CN112759346A - Underground goaf filling material and preparation method and application thereof - Google Patents
Underground goaf filling material and preparation method and application thereof Download PDFInfo
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- CN112759346A CN112759346A CN202110033821.5A CN202110033821A CN112759346A CN 112759346 A CN112759346 A CN 112759346A CN 202110033821 A CN202110033821 A CN 202110033821A CN 112759346 A CN112759346 A CN 112759346A
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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
- C04B28/14—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 calcium sulfate cements
- C04B28/142—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 calcium sulfate cements containing synthetic or waste calcium sulfate cements
- C04B28/144—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 calcium sulfate cements containing synthetic or waste calcium sulfate cements the synthetic calcium sulfate being a flue gas desulfurization product
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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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00017—Aspects relating to the protection of the environment
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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
- 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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- 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
Abstract
The invention provides an underground goaf filling material and a preparation method and application thereof, and belongs to the technical field of goaf filling. The underground goaf filling material provided by the invention is prepared from the following raw materials of fly ash, desulfurized gypsum, cement and water, wherein the mass ratio of the fly ash to the desulfurized gypsum to the cement is (2-6): (2-6): 1, the total mass of the fly ash, the desulfurized gypsum and the cement accounts for 55-75% of the mass of the filling material of the underground goaf. According to the invention, the underground goaf filling material is prepared from two industrial solid wastes of the fly ash and the desulfurized gypsum, and the cement and the water are matched, so that the strength required by an underground mining filling body can be met, the potential safety hazard of the underground goaf is eliminated, the safe mining of a mine is ensured, the resource treatment of the industrial solid wastes can be realized, the cement consumption is reduced, and the economic benefit and the social benefit of a mine enterprise are improved.
Description
Technical Field
The invention relates to the technical field of goaf filling, in particular to an underground goaf filling material and a preparation method and application thereof.
Background
The underground goaf refers to a cavity area left after underground mineral products are mined out, the existence of the underground goaf is an important problem restricting mine development, and as the mine is mined to the deep part, the ground pressure is increased, and the underground goaf is easy to collapse under strong ground pressure; a large amount of goafs remained in underground mining and roadways are not processed in time, and serious threats are brought to mine workers and equipment. Therefore, the existence of the underground goaf can directly influence the safe production problem of the mine.
The filling mining technology is an effective means for treating underground goafs, and mainly utilizes materials with certain strength to fill the underground goafs so as to avoid ground subsidence caused by mining. At present, mine tailings are generally adopted in the field of mining as filling materials for underground goafs, but part of the mine tailings contain toxic substances, such as arsenic, cyanogen and other toxic substances, and the mine tailings belong to dangerous wastes according to the national environmental protection standard and are not allowed to be used for preparing the filling materials to fill the underground goafs. Therefore, a large amount of underground goafs are left after the mining of the mine, and potential safety hazards are prominent.
Disclosure of Invention
The invention aims to provide an underground goaf filling material and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an underground goaf filling material which is prepared from the following raw materials of fly ash, desulfurized gypsum, cement and water, wherein the mass ratio of the fly ash to the desulfurized gypsum to the cement is (2-6): (2-6): 1, the total mass of the fly ash, the desulfurized gypsum and the cement accounts for 55-75% of the mass of the filling material of the underground goaf.
Preferably, the particle size distribution of the fly ash comprises: d10＝2.5～3.0μm，D30＝10.4～12.7μm，D50＝41.8～51.1μm，D60＝64.2～78.5μm，D90451.2-551.5 μm; the specific surface area of the fly ash is 368-1110 m2/kg。
Preferably, the fly ash contains 40-60 wt% of silicon dioxide, 5-9 wt% of ferric oxide, 18-22 wt% of aluminum oxide, 2-4 wt% of magnesium oxide, 12-16 wt% of calcium oxide, 0.5-1.5 wt% of sulfur trioxide and 0.5-1.5 wt% of potassium oxide.
Preferably, the particle size distribution of the desulfurized gypsum comprises: d10＝6.7～8.2μm，D30＝25.0～30.5μm，D50＝39.7～48.5μm，D60＝51.2～62.5μm，D90375.5-459.0 mu m; the specific surface area of the desulfurized gypsum is 175-530 m2/kg。
Preferably, the desulfurized gypsum contains 5-7 wt% of silicon dioxide, 0.5-1.5 wt% of ferric oxide, 1-3 wt% of aluminum oxide, 1.5-2.5 wt% of magnesium oxide, 30-50 wt% of calcium oxide, 35-45 wt% of sulfur trioxide and 0.5-1.5 wt% of potassium oxide.
