Solid waste-based self-repairing functional filler and preparation method thereof

Abstract

The invention discloses a solid waste-based self-repairing functional filler and a preparation method thereof, and belongs to the technical field of functional materials, the solid waste-based self-repairing functional filler comprises the following components by mass: 4-8% of a hydroxycarboxylic acid complexing agent, 8-12% of an aminocarboxylic acid complexing agent, 10-15% of a carbonate precipitant, 12-16% of a silicate precipitant, 25-35% of a potassium sulfate salt expanding agent and 25-32% of a solid waste-based cementing material. The solid waste-based self-repairing functional filler prepared by the invention solves the problem of cracks caused by temperature difference and harmful substance corrosion after a common cement-based building material is hydrated; after cracks appear on a common cement-based building material, the cracks cannot be repaired in time; and a new thought of large-scale application of the steel slag is expanded, a large amount of refractory metallurgical solid waste is turned into wealth, and the policy requirements of energy conservation, environmental protection and circular economy are met.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of functional materials, and particularly relates to a solid waste-based self-repairing functional filler and a preparation method thereof. BACKGROUND

[0002] The construction industry using cement as raw material not only enjoys its advantages of being solid, convenient and mature, but also faces the distress of adverse factors caused by the characteristics of cement. Among them, the crack water seepage phenomenon of cement-based building materials is the most common, which is mainly caused by various factors, including material problems, construction problems, temperature changes, foundation settlement and moisture intrusion, etc.

[0003] In the prior art, in order to solve the crack water seepage phenomenon of cement-based building materials, measures such as repairing cracks or waterproof treatment are usually used to solve water seepage, clean cracks, fill with professional wall repair materials (such as polymer cement mortar or epoxy resin), ensure that each layer is fully dried, and after the repair is completed, perform plastering and polishing treatment on the surface to make it smooth with the surrounding wall. Waterproof treatment usually installs a waterproof layer on the outer wall and uses high-performance waterproof paint (such as polyurethane, acrylate, etc.) for brushing to form an effective waterproof barrier, especially for professional sealing treatment of gaps and weak electricity, using silicone sealant, polyurethane sealant and other materials for plugging. For example, Chinese patent CN 119874269 A discloses a multi-element solid waste-based cementitious material and a preparation method thereof, by ball milling, slag with a particle size of 12-15 μm, sea silt and desulfurization gypsum with a particle size of 8-10 μm, fly ash and rice husk ash with a particle size of 3-6 μm are obtained; the raw materials are mixed uniformly to obtain a multi-element solid waste-based cementitious material, the use of sea silt, glass fiber, rice husk ash and specific particle size distribution can enrich the pore structure of the cementitious material and improve the mechanical properties and durability of the cementitious material. However, this material cannot timely and effectively repair cracks and other problems through self-repairing, and cannot improve the density and strength of cement-based building materials by cooperating with the pore closure process of cement-based building materials.

[0004] Therefore, it is urgent to solve the above problems, especially how to use the self-repairing technology of the material to induce the ability of the hydration product to form a good mechanical and waterproof structure. SUMMARY

[0005] The technical problem to be solved by the present application is to provide a solid waste-based self-repairing functional filler and a preparation method thereof to solve the problems mentioned in the background or achieve better technical effects.

[0006] In order to solve the above technical problems, the inventors have summarized and obtained the technical scheme of the present application through practice, and the present application discloses a kind of solid waste base self-repairing functional fillers, and the mass percentage of each component is as follows: hydroxyl carboxylic acid complexing agent 4~8%, amino carboxylic acid complexing agent 8~12%, carbonate precipitant 10~15%, silicate precipitant 12~16%, potassium sulfate salt expanding agent 25~35% and solid waste base cementing material 25~32%.

[0007] Further, the mass percentage of each component is as follows: hydroxyl carboxylic acid complexing agent 6~8%, amino carboxylic acid complexing agent 8~9%, carbonate precipitant 10~12%, silicate precipitant 14~16%, potassium sulfate salt expanding agent 25~29% and solid waste base cementing material 27~32%.

[0008] Further, the mass percentage of each component is as follows: hydroxyl carboxylic acid complexing agent 7%, amino carboxylic acid complexing agent 9%, carbonate precipitant 12%, silicate precipitant 16%, potassium sulfate salt expanding agent 29% and solid waste base cementing material 27%.

[0009] Further, the hydroxyl carboxylic acid complexing agent is a mixture of tartaric acid and citric acid, and the mass ratio of tartaric acid to citric acid is 10:1~3.

[0010] Further, the amino carboxylic acid complexing agent is a mixture of EDTA-4Na and HEDP-4Na, and the mass ratio of EDTA-4Na to HEDP-4Na is 1~2:2~1.

[0011] Further, the carbonate precipitant is a mixture of sodium carbonate and calcium carbonate, and the mass ratio of sodium carbonate to calcium carbonate is 10:1~3.

[0012] Further, the silicate precipitant is a mixture of sodium silicate and calcium silicate, and the mass ratio of sodium silicate to calcium silicate is 5:1~2.

[0013] Further, the potassium sulfate salt expanding agent is a mixture of potassium aluminum sulfate and potassium bitartrate, and the mass ratio of potassium aluminum sulfate to potassium bitartrate is 10:1~3.

[0014] Further, the solid waste base cementing material is a mixture of 95-grade mineral powder, 500-mesh steel slag powder, desulfurization gypsum and triethanolamine, and the mass ratio of 95-grade mineral powder, 500-mesh steel slag powder, desulfurization gypsum and triethanolamine is 7.5:1.5:0.5:0.5.

