CN114644495A - Mining hole sealing curing expansion material and preparation method thereof - Google Patents
Mining hole sealing curing expansion material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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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
- 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
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- 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
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- 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
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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/50—Defoamers, air detrainers
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- 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
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- 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
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- 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
Abstract
The invention relates to the technical field of mining hole sealing materials, in particular to a mining hole sealing curing expansion material and a preparation method thereof, wherein the mining hole sealing curing expansion material 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 an expanding agent and 3.8-4.7 parts of a stabilizing agent; the stabilizer is acid or acid salt; the expansion agent selects submicron aluminum powder with the particle size of 0.10-0.26 mu m, can more easily enter the micro-gap of the drilled hole to achieve better plugging effect, and fills the gaps between cement particles and fly ash particles and between fly ash particles; meanwhile, the added retarder and the aluminum powder expansion system are cooperatively used, the initial setting time of the expansion material is longer than 80% of the time for reaching the final expansion rate, and no through air hole is formed on the surface of the material, so that the problems of overlong curing time and unmatched curing and expansion time of the mine hole sealing material are solved; the stabilizer can inhibit the retarder or the water and the expanding agent from reacting too fast to generate gas, so that the expansion time and the curing time are better matched, and the stability of the expanding agent in a high-humidity environment is greatly improved.
Description
Technical Field
The invention relates to the technical field of mining hole sealing materials, in particular to a mining hole sealing curing expansion material and a preparation method thereof.
Background
The gas extraction and most of gas treatment measures are realized by drilling, and the drilling and hole sealing quality directly influences the exertion of the drilling energy efficiency. In the process of gas extraction from a drill hole, the quality of the drill hole sealing affects the concentration of the extraction, and the negative pressure of the extraction from an orifice is the key for determining the extraction. The cement-based hole sealing material is the hole sealing material which has the largest coal mine usage amount and is most widely applied in China at present: the cement clinker is mixed with water to form flowing cement slurry (cement mortar), and the slurry is injected into the drill hole by using an injection pump. The cement hole sealing is low in cost, wide in raw material source, easy to operate and large in hole sealing depth. The expansion of the ordinary expansive cement hole sealing material is greatly influenced by temperature and humidity, the stability is poor, the curing time and the expansion time are difficult to match, and the following defects exist: the curing time is long, the early strength is low, the shrinkage is easy to generate cracks, and the impact resistance is poor under the underground high-humidity environment, so that the modified polyurethane needs to be further modified.
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 supplements and perfects the defects of various hole sealing materials, has good material fluidity, can effectively seal the cracks around a drill hole, adds an optimized stabilizer aiming at the expansion agent, has stable expansibility of the expansion agent during curing, is slightly influenced by temperature and humidity, and always maintains better curing and expansion time matching degree; the material has expansibility, improves the defect that common cement is easy to shrink after being cured, has good early strength, and can form effective support for a drilling sealing section after being cured; thereby greatly improving the bearing capacity and the service performance of the integral structural member of the drill hole and the universal plugging property for various drill holes; in addition, the cured expansion material can improve the durability of the structure, and has good working performance, high volume stability and economy; simultaneously, the optimized early strength agent is added to improve the early strength of the cured expansion material; and simultaneously, the synergistic effect of the retarder system and the aluminum powder expanding agent is optimized, so that the expansion time is well matched with the curing time of the cured expansion material.
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 an expanding agent and 3.8-4.7 parts of a stabilizing agent.
The stabilizer is one or more of polyphosphate, organic phosphonate, polyacrylate and polyacrylate copolymer, and is further preferably one or more of sodium hexametaphosphate, sodium tripolyphosphate, amino trimethylene phosphonic acid, ethylene diamine tetramethylene phosphonic acid, hydroxy ethylidene diphosphonic acid and polyacrylate XT-1100; the expansion material slurry has a stable anti-delamination effect, and simultaneously can selectively improve the stability of the aluminum powder expanding agent and delay the expansion reaction, and further, the preferable submicron aluminum powder expanding agent with the particle size of 0.10-0.26 mu m is most sensitive to the stabilizing agent and has the lowest reaction rate and the lowest reaction delay phenomenon.
Compared with the traditional hole sealing material, the coal ash is added, and the high-quality I-grade extra-fine coal ash produced by a power plant with an advanced coal burning process is adopted; the quality of the material is not lower than the requirements of the national standard GB/T1596-plus 2005 and other related standards, the fineness of the material is 0.045mm, the screen residue of square holes is not more than 10 percent, the ignition loss is not more than 3 percent, and the SO content is not more than3The content is not more than 2 percent, the water content is not more than 1 percent, the water demand ratio is not more than 95 percent, and the specific surface area is more than 700m2/kg。
Preferably, the fly ash has an average particle size of 3 to 6 μm.
Further, the preferred expanding 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 solidified expanding material, 9.5 to 9.8 parts of lithium sulfate is added into the solidified expanding material. Further, in order to reduce the amount of bubbles in the solidified expansion material and improve the sealing effect, 0.4-1.3 parts of defoaming agent is also added into the solidified expansion material; the defoaming agent is preferably a powder defoaming agent; the powder antifoaming agent is preferably a polyether alcohol ester antifoaming agent.
Furthermore, in order to prevent the cured expansion material from being cured and condensed prematurely and reduce the sealing effect on the microcracks around the drill hole, 1.1 to 1.6 parts of retarder is also added into the cured expansion material; the retarder is preferably an inorganic metal base, and is further preferably one or more of sodium hydroxide, potassium hydroxide and calcium hydroxide. The retarder can inhibit the formation of calcium silicate precipitates at the early stage so as to inhibit the over-rapid crystallization of cement, the retarder is consumed along with the expansion of aluminum powder in the expanding agent, so that the consumption of the retarder is caused, the retarding inhibition effect on the cement is eliminated, and the cement is smoothly solidified. The delayed coagulation system needs to be used in cooperation with the expansion system, the curing time of the expansion material is controlled after the expansion material smoothly expands or the expansion material completes more than 80% of expansion, and the surface of the material has no through air holes, so that the poor sealing effect of micro cracks around the drilled hole caused by incomplete expansion is avoided.
