An industrial solid waste-based flexible composite material, its preparation method and application

Abstract

An industrial solid waste-based flexible composite material, its preparation method and application relate to the technical field of composite materials. The preparation method includes the following steps: S1. Dry-mix ultrafine sand tailings, solid waste-based cementitious materials, water-absorbing fibers and internal curing agents to obtain a solid waste-based dry mixture; S2. Mix natural rubber, butyl acrylate, zinc oxide, stearic acid, anti-aging agent, antioxidant, vulcanization accelerator and sulfur through kneading to obtain a rubber toughening material; S3. Knead the solid waste-based dry mixture obtained in S1 with the rubber toughening material obtained in S2 to obtain a solid waste-based flexible composite material; The present invention also provides a solid waste-based flexible composite material prepared by the above method and its application in composite boards; The solid waste-based flexible composite material combines the compressive strength of mortar and the high tensile strength and high elongation at break of rubber, while improving the resource utilization of industrial solid waste, effectively reducing the environmental pollution and resource waste caused by the accumulation of industrial solid waste, and has broad application prospects.

Description

Technical Field

[0001] The present invention relates to the technical field of composite materials, and particularly relates to an industrial solid waste-based flexible composite material, a preparation method thereof, and an application thereof. Background Art

[0002] Industrial solid waste refers to solid waste generated in industrial production activities, such as tailings generated in the process of mine beneficiation, slag generated in the smelting of iron and steel or other metals, fly ash generated by the combustion of pulverized coal in power plants, and so on. Due to the large amount of industrial solid waste generated and the low utilization rate, a large amount of industrial solid waste is piled up on the ground, occupying a large amount of land resources, and there are environmental pollution and safety hazards. Therefore, it is urgent to take measures for source reduction, resource utilization, and harmless treatment of industrial solid waste.

[0003] In a Chinese invention with the publication number CN116639945A, a method for preparing a cemented filling material by synergistically using multi-source industrial waste residues and ultra-fine tailings is disclosed. The cemented filling material is composed of ultra-fine tailings, an industrial solid waste-based cementitious material, and water. Among them, the industrial solid waste-based cementitious material accounts for 6.5% - 12.5% of the total mass of the filling material, water accounts for 37% - 40% of the total mass of the filling material, and the balance is ultra-fine tailings. The industrial solid waste-based cementitious material is made from steel slag, fly ash, carbide slag, desulfurized gypsum, and blast furnace slag. In a Chinese invention with the publication number CN109206116A, a method for preparing non-fired bricks using industrial tailings and fly ash is disclosed. The raw material composition of the non-fired bricks is as follows: 25 - 75% of industrial tailings; at least one of cement, fly ash, and slag is 5 - 25%; aggregate is 0 - 60%; inorganic adhesive is 0 - 30%; other additives are 0 - 10%.

[0004] Like most existing methods for treating industrial solid waste, the above two patents both recycle industrial solid waste to prepare building materials. Although the resource utilization of industrial solid waste is achieved, the building materials prepared mainly rely on inorganic materials, resulting in the fact that although the building materials can achieve relatively high compressive strength, their toughness, crack resistance strength and other properties are slightly insufficient, and the application fields are also relatively single. Summary of the Invention

[0005] Aiming at the deficiencies in the prior art, the present invention provides an industrial solid waste-based flexible composite material, a preparation method thereof, and an application thereof, which solve the problems that the properties of materials prepared from industrial solid waste in the prior art are not excellent enough and have insufficient potential.

[0006] A preparation method of an industrial solid waste-based flexible composite material includes the following steps:

[0007] S1. Dry-mix ultrafine sand tailings, solid waste-based cementitious materials, water-absorbing fibers, and internal curing agents to obtain a solid waste-based dry mix.

[0008] S2. Mix natural rubber, butyl acrylate, zinc oxide, stearic acid, anti-aging agent, antioxidant, vulcanization accelerator, and sulfur through kneading to obtain a rubber softening agent.

