clinker is mixed with water to prepare a flowing cement slurry (cement mortar), and the slurry is injected into a borehole by a grouting pump. The cement has low hole sealing cost, wide raw material sources, easy operation and large hole sealing depth. The expansion of the ordinary expansion cement hole sealing material is greatly influenced by temperature and humidity, the stability is poor, the curing and expansion time is difficult to match, and the following defects are also present: the problems of long curing time, low early strength, easy shrinkage, crack generation and poor impact resistance in a high-humidity underground environment are solved, and the modified epoxy resin is further required.
Disclosure of Invention
In order to solve at least one aspect of the technical problems, the invention provides a mining hole sealing curing expansion material, which is used for supplementing and perfecting the defects of various hole sealing materials, has good fluidity, can effectively seal cracks around a drilling hole, is added with an optimized stabilizer aiming at an expansion agent, has stable expansibility when being cured, is less influenced by temperature and humidity, and always maintains better curing and expansion time matching degree; the material has expansibility to perfect the defect of easy shrinkage after the common cement is solidified, has better early strength, and can form effective support for the sealing section of the drilling hole after solidification; thereby greatly improving the bearing capacity and the service performance of the whole drilling structural member and the universal plugging performance for various types of drilling; in addition, the cured expansion material can improve the durability of the structure and has good working performance, high volume stability and economy; meanwhile, a preferable early strength agent is added to improve the early strength of the cured expansion material; meanwhile, the synergistic effect of the retarder system and the aluminum powder expanding agent is optimized, so that the expansion time and the curing time of the cured expansion material are well matched.
The invention provides a mining hole sealing curing expansion material, which comprises the following raw materials in parts by mass:
97-118 parts of cement, 28-31 parts of fly ash, 56-66 parts of water, 2.9-3.9 parts of expanding agent and 3.8-4.7 parts of stabilizer.
The stabilizer is one or more of polyphosphate, organic phosphonate, polyacrylate and polyacrylate copolymer, and more preferably one or more of sodium hexametaphosphate, sodium tripolyphosphate, aminotrimethylene phosphonic acid, ethylenediamine tetramethylene phosphonic acid, hydroxyethylidene diphosphonic acid and polyacrylate XT-1100; the aluminum powder expanding agent has stable delamination resistance effect in the expanding material slurry, can selectively improve the stability of the aluminum powder expanding agent, delays the expanding reaction, and further, the submicron aluminum powder expanding agent with the preferable particle size of 0.10-0.26 mu m is most sensitive to the stabilizer, and has the lowest reaction rate and delayed reaction phenomenon.
Compared with the traditional hole sealing material, the coal ash is added, and the high-quality grade I superfine powder coal ash produced by an advanced coal burning process in a power plant is adopted; the quality of the cement is not lower than the specified requirements of relevant standards such as national standard ' fly ash for cement and concrete ' GB/T1596-2005 ', the fineness of the cement is not more than 10 percent, the loss on ignition is not more than 3 percent and the SO is not more than 0.045mm square hole screen residue 3 The content is not more than 2%, the water content is not more than 1%, the water demand ratio is not more than 95%, and the specific surface area is more than 700m 2 /kg。
Preferably, the fly ash has an average particle size of 3-6. Mu.m.
Further, the preferred expansion agent is submicron aluminum powder.
Further, the swelling agent limits the swelling rate to not less than 0.05%.
Further, in order to improve the early strength of the cured intumescent material, 9.5 to 9.8 parts of lithium sulfate is also added to the cured intumescent material. Further, 0.4-1.3 parts of defoaming agent is added into the cured expansion material in order to reduce the bubble amount of the cured expansion material and improve the sealing effect; the defoamer is preferably a powder defoamer; the powder defoamer is preferably a polyether alcohol ester defoamer.
Further, in order to prevent the solidified expansion material from being solidified and coagulated too early and reduce the micro-crack sealing effect on the periphery of the drill hole, 1.1-1.6 parts of retarder is also added into the solidified expansion material; the retarder is preferably an inorganic metal base, and more preferably one or more of sodium hydroxide, potassium hydroxide and calcium hydroxide. The early-stage retarder can inhibit calcium silicate precipitation to form and further inhibit cement from crystallizing too fast, aluminum powder in the expander expands and simultaneously consumes the retarder, so that the retarder is consumed, the inhibition effect on cement retarding is eliminated, and cement is smoothly solidified. The retarder system needs to be used cooperatively with the expansion system, the curing time of the expansion material is controlled after the expansion material expands smoothly or the expansion material has completed more than 80 percent of expansion, and the surface of the material has no through air holes, so that the poor micro-crack sealing effect of the periphery of the drill hole caused by incomplete expansion is avoided.
Further, in order to improve the affinity between cement, fly ash filler, expanding agent and other substances in the curing expansion material and defoamer and the like, and further improve the mechanical properties of the system, 1.2-1.9 parts of coupling agent, preferably coupling agent aluminate coupling agent, is added in the curing expansion material, and compared with the common coupling agent, the coupling agent aluminate coupling agent can be rapidly decomposed to generate a mixed system containing aluminum hydroxide and an organic component system when in use, and the silane coupling agent and the like generate a silicic acid group and a plurality of organic groups after hydrolysis, and the aluminate coupling agent has more inorganic phases than the common silane coupling agent and the like and is more suitable for the expansion material system with the inorganic filler.
The compressive strength of the cured expansion material after curing is 63-75KN, the stress peak value is 12.6MPa, and the initial setting time is not less than 17.2min; the time for the expansion rate to reach 80% of the final expansion rate is 10-20min; the cohesiveness test result was 1800-2800 mPa.s.
