Grouting material based on magnetic particle tracing, preparation method and application thereof

Abstract

The present application embodiment proposes a grouting material, preparation method and application based on magnetic particle tracing, wherein the preparation method includes adding magnetic particles with active hydroxyl sites on the surface to a polyol mixture, and performing polymerization reaction under the catalytic action of a composite catalyst and a protective atmosphere to obtain polyol-modified magnetic nanoparticles; adding 12-15 parts by mass of polyol-modified magnetic nanoparticles and 5-13 parts by mass of an auxiliary agent to a gelling material of 100-120 parts by mass, and mixing the dry powder to obtain the result. The grouting material of the present application includes polyol-modified magnetic nanoparticles, which can be used as a magnetic particle tracing component. When the grouting material is injected into the cracks in the surrounding rock of the roadway, the polyol-modified magnetic nanoparticles diffuse and flow along the cracks in the surrounding rock of the roadway, and can be monitored and tracked by detection equipment, thereby completing dynamic detection of the cracks in the surrounding rock of the roadway and the diffusion of the grouting material.

Description

Technical Field

[0001] The present application relates to the field of mining engineering technology, and in particular to a grouting material based on magnetic particle tracing, a preparation method and an application thereof. Background Art

[0002] The field of coal mine roadway surrounding rock control has gradually formed a "support-modification-unloading" coordinated control technology. Grouting reinforcement, as an effective means of roadway surrounding rock control, has been widely used in the field of coal mine roadway surrounding rock control. Due to the concealment of grouting slurry penetrating into the internal cracks of the roadway surrounding rock, coupled with the complex characteristics of the coal mine roadway itself, such as anisotropy, it is difficult to accurately understand the flow and diffusion patterns of slurry in the internal cracks of the coal mine roadway surrounding rock, resulting in the difficulty in judging the effectiveness of grouting reinforcement of coal mine roadway surrounding rock. At present, the flow distribution state of slurry during the grouting process is still concentrated on model simulation, lacking real-time and detailed intuitive characterization methods, making it difficult to reveal the penetration and diffusion mechanism of slurry in the fractured rock mass of the coal mine roadway surrounding rock. Summary of the Invention

[0003] The present application aims to solve, at least to some extent, one of the technical problems in the related art. The present application provides a grouting material based on magnetic particle tracing, a preparation method, and its application. The grouting material includes polyol-modified magnetic nanoparticles, which can serve as a magnetic particle tracing component. When the grouting material is injected into the cracks in the surrounding rock of a roadway, the polyol-modified magnetic nanoparticles diffuse and flow along the cracks in the surrounding rock of the roadway, and can be monitored and tracked using detection equipment, completing dynamic detection of the cracks in the surrounding rock of the roadway and the diffusion of the grouting material.

[0004] To achieve the above-mentioned object, according to a first aspect of the present application, a method for preparing a grouting material based on magnetic particle tracing is proposed, comprising the following steps:

[0005] The magnetic particles with active hydroxyl sites on the surface are added to a polyol mixture, and a polymerization reaction is carried out under the catalytic action of a composite catalyst and a protective atmosphere to obtain polyol-modified magnetic nanoparticles;

[0006] The polyol-modified magnetic nanoparticles in 12-15 parts by weight and the auxiliary agent in 5-13 parts by weight are added to 100-120 parts by weight of the gelling material, and the dry powder is stirred to obtain the product.

[0007] In some embodiments, based on weight, the magnetic particles account for 20 parts; the polyol mixture accounts for 70-80 parts; and the composite catalyst accounts for 5-8 parts.

[0008] In some embodiments, the magnetic particles are obtained by plasma-treating iron oxide nanoparticles, iron silicate nanoparticles, and aluminum nickel cobalt nanoparticles, and the mass ratio of the iron oxide nanoparticles, the iron silicate nanoparticles, and the aluminum nickel cobalt nanoparticles is (2-5): (1-2): (2-4).

[0009] In some embodiments, the parameters of the plasma treatment are power 5-6 kW, frequency 2450-2500 MHz, density 25-28 W / cm 2 , time 15-18 minutes.

[0010] In some embodiments, the polyol mixture includes ethylene glycol, glycerol, and octanediol in a mass ratio of 2:1:1.

[0011] In some embodiments, the composite catalyst includes nickel octadienediyl, nickel cobalt sulfide, and nickel acetylacetonate in a mass ratio of 1:1:3.

[0012] In some embodiments, the protective atmosphere is an inert gas, including nitrogen, helium, or neon.

[0013] In some embodiments, the polymerization reaction parameters are 190-200° C. and reaction time of 50 min.

[0014] In some embodiments, the additives include, by weight, 1-2 parts of a dispersant, 1-3 parts of a coagulant, 1 part of a toughening agent, 1-5 parts of a reinforcing agent, and 1-2 parts of a fluid loss additive.