Preferably, the cement is ordinary portland cement, with a strength grade of 42.5R or 52.5R.
Preferably, the cement contains 15-25 wt% of silicon dioxide, 2.5-3.5 wt% of ferric oxide, 4-6 wt% of aluminum oxide, 0.5-1.5 wt% of magnesium oxide, 55-65 wt% of calcium oxide, 1.5-2.5 wt% of sulfur trioxide and 0.1-0.5 wt% of potassium oxide.
The invention provides a preparation method of an underground goaf filling material, which comprises the following steps:
and fully stirring the fly ash, the desulfurized gypsum, the cement and the water to obtain the underground goaf filling material.
The invention provides an application of the underground goaf filling material in the technical scheme or the underground goaf filling material prepared by the preparation method in the technical scheme in the field of mining.
Preferably, the method of application comprises the steps of:
filling the underground goaf filling material into the underground goaf, and forming a filling body after hydration reaction.
The invention provides an underground goaf filling material which is prepared from the following raw materials of fly ash, desulfurized gypsum, cement and water, wherein the mass ratio of the fly ash to the desulfurized gypsum to the cement is (2-6): (2-6): 1, the total mass of the fly ash, the desulfurized gypsum and the cement accounts for 55-75% of the mass of the filling material of the underground goaf. According to the invention, the underground goaf filling material is prepared from two industrial solid wastes of the fly ash and the desulfurized gypsum, and the cement and the water are matched, so that the strength required by an underground mining filling body can be met, the potential safety hazard of the underground goaf is eliminated, and the safe mining of a mine is ensured; the fly ash and the desulfurized gypsum are used as the municipal industrial solid wastes, the surface stockpiling not only occupies a large amount of land, but also pollutes water and air due to raised dust caused by wind.
Drawings
FIG. 1 is a graph showing a comparison of uniaxial compressive strengths of test pieces obtained by curing the underground gob filling material for 7 days and 14 days after molding in examples 1 to 3 and comparative examples 1 to 2, respectively;
FIG. 2 is a scanning electron microscope image of the test pieces obtained by curing 7 days after the underground gob filling material is molded in example 1 and comparative example 2;
FIG. 3 is an element distribution diagram of a test piece obtained by curing 7 days after the filling material of the underground goaf is molded in example 1;
FIG. 4 is an element distribution diagram of a test piece obtained by curing 7 days after the formation of the underground gob filling material in comparative example 2.
Detailed Description
The invention provides an underground goaf filling material which is prepared from the following raw materials of fly ash, desulfurized gypsum, cement and water, wherein the mass ratio of the fly ash to the desulfurized gypsum to the cement is (2-6): (2-6): 1, the total mass of the fly ash, the desulfurized gypsum and the cement accounts for 55-75% of the mass of the filling material of the underground goaf. In the invention, the mass ratio of the total mass of the fly ash and the desulfurized gypsum to the cement is preferably (7-9): 1, more preferably 8: 1; the total mass of the fly ash, the desulfurized gypsum and the cement is preferably 60-70% of the mass of the filling material of the underground goaf.
The underground goaf filling material is prepared from two industrial solid wastes, namely fly ash and desulfurized gypsum, and cement and water, wherein the fly ash, desulfurized gypsum and cement are subjected to hydration reaction with the water to generate hydration products, so that the filling body is ensured to have higher strength; meanwhile, the cement has the main effects that the cohesive force among particles is improved through hydration reaction, so that the strength of the filling body is improved, and the filling cost is suddenly increased and the economic benefit of mine enterprises is damaged due to the excessive addition amount of the cement; the addition amount of the additive is too small, the hydration effect of the fly ash and the desulfurized gypsum is poor, the strength of the filling body is reduced, and the design requirement of the strength of the mine filling body cannot be met. According to the invention, the proportion of the fly ash, the desulfurized gypsum, the cement and the water is controlled within the range, so that a filling body with higher strength can be obtained on the basis of ensuring lower cost.