The preparation method of the mining hole sealing curing expansion material is used for preparing the curing expansion material and comprises the following steps:
uniformly stirring the stabilizer into water to obtain a first mixed solution, and uniformly mixing the expanding agent into cement to obtain a second mixed solution;
uniformly stirring the mixture II and part of the mixed solution I according to the weight ratio, and then adding fly ash, retarder, coupling agent and lithium sulfate according to the given weight ratio;
and adding the defoaming agent and the rest mixed solution I, uniformly stirring, standing, and then uniformly stirring and discharging to obtain the cured expansion material.
Preferably, the raw materials comprise the following components: 97-118 parts of cement, 28-31 parts of fly ash, 56-66 parts of water, 2.9-3.9 parts of expanding agent, 0.4-1.3 parts of defoaming agent, 1.1-1.6 parts of retarder, 1.2-1.9 parts of coupling agent and 3.8-4.7 parts of stabilizer; 4-6 parts of first mixed solution is added for further improving the mixing uniformity and improving the strength and sealing integrity of the cured expansion material; 57.4-70.8 parts of mixed liquor is added for the second time.
The beneficial effects are that:
1. in order to improve the bulk strength of the expansion material, an equivalent substitution method is adopted to replace part of cement by adding active mineral admixture (extra fine powder coal ash), volcanic ash reaction, enhancement effect, filling effect and durability improvement effect of expanding agent, fly ash and the like are utilized, and the composite doping of the expanding agent, the fly ash and the like and the super-superposition effect generated by the composite admixture of the expanding agent, the fly ash and the like and the high-efficiency coupling agent are fully utilized. According to the characteristic that the particle sizes of the cement particles and the cement particles are not in the same level, the particle size distribution of the cementing material part in the cured expansion material is optimized, and the fly ash can fill the pores among cement particles, so that the interface structure between the materials and the pore structure of the cement stone are greatly improved, the compactness and the impermeability of the cement stone are improved, and meanwhile, the typical compact structure can be expanded to the surface of the aggregate, so that the whole material is more compact and hard, and the mechanical property (especially the bonding property with the wall of a drilling hole), the durability and the working property of the material are greatly improved.
2. The submicron aluminum powder is selected as the efficient active metal ion expanding agent, and the addition of the aluminum powder can prevent or reduce the volume shrinkage cracking caused by chemical reaction, physical reaction and thermodynamic reaction in hydration and hardening of the solidified expanding material to compensate, and can fill and block various capillary pores so that the internal structure of the material is more compact, thus not only greatly improving the crack resistance and seepage resistance and volume stability of the material, but also further improving the compactness and strength of the material; the shrinkage performance of the ordinary cement material is improved, the volume shrinkage cracking generated by the hardening reaction of the material can be compensated, various capillary pores in the material can be filled and blocked, and the overall crack resistance and seepage resistance, the compactness, the strength and the volume stability of the material are improved.
3. In order to improve the solidification time and expansion time matching degree of the expansion material, an expansion-retarding system of aluminum powder combined with inorganic metal alkali is adopted, calcium silicate precipitate formation can be restrained at the early stage of retarder so as to restrain the too fast crystallization of cement, sodium hydroxide is consumed along with the expansion of the aluminum powder in the expansion agent, so that the sodium hydroxide consumption is caused, the retarding inhibition effect on cement is eliminated, and the cement is smoothly solidified; the retarder system needs to be used cooperatively with the aluminum powder expansion system, the curing time of the expansion material is controlled after the expansion material is smoothly expanded or the expansion material is expanded by more than 80%, and no through air holes exist on the surface of the expansion material, so that the problem that the micro-crack sealing effect around the drill hole is poor due to incomplete expansion is avoided, and the problems of long curing time and mismatching of curing and expansion time of the mining hole sealing material are avoided.
4. Phosphate, organic phosphonate and polyacrylate substances are added as stabilizers to passivate the aluminum expanding agent, the stabilizers are easily adsorbed on the surface of aluminum powder under the action of surface charges, the PH environment is changed in a small range, the original hydroxide concentration is reduced, and the reaction rate of the aluminum powder and water is further inhibited, so that the reaction with water is delayed; further, the stabilizer has selectivity on particle size of aluminum powder particles, has better inhibition effect on submicron aluminum powder with the particle size of 0.10-0.26 mu m, can be used as a regulator for regulating expansion rate, improves matching degree of expansion rate and solidification rate, and improves sealing integrity.
5. The fluidity, cohesiveness and water retention of the cured expansion material can be improved by adding a proper amount of fly ash, but the early strength of the material can be reduced to a certain extent by replacing part of cement with the fly ash, and the strength and durability of the cured expansion material can be obviously improved by adding a proper amount of lithium sulfate; on the one hand SO in lithium sulfate 4 2- With cement hydration product Ca (OH) 2 The calcium sulfate with high dispersity is generated by the reaction, the lithium ions are helpful for controlling the morphology, and the added calcium sulfate is easier to react with tricalcium aluminate serving as a cement component to generate needle-shaped, rod-shaped and hollow tubular calcium sail stone crystals, so that an early frame structure for the strength development of the cement stone is formed; on the other hand SO 4 2- Consumption C 3 S、C 2 S hydration-generated Ca (OH) 2 Promote C 3 S、C 2 S, hydration; the combined use of the fly ash and the lithium sulfate can improve the overall compactness of the expansion material, thereby improving the bonding performance between the material and the borehole wall.