[0015] In some embodiments, the cementitious material includes sulphoaluminate clinker, ferroaluminate clinker and aluminate clinker mixed in a mass ratio of 1:1:2.

[0016] According to another purpose of the present application, a grouting material based on magnetic particle tracing is proposed, which includes a mixture A and a cementitious material; in terms of mass parts, the mixture A includes 12-15 parts of polyol-modified magnetic nanoparticles and 5-13 parts of additives; the cementitious material has a mass part of 100-120 parts and includes sulfoaluminate clinker, ferroaluminate clinker and aluminate clinker mixed in a mass ratio of 1:1:2.

[0017] In some embodiments, the additives include, by weight, 1-2 parts of a dispersant, 1-3 parts of a coagulant, 1 part of a toughening agent, 1-5 parts of a reinforcing agent, and 1-2 parts of a fluid loss additive.

[0018] In some embodiments, the polyol-modified magnetic nanoparticles are obtained by adding magnetic particles having active hydroxyl sites on the surface to a polyol mixture and performing a polymerization reaction under the catalytic action of a composite catalyst and a protective atmosphere.

[0019] According to another purpose of the present application, it is proposed that the grouting material described in any of the above embodiments be used in magnetic particle tracer grouting in large deformation tunnels in coal mines, and the grouting material described in any of the above embodiments be used as a tracer in large deformation tunnels.

[0020] Compared with the prior art, this application has the following advantages:

[0021] In the present application, the magnetic particles having active hydroxyl sites on the surface are modified with a polyol mixture, which can reduce the interfacial tension of the polyol-modified magnetic nanoparticles, prevent the agglomeration of the polyol-modified magnetic nanoparticles, and improve the uniform dispersion of the polyol-modified magnetic nanoparticles in the gelling material; at the same time, the polyol-modified magnetic nanoparticles present a spherical shape, and the ball effect can reduce the flow friction resistance of the grouting material and improve the fluidity of the grouting material.

[0022] After the grouting material is injected into the cracks in the tunnel surrounding rock, the polyol-modified magnetic nanoparticles in the grouting material diffuse and flow along the cracks, and are monitored and tracked by detection equipment to achieve dynamic detection of the cracks in the tunnel surrounding rock and the diffusion of slurry; in addition, the surface of the polyol-modified magnetic nanoparticles has a variety of hydroxyl functional groups, which form hydrogen bonds with the hydroxyl groups on the surface of the coal rock mass, thereby improving the interface bonding strength between the grouting stone formed by the grouting material and the coal rock mass, thereby improving the grouting reinforcement effect.

[0023] Additional aspects and advantages of the present application will be given in part in the description below, and in part will become apparent from the description below, or will be learned through practice of the present application. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] The above and / or additional aspects and advantages of the present application will become apparent and easily understood from the following description of the embodiments in conjunction with the accompanying drawings, in which:

[0025] Figure 1 This is a flow chart of a method for preparing a grouting material based on magnetic particle tracing in one embodiment of the present application.

[0026] Figure 2 yes Figure 1 Detailed flow chart. DETAILED DESCRIPTION

[0027] The embodiments of the present application are described in detail below. Examples of the embodiments are shown in the accompanying drawings, wherein the same or similar reference numerals throughout represent the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are intended only to explain the present application and are not to be construed as limiting the present application. On the contrary, the embodiments of the present application include all variations, modifications, and equivalents that fall within the spirit and scope of the appended claims.

[0028] like Figure 1 As shown, in order to achieve the above purpose, according to the first aspect of the present application, a preparation method of a grouting material based on magnetic particle tracing is proposed, comprising the following steps:

[0029] S1: adding magnetic particles having active hydroxyl sites on the surface to a polyol mixture, and performing a polymerization reaction under the catalytic action of a composite catalyst and a protective atmosphere to obtain polyol-modified magnetic nanoparticles;

[0030] S2: Add 12-15 parts by weight of polyol-modified magnetic nanoparticles and 5-13 parts by weight of an auxiliary agent to 100-120 parts by weight of a gelling material, and stir to obtain a dry powder.

[0031] Among them Figure 2 As shown, in S1, iron oxide nanoparticles, iron silicate nanoparticles and aluminum nickel cobalt nanoparticles are mixed in a mass ratio of (2-5): (1-2): (2-4), and plasma treated to obtain magnetic particles with active hydroxyl sites on the surface, wherein the parameters of the plasma treatment are power 5-6kW, frequency 2450-2500MHz, density 25-28W / cm 2 , time 15-18 minutes.