Furthermore, in order to improve the affinity of cement, fly ash filler, expanding agent and the like with substances such as defoaming agent and the like in the cured expansion material and further improve the mechanical property of the system, 1.2-1.9 parts of coupling agent is added in the cured expansion material, preferably, the coupling agent is aluminate coupling agent, compared with common coupling agent, the coupling agent can be rapidly decomposed with water to generate a mixed system containing aluminum hydroxide and an organic component system, silane coupling agent and the like are hydrolyzed to generate a silicic acid group and a plurality of organic groups, and the aluminate coupling agent has more inorganic phases and is more suitable for the expansion material system with the dominant inorganic filler than common silane coupling agent and the like.
After the solidified expansion material is solidified, the solidified expansion material has the compressive strength of 63-75KN, the stress peak value is 12.6MPa, and the initial setting time is not less than 17.2 min; the time for the expansion rate to reach 80 percent of the final expansion rate is 10-20 min; the result of the cohesiveness test was 1800 and 2800 mPas.
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 mixing a stabilizer into water to obtain a first mixed solution, and uniformly mixing an expanding agent into cement to obtain a second mixture;
uniformly stirring the mixture II and part of the mixed solution I according to the weight ratio, and then adding the fly ash, the retarder, the coupling agent and the lithium sulfate according to the given weight ratio;
and adding the defoaming agent and the residual mixed solution I, uniformly stirring, standing, then uniformly stirring, and discharging to obtain the cured expansion material.
Preferably, the raw materials comprise: 97-118 parts of cement, 28-31 parts of fly ash, 56-66 parts of water, 2.9-3.9 parts of an expanding agent, 0.4-1.3 parts of a defoaming agent, 1.1-1.6 parts of a retarder, 1.2-1.9 parts of a coupling agent and 3.8-4.7 parts of a stabilizer; in order to further improve the mixing uniformity and improve the strength and the sealing integrity of the solidified expanding material, 4-6 parts of first mixed liquid are added for the first time; and adding 57.4-70.8 parts of the mixed solution for the second time.
Has the advantages that:
1. in order to improve the bulk strength of the expansion material, an active mineral admixture (superfine fly ash) is added, an equivalent substitution method is adopted to replace part of cement, the volcanic ash reaction, the enhancement effect, the filling effect and the durability improvement effect of the expanding agent, the fly ash and the like are utilized, and the super superposition effect generated by the composite admixture of the expanding agent, the fly ash and the like and the composite admixture of the expanding agent, the fly ash and the high-efficiency coupling agent is fully utilized. The particle grading of the cementing material part in the solidified expanding material is optimized according to the characteristic that the particle sizes of the cementing material part and the cement particles are not in the same grade, the fly ash can fill the pores among the cement particles, so that the interface structure between the material and the pore structure of the set cement are both greatly improved, the density and the impermeability of the set cement are improved, and meanwhile, the typical compact structure can be expanded to the surface of an aggregate, so that the whole material is more compact and hard, and the mechanical property (especially the bonding property between the material and a drilling hole wall), the durability and the working performance of the material are all greatly improved.
2. Submicron aluminum powder is selected as an active metal ion efficient expanding agent, the addition of the aluminum powder can prevent or reduce the hydration of a solidified expanding material, compensate volume shrinkage cracking caused by chemical reaction, physical reaction and thermodynamic reaction in hardening, and can fill and block various capillary gaps to enable the internal structure of the material to be more compact, so that the cracking resistance and the seepage resistance of the material are greatly improved, and the compactness and the strength of the material are further improved; the shrinkage performance of the common 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, the seepage resistance, the compactness, the strength and the volume stability of the material are improved.
3. In order to improve the matching degree of the curing time and the expansion time of the expansion material, an expansion-retarding system of aluminum powder and inorganic metal alkali is adopted, the retarder can inhibit the formation of calcium silicate precipitate in the early stage so as to inhibit the over-rapid crystallization of the cement, and the aluminum powder expands in the expanding agent and simultaneously consumes sodium hydroxide, so that the sodium hydroxide is consumed, the retarding inhibition effect on the cement is eliminated, and the cement is smoothly solidified; the slow setting system needs to be used in cooperation with the aluminum powder expansion system, the curing time of the expansion material is controlled to be after the expansion material smoothly expands or the expansion material completes more than 80% of expansion, and no through air hole exists on the surface of the material, so that the problem that the micro-crack sealing effect on the periphery of a drill hole is poor due to incomplete expansion is avoided, and the problems that the curing time of the mining hole sealing material is long and the curing time and the expansion time are not matched are solved.
4. Phosphate, organic phosphonate and polyacrylate are added as stabilizers to passivate the aluminum expanding agent, the stabilizers are easily adsorbed on the surface of the 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 inhibited, so that the reaction with the water is delayed; furthermore, the stabilizer has selectivity on the particle size of aluminum powder particles, has a better inhibiting effect on 0.10-0.26 mu m submicron aluminum powder, can be used as a regulator for regulating the expansion rate, improves the matching degree of the expansion rate and the curing rate, and improves the sealing integrity.
5. Because the fluidity, cohesiveness and water-retaining property of the solidified expanding material can be solidified by adding a proper amount of fly ash, 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 solidified expanding material can be obviously improved by adding a proper amount of lithium sulfate; on the one hand, SO in lithium sulfate4 2-With cement hydration products Ca (OH)2The calcium sulfate with high dispersity is generated through reaction, lithium ions are beneficial to controlling the appearance, and the calcium sulfate is easier to react with a cement component, namely the aluminateThe calcium reacts to generate needle-shaped, rod-shaped and hollow tubular calcium sailstone crystals, and an early frame structure for the strength development of the set cement is formed; SO on the other hand4 2-Consumption C3S、C2Ca (OH) produced by hydration of S2Promoting C3S、C2Hydrating the S; the common use of the fly ash and the lithium sulfate can improve the integral compactness of the expansion material, thereby improving the bonding property between the material and the wall of a drilled hole.