6. The invention is preferably aluminate coupling agent, compared with common silane coupling agent, the invention can be decomposed rapidly when meeting water to generate a mixed system containing aluminum hydroxide and organic component system, has more inorganic phases and is more suitable for curing expansion material system with dominant inorganic filler.
7. The polyether alcohol ester defoamer is selected to be used in the invention, so that a large amount of microbubbles which are formed in the stirring process of the material and remain in the material after compaction by vibration can be defoamed, the compactness of the material is effectively improved, the phenomenon that holes in the material are mutually communicated to form cracks under the action of mining stress and ground stress to cause drilling gas leakage is avoided, and the durability and the shearing stability of the material are enhanced.
8. The raw materials of the curing expansion material contain a large amount of fly ash, active metal ions and inorganic nonmetallic alkaline ions, which are industrial waste materials, the digestion of the materials can greatly contribute to environmental protection, the requirements of sustainable development are met, and the curing expansion material is a green material and an environment-friendly material; meanwhile, the method for reducing the cement particles, the additive particles and the superfine active mineral particles to the greatest extent is realized by the method of flying and feeding the materials everywhere during stirring the materials, the preparation process is simple and easy to realize, is suitable for engineering and industrialization, is convenient for large-scale popularization and application, realizes the utilization of the fly ash waste, and has better social benefit.
Drawings
FIG. 1 shows the axial stress-strain curves for the samples of example 1 and comparative examples 1-3;
FIG. 2 shows an SEM image of example 1;
FIG. 3 shows an SEM image of comparative example 6;
FIG. 4 shows an SEM image of comparative example 7;
FIG. 5 shows an SEM image of comparative example 8;
FIG. 6 shows the results of the cohesiveness test of the blank, example 1, and experimental examples 1-2;
FIG. 7 shows the expansion-time effect law of example 1 and experimental examples 3-5;
fig. 8 shows the expansion-time effect law of example 1 and experimental examples 6-7.
Detailed Description
The present disclosure will now be discussed with reference to several exemplary embodiments. It should be understood that these embodiments are discussed only to enable those of ordinary skill in the art to better understand and thus practice the teachings of the present invention, and are not meant to imply any limitation on the scope of the invention.
As used herein, the term "comprising" and variants thereof are to be interpreted as meaning "including but not limited to" open-ended terms. The term "based on" is to be interpreted as "based at least in part on". The terms "one embodiment" and "an embodiment" are to be interpreted as "at least one embodiment. The term "another embodiment" is to be interpreted as "at least one other embodiment".
The invention develops the curing expansion material for mine, which adopts similar materials-cement and water as common cement sealing materials, and also adds the indispensable components: retarder, coupling agent, stabilizer, high-efficiency expanding agent, fly ash and the like (aluminum powder, fly ash), and powder defoamer is additionally added. Compared with common cement hole sealing materials, the strength and the performance of the mine curing expansion material are improved in different degrees compared with common cement materials. By adding the superfine active mineral material and utilizing the volcanic ash reaction, (micro) filling effect and plasticizing effect of the superfine active mineral material, the grain composition of the cementing material part in the cured expansion material is optimized, so that the interface structure pore structure between the cured expansion materials is greatly improved, the compactness and the impermeability of the cement stone are improved, and meanwhile, the typical compact structure can be expanded to the surface of the material, so that the cured expansion material is more compact and hard, and the mechanical property (especially the bonding property between the cured expansion material and the borehole wall) and the durability of the cured expansion material are greatly improved. Meanwhile, by doping the powder defoaming agent, a large amount of bubbles which are formed in the stirring process of the curing expansion material and remain in the cement slurry in the material or in the interface transition area after compaction by vibration can be reduced, so that the compactness of the curing expansion material is effectively improved, and the mechanical property (including the bonding property with the wall of a drilling hole) and the durability of the curing expansion material are improved. In addition, by adding the expanding agent, the material has certain expansibility, improves the shrinkage performance of the ordinary cement material, compensates the volume shrinkage cracking generated by the hardening reaction of the material, can fill and block various capillary pores in the material, and improves the overall anti-cracking and anti-seepage performance, the compactness, the strength and the volume stability of the material; the activity of the fly ash can be enhanced, the power of the forward hydration reaction is improved, and the strength of the prepared cured expansion material is obviously improved; the addition of the retarder prolongs the curing time of the curing expansion material, is favorable for the slurry to permeate into cracks around the drill hole under the action of grouting pressure in the initial stage, and seals coal and rock mass around the drill hole, so that the stability and the tightness of the whole structure of the drill hole are improved, meanwhile, the aluminum powder expansion agent and the retarder react, and the inhibition of the retarder on the curing of the material is gradually relieved while the expansion is carried out, so that the curing time and the expansion time are well matched.
The key technical problem to be solved by the invention is to ensure that the curing time of the curing expansion material is matched with the expansion time, and ensure the stability of the expansion time of the expansion agent system, especially under the high-temperature and high-humidity environment, the retarder is preferably inorganic metal alkali; further preferably, soluble inorganic metal alkali such as sodium hydroxide, potassium hydroxide, calcium hydroxide and the like can react with the aluminum powder expanding agent, and the retarder is consumed while the aluminum powder expands, so that the curing inhibition is gradually released, and the curing time and the expansion time can be matched; one or more of polyphosphate, organic phosphonate, polyacrylate and polyacrylate copolymer is adopted, and further preferably one or more of sodium hexametaphosphate, sodium tripolyphosphate, aminotrimethylene phosphonic acid, ethylenediamine tetramethylene phosphonic acid, hydroxyethylidene diphosphonic acid and polyacrylate XT-1100 are adopted, and the stabilizer can inhibit the expansion agent and retarder or water from generating gas to expand in the early reaction stage, so that the problems of excessively high expansion time and unmatched expansion time are avoided; and simultaneously improves the stability of the expanding agent under the high-humidity environment.