[0032] The method comprises the following steps: taking 20 parts by mass of magnetic particles and adding them to 70-80 parts of a polyol mixture, wherein the polyol mixture includes ethylene glycol, propylene glycol and octanediol in a mass ratio of 2:1:1; and adding 5-8 parts of a composite catalyst, wherein the composite catalyst includes octadienediyl nickel, cobalt nickel sulfide and acetylacetonate nickel in a mass ratio of 1:1:3; auxiliary heating is performed in a microwave reaction tube to promote the polymerization reaction, and an inert gas protection such as nitrogen, helium or neon is introduced. The reaction is carried out at 190-200°C in the microwave reaction tube for 50 minutes to prepare polyol-modified magnetic nanoparticles.

[0033] In this embodiment, active hydroxyl sites are formed on the surface of iron oxide nanoparticles, iron silicate nanoparticles, and aluminum nickel cobalt nanoparticles by plasma treatment. The particles are then added to a mixture of ethylene glycol, glycerol, and octanediol monomers, followed by the addition of nickel octadiene, nickel cobalt sulfide, and nickel acetylacetonate composite catalysts. Auxiliary heating is then used to promote the polymerization reaction, and an inert gas shield is introduced. The polymerization reaction is then carried out in a microwave reaction tube to produce polyol-modified magnetic nanoparticles. The polyol-modified magnetic nanoparticles obtained in this application are modified with polyols to reduce their interfacial tension, prevent agglomeration, and improve their uniform dispersion in the substrate. Furthermore, the polyol-modified magnetic nanoparticles exhibit a spherical morphology. When used as a grouting material, their ball-like effect can reduce the frictional resistance of the grouting material slurry, thereby improving the fluidity of the grouting material.

[0034] like Figure 2 In S2, 12-15 parts by mass of the polyol-modified magnetic nanoparticles obtained in S1 and 5-13 parts by mass of the auxiliary agent are added to 100-120 parts by mass of the gelling material, and the mixture is stirred and mixed in a dry powder mixer for 30 minutes. The auxiliary agents include 1-2 parts of dispersant, 1-3 parts of coagulant, 1 part of toughening agent, 1-5 parts of reinforcing agent and 1-2 parts of fluid loss reducer; the dispersant includes ethylene bisstearamide, monoglyceride of stearic acid, copper stearate and magnesium stearate, and their mass ratios are 2:2:1:1 respectively; the coagulant includes magnesium oxide, magnesium chloride, magnesium sulfate and disodium magnesium ethylenediaminetetraacetate, and their mass ratios are 1:4:1:2 respectively; the toughening agent includes polyacrylamide, polyethyleneimine and polyethylene oxide, and their mass ratios are 1:1:7 respectively; the reinforcing agent includes tetraammine copper sulfate, potassium trichloro(ethylene)platinate(II) and monochloropentamminecobalt(III) sulfate, and their mass ratios are 2:1:9 respectively; the fluid loss reducer includes sodium humate and sulfomethylphenolic resin in a mass ratio of 1:5. In this embodiment, the cementitious material includes sulphoaluminate clinker, ferroaluminate clinker and aluminate clinker mixed in a mass ratio of 1:1:2, for example, 30 parts of sulphoaluminate clinker, 30 parts of ferroaluminate clinker and 60 parts of aluminate clinker.

[0035] In this embodiment, the prepared polyol-modified magnetic nanoparticles, dispersants, coagulants, toughening agents, reinforcing agents, and fluid loss reducers are added to sulphoaluminate, ferroaluminate, and aluminate clinker cementitious materials to prepare a grouting material based on magnetic particle tracing suitable for large-deformation coal mine roadways and its preparation method. In the grouting material of this embodiment, the polyol-modified magnetic nanoparticles are injected into the cracks of the roadway surrounding rock along with the grouting material. The polyol-modified magnetic nanoparticles diffuse and flow along the cracks, and are monitored and tracked by detection equipment to achieve dynamic detection of the cracks in the roadway surrounding rock and the diffusion of slurry; in addition, the surface of the polyol-modified magnetic nanoparticles has a variety of hydroxyl functional groups, which form hydrogen bonding forces with the hydroxyl groups on the surface of the coal rock mass, thereby improving the interfacial bonding strength between the grouting stone formed by the grouting material and the coal rock mass, thereby improving the grouting reinforcement effect. Ultimately, the grouting material of this application realizes a simple, low-cost, and tracing function-based preparation method of a grouting material based on magnetic particle tracing suitable for large-deformation coal mine roadways.

[0036] According to another purpose of the present application, a grouting material based on magnetic particle tracing is proposed, which includes a mixture A and a cementitious material; in terms of mass parts, the mixture A includes 12-15 parts of polyol-modified magnetic nanoparticles and 5-13 parts of additives; the cementitious material has a mass part of 100-120 parts and includes sulfoaluminate clinker, ferroaluminate clinker and aluminate clinker mixed in a mass ratio of 1:1:2.

