A method for preparing a water-absorbing material with all-time controllable properties and its fluidized solidified soil building material

Abstract

This invention relates to the field of building material preparation technology, specifically disclosing a method for preparing a fully controllable water-absorbing material and its fluidized solidified soil building material. The method includes: (1) degumming natural silk, washing and drying it, then dissolving the degummed silk and removing salt to obtain a silk fibroin solution. (2) acid washing and alkali washing of zeolite powder, followed by washing to obtain pretreated zeolite powder. Then, it is made into a suspension, and the silk fibroin solution is added to it and stirred. After completion, the solid product is separated, placed in an alcohol solution for induced modification, and then the obtained product is dried to obtain SF@zeolite powder. (3) The SF@zeolite powder is mixed with glutaraldehyde aqueous solution, and then the solid is separated, washed, and dried to obtain the water-absorbing material. This invention effectively ensures the initial fluidity of the fluidized solidified soil while achieving fully controllable water seepage, compensating for shrinkage, and improving the strength of the fluidized solidified soil.

Description

Technical Field

[0001] This invention relates to the field of building material preparation technology, specifically to a method for preparing a fully controllable water-absorbing material and its fluidized solidified soil building material. Background Technology

[0002] The information disclosed in this background section is intended only to enhance understanding of the overall background of the invention and is not necessarily to be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.

[0003] Fluidized solidified soil, as an innovative building material, plays a vital role in engineering fields such as transportation facilities and urban infrastructure. Traditional backfilling mainly relies on compacted soil matrices, but the surface properties of soil solidified using traditional compaction processes are unstable, making it prone to settlement when exposed to moisture infiltration. Simultaneously, weathering causes fine soil particles to generate dust. Fluidized solidified soil effectively solves the problems of settlement and poor stability associated with traditional solidified soil. Its core characteristics, such as high fluidity, pumpability, self-leveling, adjustable strength, and chemical stability, make it highly applicable in construction scenarios such as mine pit filling, urban ditch filling, and roadbed engineering.

[0004] In current applications of fluidized bed solidified soil, high water-cement ratio formulations are commonly used to meet the construction requirements of pumpability and self-leveling (flowability > 140mm). This leads to an excess of free water in the system, easily causing early bleeding and later drying shrinkage, resulting in a significant reduction in the strength of the solidified soil and even the formation of through cracks, affecting structural stability and durability. Traditional solutions to bleeding generally involve adding water-absorbing materials such as superabsorbent resins. However, superabsorbent resins have poor compatibility with fluidized bed solidified soil slurry, and rapid initial water absorption leads to a significant loss of fluidity in the solidified soil slurry. Later water loss also results in incomplete hydration of the cementitious components, affecting the strength of the solidified soil. While adding water-reducing agents can improve fluidity, it exacerbates the bleeding problem. Cellulose ethers are needed to maintain slurry stability, but the addition of multiple admixtures drastically increases costs and introduces further problems. Summary of the Invention

[0005] In view of this, the present invention provides a method for preparing a fully controllable water-absorbing material and a fluidized solidified soil building material thereof, which effectively ensures the initial fluidity of the fluidized solidified soil during mixing, while also achieving fully controllable water seepage, compensating for shrinkage, and improving the strength of the fluidized solidified soil. Specifically, the technical solution of the present invention is as follows.

[0006] First, this invention provides a method for preparing a water-absorbing material with all-time controllable properties, comprising the following steps:

[0007] (1) After degumming the natural silk, wash and dry it. Then dissolve the degummed silk and remove the salt to obtain a silk fibroin (SF) solution for later use.

[0008] (2) The zeolite powder is first acid-washed and then alkali-washed. After washing, the residual alkali solution is removed to obtain pretreated zeolite powder. Then, it is made into a suspension, and the silk fibroin solution is added to it and stirred. After completion, the solid product is separated and placed in an alcohol solution for induced modification. Then, the obtained product is dried to obtain SF@zeolite powder for later use.

[0009] (3) Mix the SF@zeolite powder with glutaraldehyde aqueous solution, then separate the solids, wash and dry them to obtain the water-absorbing material.

[0010] Further, in step (1), the natural silk is placed in a sodium carbonate solution and degummed under heating and stirring conditions. Optionally, the mass fraction of the sodium carbonate solution is 0.1~0.3%. The heating temperature is 90~95℃, and the stirring time is 20~30min.

[0011] Further, in step (1), the mass ratio of the natural silk to the sodium carbonate solution is 1:45~50.

[0012] Further, in step (1), the degummed silk is dissolved using any solvent selected from LiBr solution, thiocyanate solution, etc., under heating and stirring conditions. Optionally, the concentration of the solvent is 9.2~9.4 mol / L. The heating temperature is 55~65℃, and the stirring time is 1.5~2 hours. The mass ratio of the degummed silk to the solvent is 1:9~11.

[0013] Furthermore, in step (1), any one of the methods such as dialysis, ultrafiltration, and gel filtration chromatography can be used to perform the desalination, so as to reduce the defects in the coating film formed on the zeolite particles caused by the electrostatic adsorption of impurity ions with silk fibroin or zeolite.