When the raw materials are selected, the prepared cured expansion material is considered to have higher strength, and the grain composition in the material is optimized according to the maximum compactness theory, so that coarse and fine grains are well filled with each other, and the void ratio in the material is reduced; meanwhile, the average particle diameter of the cement is 20-30 μm, and the particles smaller than 10 μm are not much. The particle size of the expanding agent, the fly ash and the like is far smaller than that of cement particles, and the average particle size of the superfine fly ash is 3-6 mu m, so that the superfine fly ash can be used for the cementThe average particle diameter of submicron aluminum powder is also very small and is 0.10-0.26 mu m, so that the gaps between cement particles and ultrafine fly ash particles and the gaps or gaps between gelled particles and the gaps between gelled particles and interface structures can be filled, and the particle grading of the gelled material part is also very important to the prepared cured and expanded material. The mixing of expanding agent, flyash, etc. reduces the void ratio between cement grains and interface, makes the cement stone structure and interface structure compact, and blocks the permeation passage, so that the impermeability of the prepared solidified expanding material is greatly raised, and the water and other various erosion mediums (Cl) - 、SO 4 2- 、CO 2 Etc.) are difficult to enter the material, and the occurrence probability of alkali-silicon reaction and the generation probability of calcium hypochlorite can be reduced, and the strength and durability of the material are greatly improved. Namely, when the macropore content of more than 0.1 mu m in the cement stone structure and the interface structure is lower, the preparation method is favorable for improving various properties of the prepared cured expansion material, otherwise, the prepared cured expansion material is unfavorable in strength, impermeability, corrosion resistance and durability.
After replacing part of cement with expanding agent, flyash, etc., part of water in the gaps of cement particles can be replaced by mineral admixture filled in the gaps, so that the cohesiveness (viscosity) and fluidity of cement paste can be reduced and increased. In order to ensure the high working performance of the developed cured expansion material, the invention adopts a method of compounding and doping retarder, expanding agent, fly ash and the like, and under the cooperative work of the retarder, the fine particles of the active mineral doping material not only fully exert the (micro) filling effect of the active mineral doping material, but also displace the water filled in the gaps, so that the interval water layer among the particles is thickened; in addition, the micro-particles of the expanding agent, the fly ash and the like absorb material molecules, electrostatic repulsive force generated by electric double layer potential formed on the surface of the micro-particles is larger than universal gravitation among powder particles, so that the powder particles are promoted to be dispersed, the dispersion of cement particles is further enhanced, the fluidity of cement paste is increased, and the fluidity of the mixture is effectively improved; meanwhile, the composite doping of the superfine expanding agent, the fly ash and the like reduces the hydration heat, and can improve the volume stability of the solidified expanding material.
Because the occurrence depths of the coal beds are extremely different, the pressure born by the drilling holes with different depths is also different due to the dead weight stress of the overlying strata and the other complicated stress conditions around the overlying strata, so that the expansion materials with different strengths are researched and developed so as to be suitable for the coal beds with different burial depths, and the performances of the materials are furthest exerted while the hole sealing requirements are met. According to the strength characteristics and the material characteristics of the cured expansion material, the cured expansion material is suitable for coal beds with burial depths ranging from 0m to 500m, the drill holes are effectively supported in the range, and if the stress born by the drill holes is large in the range, the proportions of all components in the cured expansion material can be properly adjusted to plug the drill holes.
The invention is further illustrated by the following specific examples:
raw materials (one)
1. Cement and its preparation method
PO cement (ordinary Portland cement) with stable quality is selected, and the performance index of the selected cement meets the requirements of the national current relevant standards, and has the advantages of low alkali content, low hydration heat and low water demand.
2. Fly ash
The high-quality grade I superfine powder coal ash produced by a power plant with advanced coal burning technology is adopted. The quality of the cement powder meets the specified requirements of national standard GB/T1596-2005 and related standards of fly ash used in cement and concrete, the fineness (0.045 mm square hole screen residue,%) is not more than 5%, the loss on ignition is 2.2%, and the SO 3 The content is 1.2-1.9%, the water demand ratio is less than 95%, and the specific surface area is about 1000m 2 /kg。
3. Expanding agent
The quality of the selected submicron aluminum powder meets the requirements of related standards such as national standard 'mineral admixture for high-strength high-performance concrete', GB/T18736-2002, the water content of the submicron aluminum powder is less than 1%, the loss on ignition is not more than 3%, and the volcanic ash activity index is more than 95%. The specific surface area of the submicron aluminum powder is about 27000m 2 /kg。
Through a large number of trial comparison tests and cement compatibility tests, the expansion agent selected by the invention is submicron aluminum powder with the diameter of 0.1-0.26 mu m, the quality of the expansion agent meets the requirements of related standards such as national standard ' concrete expansion agent ' GB 23439-2009 ', the fineness (0.08 mm square hole sieve residue,%) of the expansion agent is not more than 10%, and the specific surface area is about 400m 2 /kg, limiting the expansion rate (7 days in water) to not less than 0.05%. The aluminum expansion agents described herein refer to sub-micron aluminum powders of 0.1-0.26 μm unless specified; the expanding agent can be aluminum powder with different particle sizes or aluminum powder combination with different particle sizes.