The particle size distribution of the fly ash of the present invention preferably comprises: d10＝2.5～3.0μm，D30＝10.4～12.7μm，D50＝41.8～51.1μm，D60＝64.2～78.5μm，D90451.2-551.5 μm; more preferably, it comprises: d10＝2.6～2.9μm，D30＝11.0～12.1μm，D50＝44.1～48.8μm，D60＝67.8～74.9μm，D90476.3-526.4 mu m; in the embodiment of the invention, the particle size distribution of the fly ash is D10＝2.786μm，D30＝11.584μm，D50＝46.466μm，D60＝71.353μm，D90501.330 μm. In the invention, the specific surface area of the fly ash is preferably 368-1110 m2Per kg, more preferably 550 to 920m2Per kg, more preferably 700 to 750m2Per kg; in the embodiment of the invention, the specific surface area of the fly ash is 737.135m2In terms of/kg. The invention preferably adopts the fly ash with the particle size distribution and the specific surface area, and is matched with the desulfurized gypsum, the cement and the water, thereby being beneficial to obtaining the filling body with higher strength. In the invention, the content of silicon dioxide in the fly ash is preferably 40-60 wt%, and more preferably 51.5 wt%; the content of the ferric oxide is preferably 5-9 wt%, and more preferably 7.5 wt%; the content of the aluminum oxide is preferably 18-22 wt%, and more preferably 19.4 wt%; the content of the magnesium oxide is preferably 2-4 wt%, and more preferably 2.8 wt%; the content of calcium oxide is preferably 12-16 wt%, and more preferably 13.9 wt%; the content of sulfur trioxide is preferably 0.5-1.5 wt%, and more preferably 1.2 wt%; the content of potassium oxide is preferably 0.5 to 1.5 wt%, more preferably 1.3 wt%.
In the present invention, the particle size distribution of the desulfurized gypsum preferably comprises: d10＝6.7～8.2μm，D30＝25.0～30.5μm，D50＝39.7～48.5μm，D60＝51.2～62.5μm，D90375.5-459.0 mu m; more preferably D10＝7.1～7.8μm，D30＝26.4～29.2μm，D50＝41.9～46.3μm，D60＝54.0～59.7μm，D90396.4-438.1 mu m; in the embodiment of the invention, the particle size distribution of the desulfurized gypsum is D10＝7.422μm，D30＝27.763μm，D50＝44.112μm，D60＝56.837μm，D90417.245 μm; the specific surface area of the desulfurized gypsum is preferably 175-530 m2/kg, more preferably 265 to 442m2Per kg, more preferably 300 to 400m2Per kg; in an embodiment of the present invention, theThe specific surface area of the desulfurized gypsum is specifically 353.377m2In terms of/kg. The invention preferably adopts the desulfurized gypsum with the particle size distribution and the specific surface area, and is matched with the fly ash, the cement and the water, so that a filling body with higher strength can be obtained. In the invention, the content of silicon dioxide in the desulfurized gypsum is preferably 5-7 wt%, and more preferably 6.7 wt%; the content of the ferric oxide is preferably 0.5-1.5 wt%, and more preferably 1.2 wt%; the content of the aluminum oxide is preferably 1-3 wt%, and more preferably 2.6 wt%; the content of the magnesium oxide is preferably 1.5-2.5 wt%, and more preferably 1.9 wt%; the content of calcium oxide is preferably 30-50 wt%, and more preferably 44.1 wt%; the content of sulfur trioxide is preferably 35-45 wt%, and more preferably 41.2 wt%; the content of potassium oxide is preferably 0.5 to 1.5 wt%, more preferably 0.9 wt%.
In the present invention, the cement is preferably ordinary portland cement, and the strength grade of the ordinary portland cement is preferably 42.5R or 52.5R. In the invention, the content of the silicon dioxide in the cement is preferably 15-25 wt%, and more preferably 20.1 wt%; the content of the ferric oxide is preferably 2.5-3.5 wt%, and more preferably 2.91 wt%; the content of the aluminum oxide is preferably 4-6 wt%, and more preferably 5.11 wt%; the content of the magnesium oxide is preferably 0.5-1.5 wt%, and more preferably 1.57 wt%; the content of calcium oxide is preferably 55-65 wt%, and more preferably 61.8 wt%; the content of sulfur trioxide is preferably 1.5-2.5 wt%, and more preferably 1.98 wt%; the content of potassium oxide is preferably 0.1 to 0.5 wt%, more preferably 0.37 wt%.
In the present invention, the water is preferably tap water.
The invention provides a preparation method of an underground goaf filling material, which comprises the following steps:
and fully stirring the fly ash, the desulfurized gypsum, the ordinary portland cement and water to obtain the underground goaf filling material.