[0009] S3. Knead the solid waste-based dry mix obtained in S1 and the rubber softening agent obtained in S2 to obtain a solid waste-based flexible composite material.

[0010] Preferably, in step S1, the particle size of the ultrafine sand tailings is 0.063 - 0.125 mm.

[0011] Preferably, in step S1, the addition amount of the solid waste-based cementitious material accounts for 45% - 55% of the mass of the ultrafine sand tailings, the addition amount of the water-absorbing fibers accounts for 8% - 12% of the mass of the ultrafine sand tailings, and the addition amount of the internal curing agent accounts for 2% - 4% of the mass of the ultrafine sand tailings.

[0012] Preferably, in step S1, the solid waste-based cementitious material includes slag powder, fly ash, and sodium silicate with a mass ratio of 1:1:0.3, where the fly ash is grade I fly ash and the modulus of the sodium silicate is 1.5.

[0013] Preferably, in step S1, the water-absorbing fibers are cotton fibers with a length of 8 - 10 mm, and the internal curing agent is a superabsorbent resin with a particle size of 0.1 mm.

[0014] Preferably, step S2 is specifically: Mix natural rubber and butyl acrylate at 110°C for 6 min, then add zinc oxide, stearic acid, anti-aging agent, antioxidant, and vulcanization accelerator and continue to knead for 6 min, then cool down to 60°C and add sulfur and continue to knead for 3 min to obtain a rubber softening agent.

[0015] Preferably, in step S2, the mass ratio of natural rubber, butyl acrylate, zinc oxide, stearic acid, anti-aging agent, antioxidant, vulcanization accelerator, and sulfur is 100:(20 - 40):(4.8 - 5.2):(1.8 - 2.2):(0.8 - 1.2):(0.8 - 1.2):(0.8 - 1.2):(1.8 - 2.2).

[0016] Preferably, in step S3, by mass, the solid waste-based dry mix is 30 - 50 parts, and the rubber softening agent is 50 - 70 parts.

[0017] The present invention also provides an industrial solid waste-based flexible composite material prepared by the above preparation method.

[0018] The present invention also provides an application of the industrial solid waste-based flexible composite material in composite boards.

[0019] Compared with the prior art, the present invention has the following beneficial effects:

[0020] 1. In the present invention, ultrafine sand tailings are mixed with a solid waste-based cementitious material to form an industrial solid waste-based solidified material, and a superabsorbent resin and cotton fibers are added as a water diversion channel and an internal curing agent. Then, dry mixing is carried out in a state without adding water, and it is blended with an organic rubber having high elasticity and high tensile strength to form an organic-inorganic double continuous phase structure. At the same time, polybutyl acrylate with high viscosity is used to modify the viscosity of natural rubber to improve the interfacial bonding strength between natural rubber and the solid waste-based dry mixture. Moreover, during the application process of this industrial solid waste-based flexible composite material, the water diversion channel formed by cotton fibers can absorb external moisture into the interior of the industrial solid waste-based flexible composite material. After the superabsorbent resin inside receives the moisture, it will store the water to form small internal curing ponds, providing sufficient moisture for the hydration process of the industrial solid waste-based solidified material. Externally, due to the prestress fixation of the rubber, no cracks are generated.

[0021] 2. The industrial solid waste-based flexible composite material prepared by the present invention combines the compressive strength of mortar and the high tensile strength and high elongation at break of rubber. At the same time, it improves the resource utilization of industrial solid waste, effectively reduces environmental pollution and resource waste caused by the accumulation of industrial solid waste, and has broad application prospects. Specific Embodiments

[0022] In order to make the technical means, creative features, achieved purposes and functions of the present invention clearer and easier to understand, the present invention will be further described below in conjunction with specific embodiments:

[0023] Example 1

[0024] S1. Take 100 parts of ultrafine sand tailings, 20 parts of slag powder, 20 parts of Class 1 fly ash, 6 parts of water glass, 10 parts of superabsorbent resin and 3 parts of cotton fibers, and place them in a mixer for dry mixing for 30 min to obtain a solid waste-based dry mixture;

[0025] S2. First, mix 100 parts of natural rubber and 30 parts of polybutyl acrylate in a two-roll internal mixer at 110 °C for 6 min, then add 5 parts of zinc oxide, 2 parts of stearic acid, 1 part of anti-aging agent, 1 part of antioxidant and 1 part of vulcanization accelerator, continue mixing for 6 min, and then reduce the temperature of the two rolls to 60 °C and add 2 parts of sulfur and continue mixing for 3 min to obtain a rubber softening agent;

[0026] S3. Take 60 parts of the solid waste-based dry mixture prepared in S1 and 40 parts of the rubber softening agent prepared in S2, and mix them for 6 min to obtain a solid waste-based flexible composite material.

[0027] Example 2

[0028] S1. Take 100 parts of ultrafine sand tailings, 22 parts of slag powder, 22 parts of Class 1 fly ash, 6.6 parts of water glass, 8 parts of superabsorbent resin, and 2 parts of cotton fiber, and place them in a blender for dry mixing for 30 min to obtain a solid waste-based dry mix;

[0029] S2. First, mix 100 parts of natural rubber and 30 parts of butyl acrylate in a two-roll internal mixer at 110 °C for 6 min, then add 5 parts of zinc oxide, 2 parts of stearic acid, 1 part of anti-aging agent, 1 part of antioxidant, and 1 part of vulcanization accelerator, and continue mixing for 6 min. Then, lower the temperature of the two rolls to 60 °C and add 2 parts of sulfur and continue mixing for 3 min to obtain a rubber softening agent;

[0030] S3. Take 50 parts of the solid waste-based dry mix prepared in S1 and 50 parts of the rubber softening agent prepared in S2, and mix them for 6 min to obtain a solid waste-based flexible composite material.

[0031] Example 3

[0032] S1. Take 100 parts of ultrafine sand tailings, 24 parts of slag powder, 24 parts of Class 1 fly ash, 7.2 parts of water glass, 12 parts of superabsorbent resin, and 4 parts of cotton fiber, and place them in a blender for dry mixing for 30 min to obtain a solid waste-based dry mix;

[0033] S2. First, mix 100 parts of natural rubber and 30 parts of butyl acrylate in a two-roll internal mixer at 110 °C for 6 min, then add 5 parts of zinc oxide, 2 parts of stearic acid, 1 part of anti-aging agent, 1 part of antioxidant, and 1 part of vulcanization accelerator, and continue mixing for 6 min. Then, lower the temperature of the two rolls to 60 °C and add 2 parts of sulfur and continue mixing for 3 min to obtain a rubber softening agent;

[0034] S3. Take 70 parts of the solid waste-based dry mix prepared in S1 and 30 parts of the rubber softening agent prepared in S2, and mix them for 6 min to obtain a solid waste-based flexible composite material.

[0035] Example 4

[0036] S1. Take 100 parts of ultrafine sand tailings, 20 parts of slag powder, 20 parts of Class 1 fly ash, 6 parts of water glass, 10 parts of superabsorbent resin, and 3 parts of cotton fiber, and place them in a blender for dry mixing for 30 min to obtain a solid waste-based dry mix;

[0037] S2. First, mix 100 parts of natural rubber and 20 parts of butyl acrylate in a two-roll internal mixer at 110 °C for 6 min, then add 4.8 parts of zinc oxide, 1.8 parts of stearic acid, 0.8 parts of anti-aging agent, 0.8 parts of antioxidant, and 0.8 parts of vulcanization accelerator, and continue mixing for 6 min. Then, lower the temperature of the two rolls to 60 °C and add 1.8 parts of sulfur and continue mixing for 3 min to obtain a rubber softening agent;

[0038] S3. Take 60 parts of the solid waste-based dry mix prepared in S1 and 40 parts of the rubber softening agent prepared in S2, and knead them for 6 min to obtain a solid waste-based flexible composite material.