4. Lithium sulfate
Lithium sulfate has a coordinated effect with organic components and has the effect of promoting cement to hydrate early, and the concrete reason is that: on the one hand SO 4 2- With cement hydration product Ca (OH) 2 The calcium sulfate with high dispersity is generated by the reaction, and is easier to react with tricalcium aluminate serving as a cement component to generate needle-shaped, rod-shaped and hollow tubular calcium sail stone crystals than the added calcium sulfate, so that an early frame structure for the strength development of the cement stone is formed; on the other hand SO 4 2- Consumption C 3 S、C 2 S hydration-generated Ca (OH) 2 Promote C 3 S、C 2 Hydration of S.
5. Coupling agent
Coupling agents are used as a plastics additive for improving the interfacial properties of inorganic fillers or reinforcing materials, generally in amounts of 0.5% to 2%. The coupling agent is generally an aluminate coupling agent, the organophilic groups may interact with the inorganic filler or reinforcing material, and the organophilic groups may interact with the organic component.
6. Stabilizing agent
The stabilizer is selected from one or more of polyphosphate, organic phosphonate, polyacrylate, and polyacrylate copolymer, and more preferably one or more of sodium hexametaphosphate, sodium tripolyphosphate, aminotrimethylene phosphonic acid, ethylenediamine tetramethylene phosphonic acid, hydroxyethylidene diphosphonic acid, and polyacrylate XT-1100.
7. Mixing water
Tap water is selected as mixing water, the quality of the mixing water meets the specified requirements of the relevant standards of the State Ministry of construction standard for concrete mixing Water Standard JGJ63-2006, and the alkali content is less than 800mg/L.
8. Defoaming agent
The defoamer is preferably a powder defoamer; in particular to polyether alcohol ester defoamer, white powder with the pH of 5-8.
(II) mixing ratio
The invention is shown in the table 1 for the compounding ratio of examples 1-3 provided by the curing expansion material for sealing holes in mines, wherein the retarder of example 1 is sodium hydroxide and the stabilizer is ethylenediamine tetramethylene phosphonic acid; the retarder in the embodiment 2 is potassium hydroxide and the stabilizer is sodium hexametaphosphate; example 3 the retarder was a mixture of sodium hydroxide and potassium hydroxide and the stabilizer was polyacrylate XT-1100; PO32.5R, PO42.5R and PO52.5R represent different strength ratings of cement.
Table 1 mixing ratio (parts by mass) of mining hole sealing curing expansion material
Figure BDA0003621271770000081
To further verify the preferred rationality of the formulations of the present invention, comparative examples 1-8 were set up:
the proportion of submicron aluminum powder in the expanding agent of comparative example 1 is higher than the mass range defined herein, the total amount of the expanding agent is still 2.9 parts by mass, and the other components are used in the same amount as in example 1; the proportion of submicron aluminum powder in the expanding agent of comparative example 2 is lower than the limit range, the total amount of the expanding agent is still 2.9 parts by mass, and the rest components are used in the same amount as in example 1; comparative examples 1 and 2 are used to demonstrate the adverse effects of sub-micron aluminum powder usage beyond the set ranges set herein;
in the comparative example 3, 10-100um aluminum powder in the prior art is used as an expanding agent, the total amount of the expanding agent is still 2.9 parts by mass, and the other components are used in the same amount as in the example 1, so as to be used for comparing with the example 1 in the application to prove that the adverse effect is brought by exceeding the set grain size composition range of the aluminum powder in the application;
comparative example 4 the amount of stabilizer used was less than the mass range defined herein, the type of stabilizer was still the same as in example 1, and the amounts of the remaining components were all the same as in example 1; comparative example 5 the amount of stabilizer used was above the limits defined herein, the type of stabilizer was still the same as in example 1, the amounts of the remaining components were the same as in example 1; comparative examples 4 and 5 are used to demonstrate the adverse effects of stabilizer amounts outside the ranges set forth herein;
comparative example 6 retarder was used in an amount less than the mass range defined herein, the retarder type was still the same as in example 1, and the remaining components were used in the same amounts as in example 1; comparative example 7 retarder levels above the ranges defined herein, retarder types remain the same as in example 1, with the remainder of the components being used in the same amounts as in example 1; comparative example 4 and comparative example 5 are used to demonstrate the adverse effects of retarder usage outside the ranges set forth herein;
the comparative example 8 adopts a common citric acid retarder, the retarder dosage is the same as that of the example 1, and the other components are the same as that of the example 1; for comparison with example 1.
To further address the effect of the usual stabilizer selection on the expansibility of the expansion agent in the expansion material, a blank and experimental examples 1-2 were set up:
the blank contains no stabilizer, as in example 1; experimental example 1 the stabilizer was sodium polyphosphate with the equivalent amount of the stabilizer of example 1, the remainder being the same as in example 1; experimental example 2 stabilizer used the equivalent amount of the stabilizer of example 1 instead of the stabilizer used sodium polyphosphate equivalent amount of the stabilizer of example 1, the remainder was the same as in example 1, and the remainder was the same as in example 1.
