High-durability type flow-state solidified soil and preparation method thereof
By optimizing the composition of fluidized solidified soil and forming a dense network with multi-target synergistic effects, the problems of drying shrinkage cracking, poor water stability, and insufficient durability of fluidized solidified soil are solved, thereby improving the high strength and water resistance of fluidized solidified soil, making it suitable for modern engineering construction.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- GUANGZHOU SHIWEI NEW MATERIAL TECHNOLOGY CO LTD
- Filing Date
- 2026-01-19
- Publication Date
- 2026-04-14
AI Technical Summary
Existing fluidized solidified soils have problems such as drying shrinkage cracking, poor water stability, and insufficient durability, making it difficult to meet the requirements of modern engineering for long-term service safety. Furthermore, the performance control of geopolymer solidifiers is difficult.
The composition of the highly durable fluidized solidified soil is optimized, including the combined use of soil, cementitious materials, oxime complexing agents, toughening agents and stabilizers to form a dense composite cross-linked network with multi-target synergistic effects. The strength and water resistance are improved through the formation of chemical bonds and hydrogen bonds.
It significantly improves the strength, water resistance and durability of fluidized solidified soil, making it suitable for large-scale application and meeting the stringent requirements of engineering construction.
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of building materials technology, specifically relating to a high-durability fluidized solidified soil and its preparation method. Background Technology
[0002] Fluidized solidified soil is a highly fluid and environmentally friendly material made by mixing engineering waste soil, silt and other main materials with a solidifying agent containing active Al2O3, SiO2, CaO and water. Before solidification, it has high fluidity and self-compacting properties, and after solidification, it has certain strength, stability and load-bearing capacity.
[0003] Currently, fluidized solidified soils are mainly divided into two categories. One category uses cement, lime, etc. as solidifying agents. This type of fluidized solidified soil can improve the basic strength of the soil, but the solidified soil generally suffers from problems such as drying shrinkage cracking, poor water stability, and insufficient durability, making it difficult to meet the requirements of modern engineering for long-term service safety. The other category uses geopolymers as solidifying agents, which have the characteristics of low pollution and low energy consumption. However, the interaction mechanism between geopolymers and soil is complex, and its performance is significantly affected by factors such as the type of precursor, the ratio of activator, and differences in soil quality, making it difficult to control its performance. In addition, it often has performance defects such as low early strength and high brittleness, which restricts its large-scale application.
[0004] Therefore, it is necessary to provide a high-durability fluidized solidified soil and its preparation method to effectively improve the strength, durability and other properties of fluidized solidified soil, so as to meet the increasingly stringent performance requirements of fluidized solidified soil in the field of engineering construction. Summary of the Invention
[0005] To overcome the problems in the prior art, the present invention optimizes the composition of fluidized solidified soil, thereby effectively improving the strength, water resistance and durability of fluidized solidified soil.
[0006] To achieve the above objectives, the present invention is implemented through the following technical solution: The present invention proposes a high-durability fluidized solidified soil, wherein the fluidized solidified soil comprises, by weight: 60-80 parts of soil, 12-30 parts of cementitious material, 10-25 parts of oxime complexing agent, 4-10 parts of toughening agent, 3-8 parts of stabilizer, and 8-24 parts of water.
[0007] Preferably, the oxime complexing agent includes at least one of acetone oxime, cyclohexanone oxime, and propionaldehyde oxime.
[0008] Preferably, the soil is dry silt.
[0009] Preferably, the cementitious material comprises, by weight, 10-20 parts cement, 6-14 parts fly ash, 7-18 parts slag, and 4-8 parts phosphogypsum.
[0010] Slag is a byproduct of the blast furnace ironmaking process. During ironmaking, iron oxide is reduced to metallic iron at high temperatures. Impurities such as silica and alumina in the iron ore react with lime and other materials to form a molten material mainly composed of silicates and aluminosilicates. After quenching, it becomes a loose, porous granular material, which is blast furnace slag, or slag for short.
[0011] Phosphogypsum is a solid waste produced by phosphate chemical companies during the production of phosphoric acid and other products using wet processes (decomposing phosphate rock with sulfuric acid, nitric acid, or hydrochloric acid). Its main component is calcium sulfate dihydrate, and it also contains free phosphoric acid, fluoride, phosphorus pentoxide, phosphate, and small amounts of heavy metals and other impurities.