[0014] Further, in step (2), the acid washing and alkaline washing are performed using acid and alkaline solutions respectively. Optionally, the acid solution includes at least one of hydrochloric acid, phosphoric acid, and nitric acid. The alkaline solution includes at least one of sodium hydroxide, potassium hydroxide, and lithium hydroxide.

[0015] Further, in step (2), the mass ratio of the zeolite powder to the acid solution is 1:4~6. Optionally, the mass fraction of the acid solution is 4.5~5.5%. The acid washing can remove impurities such as oxides from the zeolite and increase the density of Si-OH.

[0016] Further, in step (2), the mass ratio of the zeolite powder to the alkaline solution is 1:4~6. Optionally, the mass fraction of the alkaline solution is 5~7%. The alkaline washing can promote the breaking of Al-O bonds in the zeolite and increase the Al-OH active sites.

[0017] Further, in step (2), the pretreated zeolite powder is added to water and ultrasonically treated to obtain the suspension. Optionally, the mass ratio of the pretreated zeolite powder to water is 1:4~6.

[0018] Further, in step (2), the mass ratio of the suspension to the silk fibroin solution is 1:3~5. Optionally, the stirring time is 1~1.5 hours. This invention utilizes the special functional groups between SF and zeolite to form an SF-coated shell on the surface of zeolite particles.

[0019] Further, in step (2), the mass ratio of the solid product to the alcohol solution is 1:25~30. Optionally, the mass fraction of the alcohol solution is 70~75%. Optionally, the alcohol solution includes at least one of methanol, ethanol, isopropanol, etc. In this step, the present invention utilizes the alcohol solution to induce the transformation of SF on the surface of zeolite particles from a random coiled state to β-fold, preventing the shell from falling off.

[0020] Furthermore, in step (2), the drying temperature is 60~80℃ and the time is 2~3h.

[0021] Further, in step (3), the mass ratio of the SF@zeolite powder to the glutaraldehyde aqueous solution is 1:0.5~0.8. Optionally, the mass fraction of the glutaraldehyde aqueous solution is 0.3~0.7%. This invention utilizes the reaction between -CHO in the glutaraldehyde and -NH2 in the SF coating membrane to form a -CH=N- structure, preventing the membrane from detaching due to shear force during the mixing process of the fluidized solidified soil.

[0022] Secondly, the present invention provides a fluidized solidified soil building material, comprising the following components in the following proportions: 800-850 parts by weight of base soil, 100-120 parts by weight of curing agent, 5-12 parts by weight of the water-absorbing material, and mixing water, wherein the ratio of water to the total mass of the base soil and curing agent is 0.45-0.5:1, that is, the water-solid ratio is 0.45-0.5.

[0023] Furthermore, the curing agent is formed from the following components in the following proportions: 10-13 parts by weight of desulfurization ash, 9-12 parts by weight of waste gypsum, 28-31 parts by weight of fly ash, 24-27 parts by weight of slag, 15-18 parts by weight of cement, and 0.45-0.5 parts by weight of water-reducing agent.

[0024] Optionally, the waste gypsum includes at least one of fluorogypsum, desulfurized gypsum, phosphogypsum, etc.

[0025] Optionally, the water-reducing agent includes at least one of polycarboxylate water-reducing agents, naphthalene-based water-reducing agents, etc.

[0026] Compared with the prior art, the technical solution of the present invention has at least the following beneficial effects:

[0027] The water-absorbing material prepared by the method of this invention can effectively avoid the problem of a significant decrease in the fluidity of solidified soil building materials caused by the large amount of water absorption in the early stage of traditional water-absorbing resin materials, and achieves full-time control of water bleeding and shrinkage of fluidized solidified soil. To this end, this invention first uses silk fibroin to coat the surface of pretreated zeolite, utilizing the -NH- and -NH2 groups provided by silk fibroin (SF) to form Si-OH groups with the Si-OH groups provided by zeolite. … NH-, Si-OH … NH2 hydrogen bonds, and the protonation of -NH3 provided by SF + The SF-coated shell is formed on the surface of zeolite by electrostatic attraction between the functional groups and the negative charge on the zeolite surface. However, this invention found that the chemical bond energy of this shell is low, making it prone to peeling off under shear force during the mixing process of fluidized solidified soil. To address this, this invention further employs ethanol-induced modification to transform the SF molecules in the shell from a randomly coiled state to a β-sheet crystalline structure. This, in turn, utilizes the numerous hydrogen bonds formed between the molecular chains to densify the SF shell, effectively preventing the aforementioned peeling problem. Furthermore, this invention utilizes the reaction of -CHO in glutaraldehyde with -NH2 provided by SF in the coating membrane to generate a covalent bond -CH=N-. Moreover, since each glutaraldehyde molecule has two aldehyde groups, they can react with the amino groups in the two SF groups respectively, thereby enabling the SF molecules in the coating membrane to be bonded together in the form of covalent bonds, constructing a stable three-dimensional network structure. This not only helps to further prevent the coating membrane from peeling off, but also enhances the stability of the coating membrane, making it easier for it to remain intact in the early stage of soil solidification or in the initial stage of mixing and pouring. This avoids excessive absorption of water in the solidified soil at this stage, which would lead to a significant decrease in fluidity, and facilitates the phased control and precise suppression of water bleeding.