[0037] This embodiment proposes a grouting material based on magnetic particle tracing, comprising a mixture A and a cementitious material. Mixture A comprises 12-15 parts of polyol-modified magnetic nanoparticles and 5-13 parts of additives. The polyol-modified magnetic nanoparticles are obtained according to the method described in the above embodiment and will not be described in detail. The additives comprise, by weight, 1-2 parts of a dispersant, 1-3 parts of a coagulant, 1 part of a toughening agent, 1-5 parts of a reinforcing agent, and 1-2 parts of a fluid loss additive. The cementitious material comprises 30-35 parts of sulfoaluminate clinker, 30-40 parts of ferroaluminate clinker, and 40-45 parts of aluminate clinker.

[0038] According to another object of the present application, it is proposed that the grouting material in any of the above embodiments be used in magnetic particle tracing grouting in coal mine roadways with large deformation, and the grouting material in any of the above embodiments be used as a tracer in the roadways with large deformation.

[0039] The following is a specific example of the preparation method of the magnetic particle tracer grouting material.

[0040] Example 1

[0041] 10 kg of iron oxide nanoparticles, 5 kg of iron silicate nanoparticles and 10 kg of aluminum nickel cobalt nanoparticles were mixed and subjected to a plasma power of 6 kW, a plasma frequency of 2500 MHz and a plasma density of 28 W / cm 2 Magnetic particles were then added to a polyol mixture consisting of 40 kg of ethylene glycol, 20 kg of glycerol, and 20 kg of octanediol, along with a composite catalyst consisting of 1 kg of nickel octadienediyl, 1 kg of nickel cobalt sulfide, and 3 kg of nickel acetylacetonate. The polymerization reaction was then accelerated by heating, protected by nitrogen, and allowed to react in a microwave reaction tube at 200°C for 50 minutes to produce polyol-modified magnetic nanoparticles.

[0042] Component B is a cementitious material. 110 kg of cementitious material is prepared by mixing 27.5 kg of sulphoaluminate clinker, 27.5 kg of ferroaluminate clinker and 55 kg of aluminate clinker.

[0043] Prepare 10 kg of additives by mixing 2 kg of dispersant, 3 kg of accelerator, 1 kg of toughening agent, 2 kg of reinforcing agent and 2 kg of fluid loss additive;

[0044] 13 kg of the polyol-modified magnetic nanoparticles and 10 kg of the additive in this embodiment were added to 100 kg of the gelling material, and the mixture was stirred in a dry powder mixer for 30 minutes to obtain a grouting material, and the product quality indicators were tested.

[0045] Magnetic nanoparticle dispersion coefficient: 1.27;

[0046] Magnetic nanoparticle size: 47 nm;

[0047] Magnetic nanoparticle magnetic field strength: 79 emu / g.

[0048] Compressive strength of grouting material: 47 MPa.

[0049] Example 2

[0050] 10 kg of iron oxide nanoparticles, 5 kg of iron silicate nanoparticles and 15 kg of aluminum nickel cobalt nanoparticles were mixed and subjected to a plasma power of 5 kW, a plasma frequency of 2450 MHz and a plasma density of 25 W / cm 2The magnetic particles were then added to a polyol mixture consisting of 40 kg of ethylene glycol, 20 kg of glycerol, and 20 kg of octanediol, along with a composite catalyst consisting of 1 kg of nickel octadiene, 1 kg of nickel cobalt sulfide, and 3 kg of nickel acetylacetonate. The polymerization reaction was then accelerated by heating, protected by nitrogen, and allowed to react in a microwave reaction tube at 190°C for 50 minutes to produce polyol-modified magnetic nanoparticles.

[0051] Component B is a cementitious material. 110 kg of cementitious material is prepared by mixing 27.5 kg of sulphoaluminate clinker, 27.5 kg of ferroaluminate clinker and 55 kg of aluminate clinker.

[0052] Prepare 10 kg of additives by mixing 2 kg of dispersant, 3 kg of accelerator, 1 kg of toughening agent, 2 kg of reinforcing agent and 2 kg of fluid loss additive;

[0053] 13 kg of the polyol-modified magnetic nanoparticles and 10 kg of the additive in this embodiment were added to 100 kg of the gelling material, and the mixture was stirred in a dry powder mixer for 30 minutes to obtain a grouting material, and the product quality indicators were tested.

[0054] Magnetic nanoparticle dispersion coefficient: 1.24;

[0055] Magnetic nanoparticle size: 42 nm;

[0056] Magnetic nanoparticle magnetic field strength: 86 emu / g.

[0057] Compressive strength of grouting material: 49 MPa.