To further illustrate the effect of the expansion rate of the stabilizer on the aluminum powder expansion agent of different particle sizes, further preferred tests were performed in any of the above systems of examples 1-3, and for ease of illustration, applicants set up experimental examples 3-5 to illustrate the system of example 1:
experimental example 3 the expanding agent is nano aluminum powder of 50-90nm, and the rest is the same as in example 1; experimental example 4 the swelling agent is submicron aluminum powder of 0.50-1 μm, and the rest is the same as in example 1; experimental example 5 the swelling agent is 5-50 μm of micron aluminum powder, and the rest is the same as in example 1; experimental example 6 the stabilizer is sodium polyphosphate, the expanding agent is submicron aluminum powder of 0.50-1 mu m, and the rest is the same as in the experimental example 1; experimental example 7 the stabilizer was sodium polyphosphate, the swelling agent was 5-50 μm of aluminum powder, and the rest was the same as in example 1.
Table 2 Experimental examples 1-7 mixing ratio (parts by mass)
Figure BDA0003621271770000091
(III) stirring process
The invention adopts an improved concrete stirring process, and the concrete process comprises the following steps:
the invention adopts an improved concrete stirring process during preparation, and the concrete is stirred in a forced stirrer, and the feeding sequence is as follows:
uniformly stirring the stabilizer into water to obtain a first mixed solution, and uniformly mixing the expanding agent into cement to obtain a second mixed solution;
uniformly stirring the mixture II and part of the mixed solution I according to the weight ratio, and then adding fly ash, retarder, coupling agent and lithium sulfate according to the given weight ratio;
and adding the defoaming agent and the rest mixed solution I, uniformly stirring, standing, and then uniformly stirring and discharging to obtain the cured expansion material.
Preferably, the raw materials comprise the following components: 97-118 parts of cement, 28-31 parts of fly ash, 56-66 parts of water, 2.9-3.9 parts of expanding agent, 0.4-1.3 parts of defoaming agent, 1.1-1.6 parts of retarder, 1.2-1.9 parts of coupling agent and 3.8-4.7 parts of stabilizer; 4-6 parts of first mixed solution is added for further improving the mixing uniformity and improving the strength and sealing integrity of the cured expansion material; 57.4-70.8 parts of mixed liquor is added for the second time.
The process can reduce the flying of cement particles, additive particles and superfine active mineral particles to the whole area during stirring of the materials as much as possible, can improve the strength of the prepared materials, and the prepared materials are not easy to have segregation phenomenon, have less bleeding and relatively good working performance.
(IV) test method
Cohesiveness test: GB/T10247-1988 viscosity test method.
Mechanical testing: GB/T50266-99 engineering rock mass test method standard.
Water retention test: the water retention performance was tested by the filter paper method with reference to DIN18555-7, and the change in water content of the filter paper material before and after water absorption was tested.
Flowability test: GB/T1346.
And (3) detecting the integrity of the plugging hole: and (3) carrying out negative pressure pumping test on horizontal grouting holes with the diameters of 1mm, 5mm and 10mm and the stress coefficient of 0.6 by using a negative pressure vacuum pump, and judging the integrity of the plugging holes according to the average value of the maximum negative pressure value.
Initial setting time: the materials are mixed with water according to the mass ratio of 2:1, and then are stood still, when slurry is inclined at 45 degrees and does not flow, the initial setting is achieved, and the time from the end of stirring to the occurrence of the initial setting is achieved. The curing times described herein are all initial set times, unless otherwise specified.
The expansion rate testing method comprises the following steps: preparation of V 0 Volume of test sample V after curing of the volume of expanded material slurry for a number of times 1 、V 2 .......V n The method comprises the steps of carrying out a first treatment on the surface of the Expansion rate eta n Is (V) n -V 0 )/V 0 To facilitate calculation of V 0 1L is often chosen in the experiment; the final expansion rate test method comprises the following steps: the expansion rate test changes by less than 1% three times in succession, namely (eta) n+1 -η n )/η n Sum (eta) n+2 -η n+1 )/η n+1 All are smaller than 1%, eta n Is the final expansion rate.
(fifth) test results
The results of the comparative test of the properties of the mining hole sealing and curing expansion materials prepared according to the above compounding ratio are shown in Table 3.
TABLE 3 cured intumescent materials examples 1-3 and comparative examples 1-3 performance comparative test results
Figure BDA0003621271770000101
Figure BDA0003621271770000111
As can be seen from comparison table 3, the submicron aluminum powder in comparative example 1 is smaller than the limit of the application, the expansion rate is reduced, the initial setting time is increased, but the compressive strength and stress peak value, the water retention test is reduced, the integrity test of the plugged holes is unchanged, the cohesiveness test and the fluidity test are significantly reduced, because the submicron particles are matched with the gaps between the fly ash particles and the cement, the consumption is reduced, the cohesiveness test is directly reduced, and meanwhile, the consumption of retarder is slower because the aluminum powder is reduced, the initial setting time is increased, the expansion rate is reduced, and the incomplete expansion leads to the water retention reduction.
In comparative example 2, the submicron aluminum powder is larger than the limit range of the application, but the compressive strength and the stress peak value, the water retention test and the initial setting time are reduced, the integrity detection of the plugging holes is reduced, the cohesiveness test is obviously increased, and the fluidity test is poorer, because the particle size of the submicron aluminum powder is matched with the particle size of the fly ash and the cement particles, the increasing proportion directly leads to the reduction of the cohesiveness test, the expansion rate is increased, the macropore content of more than 0.1 mu m in the matched cement stone structure and the interface structure is higher, the incomplete plugging structure is caused by the excessively rapid expansion rate, and the improvement of various properties such as the plugging integrity of the prepared cured expansion material is not facilitated, and the mechanical property and the water retention property are reduced.