6. The invention is preferably selected from an aluminate coupling agent, and compared with a common silane coupling agent and the like, the aluminate coupling agent can be rapidly decomposed in water to generate a mixed system containing aluminum hydroxide and an organic component system when in use, has more inorganic phases and is more suitable for a curing expansion material system with the dominant inorganic filler.
7. According to the invention, the polyether alcohol ester defoaming agent is selected and used, so that a large amount of micro bubbles which are formed in the material stirring process and are still remained in the material after being vibrated to be compact can be defoamed, the compactness of the material is effectively improved, the phenomenon that the inner holes of the material are communicated with each other under the action of mining stress and ground stress to form cracks to cause drilling air leakage is avoided, and the durability and the shear stability of the material are enhanced.
8. The raw materials of the solidified expansion material contain a large amount of fly ash, active metal ions and inorganic non-metal alkaline ions, which are industrial waste materials, the consumption of which can make great contribution to environmental protection, and the solidified expansion material meets the requirements of sustainable development, is a green material and is an environment-friendly material; meanwhile, the method for reducing the flying and feeding of cement particles, additive particles and ultrafine active mineral particles all over during material stirring is realized, the preparation process is simple and easy to realize, the method is suitable for engineering and industrialization, is convenient for large-scale popularization and application, realizes the utilization of fly ash waste, and has better social benefit.
Drawings
FIG. 1 shows the axial stress-strain curves of the test specimens of example 1 and comparative examples 1 to 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 photograph of comparative example 7;
FIG. 5 shows an SEM image of comparative example 8;
FIG. 6 shows the results of the cohesiveness tests of the blank group, example 1 and Experimental examples 1-2;
FIG. 7 shows the swelling-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 content of the invention will now be discussed with reference to a number of exemplary embodiments. It is to be understood that these examples are discussed only to enable those of ordinary skill in the art to better understand and thus implement the teachings of the present invention, and are not meant to imply any limitations on the scope of the invention.
As used herein, the term "include" and its variants are to be read as open-ended terms meaning "including, but not limited to. The term "based on" is to be read as "based, at least in part, on". The terms "one embodiment" and "an embodiment" are to be read as "at least one embodiment". The term "another embodiment" is to be read as "at least one other embodiment".
The invention relates to a mining solidification expansion material, which adopts similar materials-cement and water as common cement hole sealing materials, and also adds the indispensable components: retarder, coupling agent, stabilizer, high-efficiency expanding agent, fly ash and the like (aluminum powder and fly ash), and powder defoaming agent is also added. Compared with common cement hole sealing materials, the mining curing expansion material has the advantages that the strength and the performance are improved in different ranges compared with the common cement materials. By adding the superfine active mineral doped materials, the particle grading of the cementing material part in the solidified expanded material is optimized by utilizing the volcanic ash reaction, (micro) filling effect and plasticizing effect of the superfine active mineral doped materials, so that the interface structure hole structure between the solidified expanded materials is greatly improved, the density and the impermeability of the set cement are improved, and meanwhile, a typical compact structure can be expanded to the surface of the material, so that the solidified expanded material is more compact and hard, and the mechanical property (especially the adhesive property between the solidified expanded material and a drilling hole wall) and the durability of the solidified expanded 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 solidified expanded material and remain in the cement paste in the material or in an interface transition region after being vibrated to be dense can be reduced for defoaming, so that the compactness of the solidified expanded material is effectively improved, and the mechanical property (including the adhesive property with a drilling wall) and the durability of the solidified expanded material are improved. In addition, by adding the expanding agent, the material has certain expansibility, the shrinkage performance of the common cement material is improved, the volume shrinkage cracking generated by the hardening reaction of the material can be compensated, various capillary gaps in the material can be filled and blocked, and the overall anti-cracking and anti-seepage performance, compactness, strength and volume stability of the material are improved; the activity of the fly ash can be enhanced, the power of the forward hydration reaction is improved, and the strength of the prepared curing expansion material is obviously improved; the addition of the retarder prolongs the curing time of the cured expansion material, and is beneficial to the penetration of slurry into cracks around the drill hole under the action of grouting pressure at the initial stage to plug coal and rock mass around the drill hole, so that the stability and the sealing property of the whole structure of the drill hole are improved, and meanwhile, the aluminum powder expanding agent reacts with the retarder, the inhibition of the retarder on the curing of the material is gradually released while the material is expanded, so that the curing time is well matched with the expansion time.
The invention aims to solve the key technical problems that the curing time and the expansion time of a curing expansion material are matched, the expansion time of an expansion agent system is stable, and particularly, a retarder is preferably inorganic metal alkali in a high-temperature high-humidity environment; soluble inorganic metal alkali such as sodium hydroxide, potassium hydroxide, calcium hydroxide and the like is further preferably selected, and can react with the aluminum powder expanding agent, the retarder is consumed while the aluminum powder expands, and the curing inhibition is gradually released, so that the curing time and the expansion time can be matched; one or more of polyphosphate, organic phosphonate, polyacrylate and polyacrylate copolymer are adopted, and preferably one or more of sodium hexametaphosphate, sodium tripolyphosphate, amino trimethylene phosphonic acid, ethylene diamine tetramethylene phosphonic acid, hydroxy ethylidene diphosphonic acid and polyacrylate XT-1100 is further adopted, the stabilizer can inhibit gas generation and expansion in the early stage of reaction of the expanding agent and the retarder or water, and the problems of over-quick expansion time and unmatched expansion time are avoided; and simultaneously improves the stability of the expanding agent in a high-humidity environment.