[0015] Further, the preparation method of the above-mentioned solid waste base self-repairing functional filler is as follows:

[0016] S1: mixing the hydroxyl carboxylic acid complexing agent with the aminocarboxylic acid complexing agent, and obtaining a composite complexing agent after constant temperature stirring;

[0017] S2: mixing the carbonate precipitant and the silicate precipitant, and obtaining a composite precipitant after constant temperature stirring;

[0018] S3: mixing the potassium sulfate salt expanding agent, the solid waste-based cementitious material, the composite complexing agent in S1 and the composite precipitant in S2, and obtaining the solid waste-based self-repairing functional filler after constant temperature stirring.

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

[0020] (1) The carboxylic acid groups in the hydroxyl carboxylic acid complexing agent and the aminocarboxylic acid complexing agent form hydrogen bonds with water molecules and form a waterproof film, and the alkali earth metal ions are enriched to repair pores and cavities. The aminocarboxylic acid complexing agent has strong alkali resistance, and the hydroxyl carboxylic acid complexing agent has excellent biological activity, which can improve the pore closure in the cement-based building material.

[0021] (2) The carbonate and silicate in the carbonate precipitant and the silicate precipitant participate in the process of precipitating-crystallizing micro-pore closure, which can improve the density and strength of the cement-based building material. The generated carbonate precipitate and silicate gel material can optimize the pore structure and help resist the invasion of harmful substances from the outside.

[0022] (3) The sulfate in the potassium sulfate salt expanding agent and the 95-grade mineral powder, 500-mesh steel slag powder, desulfurization gypsum and triethanolamine in the solid waste-based cementitious material, as well as the carbonate precipitant, can generate calcium vanadinite through the hydrolysis process, which can enhance the mechanical properties of the cement-based building material.

[0023] (4) The dissolved product of the potassium sulfate salt expanding agent can accelerate the hydration reaction of C2S, C3S and C3A in the solid waste-based cementitious material and the silicate precipitant. The potassium ion can induce the water production to form a good mechanical and waterproof structure, which can enhance the strength and density of the cement-based building material.

[0024] (5) The potassium sulfate salt expanding agent not only provides sulfate ions, but also contains a large amount of calcium oxide and sodium oxide, which can maintain the alkaline environment inside the hydration product after the hydration process of the cement-based building material. The potassium sulfate salt expanding agent can further induce the hydration reaction of C2S, C3S and C3A in the solid waste-based cementitious material, and can induce the water production to form a good mechanical and waterproof structure, i.e. self-repairing. BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1A comparison chart of the 7d and 28d flexural strengths of the fillers prepared in Examples 1-6 and Comparative Examples 1-5 of the present application;

[0026] Figure 2 A comparison chart of the 7d and 28d compressive strengths of the fillers prepared in Examples 1-6 and Comparative Examples 1-5 of the present application;

[0027] Figure 3 Physical pictures of the solid waste-based self-repairing functional fillers prepared in Examples 1-6 of the present application after self-repairing; wherein (a) Example 1; (b) Example 2; (c) Example 3; (d) Example 4; (e) Example 5; (f) Example 6;

[0028] Figure 4 Physical pictures of the solid waste-based self-repairing functional fillers prepared in Comparative Examples 1-5 of the present application after self-repairing; wherein (a) Comparative Example 1; (b) Comparative Example 2; (c) Comparative Example 3; (d) Comparative Example 4; (e) Comparative Example 5. DETAILED DESCRIPTION

[0029] In order to make the above objectives, features and advantages of the present application more apparent and easy to understand, the specific embodiments of the present application will be described in detail below.

[0030] The raw materials or reagents used in the following examples and comparative examples are commercially available products or products prepared by conventional technical means, unless otherwise specified;

[0031] The detection method of the solid waste-based self-repairing functional fillers in the following examples and comparative examples is as follows:

[0032] Mechanical properties: according to GB / T 17671-2020;

[0033] Self-repairing performance: according to GB 18445-2012.

[0034] Example 1

[0035] A solid waste-based self-repairing functional filler, the allocation ratio of each component is as follows in terms of weight percentage:

[0036] hydroxyl carboxylic acid complexing agent 4%,

[0037] amino carboxylic acid complexing agent 12%,

[0038] carbonate precipitating agent 15%,

[0039] silicate precipitating agent 12%,

[0040] potassium sulfate salt expanding agent 25%,

[0041] solid waste-based cementitious material 32%.

[0042] The hydroxyl carboxylic acid complexing agent is a mixture of tartaric acid and citric acid, the mass ratio of tartaric acid to citric acid is 10:1; the amino carboxylic acid complexing agent is a mixture of EDTA-4Na (tetrasodium ethylenediaminetetraacetate) and HEDP-4Na (tetrasodium 1-hydroxyethyl-1,1-diphosphonate), the mass ratio of EDTA-4Na (tetrasodium ethylenediaminetetraacetate) to HEDP-4Na (tetrasodium 1-hydroxyethyl-1,1-diphosphonate) is 1:1; the carbonate precipitant is a mixture of sodium carbonate and calcium carbonate, the mass ratio of sodium carbonate to calcium carbonate is 10:3; the silicate precipitant is a mixture of sodium silicate and calcium silicate, the mass ratio of sodium silicate to calcium silicate is 5:1; the potassium sulfate salt expanding agent is a mixture of potassium aluminum sulfate and potassium bitartrate, the mass ratio of potassium aluminum sulfate to potassium bitartrate is 10:3. The solid waste-based cementitious material is a mixture of 95-grade mineral powder, 500-mesh steel slag powder, desulfurization gypsum and triethanolamine, the mass ratio of 95-grade mineral powder, 500-mesh steel slag powder, desulfurization gypsum and triethanolamine is 7.5:1.5:0.5:0.5.