From the above, the proportion of the submicron aluminum powder is beyond the limit of the application, which leads to the decrease of mechanical property, water-retaining property, cohesiveness and initial setting time, and is unfavorable for improving the operability, plugging property and mechanical property of the product.
In comparative example 3, aluminum powder with the particle size of 10-100um in the prior art is used for replacing the swelling agent system, the specific surface area is small, the reactivity is poor, the swelling rate is obviously lower than that of example 1, and meanwhile, the consumption rate of the retarder by the aluminum powder is far lower than that of example 1, so that the initial setting time is far longer than that of the scheme of the embodiment 1. From the above, the scheme of using aluminum powder with the particle size of 10-100um to replace the expanding agent system in the application is far inferior to that of the embodiment 1 in the application in terms of product operability and blocking integrity.
Fig. 1 shows the axial stress-strain curves of the samples of example 1 and comparative examples 1-3, wherein the slope of the stress change with strain of example 1 is the largest and the stress peak is the largest, which indicates that example 1 has stronger rigidity and the maximum strength and bearing capacity after curing. Watch (watch)
TABLE 4 comparative examples 4-5 comparative test results of properties of cured intumescent materials
Figure BDA0003621271770000121
As can be seen from comparison Table 4, the ethylenediamine tetramethylene phosphonic acid in comparative example 4 is less than 3.8-4.7 parts of the range defined in the application, the expansion rate is obviously reduced compared with that in example 1, the initial setting time is obviously reduced, but the cohesiveness test is increased due to the too fast reaction, and the water retention and the blocking integrity test are obviously reduced. In comparative example 5, the ethylenediamine tetramethylene phosphonic acid is more than 3.8-4.7 parts of the limiting range of the application, the expansion rate is obviously reduced, and the initial setting time is obviously prolonged compared with that of example 1, because the ethylenediamine tetramethylene phosphonic acid and the aluminum powder serving as the expansion agent are easily adsorbed on the surface of the aluminum powder under the action of surface charges, the PH environment is changed within a small range, the original hydroxyl concentration is reduced, the reaction rate of the aluminum powder and water is further inhibited, the reaction competition between the aluminum powder and the water is realized, the excessive rapid solidification of the cement component of the expansion agent caused by the excessive rapid reaction of the retarder and the aluminum powder can be inhibited, the inhibition effect of the retarder is longer, and the stability of the expansion agent of the aluminum powder is improved.
From the above, the proportion of the stabilizer exceeding the limit of the application can lead to the reduction of mechanical properties, water retention, blocking integrity and cohesiveness, and is unfavorable for improving the operability, blocking integrity and mechanical properties of the product.
TABLE 5 comparative test results of the properties of cured intumescent materials comparative examples 6-8
Figure BDA0003621271770000122
Figure BDA0003621271770000131
As can be seen from comparison Table 5, the retarder in comparative example 6 is less than 1.1-1.6 parts defined in the application, the expansion ratio is obviously reduced compared with that in example 1, the initial setting time is obviously reduced, but the cohesiveness test is increased due to the too fast reaction, and the water retention and blocking integrity test are obviously reduced. As further explained in comparative example 6 with reference to FIG. 3, the reaction rate was too fast due to too little retarder, the surface of FIG. 3 was flat, and the swelling agent bubbles were not released to the surface; whereas example 1 corresponds to fig. 2 showing a fine bubble structure within the intumescent material, this structure helps the intumescent material migrate to the fine crevices and tends to achieve better closure integrity.
The retarder in comparative example 7 is more than 1.1-1.6 parts of the limited range of the application, the expansion rate is obviously reduced compared with that of example 1, the initial setting time is obviously reduced, the cement curing speed is slowed down by excessive retarder, the initial setting time is greatly increased, and the excessive retarder reacts with the expansion agent to further cause advanced expansion, so that the water retention property and the plugging integrity are reduced. As further explained in comparative example 7 with reference to fig. 4, in fig. 4, bubbles appear larger than in fig. 2, and the bubbles have penetrated to the surface which further illustrates that excess retarder reacts with the expansion agent to cause premature expansion, whereas cement fails to cure in time under the effect of the retarder, resulting in a large amount of expansion agent to generate gas escape and form escape channels, resulting in reduced water retention and plugging integrity.
In comparative example 8, cement is usually used as retarder citric acid, but the water retention and the blocking integrity are affected due to the fact that cement cannot be cured in time because retarder can not be timely released after expansion of the expanding agent is completed; as further explained in connection with FIG. 5, comparative example 8, where the relatively flat surface of FIG. 5 is partially perforated, may also result in gas escape of the expanding agent and formation of escape channels, resulting in reduced water retention and seal integrity.
From the above, the proportion range of retarder exceeding the limit range of the application can lead to the decrease of water retention and blocking integrity, and is unfavorable for improving the operability, blocking integrity and mechanical property of the product; the traditional retarder and the aluminum powder expansion system are difficult to match in expansion and solidification time, and the water-retaining property and the blocking integrity are reduced.