When the raw materials are selected, the prepared curing 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 the coarse and fine grains are well filled with each other, and the void ratio in the material is reduced; meanwhile, the average particle size of the cement is generally 20 to 30 μm, and the number of particles smaller than 10 μm is not large. The particle diameters of the expanding agent, the fly ash and the like are far smaller than those of cement particles, the average particle diameter of the ultrafine fly ash is 3-6 microns, gaps among the cement particles can be filled, the average particle diameter of the submicron aluminum powder is also very small and is 0.10-0.26 micron, and the gaps among the cement particles and the ultrafine fly ash particles, the gaps among the ultrafine fly ash particles and fine gaps or gaps among the gel particles and the interface structures can be filled, so that the prepared curing and expanding material is also vital to optimizing the particle grading of the gel material part. The addition of expanding agent and flyash can reduce the porosity between cement grains and interface, make the cement stone structure and interface structure more compact, block the possible formed permeation path, raise the impermeability of the prepared cured expanding material greatly, and raise the permeability of water and other corrosive medium (Cl)-、SO4 2-、CO2Etc.) are difficult to enter the interior of the material, and the probability of alkali-silicon reaction and the probability of calcium hypochlorite generation can be reduced, and the strength and durability of the material are greatly improved. That is, when the content of macropores larger than 0.1 μm in the cement structure and the interface structure is low, the improvement of various properties of the prepared cured and expanded material is facilitated, otherwise, the strength, the impermeability, the corrosion resistance and the durability of the prepared cured and expanded material are not good.
After the cement is partially replaced by the expanding agent, the fly ash and the like, part of water in the gaps of cement particles can be replaced by the mineral admixture filled in the cement particles, and the cohesiveness (viscosity) of the cement paste can be reduced and the fluidity of the cement paste can be increased. In order to ensure the high working performance of the developed solidified expanding material, the invention adopts a method of compounding and doping retarder, expanding agent, fly ash and the like, under the cooperative work of the retarder, the expanding agent and the fly ash, the fine particles of the active mineral admixture not only fully exert the (micro) filling effect of the active mineral admixture, but also displace the water filled in the gaps, so that the water layer at intervals among the particles is thickened; in addition, the material molecules are adsorbed by the fine particles of the expanding agent, the fly ash and the like, and the electrostatic repulsion generated by the electric double layer potential formed on the surface of the material molecules is larger than the universal attraction among the powder particles, so that the powder particles are dispersed, the dispersion of the cement particles is further intensified, the fluidity of the cement paste is increased, and the fluidity of the mixture is effectively improved; meanwhile, the compound 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 coal seams have different depths, the coal seams at various depth stages have different pressures due to the dead weight stress of overlying strata and other complex stress conditions around the overlying strata, and the drill holes at different depths bear different pressures, so that the expansion material under different strengths is researched and developed to be suitable for the coal seams at different burial depths, and the performance of the material is exerted to the maximum extent while the requirement of hole sealing is met. According to the strength characteristics and the material characteristics of the solidified expansion material, the solidified expansion material is suitable for coal beds with the burial depth of 0-500m, the drill holes are effectively supported in the range, and if the stress borne by the drill holes is larger in the range, the proportion of each component in the solidified expansion material can be properly adjusted to plug the drill holes.
The following specific examples are given to further illustrate the invention:
(I) raw Material
1. Cement
The PO cement (ordinary portland cement) with stable quality is selected, the performance index of the selected cement meets the requirements of the national current relevant standard, and the PO cement has low alkali content, low hydration heat and low water requirement.
2. Fly ash
High-quality I-grade superfine fly ash produced by a power plant with an advanced coal-fired process is adopted. The quality of the product meets the national standard of' useThe specified requirements of related standards such as fly ash in cement and concrete GB/T1596-3The content is 1.2-1.9%, the water demand ratio is less than 95%, and the specific surface area is about 1000m2/kg。
3. Expanding agent
The quality of the submicron aluminum powder meets the requirements of the national standard GB/T18736-. The specific surface area of the submicron aluminum powder is about 27000m2/kg。
Through a large number of trial comparative tests and cement compatibility tests, the expanding agent selected by the invention is 0.1-0.26 mu m submicron aluminum powder, the quality of the expanding agent meets the requirements of the related standards of the national standard of concrete expanding agent GB 23439-2Kg, limiting expansion (7 days in water) not less than 0.05%. Unless otherwise specified, the aluminum swelling agents described herein all refer to submicron aluminum powders of 0.1-0.26 μm; the expanding agent can be aluminum powder with different grain diameters or a combination of aluminum powder with different grain diameters.
4. Lithium sulfate
The lithium sulfate has a coordination effect with organic components, and has an effect of promoting early hydration of cement, and the specific reasons are as follows: on the one hand SO4 2-With cement hydration products Ca (OH)2The calcium sulfate with high dispersity is generated through reaction, and is easier to react with tricalcium aluminate which is a cement component to generate needle-shaped, rod-shaped and hollow tubular calcium sailstone crystals compared with the added calcium sulfate, so that an early frame structure for the strength development of the cement stone is formed; SO on the other hand4 2-Consumption C3S、C2Ca (OH) produced by hydration of S2Promoting C3S、C2And (4) hydrating the S.
5. Coupling agent
The coupling agent is a plastic additive for improving the interfacial properties of inorganic fillers or reinforcing materials, and is generally used in an amount of 0.5% to 2%. The coupling agent is generally an aluminate coupling agent, the organophilic groups are capable of reacting with the inorganic filler or reinforcing material, and the organophilic groups are capable of reacting with the organic component.