[0028] When the water-absorbing material of this invention is added to the solidified soil building material, during the initial mixing and pouring stages, due to the abundance of free water in the system, the SF on the surface of the water-absorbing material, which has a β-folded crystalline structure, still retains some hydrophilic groups (such as -NH2, -COOH). These groups can quickly adsorb the free water to form a thin hydration shell, thereby reducing the formation of seepage channels, significantly reducing the rise of free water, and preventing seepage. As the solidifying agent in the solidified soil hydrates, the released hydration product, calcium hydroxide, gradually hydrolyzes the cross-linked covalent bonds in the SF shell. Simultaneously, some metal cations (Ca...) released by the solidifying agent... 2+ Al 3+ Fe3+ Coordination catalysis of (etc.) and weak basic ions (CO3) 2- SiO3 2- With the assistance of gentle erosion by the zeolite (such as...), weak areas on the coating membrane are opened, forming pores that allow water to enter and be stored inside the zeolite. As the hydration process progresses into the later stages, the free water in the system is gradually consumed by the hydration reaction of the curing agent. The water adsorbed in the zeolite is gradually released outward from the pores through the osmotic pressure difference, providing a water source for the continuous generation of subsequent hydration products (CSH gel and AFt), preventing insufficient strength of the solidified soil due to incomplete hydration in the later stages. Simultaneously, the zeolite particles provided by the water-absorbing material can fill the pores in the solidified soil, increasing density and contributing to improved mechanical properties. Attached Figure Description

[0029] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an improper limitation of the invention.

[0030] Figure 1 The image shows a sample of the absorbent material prepared in Example 1 below.

[0031] Figure 2 The following are test graphs showing the initial flowability (A) and 0.5h flowability (B) of Example 1.

[0032] Figure 3 The following is a diagram showing the compressive strength test results for Example 1.

[0033] Figure 4 The image shows a sample of the absorbent material prepared in Example 2 below.

[0034] Figure 5 The following are test graphs showing the initial flowability (A) and 0.5h flowability (B) of Example 2.

[0035] Figure 6 The following is a diagram showing the compressive strength test results for Example 2.

[0036] Figure 7 The image shows a sample of the absorbent material prepared in Example 3 below.

[0037] Figure 8 The following are test graphs showing the initial flowability (A) and 0.5h flowability (B) of Example 3.

[0038] Figure 9 The following is a diagram showing the compressive strength test results for Example 3.

[0039] Figure 10 The image shows a sample of the absorbent material prepared in Example 4 below.

[0040] Figure 11 The following are test graphs showing the initial flowability (A) and 0.5h flowability (B) of Example 4.

[0041] Figure 12 The following is a diagram showing the compressive strength test results for Example 4.

[0042] Figure 13 The image shows a sample of the absorbent material prepared in Example 5 below.

[0043] Figure 14 The following are test graphs showing the initial flowability (A) and 0.5h flowability (B) of Example 5.

[0044] Figure 15 The following is a diagram showing the compressive strength test results for Example 5.

[0045] Figure 16 The image shows a sample of the absorbent material prepared in Example 6 below.

[0046] Figure 17 The following are test graphs showing the initial flowability (A) and 0.5h flowability (B) of Example 6.

[0047] Figure 18 The following is a diagram showing the compressive strength test results for Example 6.

[0048] Figure 19 The image shows a sample of the absorbent material prepared in Example 7 below.

[0049] Figure 20 The following are test graphs showing the initial flowability (A) and 0.5h flowability (B) of Example 7.

[0050] Figure 21 The following is a diagram showing the compressive strength test results for Example 7.

[0051] Figure 22 The image shows a sample of the absorbent material prepared in Example 8 below.

[0052] Figure 23 The following is a graph showing the initial flowability test results for Example 8.

[0053] Figure 24 The following is a diagram showing the compressive strength test results for Example 8. Detailed Implementation

[0054] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Experimental methods in the following embodiments, unless otherwise specified, are generally performed under conventional conditions or as recommended by the manufacturer.

[0055] Unless otherwise defined, all technical and scientific terms used in this invention have the same meaning as those skilled in the art. All reagents and raw materials used in this invention are readily available through conventional means, and unless otherwise specified, they shall be used in accordance with conventional methods in the art or as per the product instructions.

[0056] Furthermore, any methods and materials similar to or equivalent to those described herein can be applied to the method of this invention. The technical solution of this invention will now be further described in conjunction with the accompanying drawings and specific embodiments.

[0057] Example 1: A method for preparing a fluidized solidified soil building material, comprising the following steps:

[0058] (1) Cut the natural silk into small pieces and place them in a 0.2% sodium carbonate solution at a mass ratio of 1:45. Then heat to 90°C and stir continuously at 100 rpm for 30 min to degumme the silk. After degumming, wash with deionized water to remove residual sodium carbonate, and then dry with a forced air to remove moisture to obtain degummed silk for later use.

[0059] (2) The degummed silk was dissolved in a 9.25 mol / L LiBr solution at a mass ratio of 1:10. The solution was then heated to 60°C and stirred for 2 hours to fully dissolve the degummed silk. The resulting solution was then injected into a dialysis bag, which was placed in a container filled with deionized water, ensuring the solution in the dialysis bag was below the surface of the deionized water. The solution was then slowly stirred, with the deionized water in the container replaced every 3 hours for the first 12 hours, every 6 hours from the 12th to the 24th hour, and every 12 hours from the 24th to the 48th hour. After completion, the solution in the dialysis bag was filtered to remove solids, yielding a transparent silk fibroin solution for later use.