According to the invention, fly ash, desulfurized gypsum and ordinary portland cement are preferably subjected to first stirring and mixing to obtain a mixed dry material; and then, carrying out second stirring and mixing on the mixed dry material and water to obtain the underground goaf filling material. In the invention, the time for the first stirring and mixing and the second stirring and mixing is preferably 2-5 min independently. The invention adopts the mixing mode, which is beneficial to ensuring that all components are uniformly mixed and dispersed. The stirring speed in the mixing process is not particularly limited in the invention, and the stirring speed known to those skilled in the art can be adopted.
The invention provides an application of the underground goaf filling material in the technical scheme or the underground goaf filling material prepared by the preparation method in the technical scheme in the field of mining. In the present invention, the method of application preferably comprises the steps of:
filling the underground goaf filling material into the underground goaf, and forming a filling body after hydration reaction.
According to the invention, the fly ash, the desulfurized gypsum, the ordinary portland cement and the water are preferably fully stirred according to the proportion to obtain the filling material for the underground goaf, then the filling material for the underground goaf is filled into the underground goaf through a pipeline by self weight or pumping, the filling material for the underground goaf forms a filling body with higher strength after hydration reaction, and the filling body is fully contacted with surrounding rocks of the underground goaf to achieve the effect of treating the underground goaf.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Examples 1 to 3
Stirring and dry-mixing the fly ash, the desulfurized gypsum and the ordinary portland cement P.O.42.5R for 3min to obtain a mixed dry material; stirring and mixing the mixed dry material and water to obtain an underground goaf filling material; the main chemical components of the fly ash, the desulfurized gypsum and the ordinary portland cement P.O.42.5R are shown in table 1, the particle size distribution and the specific surface area of the fly ash and the desulfurized gypsum are shown in table 2, and the using amount of each component in the underground goaf filling material is shown in table 3.
Comparative examples 1 to 2
The underground gob filling material was prepared according to the method of example 1, except for the amounts of the components used in the underground gob filling material, as shown in table 3.
TABLE 1 chemical composition of Cement, fly ash and desulfurized Gypsum
TABLE 2 particle size distribution and specific surface area of fly ash and desulfurized gypsum
| Variety of solid wastes | D10(μm) | D30(μm) | D50(μm) | D60(μm) | D90(μm) | Specific surface area m2/kg |
| Fly ash | 2.786 | 11.584 | 46.466 | 71.353 | 501.330 | 737.135 |
| Desulfurized gypsum | 7.422 | 27.763 | 44.112 | 56.837 | 417.245 | 353.377 |
TABLE 3 proportioning of cement, solid waste (fly ash and desulfurized gypsum) and water
Performance testing and characterization
The underground goaf filling materials prepared in examples 1 to 3 and comparative examples 1 to 2 were poured into molds (50mm × 100mm) respectively, the molds were hammered and compacted by a thin iron rod, and then the molds were placed in an HSBY-40B constant temperature and humidity (temperature 20 ± 1 ℃, humidity 90 ± 5%) curing box and cured for 7 days and 14 days, respectively, the underground goaf filling materials were cured to form hardened bodies, and uniaxial compressive strength tests were performed using the hardened bodies as test pieces to obtain mechanical strength properties of the test pieces, and the results are shown in fig. 1. As can be seen from fig. 1, after 7 days and 14 days of curing, the test pieces prepared based on the underground gob filling material in example 1, i.e., the mass ratio of cement to fly ash to desulfurized gypsum, was 1: 6: 2, the uniaxial compressive strength of the test piece is the highest, the uniaxial compressive strength of the test piece maintained for 7 days is 2.45MPa, and the uniaxial compressive strength of the test piece maintained for 14 days is 4.2MPa, so that the engineering requirement can be met.