6. Stabilizer
The stabilizer is selected from one or more of polyphosphate, organic phosphonate, polyacrylate and polyacrylate copolymer, and is preferably one or more of sodium hexametaphosphate, sodium tripolyphosphate, amino trimethylene phosphonic acid, ethylene diamine tetramethylene phosphonic acid, hydroxy ethylidene diphosphonic acid and polyacrylate XT-1100.
7. Mixing water
Tap water is selected as mixing water, the quality of the mixing water meets the requirements of the relevant standards of national construction institute standard concrete mixing water standard JGJ 63-2006, and the alkali content is less than 800 mg/L.
8. Defoaming agent
The defoaming agent is preferably a powder defoaming agent; in particular to a polyether alcohol ester defoaming agent and white powder with the PH value of-5 to 8.
(II) mixing ratio
The formulation of examples 1-3 provided by the invention for a cured expansion material to be used in hole sealing in mines is shown in table 1, wherein the retarder in example 1 is sodium hydroxide, and the stabilizer is ethylenediamine tetramethylene phosphonic acid; example 2 the retarder was potassium hydroxide and the stabilizer was sodium hexametaphosphate; the retarder of the embodiment 3 is a mixture of sodium hydroxide and potassium hydroxide, and the stabilizer is polyacrylate XT-1100; PO32.5R, PO42.5R and PO52.5R represent different strength grades of cement.
TABLE 1 mixing ratio (parts by mass) of the curing expansion material for mine sealing
To further verify the optimization rationality of the formula of the invention, comparative examples 1-8 were set:
comparative example 1 the proportion of sub-micron aluminum powder in the expanding agent is higher than the mass range defined herein, the total amount of the expanding agent is still 2.9 parts by mass, and the amounts of the other components are the same as those in example 1; comparative example 2 the proportion of submicron aluminum powder in the expanding agent is lower than the range defined herein, the total amount of the expanding agent is still 2.9 parts by mass, and the amounts of the other components are the same as those in example 1; comparative examples 1 and 2 are used to demonstrate the adverse effects of submicron aluminum powder usage outside the ranges set forth herein;
comparative example 3 adopts 10-100um aluminum powder in the prior art as the expanding agent, the total amount of the expanding agent is still 2.9 parts by mass, and the use amounts of the other components are the same as those in example 1, so that the adverse effect caused by exceeding the particle size composition range of the aluminum powder set in the application is proved by comparison with the example 1 in the application;
comparative example 4 the amount of stabilizer used is below the mass range defined herein, the stabilizer type is the same as in example 1, and the remaining components are used in the same amounts as in example 1; comparative example 5 the amount of stabilizer is higher than the range defined herein, the type of stabilizer is the same as in example 1, and the other components are used in the same amounts as in example 1; comparative examples 4 and 5 are intended to demonstrate the adverse effects of stabilizer levels outside the ranges set forth herein;
comparative example 6 the retarder type was the same as example 1, the remaining components were the same as example 1, the amount of retarder was below the mass range defined herein; comparative example 7 the retarder type was the same as example 1, and the other components were used in the same amounts as in example 1; comparative examples 4 and 5 are used to demonstrate the adverse effects of retarder use levels outside the ranges set forth herein;
comparative example 8 adopts a common citric acid retarder, the dosage of the retarder is the same as that of example 1, and the dosages of the other components are the same as that of example 1; used to compare the retarder effect with example 1.
In order to further influence the selection of commonly used stabilizers on the expansibility of the intumescent materials, blanks 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 replaced with the same amount of the stabilizer of example 1, and the remainder was the same as in example 1; experimental example 2 stabilizer replacement of equivalent amount of stabilizer with example 1 stabilizer sodium polyphosphate replaced equivalent amount of stabilizer with example 1, the remainder of example 1, and the remainder of example 1.
To further illustrate the effect of the swelling rate of the aluminum powder swelling agent of different particle sizes of the stabilizer, a further preferred test was conducted on any of the systems of examples 1-3 above, and for the purpose of illustration, the applicant set experimental examples 3-5, taking the system of example 1 as an example:
experimental example 3 the swelling agent is 50-90nm nano aluminum powder, and the rest is the same as the example 1; experimental example 4 the swelling agent was 0.50-1 μm submicron aluminum powder, and the rest is the same as in example 1; experimental example 5 the swelling agent is 5-50 μm micrometer aluminum powder, and the rest is the same as example 1; experimental example 6 the stabilizer is sodium polyphosphate, the swelling agent is submicron aluminum powder with 0.50-1 μm, and the rest is the same as in example 1; experimental example 7 the stabilizer is sodium polyphosphate, the swelling agent is 5-50 μm micrometer aluminum powder, and the rest is the same as example 1.
TABLE 2 EXAMPLES 1 to 7 compounding ratios (parts by mass)
(III) stirring process
The invention adopts an improved concrete stirring process, which comprises the following specific process steps:
the invention adopts an improved concrete stirring process during preparation, the concrete is stirred in a forced stirrer, and the feeding sequence is as follows:
uniformly mixing a stabilizer into water to obtain a first mixed solution, and uniformly mixing an expanding agent into cement to obtain a second mixture;
uniformly stirring the mixture II and part of the mixed solution I according to the weight ratio, and then adding the fly ash, the retarder, the coupling agent and the lithium sulfate according to the given weight ratio;
and adding the defoaming agent and the residual mixed solution I, uniformly stirring, standing, then uniformly stirring, and discharging to obtain the cured expansion material.
Preferably, the raw materials comprise: 97-118 parts of cement, 28-31 parts of fly ash, 56-66 parts of water, 2.9-3.9 parts of an expanding agent, 0.4-1.3 parts of a defoaming agent, 1.1-1.6 parts of a retarder, 1.2-1.9 parts of a coupling agent and 3.8-4.7 parts of a stabilizer; in order to further improve the mixing uniformity and improve the strength and the sealing integrity of the solidified expanding material, 4-6 parts of first mixed liquid are added for the first time; and adding 57.4-70.8 parts of the mixed solution for the second time.