[0043] The preparation method of the solid waste-based self-repairing functional filler described above, the steps are as follows:

[0044] (1) Mix the hydroxyl carboxylic acid complexing agent and the amino carboxylic acid complexing agent, use a constant-temperature magnetic stirrer to stir at a speed of 200 r / min at room temperature for 25 min to obtain a composite complexing agent;

[0045] (2) Mix the carbonate precipitant and the silicate precipitant, use a constant-temperature magnetic stirrer to stir at a speed of 300 r / min at room temperature for 20 min to obtain a composite precipitant;

[0046] (3) Mix the composite complexing agent obtained in step (1), the composite precipitant obtained in step (2), the potassium sulfate salt expanding agent and the solid waste-based cementitious material, use a constant-temperature magnetic stirrer to stir at a speed of 300 r / min at room temperature for 45 min to obtain the solid waste-based self-repairing functional filler.

[0047] Example 2

[0048] A solid waste-based self-repairing functional filler, the allocation ratio of each component is as follows in terms of weight percentage:

[0049] hydroxyl carboxylic acid complexing agent 8%,

[0050] amino carboxylic acid complexing agent 8%,

[0051] carbonate precipitant 10%,

[0052] silicate precipitant 17%,

[0053] Potassium sulfate salt expanding agent 27%,

[0054] Solid waste-based cementitious material 30%;

[0055] The hydroxyl carboxylic acid complexing agent is a mixture of tartaric acid and citric acid, and the mass ratio of tartaric acid to citric acid is 10:3; the amino carboxylic acid complexing agent is a mixture of EDTA-4Na (tetrasodium ethylenediaminetetraacetate) and HEDP-4Na (tetrasodium 1-hydroxyethyl 1,1-diphosphonate), and the mass ratio of EDTA-4Na (tetrasodium ethylenediaminetetraacetate) to HEDP-4Na (tetrasodium 1-hydroxyethyl 1,1-diphosphonate) is 2:1; the carbonate precipitant is a mixture of sodium carbonate and calcium carbonate, and the mass ratio of sodium carbonate to calcium carbonate is 10:2; the silicate precipitant is a mixture of sodium silicate and calcium silicate, and the mass ratio of sodium silicate to calcium silicate is 5:2; the potassium sulfate salt expanding agent is a mixture of potassium aluminum sulfate and potassium bitartrate, and the mass ratio of potassium aluminum sulfate to potassium bitartrate is 10:2. The solid waste-based cementitious material is a mixture of 95-grade mineral powder, 500-mesh steel slag powder, desulfurization gypsum, and triethanolamine, and the mass ratio of 95-grade mineral powder, 500-mesh steel slag powder, desulfurization gypsum, and triethanolamine is 7.5:1.5:0.5:0.5.

[0056] The preparation method of the solid waste-based self-repairing functional filler described above has the following steps:

[0057] (1) Mix the hydroxyl carboxylic acid complexing agent and the amino carboxylic acid complexing agent, and use a constant-temperature magnetic stirrer to stir at a speed of 300 r / min for 20 min at room temperature to obtain a composite complexing agent;

[0058] (2) Mix the carbonate precipitant and the silicate precipitant, and use a constant-temperature magnetic stirrer to stir at a speed of 250 r / min for 30 min at room temperature to obtain a composite precipitant;

[0059] (3) Mix the composite complexing agent obtained in step (1), the composite precipitant obtained in step (2), the potassium sulfate salt expanding agent, and the solid waste-based cementitious material, and use a constant-temperature magnetic stirrer to stir at a speed of 350 r / min for 30 min at room temperature to obtain the solid waste-based self-repairing functional filler.

[0060] Example 3

[0061] A solid waste-based self-repairing functional filler, and the allocation ratio of each component is as follows in terms of weight percentage:

[0062] Hydroxyl carboxylic acid complexing agent 5%,

[0063] Amino carboxylic acid complexing agent 10%,

[0064] Carbonate precipitant 11%,

[0065] Silicate precipitant 13%,

[0066] Potassium sulfate salt expanding agent 35%,

[0067] Solid waste-based cementitious material 26%;

[0068] The hydroxyl carboxylic acid complexing agent is a mixture of tartaric acid and citric acid, and the mass ratio of tartaric acid to citric acid is 10:2; the amino carboxylic acid complexing agent is a mixture of EDTA-4Na (tetrasodium ethylenediaminetetraacetate) and HEDP-4Na (tetrasodium 1-hydroxyethyl 1,1-diphosphonate), and the mass ratio of EDTA-4Na (tetrasodium ethylenediaminetetraacetate) to HEDP-4Na (tetrasodium 1-hydroxyethyl 1,1-diphosphonate) is 1:2; the carbonate precipitant is a mixture of sodium carbonate and calcium carbonate, and the mass ratio of sodium carbonate to calcium carbonate is 10:1; the silicate precipitant is a mixture of sodium silicate and calcium silicate, and the mass ratio of sodium silicate to calcium silicate is 5:1.5; the potassium sulfate salt expanding agent is a mixture of potassium aluminum sulfate and potassium bitartrate, and the mass ratio of potassium aluminum sulfate to potassium bitartrate is 10:1. The solid waste-based cementitious material is a mixture of 95-grade mineral powder, 500-mesh steel slag powder, desulfurization gypsum, and triethanolamine, and the mass ratio of 95-grade mineral powder, 500-mesh steel slag powder, desulfurization gypsum, and triethanolamine is 7.5:1.5:0.5:0.5.