[0060] (3) First, mix zeolite powder (fineness 200~300 mesh) with 5% hydrochloric acid at a mass ratio of 1:5 and stir for 10 min. Then filter out the zeolite powder and place it in a 6% sodium hydroxide solution at a mass ratio of 1:5.5. Stir for 20 min and filter out the zeolite powder. Wash to remove residual alkali solution to obtain pretreated zeolite powder for later use.

[0061] (4) Add the pretreated zeolite powder to water at a mass ratio of 1:4, and then sonicate for 10 minutes to obtain a suspension for later use.

[0062] (5) Under stirring conditions, the silk fibroin solution was added dropwise to the suspension above, with a mass ratio of 3.5:1. Then, stirring was continued for 1.5 hours. After completion, the solid product was filtered out and placed in a 75% ethanol aqueous solution for induced modification, with a mass ratio of 1:28. After completion, the solid was filtered out and dried at 80°C for 2 hours to obtain SF@zeolite powder for later use.

[0063] (6) The SF@zeolite powder and a 0.4% glutaraldehyde aqueous solution are mixed at a mass ratio of 1:0.65 and stirred evenly. The solid is then filtered out and rinsed with deionized water to remove residual glutaraldehyde. The mixture is then dried at 75°C for 2 hours to obtain the absorbent material. Figure 1 As shown.

[0064] (7) Take the following raw materials in the following proportions: 820 parts by weight of matrix soil, 115 parts by weight of curing agent, and 9 parts by weight of water-absorbing material in this embodiment. Wherein: the curing agent is formed by the following components in the following proportions: 12 parts by weight of desulfurization ash, 10 parts by weight of fluorogypsum, 30 parts by weight of fly ash, 26 parts by weight of slag, 17 parts by weight of cement, and 0.48 parts by weight of polycarboxylate superplasticizer. Dry mix the above raw materials in a mixer for 4 minutes, then add 448.8 parts by weight of mixing water and continue mixing for 3 minutes to obtain the fluidized solidified soil building material.

[0065] Performance testing: 1. Test the initial flowability and 0.5h flowability of the fluidized solidified soil building material prepared in this embodiment (as shown in the figures below). Figure 2 (As shown in A and B), and calculate the fluidity retention rate. The higher the value, the greater the fluidity loss of the solidified soil building material in the early stage, resulting in poorer pumpability and self-leveling performance. 2. Test the bleeding rate of the solidified soil building material according to the "Technical Standard for Application of Premixed Solidified Soil in Urban Rail Transit Engineering". 3. Test the compressive strength of the solidified soil building material according to the "Standard for Basic Performance Test Methods of Building Mortar" (JGJ / T70-2009). Figure 3 (As shown), the results are shown in the table below:

[0066]

[0067] Example 2: A method for preparing a fluidized solidified soil building material, comprising the following steps:

[0068] (1) Cut the natural silk into small pieces and place them in a 0.1% sodium carbonate solution at a mass ratio of 1:50. Then heat to 90°C and stir continuously at 100 rpm for 20 min to degumme the silk. After degumming, wash with deionized water to remove residual sodium carbonate, and then dry with a forced air to remove moisture to obtain degummed silk for later use.

[0069] (2) The degummed silk was dissolved in a 9.2 mol / L LiBr solution at a mass ratio of 1:11. The solution was then heated to 55°C and stirred for 2 hours to fully dissolve the degummed silk. The resulting solution was then injected into a dialysis bag, which was placed in a container filled with deionized water, ensuring the solution in the dialysis bag was below the surface of the deionized water. The solution was then slowly stirred, with the deionized water in the container replaced every 3 hours for the first 12 hours, every 6 hours from the 12th to the 24th hour, and every 12 hours from the 24th to the 48th hour. After completion, the solution in the dialysis bag was filtered to remove solids, yielding a transparent silk fibroin solution for later use.

[0070] (3) First, mix zeolite powder (fineness 200~300 mesh) with 5.5% nitric acid at a mass ratio of 1:4 and stir for 10 min. Then filter out the zeolite powder and place it in a 7% sodium hydroxide solution at a mass ratio of 1:4. Stir for 20 min and filter out the zeolite powder. Wash to remove residual alkali solution to obtain pretreated zeolite powder for later use.

[0071] (4) Add the pretreated zeolite powder to water at a mass ratio of 1:5, and then sonicate for 10 minutes to obtain a suspension for later use.

[0072] (5) Under stirring conditions, the silk fibroin solution is added dropwise to the above suspension at a mass ratio of 3:1. Then, stirring is continued for 1 hour. After completion, the solid product is filtered out and placed in a 70% methanol aqueous solution for induced modification at a mass ratio of 1:25. After completion, the solid is filtered out and dried at 60°C for 3 hours to obtain SF@zeolite powder for later use.