The process can reduce the cement particles, the additive particles and the superfine active mineral particles from flying everywhere during the material stirring as much as possible, can improve the strength of the prepared material, and the prepared material is not easy to separate, has less bleeding and relatively good working performance.
(IV) test method
Cohesiveness test: GB/T10247-1988 viscosity test method.
And (3) mechanical testing: GB/T50266-99 engineering rock mass test method standard.
Testing the water retention: the change in the water content of the material before and after the absorption of water by the filter paper was measured by testing the water retention performance by the filter paper method in accordance with DIN 18555-7.
And (3) testing the fluidity: GB/T1346.
And (3) detecting the integrity of the plugging hole: and (3) performing negative pressure pumping test on horizontal grouting holes with the stress coefficient of 0.6 and the diameters of 1mm, 5mm and 10mm 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 material is mixed with water according to the mass ratio of the material to the water of 2: 1, the mixture is stirred and then is kept stand, initial setting is carried out when the slurry is inclined at 45 degrees and does not flow, and the time from the end of stirring to the initial setting generation process is the initial setting time. Unless otherwise stated, the curing times described herein are all initial setting times.
Expansion ratio test method: preparation of V0Volume V of test sample after curing of voluminous slurry of intumescent material for a number of times1、V2.......Vn(ii) a Expansion ratio etanIs (V)n-V0)/V0To facilitate the calculation of V01L is often selected in experiments; the final expansion ratio test method comprises the following steps: the change of the expansion ratio is less than 1 percent in three consecutive tests, namely (eta)n+1-ηn)/ηnAnd (η)n+2-ηn+1)/ηn+1Are all less than 1%,. etanThe final expansion ratio.
(V) test results
The comparative performance test results of the mining hole sealing curing expansion material prepared according to the mixing ratio are shown in table 3.
TABLE 3 cured intumescent materials examples 1-3 and comparative examples 1-3 Performance comparative test results
As can be seen from comparison of Table 3, in comparative example 1, the submicron aluminum powder is smaller than the range limited by the application, the expansion rate is reduced, the initial setting time is increased, but the compressive strength and the stress peak value are reduced, the water retention property is tested and reduced to some extent, the integrity of the plugging hole is detected unchanged, the cohesiveness test and the fluidity test are obviously reduced, because the submicron particles are matched with the gaps between the fly ash particles and the cement, the reduction of the using amount directly causes the reduction of the cohesiveness test, and meanwhile, because the aluminum powder is reduced, the consumption retarder has a slower speed, which is beneficial to increasing the initial setting time, the expansion rate is reduced, and the incomplete expansion causes the reduction of the water retention property.
In the comparative example 2, the submicron aluminum powder is larger than the range limited by the application, but the compressive strength and the stress peak value are higher, the water retention test and the initial setting time are reduced, the detection of the integrity of the plugging hole 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 cement particles, the cohesiveness test is directly reduced due to the increased proportion, the expansion rate is increased, the content of macropores with the diameter of more than 0.1 mu m in a matchability-degraded cement stone structure and an interface structure is higher, the plugging structure is incomplete due to the too fast expansion rate, the improvement of various properties such as the plugging integrity of the prepared curing expansion material is not facilitated, and the mechanical property and the water retention property are reduced.
From the above, when the proportion range of the submicron aluminum powder exceeds the range defined by the application, the mechanical property, the water retention property, the cohesiveness and the initial setting time are reduced, and the operability, the blocking property and the mechanical property of the product are not improved.
And in the comparative example 3, the aluminum powder with the particle size of 10-100um in the prior art is selected to replace the expanding agent system, the specific surface area is small, the reactivity is poor, the expansion rate is obviously lower than that of the example 1, and meanwhile, the consumption rate of the aluminum powder to the retarder is far lower than that of the example 1, so that the initial setting time is far longer than that of the scheme of the example 1. As can be seen from the above, the aluminum powder with the particle size of 10-100um is adopted to replace the scheme of the expanding agent system, and the operability and the plugging integrity of the product are far inferior to those of the product in the embodiment 1 of the scheme.
FIG. 1 shows the axial stress-strain curves of the samples of example 1 and comparative examples 1-3, wherein the gradient of the stress along with the change of the strain of example 1 is the largest and the stress peak value is the largest, which shows that example 1 has stronger rigidity and the maximum bearing capacity of the strength after curing is strongest. Watch (A)
Table 4 cured intumescent materials comparative examples 4-5 comparative performance test results
As can be seen from comparison of Table 4, in comparative example 4, the amount of EDTA is less than the range of 3.8-4.7 parts, the swelling rate is significantly reduced and the initial setting time is significantly reduced compared with that of example 1, but the reaction is too fast, which results in an increase in the cohesiveness test and a significant decrease in both the water retention and the plugging integrity test. In the comparative example 5, the weight of the ethylenediamine tetramethylene phosphonic acid is 3.8-4.7 parts larger than the limited range of the application, the expansion rate is obviously reduced and the initial setting time is obviously increased compared with the example 1, because the ethylenediamine tetramethylene phosphonic acid and the aluminum powder serving as the expanding agent are easy to adsorb the stabilizing agent on the surface of the aluminum powder under the action of surface charges, the pH environment is changed in a small range, the original hydroxyl concentration is reduced, the reaction rate of the aluminum powder and water is further inhibited, the competitive action is realized with the reaction of the retarder and the aluminum powder, the too fast reaction of the retarder and the aluminum powder can be inhibited, so that the cement component of the expanding agent is cured too fast, the retarding effect of the retarder is longer, and the stability of the aluminum powder expanding agent is improved.
From the above, the proportion range of the stabilizer beyond the range defined in the present application may result in the decrease of mechanical properties, water retention, plugging integrity and cohesiveness, and is not favorable for the improvement of product operability, plugging integrity and mechanical properties.