[0058] Example 3

[0059] 10 kg of iron oxide nanoparticles, 10 kg of iron silicate nanoparticles and 10 kg of aluminum nickel cobalt nanoparticles were mixed and subjected to a plasma power of 6 kW, a plasma frequency of 2500 MHz and a plasma density of 28 W / cm 2 Magnetic particles were then added to a polyol mixture consisting of 40 kg of ethylene glycol, 20 kg of glycerol, and 20 kg of octanediol, along with a composite catalyst consisting of 1 kg of nickel octadienediyl, 1 kg of nickel cobalt sulfide, and 3 kg of nickel acetylacetonate. The polymerization reaction was then accelerated by heating, protected by nitrogen, and allowed to react in a microwave reaction tube at 200°C for 50 minutes to produce polyol-modified magnetic nanoparticles.

[0060] Component B is a cementitious material. 110 kg of cementitious material is prepared by mixing 27.5 kg of sulphoaluminate clinker, 27.5 kg of ferroaluminate clinker and 55 kg of aluminate clinker.

[0061] Prepare 10 kg of additives by mixing 2 kg of dispersant, 3 kg of accelerator, 1 kg of toughening agent, 2 kg of reinforcing agent and 2 kg of fluid loss additive;

[0062] 15 kg of the polyol-modified magnetic nanoparticles and 10 kg of the additives in this embodiment were added to 100 kg of the gelling material, and the mixture was stirred in a dry powder mixer for 30 minutes to obtain a grouting material, and the product quality indicators were tested;

[0063] Magnetic nanoparticle dispersion coefficient: 1.22;

[0064] Magnetic nanoparticle size: 40 nm;

[0065] Magnetic nanoparticle magnetic field strength: 94 emu / g.

[0066] Compressive strength of grouting material: 50 MPa.

[0067] Example 4

[0068] 10 kg of iron oxide nanoparticles, 5 kg of iron silicate nanoparticles and 10 kg of aluminum nickel cobalt nanoparticles were mixed and subjected to a plasma power of 5 kW, a plasma frequency of 2450 MHz and a plasma density of 25 W / cm 2 The magnetic particles were then added to a polyol mixture consisting of 40 kg of ethylene glycol, 20 kg of glycerol, and 20 kg of octanediol, along with a composite catalyst consisting of 1 kg of nickel octadiene, 1 kg of nickel cobalt sulfide, and 3 kg of nickel acetylacetonate. The polymerization reaction was then accelerated by heating, protected by nitrogen, and allowed to react in a microwave reaction tube at 190°C for 50 minutes to produce polyol-modified magnetic nanoparticles.

[0069] Component B is a cementitious material. 110 kg of cementitious material is prepared by mixing 27.5 kg of sulphoaluminate clinker, 27.5 kg of ferroaluminate clinker and 55 kg of aluminate clinker.

[0070] Prepare 10 kg of additives by mixing 2 kg of dispersant, 3 kg of accelerator, 1 kg of toughening agent, 2 kg of reinforcing agent and 2 kg of fluid loss additive;

[0071] 12 kg of the polyol-modified magnetic nanoparticles and 10 kg of the additive in this embodiment were added to 100 kg of the gelling material, and the mixture was stirred in a dry powder mixer for 30 minutes to obtain a grouting material, and the product quality indicators were tested.

[0072] Magnetic nanoparticle dispersion coefficient: 1.20;

[0073] Magnetic nanoparticle size: 36 nm;

[0074] Magnetic nanoparticle magnetic field strength: 96 emu / g.

[0075] Compressive strength of grouting material: 54 MPa.

[0076] Example 5

[0077] 10 kg of iron oxide nanoparticles, 5 kg of iron silicate nanoparticles and 10 kg of aluminum nickel cobalt nanoparticles were mixed and subjected to a plasma power of 5 kW, a plasma frequency of 2450 MHz and a plasma density of 25 W / cm 2 The magnetic particles were then added to a polyol mixture consisting of 40 kg of ethylene glycol, 20 kg of glycerol, and 20 kg of octanediol, along with a composite catalyst consisting of 1 kg of nickel octadiene, 1 kg of nickel cobalt sulfide, and 3 kg of nickel acetylacetonate. The polymerization reaction was then accelerated by heating, protected by nitrogen, and allowed to react in a microwave reaction tube at 190°C for 50 minutes to produce polyol-modified magnetic nanoparticles.

[0078] Component B is a cementitious material. 110 kg of cementitious material is prepared by mixing 27.5 kg of sulphoaluminate clinker, 27.5 kg of ferroaluminate clinker and 55 kg of aluminate clinker.