[0039] Example 5

[0040] S1. Take 100 parts of ultrafine sand tailings, 20 parts of slag powder, 20 parts of Class 1 fly ash, 6 parts of water glass, 10 parts of superabsorbent resin, and 3 parts of cotton fiber, and place them in a mixer for dry mixing for 30 min to obtain a solid waste-based dry mix;

[0041] S2. First, knead 100 parts of natural rubber and 40 parts of butyl acrylate in a two-roll internal mixer at 110 °C for 6 min, then add 5.2 parts of zinc oxide, 2.2 parts of stearic acid, 1.2 parts of anti-aging agent, 1.2 parts of antioxidant, and 1.2 parts of vulcanization accelerator, continue to knead for 6 min, then lower the temperature of the two rolls to 60 °C and add 2.2 parts of sulfur and continue to knead for 3 min to obtain a rubber softening agent;

[0042] S3. Take 60 parts of the solid waste-based dry mix prepared in S1 and 40 parts of the rubber softening agent prepared in S2, and knead them for 6 min to obtain a solid waste-based flexible composite material.

[0043] Comparative Example 1

[0044] Compared with Example 1, steps S2 and S3 are not carried out, and only step S1 is carried out.

[0045] Comparative Example 2

[0046] Compared with Example 1, the superabsorbent resin and cotton fiber are not added in step S1, and the other steps are the same.

[0047] Comparative Example 3

[0048] Compared with Example 1, butyl acrylate is not added in step S2, and the other steps are the same.

[0049] Place the solid waste-based flexible composite materials prepared in Examples 1-5 and Comparative Examples 2-3 in a mold of 150 mm × 150 mm × 4 mm, keep the temperature and pressure constant at 150 °C and 15 MPa for 20 min, cool, soak in water for 24 h, then take out and place in a standard curing room (constant temperature 20 °C, humidity 95%) for curing for 28 days, and dry to obtain a composite board.

[0050] Add 25 parts of water to the solid waste-based dry mix prepared in Comparative Example 1, mix well, place it in a mold of 150 mm × 150 mm × 4 mm, then place it in a standard curing room (constant temperature 20 °C, humidity 95%) for curing for 28 days, and dry to obtain a composite board.

[0051] The compressive strength of each of the above composite boards was detected according to the "Test Method for Compressive Properties of Plastics" (GB / T 1041-1992).

[0052] According to the "Determination of Tensile Properties of Plastics" (GB / T 1040.1-2018), the tensile strength and elongation at break of each of the above composite boards were detected, and the results are shown in the following table.

[0053]

[0054] As can be seen from the above table, the composite boards prepared in Examples 1-5 have good compressive strength, tensile strength and elongation at break. Moreover, from the performance data of the composite boards prepared in Examples 1-3, it can be seen that the more the addition amount of the solid waste-based dry mix, the better its compressive strength, but the tensile strength and elongation at break will decrease correspondingly. On the contrary, the compressive strength decreases, and the tensile strength and elongation at break increase. Therefore, the selection of the addition amounts of the solid waste-based dry mix and the rubber softening agent is the key to balancing the compressive strength, tensile strength and elongation at break.

[0055] From the performance data of the composite boards prepared in Example 1, Examples 4-5 and Comparative Example 3, it can be seen that if the addition amount of butyl acrylate is small or not added at all, it will lead to poor interfacial force between natural rubber and the solid waste-based dry mix, which will comprehensively affect the compressive strength, tensile strength and elongation at break.