[0012] Preferably, the toughening agent includes at least one of lignin-grafted polylactic acid ester, lignin-grafted polycaprolactone, and lignin-grafted polybutylene succinate.
[0013] Preferably, the stabilizer includes at least one of tetrabutylammonium bromide, tetrabutylammonium chloride, and tetrabutylammonium iodide.
[0014] In another aspect, this invention provides a method for preparing the aforementioned high-durability fluidized solidified soil, the method comprising the following steps: (1) Mix the soil, cementitious materials and toughening agent to obtain mixture A.
[0015] (2) Add water, complexing agent and stabilizer to mixture A and stir to obtain high-durability fluidized solidified soil.
[0016] Preferably, in step (1), the stirring speed is 20~60 r / min and the stirring time is 2~5 min; Preferably, in step (2), the stirring speed is 50~100 r / min and the stirring time is 4~10 min.
[0017] Preferably, in step (1), the specific preparation method of the cementitious material is as follows: cement, fly ash, slag and phosphogypsum are mixed and stirred evenly according to the following mass parts: 10-20 parts cement, 6-14 parts fly ash, 7-18 parts slag and 4-8 parts phosphogypsum.
[0018] The beneficial effects of this invention are: 1. This invention utilizes an oxime complexing agent to form a multi-target synergistic effect with multiple components, wherein the oxime complexing agent interacts with the Ca²⁺ hydrated cementitious material. 2+ Al 3+The process involves forming a polynuclear complex (first target), which condenses with the carboxyl groups on the toughening agent surface to form an oxime ester bond (second target). Simultaneously, hydrogen bonds are formed between hydrogen atoms and the silanol groups of soil particles (third target). This process gradually constructs a dense composite cross-linked network of "complex bond-chemical bond-hydrogen bond" within the fluidized solidified soil. Through the synergistic effect of the various components of the fluidized solidified soil, the strength of the fluidized solidified soil is effectively improved, and the penetration of water, salt, and other substances is greatly delayed, thereby improving the water resistance and durability of the fluidized solidified soil.
[0019] 2. The toughening agent of this invention is anchored in the network through chemical bonds, achieving a dual strengthening effect of "physical strengthening + chemical binding". It can not only effectively improve the tensile strength and elastic modulus of fluidized solidified soil, but also improve the cohesion, mixing uniformity and workability of fluidized solidified soil, further improving the integrity of sulfided solidified soil and preventing discrete damage.
[0020] 3. The raw materials used in this invention are inexpensive and readily available, have minimal negative impact on the environment, and the fluidized solidified soil exhibits superior comprehensive performance, making it suitable for large-scale promotion and application. Detailed Implementation
[0021] The present invention will be further described in detail below with reference to specific embodiments, but the scope of protection of the present invention is not limited to the content described.
[0022] In the embodiments and comparative examples of this invention, the raw materials, reagents, instruments and equipment, unless otherwise specified, can all be purchased from the market or prepared by existing methods.
[0023] Example 1 This embodiment prepares fluidized solidified soil using the following method: (1) Weigh out the raw materials according to the mass parts of cement, fly ash, slag and phosphogypsum as 17 parts, 9 parts, 12 parts and 5 parts respectively, add the raw materials into the container and stir evenly to obtain the cementitious material.
[0024] (2) Add 68 parts of dry silt, 22 parts of prepared cementitious material, and 8 parts of toughening agent lignin-grafted polylactic acid to an automatic mixer and stir at 30 r / min for 5 min to obtain mixture A.
[0025] (3) Add 18 parts of oxime complexing agent acetone oxime, 15 parts of tap water and 5 parts of stabilizer tetrabutylammonium bromide to mixture A, and stir at 80 r / min for 8 min to obtain high-durability fluidized solidified soil.
[0026] Example 2 This embodiment prepares fluidized solidified soil using the following method: (1) Weigh out the raw materials according to the mass parts of cement, fly ash, slag and phosphogypsum as 16 parts, 7 parts, 15 parts and 4 parts respectively, add the raw materials into the container and stir evenly to obtain the cementitious material.
[0027] (2) Add 75 parts of dry silt, 20 parts of prepared cementitious material, and 5 parts of toughening agent lignin-grafted polycaprolactone into an automatic mixer and stir at 40 r / min for 3 min to obtain mixture A.