[0079] Prepare 13 kg of additives by mixing 2 kg of dispersant, 3 kg of accelerator, 1 kg of toughening agent, 5 kg of reinforcing agent and 2 kg of fluid loss additive;

[0080] 13 kg of the polyol-modified magnetic nanoparticles and 13 kg of the additive in this embodiment were added to 100 kg of the gelling material, and the mixture was stirred in a dry powder mixer for 30 minutes to obtain a grouting material, and the product quality indicators were tested.

[0081] Magnetic nanoparticle dispersion coefficient: 1.18;

[0082] Magnetic nanoparticle size: 31 nm;

[0083] Magnetic field strength of magnetic nanoparticles: 107 emu / g.

[0084] Compressive strength of grouting material: 55 MPa.

[0085] Example 6

[0086] 10 kg of iron oxide nanoparticles, 5 kg of iron silicate nanoparticles and 10 kg of aluminum nickel cobalt nanoparticles were mixed and subjected to a plasma power of 5 kW, a plasma frequency of 2450 MHz and a plasma density of 25 W / cm 2 The magnetic particles were then added to a polyol mixture consisting of 40 kg of ethylene glycol, 20 kg of glycerol, and 20 kg of octanediol, along with a composite catalyst consisting of 1 kg of nickel octadiene, 1 kg of nickel cobalt sulfide, and 3 kg of nickel acetylacetonate. The polymerization reaction was then accelerated by heating, protected by nitrogen, and allowed to react in a microwave reaction tube at 190°C for 50 minutes to produce polyol-modified magnetic nanoparticles.

[0087] Component B is a cementitious material. 110 kg of cementitious material is prepared by mixing 27.5 kg of sulphoaluminate clinker, 27.5 kg of ferroaluminate clinker and 55 kg of aluminate clinker.

[0088] Prepare 5 kg of additives by mixing 1 kg of dispersant, 1 kg of accelerator, 1 kg of toughening agent, 1 kg of reinforcing agent and 1 kg of fluid loss additive;

[0089] 13 kg of the polyol-modified magnetic nanoparticles and 5 kg of the additives in this embodiment were added to 100 kg of the gelling material, and the mixture was stirred in a dry powder mixer for 30 minutes to obtain a grouting material, and the product quality indicators were tested.

[0090] Magnetic nanoparticle dispersion coefficient: 1.15;

[0091] Magnetic nanoparticle size: 27 nm;

[0092] Magnetic field strength of magnetic nanoparticles: 105emu / g.

[0093] Compressive strength of grouting material: 50 MPa.

[0094] Example 7

[0095] 10 kg of iron oxide nanoparticles, 5 kg of iron silicate nanoparticles and 10 kg of aluminum nickel cobalt nanoparticles were mixed and subjected to a plasma power of 5 kW, a plasma frequency of 2450 MHz and a plasma density of 25 W / cm 2The magnetic particles were then added to a polyol mixture consisting of 40 kg of ethylene glycol, 20 kg of glycerol, and 20 kg of octanediol, along with a composite catalyst consisting of 1 kg of nickel octadiene, 1 kg of nickel cobalt sulfide, and 3 kg of nickel acetylacetonate. The polymerization reaction was then accelerated by heating, protected by nitrogen, and allowed to react in a microwave reaction tube at 190°C for 50 minutes to produce polyol-modified magnetic nanoparticles.

[0096] Component B is a cementitious material. 120 kg of cementitious material is prepared by mixing 30 kg of sulphoaluminate clinker, 30 kg of ferroaluminate clinker and 60 kg of aluminate clinker.

[0097] Prepare 10 kg of additives by mixing 2 kg of dispersant, 3 kg of accelerator, 1 kg of toughening agent, 2 kg of reinforcing agent and 2 kg of fluid loss additive;

[0098] 13 kg of the polyol-modified magnetic nanoparticles and 5 kg of the additives in this embodiment were added to 100 kg of the gelling material, and the mixture was stirred in a dry powder mixer for 30 minutes to obtain a grouting material, and the product quality indicators were tested.

[0099] Magnetic nanoparticle dispersion coefficient: 1.19;

[0100] Magnetic nanoparticle size: 32 nm;

[0101] Magnetic field strength of magnetic nanoparticles: 106 emu / g.

[0102] Compressive strength of grouting material: 56 MPa.

[0103] Example 8

[0104] 10 kg of iron oxide nanoparticles, 5 kg of iron silicate nanoparticles and 10 kg of aluminum nickel cobalt nanoparticles were mixed and subjected to a plasma power of 5 kW, a plasma frequency of 2450 MHz and a plasma density of 25 W / cm 2 The magnetic particles were then added to a polyol mixture consisting of 40 kg of ethylene glycol, 20 kg of glycerol, and 20 kg of octanediol, along with a composite catalyst consisting of 1 kg of nickel octadiene, 1 kg of nickel cobalt sulfide, and 3 kg of nickel acetylacetonate. The polymerization reaction was then accelerated by heating, protected by nitrogen, and allowed to react in a microwave reaction tube at 190°C for 50 minutes to produce polyol-modified magnetic nanoparticles.