[0073] (6) The SF@zeolite powder and a 0.7% glutaraldehyde aqueous solution are mixed at a mass ratio of 1:0.5 and stirred evenly. The solid is then filtered out and rinsed with deionized water to remove residual glutaraldehyde. The mixture is then dried at 65°C for 3 hours to obtain the absorbent material. Figure 4 As shown.

[0074] (7) Take the following raw materials in the following proportions: 800 parts by weight of matrix soil, 100 parts by weight of curing agent, and 5 parts by weight of water-absorbing material in this embodiment. Wherein: the curing agent is formed from the following components in the following proportions: 10 parts by weight of desulfurization ash, 9 parts by weight of phosphogypsum, 28 parts by weight of fly ash, 24 parts by weight of slag, 15 parts by weight of cement, and 0.45 parts by weight of polycarboxylate superplasticizer. Dry mix the above raw materials in a mixer for 4 minutes, then add 405 parts by weight of mixing water and continue mixing for 3 minutes to obtain the fluidized solidified soil building material.

[0075] Performance testing: The bleeding rate and compressive strength (e.g., ) of the fluidized solidified soil building material prepared in this embodiment were tested using the same method as in Example 1 above. Figure 6 As shown), initial flowability and 0.5-hour flowability (as shown respectively). Figure 5 (As shown in A and B), and the flow retention rate was calculated. The results are shown in the table below:

[0076]

[0077] Example 3: A method for preparing a fluidized solidified soil building material, comprising the following steps:

[0078] (1) Cut the natural silk into small pieces and place them in a 0.3% sodium carbonate solution at a mass ratio of 1:47. Then heat to 90°C and stir continuously at 100 rpm for 25 min to degumme the silk. After degumming, wash with deionized water to remove residual sodium carbonate, and then dry with a forced air to remove moisture to obtain degummed silk for later use.

[0079] (2) The degummed silk was dissolved in a 9.4 mol / L sodium thiocyanate solution at a mass ratio of 1:9. The solution was then heated to 65°C and stirred for 1.5 hours to fully dissolve the degummed silk. The resulting solution was then injected into a dialysis bag, which was placed in a container filled with deionized water, ensuring the solution in the dialysis bag was below the surface of the deionized water. The solution was then slowly stirred, with the deionized water in the container replaced every 3 hours for the first 12 hours, every 6 hours from the 12th to the 24th hour, and every 12 hours from the 24th to the 48th hour. After completion, the solution in the dialysis bag was filtered to remove solids, yielding a transparent silk fibroin solution for later use.

[0080] (3) First, mix zeolite powder (fineness 200~300 mesh) with 4.5% phosphoric acid at a mass ratio of 1:6 and stir for 10 min. Then filter out the zeolite powder and place it in a 5% potassium hydroxide solution at a mass ratio of 1:6. Stir for 20 min and filter out the zeolite powder. Wash to remove residual alkali solution to obtain pretreated zeolite powder for later use.

[0081] (4) Add the pretreated zeolite powder to water at a mass ratio of 1:6, and then sonicate for 10 minutes to obtain a suspension for later use.

[0082] (5) Under stirring conditions, the silk fibroin solution was added dropwise to the suspension above, with a mass ratio of 5:1. Then, stirring was continued for 1.5 hours. After completion, the solid product was filtered out and placed in a 70% isopropanol aqueous solution for induced modification, with a mass ratio of 1:30. After completion, the solid was filtered out and dried at 75°C for 2 hours to obtain SF@zeolite powder for later use.

[0083] (6) The SF@zeolite powder and a 0.3% glutaraldehyde aqueous solution are mixed at a mass ratio of 1:0.65 and stirred evenly. The solid is then filtered out and rinsed with deionized water to remove residual glutaraldehyde. The mixture is then dried at 70°C for 2.5 hours to obtain the absorbent material. Figure 7 As shown.

[0084] (7) Take the following raw materials in the following proportions: 850 parts by weight of matrix soil, 120 parts by weight of curing agent, and 12 parts by weight of water-absorbing material in this embodiment. Wherein: the curing agent is formed from the following components in the following proportions: 13 parts by weight of desulfurized ash, 12 parts by weight of desulfurized gypsum, 31 parts by weight of fly ash, 27 parts by weight of slag, 18 parts by weight of cement, and 0.48 parts by weight of naphthalene-based water-reducing agent. Dry mix the above raw materials in a mixer for 4 minutes, then add 485 parts by weight of mixing water and continue mixing for 3 minutes to obtain the fluidized solidified soil building material.

[0085] Performance testing: The bleeding rate and compressive strength (e.g., ) of the fluidized solidified soil building material prepared in this embodiment were tested using the same method as in Example 1 above. Figure 9 As shown), initial flowability and 0.5-hour flowability (as shown respectively). Figure 8 (As shown in A and B), and the flow retention rate was calculated. The results are shown in the table below:

[0086]

[0087] Example 4: A method for preparing a fluidized solidified soil building material, comprising the following steps:

[0088] (1) First, mix zeolite powder (fineness 200~300 mesh) with 5% hydrochloric acid at a mass ratio of 1:5 and stir for 10 min. Then filter out the zeolite powder and place it in a 6% sodium hydroxide solution at a mass ratio of 1:5.5. Stir for 20 min and filter out the zeolite powder. Wash to remove residual alkali solution to obtain pretreated zeolite powder (e.g. Figure 10 (As shown), for later use.