[0069] The preparation method of the solid waste-based self-repairing functional filler described above has the following steps:

[0070] (1) Mix the hydroxyl carboxylic acid complexing agent and the amino carboxylic acid complexing agent, and use a constant-temperature magnetic stirrer to stir at a constant temperature for 30 min at a speed of 250 r / min to obtain a composite complexing agent;

[0071] (2) Mix the carbonate precipitant and the silicate precipitant, and use a constant-temperature magnetic stirrer to stir at a constant temperature for 25 min at a speed of 200 r / min to obtain a composite precipitant;

[0072] (3) Mix the composite complexing agent obtained in step (1), the composite precipitant obtained in step (2), the potassium sulfate salt expanding agent, and the solid waste-based cementitious material, and use a constant-temperature magnetic stirrer to stir at a constant temperature for 40 min at a speed of 250 r / min to obtain the solid waste-based self-repairing functional filler.

[0073] Example 4

[0074] A solid waste-based self-repairing functional filler, and the allocation ratio of each component is as follows in terms of percentage by weight:

[0075] Hydroxyl carboxylic acid complexing agent 7%,

[0076] Amino carboxylic acid complexing agent 9%,

[0077] carbonate precipitant 12%,

[0078] silicate precipitant 16%,

[0079] potassium sulfate salt swelling agent 29%,

[0080] solid waste-based cementitious material 27%;

[0081] The hydroxyl carboxylic acid complexing agent is a mixture of tartaric acid and citric acid, and the mass ratio of tartaric acid to citric acid is 10:3; the amino carboxylic acid complexing agent is a mixture of EDTA-4Na (tetrasodium ethylenediaminetetraacetate) and HEDP-4Na (tetrasodium 1-hydroxyethyl 1,1-diphosphonate), and the mass ratio of EDTA-4Na (tetrasodium ethylenediaminetetraacetate) to HEDP-4Na (tetrasodium 1-hydroxyethyl 1,1-diphosphonate) is 1:2; the carbonate precipitant is a mixture of sodium carbonate and calcium carbonate, and the mass ratio of sodium carbonate to calcium carbonate is 10:1; the silicate precipitant is a mixture of sodium silicate and calcium silicate, and the mass ratio of sodium silicate to calcium silicate is 5:1; the potassium sulfate salt swelling agent is a mixture of potassium aluminum sulfate and potassium bitartrate, and the mass ratio of potassium aluminum sulfate to potassium bitartrate is 10:1. The solid waste-based cementitious material is a mixture of 95-grade mineral powder, 500-mesh steel slag powder, desulfurization gypsum, and triethanolamine, and the mass ratio of 95-grade mineral powder, 500-mesh steel slag powder, desulfurization gypsum, and triethanolamine is 7.5:1.5:0.5:0.5.

[0082] The preparation method of the solid waste-based self-repairing functional filler described above has the following steps:

[0083] (1) Mix the hydroxyl carboxylic acid complexing agent and the amino carboxylic acid complexing agent, and use a constant-temperature magnetic stirrer to stir at a speed of 300 r / min at room temperature for 25 min to obtain a composite complexing agent;

[0084] (2) Mix the carbonate precipitant and the silicate precipitant, and use a constant-temperature magnetic stirrer to stir at a speed of 200 r / min at room temperature for 20 min to obtain a composite precipitant;

[0085] (3) Mix the composite complexing agent obtained in step (1), the composite precipitant obtained in step (2), the potassium sulfate salt swelling agent, and the solid waste-based cementitious material, and use a constant-temperature magnetic stirrer to stir at a speed of 300 r / min at room temperature for 35 min to obtain the solid waste-based self-repairing functional filler.

[0086] Example 5

[0087] A solid waste-based self-repairing functional filler, and the allocation ratio of each component is as follows in terms of weight percentage:

[0088] hydroxycarboxylic acid complexing agent 6%,

[0089] aminocarboxylic acid complexing agent 11%,

[0090] carbonate precipitant 13%,

[0091] silicate precipitant 14%,

[0092] potassium sulfate salt swelling agent 31%,

[0093] solid waste-based cementitious material 25%;

[0094] The hydroxycarboxylic acid complexing agent is a mixture of tartaric acid and citric acid, and the mass ratio of tartaric acid to citric acid is 10:1; the aminocarboxylic acid complexing agent is a mixture of EDTA-4Na (tetrasodium ethylenediaminetetraacetate) and HEDP-4Na (tetrasodium 1-hydroxyethyl-1,1-diphosphonate), and the mass ratio of EDTA-4Na (tetrasodium ethylenediaminetetraacetate) to HEDP-4Na (tetrasodium 1-hydroxyethyl-1,1-diphosphonate) is 1:1; the carbonate precipitant is a mixture of sodium carbonate and calcium carbonate, and the mass ratio of sodium carbonate to calcium carbonate is 10:2; the silicate precipitant is a mixture of sodium silicate and calcium silicate, and the mass ratio of sodium silicate to calcium silicate is 5:1.5; the potassium sulfate salt swelling agent is a mixture of potassium aluminum sulfate and potassium bitartrate, and the mass ratio of potassium aluminum sulfate to potassium bitartrate is 10:3. The solid waste-based cementitious material is a mixture of 95-grade mineral powder, 500-mesh steel slag powder, desulfurization gypsum, and triethanolamine, and the mass ratio of 95-grade mineral powder, 500-mesh steel slag powder, desulfurization gypsum, and triethanolamine is 7.5:1.5:0.5:0.5.