[0105] Component B is a cementitious material. To prepare 100 kg of cementitious material, 25 kg of sulphoaluminate clinker, 25 kg of ferroaluminate clinker and 50 kg of aluminate clinker are mixed;

[0106] Prepare 10 kg of additives by mixing 2 kg of dispersant, 3 kg of accelerator, 1 kg of toughening agent, 2 kg of reinforcing agent and 2 kg of fluid loss additive;

[0107] 13 kg of the polyol-modified magnetic nanoparticles and 5 kg of the additives in this embodiment were added to 100 kg of the gelling material, and the mixture was stirred in a dry powder mixer for 30 minutes to obtain a grouting material, and the product quality indicators were tested.

[0108] Magnetic nanoparticle dispersion coefficient: 1.19;

[0109] Magnetic nanoparticle size: 30 nm;

[0110] Magnetic field strength of magnetic nanoparticles: 108 emu / g.

[0111] Compressive strength of grouting material: 51 MPa.

[0112] Comparative Example 1

[0113] This comparative example has the following differences compared to Example 1:

[0114] 10 kg of iron oxide nanoparticles, 5 kg of iron silicate nanoparticles and 10 kg of aluminum nickel cobalt nanoparticles were mixed and subjected to a plasma power of 6 kW, a plasma frequency of 2500 MHz and a plasma density of 28 W / cm 2 Magnetic particles were then added to a polyol mixture consisting of 40 kg of ethylene glycol, 20 kg of glycerol, and 20 kg of octanediol, along with a composite catalyst consisting of 1 kg of nickel octadienediyl, 1 kg of nickel cobalt sulfide, and 3 kg of nickel acetylacetonate. The mixture was stirred in a microwave reaction tube at room temperature for 50 minutes under nitrogen protection to produce polyol-modified magnetic nanoparticles.

[0115] Component B is a cementitious material. 110 kg of cementitious material is prepared by mixing 27.5 kg of sulphoaluminate clinker, 27.5 kg of ferroaluminate clinker and 55 kg of aluminate clinker.

[0116] Prepare 10 kg of additives by mixing 2 kg of dispersant, 3 kg of accelerator, 1 kg of toughening agent, 2 kg of reinforcing agent and 2 kg of fluid loss additive;

[0117] 13 kg of the polyol-modified magnetic nanoparticles and 10 kg of the additives were added to 100 kg of the gelling material, and the mixture was stirred in a dry powder mixer for 30 minutes to obtain a grouting material, and the product quality indicators were tested.

[0118] Magnetic nanoparticle dispersion coefficient: 1.73;

[0119] Magnetic nanoparticle size: 122 nm;

[0120] Magnetic nanoparticle magnetic field strength: 79 emu / g.

[0121] Compressive strength of grouting material: 27 MPa.

[0122] Comparative Example 2

[0123] This comparative example has the following differences compared to Example 1:

[0124] 10 kg of iron oxide nanoparticles, 5 kg of iron silicate nanoparticles and 10 kg of aluminum nickel cobalt nanoparticles were mixed and subjected to a plasma power of 6 kW, a plasma frequency of 2500 MHz and a plasma density of 28 W / cm 2 Magnetic particles were obtained by plasma treatment for 18 minutes to form active hydroxyl sites on the surface. The magnetic particles were added to 80 kg of octanediol and a composite catalyst consisting of 1 kg of nickel octadienediol, 1 kg of nickel cobalt sulfide, and 3 kg of nickel acetylacetonate. The polymerization reaction was promoted by auxiliary heating and nitrogen protection was introduced. The reaction was carried out in a microwave reaction tube at 200°C for 50 minutes to produce polyol-modified magnetic nanoparticles.

[0125] Component B is a cementitious material. 110 kg of cementitious material is prepared by mixing 27.5 kg of sulphoaluminate clinker, 27.5 kg of ferroaluminate clinker and 55 kg of aluminate clinker.

[0126] Prepare 10 kg of additives by mixing 2 kg of dispersant, 3 kg of accelerator, 1 kg of toughening agent, 2 kg of reinforcing agent and 2 kg of fluid loss additive;

[0127] 13 kg of the polyol-modified magnetic nanoparticles and 10 kg of the additives were added to 100 kg of the gelling material, and the mixture was stirred in a dry powder mixer for 30 minutes to obtain a grouting material, and the product quality indicators were tested.

[0128] Magnetic nanoparticle dispersion coefficient: 1.69;

[0129] Magnetic nanoparticle size: 143 nm;

[0130] Magnetic nanoparticle magnetic field strength: 48 emu / g.