[0089] (2) Take the following raw materials in the following proportions: 820 parts by weight of matrix soil, 115 parts by weight of curing agent, and 9 parts by weight of pretreated zeolite powder in this embodiment. Wherein: the curing agent is formed from the following components in the following proportions: 12 parts by weight of desulfurization ash, 10 parts by weight of fluorogypsum, 30 parts by weight of fly ash, 26 parts by weight of slag, 17 parts by weight of cement, and 0.48 parts by weight of polycarboxylate superplasticizer. Dry mix the above raw materials in a mixer for 4 minutes, then add 448.8 parts by weight of mixing water and continue mixing for 3 minutes to obtain the fluidized solidified soil building material.

[0090] Performance testing: The bleeding rate and compressive strength (e.g., ) of the fluidized solidified soil building material prepared in this embodiment were tested using the same method as in Example 1 above. Figure 12 As shown), initial flowability and 0.5-hour flowability (as shown respectively). Figure 11 (As shown in A and B), and the flow retention rate was calculated. The results are shown in the table below:

[0091]

[0092] Example 5: A method for preparing a fluidized solidified soil building material, comprising the following steps:

[0093] (1) Cut the natural silk into small pieces and place them in a 0.2% sodium carbonate solution at a mass ratio of 1:45. Then heat to 90°C and stir continuously at 100 rpm for 30 min to degumme the silk. After degumming, wash with deionized water to remove residual sodium carbonate, and then dry with a forced air to remove moisture to obtain degummed silk for later use.

[0094] (2) The degummed silk was dissolved in a 9.25 mol / L LiBr solution at a mass ratio of 1:10. The solution was then heated to 60°C and stirred for 2 hours to fully dissolve the degummed silk. The resulting solution was then injected into a dialysis bag, which was placed in a container filled with deionized water, ensuring the solution in the dialysis bag was below the surface of the deionized water. The solution was then slowly stirred, with the deionized water in the container replaced every 3 hours for the first 12 hours, every 6 hours from the 12th to the 24th hour, and every 12 hours from the 24th to the 48th hour. After completion, the solution in the dialysis bag was filtered to remove solids, yielding a transparent silk fibroin solution for later use.

[0095] (3) First, mix zeolite powder (fineness 200~300 mesh) with 5% hydrochloric acid at a mass ratio of 1:5 and stir for 10 min. Then filter out the zeolite powder and place it in a 6% sodium hydroxide solution at a mass ratio of 1:5.5. Stir for 20 min and filter out the zeolite powder. Wash to remove residual alkali solution to obtain pretreated zeolite powder for later use.

[0096] (4) Add the pretreated zeolite powder to water at a mass ratio of 1:4, and then sonicate for 10 minutes to obtain a suspension for later use.

[0097] (5) Under stirring conditions, the silk fibroin solution is added dropwise to the above suspension at a mass ratio of 3.5:1. Then, stirring is continued for 1.5 hours. After completion, the solid product is filtered out and dried at 80°C for 2 hours to obtain SF@zeolite powder for later use.

[0098] (6) The SF@zeolite powder and a 0.4% glutaraldehyde aqueous solution are mixed at a mass ratio of 1:0.65 and stirred evenly. The solid is then filtered out and rinsed with deionized water to remove residual glutaraldehyde. The mixture is then dried at 75°C for 2 hours to obtain the absorbent material. Figure 13 As shown.

[0099] (7) Take the following raw materials in the following proportions: 820 parts by weight of matrix soil, 115 parts by weight of curing agent, and 9 parts by weight of water-absorbing material in this embodiment. Wherein: the curing agent is formed by the following components in the following proportions: 12 parts by weight of desulfurization ash, 10 parts by weight of fluorogypsum, 30 parts by weight of fly ash, 26 parts by weight of slag, 17 parts by weight of cement, and 0.48 parts by weight of polycarboxylate superplasticizer. Dry mix the above raw materials in a mixer for 4 minutes, then add 448.8 parts by weight of mixing water and continue mixing for 3 minutes to obtain the fluidized solidified soil building material.

[0100] Performance testing: The bleeding rate and compressive strength (e.g., ) of the fluidized solidified soil building material prepared in this embodiment were tested using the same method as in Example 1 above. Figure 15 As shown), initial flowability and 0.5-hour flowability (as shown respectively). Figure 14 (As shown in A and B), and calculate the fluidity retention rate.

[0101] Example 6: A method for preparing a fluidized solidified soil building material, comprising the following steps:

[0102] (1) Cut the natural silk into small pieces and place them in a 0.1% sodium carbonate solution at a mass ratio of 1:50. Then heat to 90°C and stir continuously at 100 rpm for 20 min to degumme the silk. After degumming, wash with deionized water to remove residual sodium carbonate, and then dry with a forced air to remove moisture to obtain degummed silk for later use.

[0103] (2) The degummed silk was dissolved in a 9.2 mol / L LiBr solution at a mass ratio of 1:11. The solution was then heated to 55°C and stirred for 2 hours to fully dissolve the degummed silk. The resulting solution was then injected into a dialysis bag, which was placed in a container filled with deionized water, ensuring the solution in the dialysis bag was below the surface of the deionized water. The solution was then slowly stirred, with the deionized water in the container replaced every 3 hours for the first 12 hours, every 6 hours from the 12th to the 24th hour, and every 12 hours from the 24th to the 48th hour. After completion, the solution in the dialysis bag was filtered to remove solids, yielding a transparent silk fibroin solution for later use.