TABLE 5 cured intumescent materials comparative examples 6-8 Performance comparative test results
As can be seen from comparison of Table 5, the amount of the retarder in comparative example 6 is less than the range of 1.1-1.6 parts defined in the present application, the expansion rate is significantly reduced and the initial setting time is significantly reduced compared with that in example 1, but the reaction is too fast, so that the cohesiveness test is increased, and the water retention and plugging integrity test are both significantly reduced. As further explained with reference to comparative example 6 in FIG. 3, the reaction rate is too fast due to too little retarder, the surface is flat in FIG. 3, and the air bubbles of the expanding agent are not released to the surface in time; while example 1 corresponds to figure 2, which shows that the interior of the intumescent material has a fine bubble structure, this structure helps the intumescent material to migrate to a fine gap, tending to achieve better closure integrity.
In comparative example 7, the amount of the retarder is 1.1 to 1.6 parts greater than the range defined in the application, the expansion rate is obviously reduced and the initial setting time is obviously reduced compared with example 1, because the excessive retarder slows down the cement curing speed, the initial setting time is greatly increased, and the excessive retarder reacts with the expanding agent to cause early expansion, so that the water retention property and the plugging integrity are reduced. As further explained with reference to fig. 4 and comparative example 7, in fig. 4, larger bubbles appear than in fig. 2, and the bubbles have penetrated to the surface, which further illustrates that excessive retarder reacts with the expanding agent to cause premature expansion, and the cement fails to solidify in time under the action of the retarder, resulting in a large amount of expanding agent to generate gas to escape and form escape channels, resulting in reduced water retention and plugging integrity.
In the comparative example 8, the common cement retarder citric acid is adopted, but the retardation cannot be timely relieved after the expansion of the expanding agent is finished, so that the cement cannot be timely cured, and the water retention and the plugging integrity are influenced; as further explained with reference to fig. 5 and comparative example 8, the relatively flat surface in fig. 5 with the partially penetrating bubbles can also cause the swelling agent to generate gas to escape and form escape channels, resulting in reduced water retention and plugging integrity.
Therefore, when the proportion range of the retarder exceeds the range limited by the application, the water retention property and the plugging integrity are reduced, and the operability, the plugging integrity and the mechanical property of the product are not improved; traditional retarder and this application aluminium powder expansion system are difficult in order to match in inflation and curing time, have reduced water retention and shutoff integrality.
Further, FIGS. 6 to 8 show the change of the swelling ratio of example 1 and experimental examples 1 to 2, and show that the addition of the stabilizer has a passivating effect on the aluminum swelling agent, and delays the reaction of the aluminum swelling agent with water:
fig. 6 shows that the expansion rate change rates of the expansion materials in example 1 and experimental example 1-2, which respectively contain the stabilizers of ethylenediamine tetramethylene phosphonic acid, sodium polyphosphate and polyacrylate XT-1100, are different, but have a much slower growth rate than that of the blank group, and show that various stabilizers have obvious functions of passivating the aluminum powder expansion agent, the reaction rate inhibition effect of the stabilizers on the aluminum powder expansion agent is further researched by selecting ethylenediamine tetraacetic acid with the most obvious effect, and fig. 7 shows that the ethylenediamine tetramethylene phosphonic acid has different reaction inhibition effects on aluminum powders with different particle sizes: example 1 and experimental examples 3-5 show that ethylenediaminetetramethylenephosphonic 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, and the reason is that the aluminum powder has different surface energy and different dispersion states in the expansion material due to different particle diameters, the aggregation property and the specific surface area of the powder are two competitive factors influencing the reaction rate, the aggregation property of the aluminum powder is the largest in the 0.10-0.26 μm submicron aluminum powder range, the size of the specific surface area is moderate, the stabilizer is easily adsorbed on the surface of the aluminum powder 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.
Similarly, the attached figure 8 shows that the sodium polyphosphate used as the stabilizer in the example 1 and the experimental examples 6 to 7 has selectivity on the particle size of the aluminum powder, and has better inhibiting effect on the reaction expansion of 0.10 to 0.26 mu m submicron aluminum powder and water compared with 50 to 90nm nanometer aluminum powder and 5 to 50 mu m micron aluminum powder; the results show that the phosphate, organic phosphonate and polyacrylate 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.
The present invention is not limited to the above embodiments, and based on the technical solutions disclosed in the present invention, those skilled in the art can make some substitutions and modifications to some technical features without creative efforts based on the disclosed technical contents, and these substitutions and modifications are all within the protection scope of the present invention.
Claims (12)
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 and 2.9-3.9 parts of an expanding agent; 3.8-4.7 parts of a stabilizer;
wherein the stabilizer is one or more of polyphosphate, organic phosphonate, polyacrylate and polyacrylate copolymer; the expanding agent is aluminum powder.
2. The mining hole sealing curing expansion material as claimed in claim 1, further comprising 9.5-9.8 parts of lithium sulfate; the expanding agent is submicron aluminum powder with the particle size of 0.10-0.26 mu m.
3. The mining hole sealing curing expansion material as claimed in claim 2, further comprising 0.4-1.3 parts of defoaming agent, 1.1-1.6 parts of retarder and 1.2-1.9 parts of coupling agent.
4. The mining hole sealing and curing expansion material as claimed in claim 3, wherein the retarder is an inorganic metal base.
5. The mining hole sealing solidified expanding material of claim 4, wherein the inorganic metal base is one or more of sodium hydroxide, potassium hydroxide and calcium hydroxide.
6. The mining hole sealing cured expansion material as claimed in claim 3, wherein the coupling agent is an aluminate coupling agent.
7. The mining hole sealing and curing expansion material as claimed in any one of claims 1 to 6, wherein the stabilizer is one or more of sodium hexametaphosphate, sodium tripolyphosphate, amino trimethylene phosphonic acid, ethylene diamine tetra methylene phosphonic acid, hydroxy ethylidene diphosphonic acid and polyacrylate XT-1100.