[0095] The preparation method of the solid waste-based self-repairing functional filler described above has the following steps:

[0096] (1) Mix the hydroxycarboxylic acid complexing agent and the aminocarboxylic acid complexing agent, and use a constant-temperature magnetic stirrer to stir at a constant temperature for 20 min at a speed of 200 r / min to obtain a composite complexing agent;

[0097] (2) Mix the carbonate precipitant and the silicate precipitant, and use a constant-temperature magnetic stirrer to stir at a constant temperature for 25 min at a speed of 300 r / min to obtain a composite precipitant;

[0098] (3) Mix the composite complexing agent obtained in step (1), the composite precipitant obtained in step (2), the potassium sulfate salt swelling agent, and the solid waste-based cementitious material, and use a constant-temperature magnetic stirrer to stir at a constant temperature for 35 min at a speed of 350 r / min to obtain the solid waste-based self-repairing functional filler.

[0099] Example 6

[0100] A solid waste-based self-repairing functional filler, the allocation ratio of each component is as follows in percentage by weight:

[0101] hydroxyl carboxylic acid complexing agent 5%,

[0102] amino carboxylic acid complexing agent 8%,

[0103] carbonate precipitant 14%,

[0104] silicate precipitant 15%,

[0105] potassium sulfate salt swelling agent 33%,

[0106] solid waste-based cementitious material 25%;

[0107] The hydroxyl carboxylic acid complexing agent is a mixture of tartaric acid and citric acid, and the mass ratio of tartaric acid to citric acid is 10:2; the amino carboxylic acid complexing agent is a mixture of EDTA-4Na (tetrasodium ethylenediaminetetraacetate) and HEDP-4Na (tetrasodium 1-hydroxyethyl-1,1-diphosphonate), and the mass ratio of EDTA-4Na (tetrasodium ethylenediaminetetraacetate) to HEDP-4Na (tetrasodium 1-hydroxyethyl-1,1-diphosphonate) is 2:1; the carbonate precipitant is a mixture of sodium carbonate and calcium carbonate, and the mass ratio of sodium carbonate to calcium carbonate is 10:3; the silicate precipitant is a mixture of sodium silicate and calcium silicate, and the mass ratio of sodium silicate to calcium silicate is 5:2; the potassium sulfate salt swelling agent is a mixture of potassium aluminum sulfate and potassium bitartrate, and the mass ratio of potassium aluminum sulfate to potassium bitartrate is 10:2. The solid waste-based cementitious material is a mixture of 95-grade mineral powder, 500-mesh steel slag powder, desulfurization gypsum, and triethanolamine, and the mass ratio of 95-grade mineral powder, 500-mesh steel slag powder, desulfurization gypsum, and triethanolamine is 7.5:1.5:0.5:0.5.

[0108] The preparation method of the above-mentioned solid waste-based self-repairing functional filler, the steps are as follows:

[0109] (1) Mix the hydroxyl carboxylic acid complexing agent and the amino carboxylic acid complexing agent, and use a constant-temperature magnetic stirrer to stir at a speed of 250 r / min for 20 min at room temperature to obtain a composite complexing agent;

[0110] (2) Mix the carbonate precipitant and the silicate precipitant, and use a constant-temperature magnetic stirrer to stir at a speed of 250 r / min for 30 min at room temperature to obtain a composite precipitant;

[0111] (3) Mix the composite complexing agent obtained in step (1), the composite precipitant obtained in step (2), the potassium sulfate salt swelling agent, and the solid waste-based cementitious material, and use a constant-temperature magnetic stirrer to stir at a speed of 250 r / min for 45 min at room temperature to obtain the solid waste-based self-repairing functional filler.

[0112] Comparative Example 1

[0113] A solid waste-based self-repairing functional filler, the allocation ratio of each component is as follows in percentage by weight:

[0114] amino carboxylic acid complexing agent 13%,

[0115] carbonate precipitant 14%,

[0116] silicate precipitant 15%,

[0117] potassium sulfate salt swelling agent 33%,

[0118] solid waste-based cementitious material 25%;

[0119] The amino carboxylic acid complexing agent is a mixture of EDTA-4Na (tetrasodium ethylenediaminetetraacetate) and HEDP-4Na (tetrasodium 1-hydroxyethyl-1,1-diphosphonate), and the mass ratio of EDTA-4Na (tetrasodium ethylenediaminetetraacetate) and HEDP-4Na (tetrasodium 1-hydroxyethyl-1,1-diphosphonate) is 2:1; the carbonate precipitant is a mixture of sodium carbonate and calcium carbonate, and the mass ratio of sodium carbonate and calcium carbonate is 10:3; the silicate precipitant is a mixture of sodium silicate and calcium silicate, and the mass ratio of sodium silicate and calcium silicate is 5:2; the potassium sulfate salt swelling agent is a mixture of potassium aluminum sulfate and potassium bitartrate, and the mass ratio of potassium aluminum sulfate and potassium bitartrate is 10:2. The solid waste-based cementitious material is a mixture of 95-grade mineral powder, 500-mesh steel slag powder, desulfurization gypsum, and triethanolamine, and the mass ratio of 95-grade mineral powder, 500-mesh steel slag powder, desulfurization gypsum, and triethanolamine is 7.5:1.5:0.5:0.5.