[0131] Compressive strength of grouting material: 30 MPa.

[0132] It should be noted that, in the description of this application, the terms "first", "second", etc. are used for descriptive purposes only and should not be understood as indicating or implying relative importance. In addition, in the description of this application, unless otherwise specified, the meaning of "plurality" is two or more.

[0133] Any process or method description in a flowchart or otherwise described herein may be understood to represent a module, segment or portion of code comprising one or more executable instructions for implementing the steps of a specific logical function or process, and the scope of the preferred embodiments of the present application includes alternative implementations in which functions may be performed out of the order shown or discussed, including performing functions in a substantially simultaneous manner or in the reverse order depending on the functions involved, which should be understood by those skilled in the art to which the embodiments of the present application belong.

[0134] Throughout this specification, reference to terms such as "one embodiment," "some embodiments," "examples," "specific examples," or "some examples" means that a specific feature, structure, material, or characteristic described in conjunction with that embodiment or example is included in at least one embodiment or example of the present application. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0135] Although the embodiments of the present application have been shown and described above, it can be understood that the above embodiments are exemplary and cannot be understood as limitations on the present application. Ordinary technicians in this field can change, modify, replace and modify the above embodiments within the scope of the present application.

Claims

1. A method for preparing a grouting material based on magnetic particle tracing, characterized in that: The following steps are included: The magnetic particles having active hydroxyl sites on the surface are added to a polyol mixture, and a polymerization reaction is carried out at 190-200°C for 50 minutes under the catalytic action of a composite catalyst and a protective atmosphere to obtain polyol-modified magnetic nanoparticles having multiple hydroxyl functional groups on the surface; Wherein, in terms of parts by mass, the magnetic particles are 20 parts; the polyol mixture is 70-80 parts; and the composite catalyst is 5-8 parts; the magnetic particles are obtained by plasma treatment of iron oxide nanoparticles, iron silicate nanoparticles, and aluminum nickel cobalt nanoparticles, and the mass ratio of the iron oxide nanoparticles, the iron silicate nanoparticles, and the aluminum nickel cobalt nanoparticles is (2-5):(1-2):(2-4); the polyol mixture comprises ethylene glycol, glycerol, and octanediol in a mass ratio of 2:1:1; 12-15 parts by weight of the polyol-modified magnetic nanoparticles and 5-13 parts by weight of an auxiliary agent are added to 100-120 parts by weight of a gelling material, and the dry powder is stirred to obtain the obtained product; the various hydroxyl functional groups on the surface of the polyol-modified magnetic nanoparticles form hydrogen bonding forces with the hydroxyl groups on the surface of the coal rock mass.

2. The preparation method according to claim 1, characterized in that The parameters of the plasma treatment are power 5-6 kW, frequency 2450-2500 MHz, density 25-28 W / cm 2 , time 15-18 minutes.

3. The preparation method according to claim 1, characterized in that The protective atmosphere is an inert gas, including nitrogen, helium or neon.

4. The preparation method according to claim 1, characterized in that Calculated by weight, the additives include 1-2 parts of a dispersant, 1-3 parts of a coagulant, 1 part of a toughening agent, 1-5 parts of a reinforcing agent, and 1-2 parts of a fluid loss additive.

5. The preparation method according to claim 1, characterized in that The cementitious material includes sulphoaluminate clinker, ferroaluminate clinker and aluminate clinker mixed in a mass ratio of 1:1:

2.

6. A grouting material based on magnetic particle tracing, characterized in that: It includes a mixture A and a gelling material; in parts by mass, the mixture A includes 12-15 parts of the polyol-modified magnetic nanoparticles according to claim 1 and 5-13 parts of an auxiliary agent; the gelling material has a mass portion of 100-120 parts, and includes sulphoaluminate clinker, ferroaluminate clinker and aluminate clinker mixed in a mass ratio of 1:1:

2.

7. The grouting material according to claim 6, characterized in that Calculated by weight, the additives include 1-2 parts of a dispersant, 1-3 parts of a coagulant, 1 part of a toughening agent, 1-5 parts of a reinforcing agent, and 1-2 parts of a fluid loss additive.

8. The grouting material according to claim 6, characterized in that The polyol-modified magnetic nanoparticles are obtained by adding magnetic particles with active hydroxyl sites on the surface into a polyol mixture and performing a polymerization reaction under the catalytic action of a composite catalyst and a protective atmosphere.

9. Use of the grouting material according to any one of claims 6 to 8 in magnetic particle tracer grouting in a large deformation tunnel of a coal mine, characterized in that: The grouting material described in any one of claims 6 to 8 is also used as a tracer in large deformation tunnels.

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