[0104] (3) First, mix zeolite powder (fineness 200~300 mesh) with 5.5% nitric acid at a mass ratio of 1:4 and stir for 10 min. Then filter out the zeolite powder and place it in a 7% sodium hydroxide solution at a mass ratio of 1:4. Stir for 20 min and filter out the zeolite powder. Wash to remove residual alkali solution to obtain pretreated zeolite powder for later use.

[0105] (4) Add the pretreated zeolite powder to water at a mass ratio of 1:5, and then sonicate for 10 minutes to obtain a suspension for later use.

[0106] (5) Under stirring conditions, the silk fibroin solution is added dropwise to the above suspension at a mass ratio of 3:1. Stirring continues for 1 hour. After completion, the solid product is filtered out and placed in a 70% methanol aqueous solution for induced modification at a mass ratio of 1:25. After completion, the solid is filtered out and dried at 60°C for 3 hours to obtain SF@zeolite powder (e.g., ...). Figure 16 (As shown), for later use.

[0107] (6) Take the following raw materials in the following proportions: 800 parts by weight of matrix soil, 100 parts by weight of curing agent, and 5 parts by weight of SF@zeolite powder in this embodiment. Wherein: the curing agent is formed from the following components in the following proportions: 10 parts by weight of desulfurization ash, 9 parts by weight of phosphogypsum, 28 parts by weight of fly ash, 24 parts by weight of slag, 15 parts by weight of cement, and 0.45 parts by weight of polycarboxylate superplasticizer. Dry mix the above raw materials in a mixer for 4 minutes, then add 405 parts by weight of mixing water and continue mixing for 3 minutes to obtain the fluidized solidified soil building material.

[0108] Performance testing: The bleeding rate and compressive strength (e.g., ) of the fluidized solidified soil building material prepared in this embodiment were tested using the same method as in Example 1 above. Figure 18 As shown), initial flowability and 0.5-hour flowability (as shown respectively). Figure 17 (As shown in A and B), and the flow retention rate was calculated. The results are shown in the table below:

[0109]

[0110] Example 7: A method for preparing a fluidized solidified soil building material, comprising the following steps:

[0111] (1) Add zeolite powder (fineness 200~300 mesh) to water at a mass ratio of 1:6, and then sonicate for 10 min to obtain a suspension for later use.

[0112] (2) Under stirring conditions, the silk fibroin solution prepared in Example 1 was added dropwise to the suspension at a mass ratio of 5:1. Stirring was then continued for 1.5 hours. After completion, the solid product was filtered out and placed in a 70% isopropanol aqueous solution for induced modification at a mass ratio of 1:30. After completion, the solid was filtered out and dried at 75°C for 2 hours to obtain SF@zeolite powder for later use.

[0113] (3) The SF@zeolite powder and a 0.3% glutaraldehyde aqueous solution are mixed at a mass ratio of 1:0.65 and stirred evenly. The solid is then filtered out and rinsed with deionized water to remove residual glutaraldehyde. The mixture is then dried at 70°C for 2.5 hours to obtain the absorbent material. Figure 19 As shown.

[0114] (4) Take the following raw materials in the following proportions: 850 parts by weight of matrix soil, 120 parts by weight of curing agent, and 12 parts by weight of water-absorbing material in this embodiment. Wherein: the curing agent is formed from the following components in the following proportions: 13 parts by weight of desulfurized ash, 12 parts by weight of desulfurized gypsum, 31 parts by weight of fly ash, 27 parts by weight of slag, 18 parts by weight of cement, and 0.48 parts by weight of naphthalene-based water-reducing agent. Dry mix the above raw materials in a mixer for 4 minutes, then add 485 parts by weight of mixing water and continue mixing for 3 minutes to obtain the fluidized solidified soil building material.

[0115] Performance testing: The bleeding rate and compressive strength (e.g., ) of the fluidized solidified soil building material prepared in this embodiment were tested using the same method as in Example 1 above. Figure 21 As shown), initial flowability and 0.5-hour flowability (as shown respectively). Figure 20 (As shown in A and B), and the flow retention rate was calculated. The results are shown in the table below:

[0116]

[0117] Example 8: A method for preparing a fluidized solidified soil building material, comprising the following steps:

[0118] (1) Take the following proportions of raw materials: 1.0 parts by weight of polyvinyl alcohol, 1.0 parts by weight of sodium alginate, 5.0 parts by weight of water, and 100 parts by weight of sodium polyacrylate granular superabsorbent polymer with a particle size distribution between 0.3 and 0.5 mm. First, mix the polyvinyl alcohol, sodium alginate, and water and stir until the polyvinyl alcohol and sodium alginate are completely dissolved to obtain solution A. Then, while stirring the sodium polyacrylate granular superabsorbent polymer, spray the solution A to distribute it evenly on the surface of the superabsorbent polymer particles. After drying, the absorbent material is obtained, such as... Figure 22 As shown.