[0120] The preparation method of the above-mentioned solid waste-based self-repairing functional filler, the steps are as follows:

[0121] (1) Mix the carbonate precipitant and the silicate precipitant, and use a constant-temperature magnetic stirrer to stir at a constant temperature for 30 min at a speed of 250 r / min to obtain a composite precipitant;

[0122] (2) Mix the amino carboxylic acid complexing agent, the composite precipitant in step (1), the potassium sulfate salt swelling agent, and the solid waste-based cementitious material, and use a constant-temperature magnetic stirrer to stir at a constant temperature for 45 min at a speed of 250 r / min to obtain the solid waste-based self-repairing functional filler.

[0123] Comparative Example 2

[0124] A solid waste-based self-repairing functional filler, the allocation ratio of each component is as follows in percentage by weight:

[0125] hydroxycarboxylic acid complexing agent 13%,

[0126] carbonate precipitant 14%,

[0127] silicate precipitant 15%,

[0128] potassium sulfate salt swelling agent 33%,

[0129] solid waste-based cementitious material 25%;

[0130] The hydroxyl carboxylic acid complexing agent is a mixture of tartaric acid and citric acid, the mass ratio of tartaric acid to citric acid is 10:2; the carbonate precipitant is a mixture of sodium carbonate and calcium carbonate, the mass ratio of sodium carbonate to calcium carbonate is 10:3; the silicate precipitant is a mixture of sodium silicate and calcium silicate, the mass ratio of sodium silicate to calcium silicate is 5:2; the potassium sulfate salt swelling agent is a mixture of potassium aluminum sulfate and potassium bitartrate, the mass ratio of potassium aluminum sulfate to potassium bitartrate is 10:2. The solid waste-based cementitious material is a mixture of 95-grade mineral powder, 500-mesh steel slag powder, desulfurization gypsum and triethanolamine, the mass ratio of 95-grade mineral powder, 500-mesh steel slag powder, desulfurization gypsum and triethanolamine is 7.5:1.5:0.5:0.5.

[0131] The preparation method of the solid waste-based self-repairing functional filler described above, the steps are as follows:

[0132] (1) Mix the carbonate precipitant and the silicate precipitant, use a constant-temperature magnetic stirrer to stir at room temperature at a speed of 250 r / min for 30 min, and obtain a composite precipitant;

[0133] (2) Mix the hydroxyl carboxylic acid complexing agent, the composite precipitant in step (1), the potassium sulfate salt swelling agent and the solid waste-based cementitious material, use a constant-temperature magnetic stirrer to stir at room temperature at a speed of 250 r / min for 45 min, and obtain a solid waste-based self-repairing functional filler.

[0134] Comparative Example 3

[0135] A solid waste-based self-repairing functional filler, the allocation ratio of each component is as follows in terms of weight percentage:

[0136] hydroxyl carboxylic acid complexing agent 5%,

[0137] amino carboxylic acid complexing agent 8%,

[0138] carbonate precipitant 14%,

[0139] silicate precipitant 15%,

[0140] solid waste-based cementitious material 58%;

[0141] The hydroxyl carboxylic acid complexing agent is a mixture of tartaric acid and citric acid, the mass ratio of tartaric acid and citric acid is 10:2; the amino carboxylic acid complexing agent is a mixture of EDTA-4Na (tetrasodium ethylenediaminetetraacetate) and HEDP-4Na (tetrasodium 1-hydroxyethyl 1,1-diphosphonate), the mass ratio of EDTA-4Na (tetrasodium ethylenediaminetetraacetate) and HEDP-4Na (tetrasodium 1-hydroxyethyl 1,1-diphosphonate) is 2:1; the carbonate precipitant is a mixture of sodium carbonate and calcium carbonate, the mass ratio of sodium carbonate and calcium carbonate is 10:3; the silicate precipitant is a mixture of sodium silicate and calcium silicate, the mass ratio of sodium silicate and calcium silicate is 5:2; the solid waste-based cementitious material is a mixture of 95-grade mineral powder, 500-mesh steel slag powder, desulfurization gypsum and triethanolamine, the mass ratio of 95-grade mineral powder, 500-mesh steel slag powder, desulfurization gypsum and triethanolamine is 7.5:1.5:0.5:0.5.

[0142] The preparation method of the solid waste-based self-repairing functional filler is as follows:

[0143] (1) The hydroxyl carboxylic acid complexing agent and the amino carboxylic acid complexing agent are mixed, and a constant temperature magnetic stirrer is used to stir at a speed of 250 r / min for 20 min at room temperature to obtain a composite complexing agent;

[0144] (2) The carbonate precipitant and the silicate precipitant are mixed, and a constant temperature magnetic stirrer is used to stir at a speed of 250 r / min for 30 min at room temperature to obtain a composite precipitant;

[0145] (3) The composite complexing agent in step (1), the composite precipitant in step (2) and the solid waste-based cementitious material are mixed, and a constant temperature magnetic stirrer is used to stir at a speed of 250 r / min for 45 min at room temperature to obtain a solid waste-based self-repairing functional filler.