8. The mining hole sealing and curing expansion material as claimed in any one of claims 1 to 6, wherein the components of the fly ash which are sieved by a square hole sieve with the fineness of 0.045mm are not more than 10%; the loss on ignition at 18-25 ℃ is less than or equal to 3 percent, and SO3The content is less than or equal to 2 percent, the water content is less than or equal to 1 percent, the water demand ratio is less than or equal to 95 percent, and the specific surface area>700m2/kg。
9. The mining hole sealing and curing expansion material as claimed in any one of claims 1 to 6, wherein the average particle size of the fly ash is 3 to 6 μm.
10. The mining hole sealing solidified expanding material of claim 1, wherein the solidified expanding material has a compressive strength of 63-75KN, a stress peak value of 12.6MPa and an initial setting time of not less than 17.2min after being solidified; the time for the expansion rate to reach 80 percent of the final expansion rate is 10-20 min; the result of the cohesiveness test was 1800 and 2800 mPas.
11. The preparation method of the hole sealing curing expansion material for the mine is characterized by being used for preparing the curing expansion material as described in any one of claims 1-10, 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 mixture;
uniformly stirring the mixture II and part of the mixed solution I according to the weight ratio, and then adding the fly ash, the retarder, the coupling agent and the lithium sulfate according to the given weight ratio;
and adding the defoaming agent and the residual mixed solution I, uniformly stirring, standing, then uniformly stirring, and discharging to obtain the cured expansion material.
12. The method of claim 11, wherein the feedstock comprises: 97-118 parts of cement, 28-31 parts of fly ash, 56-66 parts of water, 2.9-3.9 parts of an expanding agent, 3.6-4.1 parts of cellulose, 0.4-1.3 parts of a defoaming agent, 1.1-1.6 parts of a retarder, 1.2-1.9 parts of a coupling agent and 3.8-4.7 parts of a stabilizer; adding 4-6 parts of mixed liquor I for the first time; and adding 57.4-70.8 parts of the mixed solution for the second time.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5006588A (en) * | 1988-08-09 | 1991-04-09 | Lockheed Corporation | Corrosion and crack growth inhibiting compound, coating, and sealant material and method of making |
| JP2003171162A (en) * | 2001-12-05 | 2003-06-17 | Denki Kagaku Kogyo Kk | Cement based grout composition |
| US20100000346A1 (en) * | 2006-09-21 | 2010-01-07 | Armin Just | Air-curing expanded concrete composed of binder-containing mixtures |
| CN102503328A (en) * | 2011-09-30 | 2012-06-20 | 北京旷世达资源环境工程发展中心 | Universal rock and soil curing agent and preparation method thereof |
| CN103849362A (en) * | 2014-02-18 | 2014-06-11 | 六盘水师范学院 | Formula of coal-bed gas extraction drilling-sealing material and preparation method thereof |
| CN104387007A (en) * | 2014-11-03 | 2015-03-04 | 河南工程学院 | Low-cost quick-setting expansible hole-sealing material applied to coal mine |
| CN104592962A (en) * | 2014-10-31 | 2015-05-06 | 河南神华能源工程有限公司 | Coal mine gas extraction hole sealing material |
| CN105622153A (en) * | 2014-11-03 | 2016-06-01 | 太原市天鼎恒砼外加剂科技发展有限公司 | Hole-sealing slurry and preparation method thereof |
| CN106220121A (en) * | 2016-07-21 | 2016-12-14 | 中煤科工集团重庆研究院有限公司 | A kind of parent's coal base mash gas pumping drilling sealing material and using method thereof |
| JP2018087376A (en) * | 2016-11-24 | 2018-06-07 | 株式会社栗本鐵工所 | Hole sealing treatment agent |
-
2022
- 2022-04-28 CN CN202210458411.XA patent/CN114644495B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5006588A (en) * | 1988-08-09 | 1991-04-09 | Lockheed Corporation | Corrosion and crack growth inhibiting compound, coating, and sealant material and method of making |
| JP2003171162A (en) * | 2001-12-05 | 2003-06-17 | Denki Kagaku Kogyo Kk | Cement based grout composition |
| US20100000346A1 (en) * | 2006-09-21 | 2010-01-07 | Armin Just | Air-curing expanded concrete composed of binder-containing mixtures |
| CN102503328A (en) * | 2011-09-30 | 2012-06-20 | 北京旷世达资源环境工程发展中心 | Universal rock and soil curing agent and preparation method thereof |
| CN103849362A (en) * | 2014-02-18 | 2014-06-11 | 六盘水师范学院 | Formula of coal-bed gas extraction drilling-sealing material and preparation method thereof |
| CN104592962A (en) * | 2014-10-31 | 2015-05-06 | 河南神华能源工程有限公司 | Coal mine gas extraction hole sealing material |
| CN104387007A (en) * | 2014-11-03 | 2015-03-04 | 河南工程学院 | Low-cost quick-setting expansible hole-sealing material applied to coal mine |
| CN105622153A (en) * | 2014-11-03 | 2016-06-01 | 太原市天鼎恒砼外加剂科技发展有限公司 | Hole-sealing slurry and preparation method thereof |
| CN106220121A (en) * | 2016-07-21 | 2016-12-14 | 中煤科工集团重庆研究院有限公司 | A kind of parent's coal base mash gas pumping drilling sealing material and using method thereof |
| JP2018087376A (en) * | 2016-11-24 | 2018-06-07 | 株式会社栗本鐵工所 | Hole sealing treatment agent |
Non-Patent Citations (1)
| Title |
|---|
| 左明扬: "《水泥生产工艺技术》", 31 December 2013, pages: 294 * |
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| CN114644495B (en) | 2023-06-13 |
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