Further, fig. 6 to 8 show the expansion rate changes of example 1 and experimental examples 1 to 2, showing that the addition of the stabilizer has a passivation effect on the aluminum expanding agent, and delays the reaction of the aluminum expanding agent and water:
fig. 6 shows that the expansion rate change rate of the expansion materials in example 1 and experimental examples 1-2, which respectively contain stabilizers of ethylenediamine tetramethylene phosphonic acid, sodium polyphosphate and polyacrylate XT-1100, is different, but each has a slower growth rate than that of the blank group, various stabilizers have obvious effects of passivating the aluminum powder expansion agent, the ethylenediamine tetraacetic acid with the most obvious effect is selected to further study the reaction rate inhibition effect of the stabilizers on the aluminum powder expansion agent, and fig. 7 shows that the ethylenediamine tetramethylene phosphonic acid has different reaction inhibition effects on aluminum powder with different particle diameters: example 1 and experimental examples 3-5 show that ethylenediamine tetramethylene phosphonic acid has better inhibition effect on 0.10-0.26 μm submicron aluminum powder than 50-90nm nanometer aluminum powder, 0.50-1 μm submicron aluminum powder and 5-50 μm micron aluminum powder, because the aluminum powder with different particle diameters has different surface energy, has different dispersion states in the expansion material, the aggregation and specific surface area of the powder are two competing factors influencing the reaction rate, the aggregation of the aluminum powder reaches the maximum in the 0.10-0.26 μm submicron aluminum powder interval, the specific surface area size is moderate, the stabilizer is easily adsorbed on the aluminum powder surface under the action of surface charge, the PH environment is changed in a small range, the original hydroxide concentration is reduced, and the reaction rate of the aluminum powder and water is inhibited.
Likewise, FIG. 8 shows that the sodium polyphosphate used as a stabilizer for the replacement of example 1 and experimental examples 6-7 also has selectivity on the particle size of aluminum powder particles, and has better inhibition effect on the reaction expansion of 0.10-0.26 mu m submicron aluminum powder and water compared with 50-90nm nanometer aluminum powder and 5-50 mu m micron aluminum powder; this shows that the phosphate, organic phosphonate and polyacrylate substances can inhibit the reaction of aluminum powder and water, and the inhibiting effect has obvious selectivity on the particle size of the aluminum powder expanding agent particles.
The invention is not limited to the above embodiments, and based on the technical solution disclosed in the invention, a person skilled in the art may make some substitutions and modifications to some technical features thereof without creative effort according to the technical content disclosed, and all the substitutions and modifications are within the protection scope of the invention.

Claims (9)

1. The mining hole sealing curing expansion material is characterized by comprising the following raw materials in parts by mass:
97-118 parts of cement, 28-31 parts of fly ash, 56-66 parts of water, 2.9-3.9 parts of expanding agent, 3.8-4.7 parts of stabilizer, 9.5-9.8 parts of lithium sulfate, 0.4-1.3 parts of defoamer, 1.1-1.6 parts of retarder and 1.2-1.9 parts of coupling agent;
wherein the stabilizer is one or more of polyphosphate, organic phosphonate, polyacrylate and polyacrylate copolymer; the expanding agent is aluminum powder, and the aluminum powder is submicron aluminum powder with the particle size of 0.10-0.26 mu m; the retarder is inorganic metal alkali; the cement is silicate PO cement.
2. The mining hole sealing curing intumescent material of claim 1 wherein the inorganic metal base is one or more of sodium hydroxide, potassium hydroxide and calcium hydroxide.
3. The mining hole sealing curing intumescent material of claim 1 wherein the coupling agent is an aluminate coupling agent.
4. A mining hole sealing curing intumescent material as claimed in any one of claims 1 to 3, wherein the stabiliser is one or more of sodium hexametaphosphate, sodium tripolyphosphate, aminotrimethylene phosphonic acid, ethylenediamine tetramethylene phosphonic acid, hydroxyethylidene diphosphonic acid and polyacrylate XT-1100.
5. The mining hole sealing curing expansion material according to any one of claims 1-3, wherein the fly ash has a composition of not more than 10% after sieving with a square-hole sieve having a fineness of 0.045 mm; loss on ignition at 18-25 ℃ is less than or equal to 3%, SO 3 The content is less than or equal to 2 percent, contains waterThe amount is less than or equal to 1%, the water demand ratio is less than or equal to 95%, and the specific surface area>700m²/kg。
6. A mining hole sealing curing intumescent material as claimed in any one of claims 1 to 3, wherein the average particle size of the fly ash is 3 to 6 μm.
7. The mining hole sealing curing expansion material according to claim 1, wherein the compressive strength of the cured expansion material is 63-75KN, the stress peak value is greater than 12.6MPa, and the initial setting time is not less than 17.2min; the time for the expansion rate to reach 80% of the final expansion rate is 10-20min; the cohesiveness test result was 1800-2800 mPa.s.
8. A method for preparing a mining hole sealing curing expansion material, which is characterized by being used for preparing the curing expansion material according to any one of claims 1-7, and comprising the following steps:
uniformly mixing a stabilizer and cellulose into water to obtain a first mixed solution, and uniformly mixing an expanding agent into cement to obtain a second mixed solution;
uniformly stirring the mixture II and part of the mixed solution I according to the weight ratio, and then adding fly ash, retarder, coupling agent and lithium sulfate according to the given weight ratio;
and adding the defoaming agent and the rest mixed solution I, uniformly stirring, standing, and then uniformly stirring and discharging to obtain the cured expansion material.
9. The preparation method according to claim 8, wherein the raw materials comprise the following components: 97-118 parts of cement, 28-31 parts of fly ash, 56-66 parts of water, 2.9-3.9 parts of expanding agent, 3.6-4.1 parts of cellulose, 0.4-1.3 parts of defoamer, 1.1-1.6 parts of retarder, 1.2-1.9 parts of coupling agent and 3.8-4.7 parts of stabilizer; adding 4-6 parts of first mixed solution; 57.4-70.8 parts of mixed liquor is added for the second time.
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