[0146] Comparative Example 4

[0147] A solid waste-based self-repairing functional filler, the allocation ratio of each component is as follows in terms of weight percentage:

[0148] hydroxyl carboxylic acid complexing agent 5%,

[0149] amino carboxylic acid complexing agent 8%,

[0150] silicate precipitant 29%,

[0151] potassium sulfate salt expanding agent 33%,

[0152] solid waste-based cementitious material 25%;

[0153] The hydroxyl carboxylic acid complexing agent is a mixture of tartaric acid and citric acid, the mass ratio of tartaric acid and citric acid is 10:2; the amino carboxylic acid complexing agent is a mixture of EDTA-4Na (tetrasodium ethylenediaminetetraacetate) and HEDP-4Na (tetrasodium 1-hydroxyethyl-1,1-diphosphonate), the mass ratio of EDTA-4Na (tetrasodium ethylenediaminetetraacetate) and HEDP-4Na (tetrasodium 1-hydroxyethyl-1,1-diphosphonate) is 2:1; the silicate precipitant is a mixture of sodium silicate and calcium silicate, the mass ratio of sodium silicate and calcium silicate is 5:2; the potassium sulfate salt expanding agent is a mixture of potassium aluminum sulfate and potassium bitartrate, the mass ratio of potassium aluminum sulfate and potassium bitartrate is 10:2; the solid waste-based cementitious material is a mixture of 95-grade mineral powder, 500-mesh steel slag powder, desulfurization gypsum and triethanolamine, the mass ratio of 95-grade mineral powder, 500-mesh steel slag powder, desulfurization gypsum and triethanolamine is 7.5:1.5:0.5:0.5.

[0154] The preparation method of the solid waste-based self-repairing functional filler described above, the steps are as follows:

[0155] (1) The hydroxyl carboxylic acid complexing agent and the amino carboxylic acid complexing agent are mixed, and a constant temperature magnetic stirrer is used to stir at room temperature at a speed of 250 r / min for 20 min to obtain a composite complexing agent;

[0156] (2) The composite complexing agent in step (1), the silicate precipitant, the potassium sulfate salt expanding agent and the solid waste-based cementitious material are mixed, and a constant temperature magnetic stirrer is used to stir at room temperature at a speed of 250 r / min for 45 min to obtain a solid waste-based self-repairing functional filler.

[0157] Comparative Example 5

[0158] A solid waste-based self-repairing functional filler, the allocation ratio of each component is as follows in terms of weight percentage:

[0159] hydroxyl carboxylic acid complexing agent 5%,

[0160] amino carboxylic acid complexing agent 8%,

[0161] carbonate precipitant 29%,

[0162] potassium sulfate salt expanding agent 33%,

[0163] solid waste-based cementitious material 25%;

[0164] The hydroxyl carboxylic acid complexing agent is a mixture of tartaric acid and citric acid, the mass ratio of tartaric acid and citric acid is 10:2; the amino carboxylic acid complexing agent is a mixture of EDTA-4Na (tetrasodium ethylenediaminetetraacetate) and HEDP-4Na (tetrasodium 1-hydroxyethyl-1,1-diphosphonate), the mass ratio of EDTA-4Na (tetrasodium ethylenediaminetetraacetate) and HEDP-4Na (tetrasodium 1-hydroxyethyl-1,1-diphosphonate) is 2:1; the carbonate precipitant is a mixture of sodium carbonate and calcium carbonate, the mass ratio of sodium carbonate and calcium carbonate is 10:3; the silicate precipitant is a mixture of sodium silicate and calcium silicate, the mass ratio of sodium silicate and calcium silicate is 5:2. The potassium sulfate salt expanding agent is a mixture of potassium aluminum sulfate and potassium bitartrate, the mass ratio of potassium aluminum sulfate and potassium bitartrate is 10:2; the solid waste-based cementitious material is a mixture of 95-grade mineral powder, 500-mesh steel slag powder, desulfurization gypsum and triethanolamine, the mass ratio of 95-grade mineral powder, 500-mesh steel slag powder, desulfurization gypsum and triethanolamine is 7.5:1.5:0.5:0.5.

[0165] The preparation method of the solid waste-based self-repairing functional filler described above, the steps are as follows:

[0166] (1) The hydroxyl carboxylic acid complexing agent is mixed with the amino carboxylic acid complexing agent, and a constant-temperature magnetic stirrer is used to stir at a speed of 250 r / min for 20 min at room temperature to obtain a composite complexing agent;

[0167] (2) The composite complexing agent in step (1), the carbonate precipitant, the potassium sulfate salt expanding agent and the solid waste-based cementitious material are mixed, and a constant-temperature magnetic stirrer is used to stir at a speed of 250 r / min for 45 min at room temperature to obtain a solid waste-based self-repairing functional filler.

[0168] The solid waste-based self-repairing functional fillers obtained in Examples 1-6 and Comparative Examples 1-5 are respectively subjected to mechanical property tests and self-repairing function tests, and the test results are shown in Tables 1 and 2, respectively.

[0169] Table 1 Mechanical property test results of solid waste-based self-repairing functional fillers in Examples 1-6 and Comparative Examples 1-5

[0170]

[0171]

[0172] From the test results of Figure 1 , Figure 2 and Table 1, it can be seen that, in Comparative Example 6 and Comparative Examples 1 and 2, the hydroxyl carboxylic acid complexing agent and the amino carboxylic acid complexing agent synergistically act, the carboxylic acid group forms a hydrogen bond with water molecules and forms a waterproof film, and the alkali earth metal ions are enriched to repair pores and cavities, thereby improving the mechanical properties.

[0173] ​As can be seen from Comparative Example 6 and Comparative Examples 3 and 4, the carbonate precipitator and the silicate precipitator synergize, the generated carbonate and silicate gel materials optimize the pore structure and help resist the invasion of harmful substances from the outside, and the mechanical properties are improved.