The test pieces obtained by curing the filling material for 7 days after forming in the underground goaf in the embodiment 1 and the comparative example 2 are observed by a scanning electron microscope, specifically, the prepared test pieces are dried, the test pieces are subjected to primary carbon spraying treatment (aiming at improving the conductivity of the test pieces) by vacuum coating, and then the observation by the scanning electron microscope is carried out. Fig. 2 is a scanning electron microscope image of the test pieces obtained by curing 7 days after the formation of the underground gob filling material in example 1 and comparative example 2, wherein (a) in fig. 2 corresponds to the underground gob filling material in example 1, and (b) in fig. 2 corresponds to the underground gob filling material in comparative example 2. Fig. 3 is an element distribution diagram of a test piece obtained by curing 7 days after the formation of the underground gob filling material in example 1, and fig. 4 is an element distribution diagram of a test piece obtained by curing 7 days after the formation of the underground gob filling material in comparative example 2. As can be seen from (a) in fig. 2, a large amount of flocculated substances appeared on the surface of the solid-phase particles in the test piece, and these flocculated substances adhered to the surface of the solid-phase particles; in conjunction with the element distribution in fig. 3, it is presumed that these flocculated substances are hydrated calcium silicate formed by the reaction of calcium oxide, aluminum oxide, silicon dioxide and water, and it is due to the presence of these hydrated calcium carbonates that the uniaxial compressive strength of the test piece is enhanced. As can be seen from fig. 2 (b), a large amount of large-particle desulfurized gypsum exists in the test piece, and the number of the holes is large and the length is large; as can be seen from the element distribution in FIG. 4, the elements of Ca, S and O are greatly concentrated among the desulfurized gypsum particles, which also results in the lowest uniaxial compressive strength of the test piece.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The underground goaf filling material is characterized by being prepared from raw materials including fly ash, desulfurized gypsum, cement and water, wherein the mass ratio of the fly ash to the desulfurized gypsum to the cement is (2-6): (2-6): 1, the total mass of the fly ash, the desulfurized gypsum and the cement accounts for 55-75% of the mass of the filling material of the underground goaf.
2. The underground gob filling material of claim 1, wherein the material is selected from the group consisting of a mineral filler, a metal filler, and a metal fillerThe particle size distribution of the fly ash comprises: d10＝2.5～3.0μm，D30＝10.4～12.7μm，D50＝41.8～51.1μm，D60＝64.2～78.5μm，D90451.2-551.5 μm; the specific surface area of the fly ash is 368-1110 m2/kg。
3. The underground goaf filling material as claimed in claim 1 or 2, wherein the fly ash contains 40-60 wt% of silicon dioxide, 5-9 wt% of ferric oxide, 18-22 wt% of aluminum oxide, 2-4 wt% of magnesium oxide, 12-16 wt% of calcium oxide, 0.5-1.5 wt% of sulfur trioxide, and 0.5-1.5 wt% of potassium oxide.
4. The underground gob filling material of claim 1, wherein the particle size distribution of the desulfurized gypsum comprises: d10＝6.7～8.2μm，D30＝25.0～30.5μm，D50＝39.7～48.5μm，D60＝51.2～62.5μm，D90375.5-459.0 mu m; the specific surface area of the desulfurized gypsum is 175-530 m2/kg。
5. An underground goaf filling material according to claim 1 or 4, wherein the desulfurized gypsum contains 5-7 wt% of silicon dioxide, 0.5-1.5 wt% of ferric oxide, 1-3 wt% of aluminum oxide, 1.5-2.5 wt% of magnesium oxide, 30-50 wt% of calcium oxide, 35-45 wt% of sulfur trioxide and 0.5-1.5 wt% of potassium oxide.
6. An underground gob filling material according to claim 1, wherein the cement is Portland cement and has a strength rating of 42.5R or 52.5R.
7. An underground goaf filling material according to claim 1 or 6, wherein the cement contains 15-25 wt% of silicon dioxide, 2.5-3.5 wt% of ferric oxide, 4-6 wt% of aluminum oxide, 0.5-1.5 wt% of magnesium oxide, 55-65 wt% of calcium oxide, 1.5-2.5 wt% of sulfur trioxide, and 0.1-0.5 wt% of potassium oxide.
8. The method for preparing the underground gob filling material according to any one of claims 1 to 7, comprising the steps of:
and fully stirring the fly ash, the desulfurized gypsum, the cement and the water to obtain the underground goaf filling material.
9. The underground gob filling material according to any one of claims 1 to 7 or the underground gob filling material prepared by the preparation method according to claim 8 is applied to the field of mining.
10. The application according to claim 9, characterized in that the method of application comprises the steps of:
filling the underground goaf filling material into the underground goaf, and forming a filling body after hydration reaction.
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| CN116161940A (en) * | 2022-12-29 | 2023-05-26 | 中煤科工开采研究院有限公司 | Coal-electricity solid waste high-concentration self-flowing filling material and preparation and application thereof |
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