[0119] (2) Take the following raw materials in the following proportions: 800 parts by weight of base soil, 100 parts by weight of curing agent, and 5 parts by weight of water-absorbing material in this embodiment. Wherein: the curing agent is formed from the following components in the following proportions: 10 parts by weight of desulfurization ash, 9 parts by weight of phosphogypsum, 28 parts by weight of fly ash, 24 parts by weight of slag, 15 parts by weight of cement, and 0.45 parts by weight of polycarboxylate superplasticizer. Dry mix the above raw materials in a mixer for 4 minutes, then add 405 parts by weight of mixing water and continue mixing for 3 minutes to obtain the fluidized solidified soil building material.

[0120] Performance testing: The bleeding rate and compressive strength (e.g., ) of the fluidized solidified soil building material prepared in this embodiment were tested using the same method as in Example 1 above. Figure 24 As shown), initial flowability and 0.5-hour flowability (as shown) Figure 23 (As shown in the figure), and the flow retention rate was calculated. The results are shown in the table below:

[0121]

[0122] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for producing a full-time controllable water-absorbing material, characterized by, The method comprises the following steps: (1) washing and drying the natural silk after degumming treatment, then dissolving the degummed silk and removing salt to obtain a silk fibroin solution for standby; (2) acid washing and alkali washing the zeolite powder, then washing to remove residual alkali liquor to obtain pretreated zeolite powder; then preparing a suspension liquid, adding the silk fibroin solution to the suspension liquid and stirring to obtain a solid product, then placing the solid product in an alcohol solution for induced modification, and then drying the product to obtain SF@zeolite powder for standby; (3) mixing the SF@zeolite powder with a glutaraldehyde aqueous solution according to a mass ratio of 1:0.5-0.8, then washing and drying the solid product to obtain the water absorption material.

2. The method for preparing a full-time controllable water-absorbing material according to claim 1, characterized by, In step (1), the natural silk is placed in a sodium carbonate solution with a mass fraction of 0.1-0.3%, and degumming treatment is performed at a heating temperature of 90-95°C and under stirring conditions for 20-30 min; the mass ratio of the natural silk to the sodium carbonate solution is 1:45-50.

3. The method of claim 1, wherein the full-time controllable water-absorbing material is prepared by adding a cross-linking agent to the water-absorbing resin. In step (1), LiBr solution or thiocyanate is used as the solvent for dissolving the degummed silk under heating and stirring conditions; the concentration of the solvent is 9.2-9.4 mol / L; the heating temperature is 55-65°C, and the stirring time is 1.5-2 hours; the mass ratio of the degummed silk to the solvent is 1:9-11.

4. The method of making a full-time controllable water-absorbing material according to claim 1, characterized in that, In step (2), acid and alkali are used for acid washing and alkali washing, respectively; the mass ratio of the zeolite powder to the acid is 1:4-6; and the mass ratio of the zeolite powder to the alkali is 1:4-6.

5. The method of producing a full-time controllable water-absorbing material according to claim 4, characterized by, The acid includes at least one of hydrochloric acid, phosphoric acid and nitric acid; Alternatively, the alkali includes at least one of sodium hydroxide, potassium hydroxide and lithium hydroxide; Alternatively, the mass fraction of the acid is 4.5-5.5%; Alternatively, the mass fraction of the alkali is 5-7%.

6. The method of making a full-time controllable water-absorbing material according to claim 1, characterized in that, In step (2), the pretreated zeolite powder is added to water for ultrasonic treatment to obtain the suspension liquid; the mass ratio of the pretreated zeolite powder to water is 1:4-6.

7. The method of making a full-time controllable water-absorbing material according to claim 1, characterized in that, In step (2), the stirring time is 1-1.5 hours; Alternatively, in step (2), the mass ratio of the solid product to ethanol is 1:25-30; Alternatively, in step (2), the mass fraction of the alcohol solution is 70-75%; Alternatively, in step (2), the alcohol solution includes at least one of methanol, ethanol and isopropanol; Alternatively, in step (2), the drying temperature is 60-80°C, and the drying time is 2-3 hours.

8. The method of making a full-time controllable water-absorbing material according to any one of claims 1 to 7, characterized in that, The mass fraction of the glutaraldehyde aqueous solution is 0.3-0.7%.

9. A fluidified soil construction material, characterized in that The components include the following proportions: 800-850 parts by weight of base soil, 100-120 parts by weight of curing agent, 5-12 parts by weight of the water absorption material prepared by the method of any one of claims 1-8, and water for mixing, and the mass ratio of the total mass of the base soil and the curing agent to the water for mixing is 0.45-0.5:

1.

10. The fluidified solidified soil construction material according to claim 9, characterized in that, The curing agent is formed by components in the following proportions: 10-13 parts by weight of desulfurization ash, 9-12 parts by weight of waste gypsum, 28-31 parts by weight of fly ash, 24-27 parts by weight of slag, 15-18 parts by weight of cement, 0.45-0.5 parts by weight of water reducing agent; Alternatively, the waste gypsum comprises at least one of fluorogypsum, desulfurization gypsum, and phosphogypsum. Alternatively, the water reducing agent comprises at least one of polycarboxylic acid water reducing agent and naphthalene series water reducing agent.

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