[0056] From the performance data of the composite boards prepared in Example 1 and Comparative Example 1, it can be seen that since no rubber softening agent is added in Comparative Example 1, the finally prepared is a traditional solid waste-based composite board, which although can have good compressive strength, but its tensile strength and elongation at break are far from those of the composite board prepared in Example 1.

[0057] From the performance data of the composite boards prepared in Example 1 and Comparative Example 2, it can be seen that the compressive strength of the composite board prepared in Comparative Example 2 is significantly insufficient. The main reason is that when the solid waste-based flexible composite material is immersed in water after being compacted, since there is no water diversion channel provided by cotton fibers inside it, water cannot enter the inside of the solid waste-based flexible composite material and cannot be stored by the superabsorbent resin, so that the inside of the solid waste-based flexible composite material cannot be hydrated and solidified, and only the surface part can be solidified. Therefore, the compressive strength is significantly lower than that of the composite board prepared in Example 1.

[0058] Moreover, the solid waste-based flexible composite material prepared by the present invention can not only be used for preparing composite boards, but also for preparing materials in other different fields.

[0059] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced without departing from the spirit and scope of the technical solutions of the present invention, and they should all be covered within the scope of the claims of the present invention.

Claims

1. A method for preparing an industrial solid waste-based flexible composite material, characterized in that: The following steps are involved: S1. Dry-mixing ultrafine sand tailings, solid waste-based cementitious materials, water-diverting fibers and internal curing agents to obtain a solid waste-based dry mix; S2. The natural rubber, polybutyl acrylate, zinc oxide, stearic acid, anti-aging agent, antioxidant, vulcanization accelerator and sulfur are mixed to obtain a rubber softening material; S3. The solid waste-based dry blend obtained in S1 is mixed with the rubber softening material obtained in S2 to obtain a solid waste-based flexible composite material; The water-inducing fiber is a cotton fiber with a length of 8 to 10 mm, and the internal curing agent is a highly absorbent resin with a particle size of 0.1 mm; In step S1, the solid waste-based cementitious material includes slag powder, fly ash and water glass in a mass ratio of 1:1:0.3, wherein the fly ash is first-grade fly ash and the modulus of the water glass is 1.5; In step S2, the mass ratio of natural rubber, polybutyl acrylate, zinc oxide, stearic acid, anti-aging agent, antioxidant, vulcanization accelerator and sulfur is 100: (20~40): (4.8~5.2): (1.8~2.2): (0.8~1.2): (0.8~1.2): (0.8~1.2): (1.8~2.2).

2. The method for preparing an industrial solid waste-based flexible composite material according to claim 1, characterized in that: In step S1, the particle size of the ultrafine sand tailings is 0.063-0.125 mm.

3. The method for preparing an industrial solid waste-based flexible composite material according to claim 1, characterized in that: In step S1, the amount of solid waste-based cementitious material added is 45% to 55% of the mass fraction of the ultrafine sand tailings, the amount of water-diverting fiber added is 8% to 12% of the mass fraction of the ultrafine sand tailings, and the amount of internal curing agent added is 2% to 4% of the mass fraction of the ultrafine sand tailings.

4. The method for preparing an industrial solid waste-based flexible composite material according to claim 1, characterized in that: Step S2 is specifically as follows: mixing natural rubber and polybutyl acrylate at 110° C. for 6 minutes, then adding zinc oxide, stearic acid, anti-aging agent, antioxidant, and vulcanization accelerator and continuing to mix for 6 minutes, then cooling to 60° C. and adding sulfur and continuing to mix for 3 minutes to obtain a rubber softening material.

5. The method for preparing an industrial solid waste-based flexible composite material according to claim 1, characterized in that: In step S3, the solid waste-based dry mix is ​​50-70 parts by weight, and the rubber softening material is 30-50 parts by weight.

6. An industrial solid waste-based flexible composite material, characterized in that: Prepared by the preparation method according to any one of claims 1 to 5.

7. Use of the industrial solid waste-based flexible composite material according to claim 6 in composite panels.

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