[0174] As can be seen from Comparative Example 6 and Comparative Example 5, the sulfate in the potassium sulfate salt expander and the 95-grade mineral powder, 500-mesh steel slag powder, desulfurization gypsum and triethanolamine in the solid waste-based cementitious material and the carbonate precipitator are used to generate calcium vanadate through the hydrolysis process of sulfate and hydrated calcium aluminate, so as to enhance the mechanical properties of the cement-based building material. The dissolution product of the potassium sulfate salt expander can accelerate the hydration reaction of C2S, C3S and C3A in the solid waste-based cementitious material and the silicate precipitator, and the potassium ion can induce the lapping and interlacing of the hydration products to form a good mechanical and waterproof structure, thereby enhancing the strength and density of the cement-based building material.

[0175] Table 2: Solid waste-based self-repairing functional fillers in Examples 1-6 and Comparative Examples 1-5

[0176] Self-repairing performance test results

[0177]

[0178] From Figure 3 , Figure 4 As can be seen from the comparison of the data in Table 2, Comparative Example 6 and Comparative Examples 1 and 2, the hydroxyl carboxylic acid complexing agent and the amino carboxylic acid complexing agent synergize, the amino carboxylic acid complexing agent has strong alkali resistance, and the hydroxyl carboxylic acid complexing agent has excellent biological activity, thereby improving the pore closure in the cement-based building material and achieving self-repairing.

[0179] As can be seen from the comparison of Comparative Example 6 and Comparative Examples 3 and 4, the carbonate precipitator and the silicate precipitator synergize, and carbonate and silicate participate in the micro-pore closure process of precipitation-crystallization together, thereby improving the density and strength of the cement-based building material and achieving self-repairing.

[0180] As can be seen from the comparison of Comparative Example 6 and Comparative Example 5, the potassium sulfate salt expander not only provides sulfate ions, but also contains a large amount of calcium oxide and sodium oxide, which can still maintain the alkaline environment inside the hydration products after the hydration process of the cement-based building material, and has the ability to re-excite the hydration reaction of C2S, C3S and C3A in the solid waste-based cementitious material, and induce the lapping and interlacing of the hydration products to form a good mechanical and waterproof structure, i.e., self-repairing.

Claims

1. A self-healing filler based on solid waste, characterized in that, The mass percentages of each component are as follows: hydroxycarboxylic acid complexing agent 4-8%, aminocarboxylic acid complexing agent 8-12%, carbonate precipitant 10-15%, silicate precipitant 12-16%, potassium sulfate expanding agent 25-35%, and solid waste-based cementitious material 25-32%.

2. The solid waste-based self-healing filler according to claim 1, characterized in that, The mass percentages of each component are as follows: hydroxycarboxylic acid complexing agent 6-8%, aminocarboxylic acid complexing agent 8-9%, carbonate precipitant 10-12%, silicate precipitant 14-16%, potassium sulfate expanding agent 25-29%, and solid waste-based cementitious material 27-32%.

3. The solid waste-based self-healing filler according to claim 2, characterized in that, The components are expressed as follows by mass percentage: 7% hydroxycarboxylic acid complexing agent, 9% aminocarboxylic acid complexing agent, 12% carbonate precipitant, 16% silicate precipitant, 29% potassium sulfate expanding agent, and 27% solid waste-based cementitious material.

4. The solid waste-based self-healing filler according to claim 1, characterized in that, The hydroxycarboxylic acid complexing agent is a mixture of tartaric acid and citric acid, wherein the mass ratio of tartaric acid to citric acid is 10:1~3.

5. The solid waste-based self-healing filler according to claim 1, characterized in that, The aminocarboxylic acid complexing agent is a mixture of EDTA-4Na and HEDP-4Na, wherein the mass ratio of EDTA-4Na to HEDP-4Na is 1~2:2~1.

6. The solid waste-based self-healing filler according to claim 1, characterized in that, The carbonate precipitant is a mixture of sodium carbonate and calcium carbonate, wherein the mass ratio of sodium carbonate to calcium carbonate is 10:1~3.

7. The solid waste-based self-healing filler according to claim 1, characterized in that, The silicate precipitant is a mixture of sodium silicate and calcium silicate, wherein the mass ratio of sodium silicate to calcium silicate is 5:1~2.

8. The solid waste-based self-healing filler according to claim 1, characterized in that, The potassium sulfate salt expanding agent is a mixture of potassium aluminum sulfate and potassium hydrogen tartrate, wherein the mass ratio of potassium aluminum sulfate to potassium hydrogen tartrate is 10:1~3.

9. The solid waste-based self-healing filler according to claim 1, characterized in that, The solid waste-based cementitious material is a mixture of 95-grade mineral powder, 500-mesh steel slag powder, desulfurized gypsum, and triethanolamine, wherein the mass ratio of the 95-grade mineral powder, the 500-mesh steel slag powder, the desulfurized gypsum, and the triethanolamine is 7.5:1.5:0.5:0.

5.

10. A method for preparing a solid waste-based self-healing functional filler as described in any one of claims 1 to 9, characterized in that, The steps are as follows: S1: Mix the hydroxycarboxylic acid complexing agent and the aminocarboxylic acid complexing agent, stir at a constant temperature, and obtain a composite complexing agent; S2: Mix the carbonate precipitant and the silicate precipitant, stir at a constant temperature, and obtain a composite precipitant; S3: Mix potassium sulfate expanding agent, solid waste-based cementitious material with composite complexing agent in S1 and composite precipitant in S2, and stir at a constant temperature to obtain solid waste-based self-healing filler.

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