[0028] (3) Add 13 parts of oxime complexing agent cyclohexanone oxime, 20 parts of tap water and 3 parts of stabilizer tetrabutylammonium chloride to mixture A, and stir at 70 r / min for 7 min to obtain high-durability fluidized solidified soil.
[0029] Example 3 This embodiment prepares fluidized solidified soil using the following method: (1) Weigh out the raw materials according to the mass parts of cement, fly ash, slag and phosphogypsum as 15 parts, 11 parts, 10 parts and 6 parts respectively, add the raw materials into the container and stir evenly to obtain the cementitious material.
[0030] (2) Add 63 parts of dry silt, 17 parts of prepared cementitious material, and 7 parts of toughening agent lignin-grafted polybutylene succinate into an automatic mixer and stir at 50 r / min for 3 min to obtain mixture A.
[0031] (3) Add 22 parts of oxime complexing agent propionaldehyde oxime, 12 parts of tap water and 7 parts of stabilizer tetrabutylammonium iodide to mixture A, and stir at 90 r / min for 5 min to obtain high-durability fluidized solidified soil.
[0032] Example 4 This embodiment prepares fluidized solidified soil using the following method: (1) Weigh out the raw materials according to the mass parts of cement, fly ash, slag and phosphogypsum as 10 parts, 6 parts, 7 parts and 8 parts respectively, add the raw materials into the container and stir evenly to obtain the cementitious material.
[0033] (2) Add 60 parts of dry powder, 12 parts of prepared cementitious material, and 4 parts of toughening agent (lignin-grafted polylactic acid ester, lignin-grafted polycaprolactone, and lignin-grafted polybutylene succinate mixed in any proportion) into an automatic mixer and stir at 20 r / min for 5 min to obtain mixture A.
[0034] (3) Add 10 parts of oxime complexing agent acetone oxime, 8 parts of tap water, and 8 parts of stabilizer (tetrabutylammonium bromide, tetrabutylammonium chloride, and tetrabutylammonium iodide mixed in any proportion) to mixture A, and stir at 50 r / min for 10 min to obtain high-durability fluidized solidified soil.
[0035] The high-durability fluidized solidified soil prepared in this embodiment has similar performance to that in Example 1.
[0036] Example 5 This embodiment prepares fluidized solidified soil using the following method: (1) Weigh out the raw materials according to the mass parts of cement, fly ash, slag and phosphogypsum as 20 parts, 14 parts, 18 parts and 5 parts respectively, add the raw materials into the container and stir evenly to obtain the cementitious material.
[0037] (2) Add 80 parts of dry powder, 30 parts of prepared cementitious material, and 10 parts of toughening agent (lignin-grafted polylactic acid ester and lignin-grafted polybutylene succinate mixed in any proportion) into an automatic mixer and stir at 60 r / min for 2 min to obtain mixture A.
[0038] (3) Add 25 parts of oxime complexing agent acetone oxime, 24 parts of tap water, and 5 parts of stabilizer (tetrabutylammonium bromide and tetrabutylammonium chloride mixed in any proportion) to mixture A, and stir at 100 r / min for 4 min to obtain high-durability fluidized solidified soil.
[0039] The high-durability fluidized solidified soil prepared in this embodiment has similar performance to that in Example 1.
[0040] Comparative Example 1 This comparative example uses the same method as Example 1 to prepare fluidized solidified soil, the difference being that no cementitious material is added in this comparative example.
[0041] Comparative Example 2 This comparative example uses the same method as Example 2 to prepare fluidized solidified soil, except that no toughening agent is added.
[0042] Comparative Example 3 This comparative example uses the same method as Example 3 to prepare fluidized solidified soil, except that no oxime complexing agent is added.
[0043] Comparative Example 4 This comparative example uses the same method as Example 1 to prepare fluidized solidified soil, except that no stabilizer is added.
[0044] Compared with Example 1, Comparative Example 4 showed a greater loss in strength after 7 days of water curing in fluidized solidified soil and after water curing at 20℃ + 50℃.
[0045] The lack of stabilizer may have exacerbated the aggregation of cement particles and soil particles in Comparative Example 4, forming local pores and creating weak areas. This leads to uneven distribution of the properties of the fluidized solidified soil and causes instability in its properties. In addition, the formation of local pores makes it easy for moisture to migrate to the surface of the solidified soil, causing the surface to dry too quickly and the internal hydration to be insufficient.
[0046] Comparative Example 5 This comparative example uses the same method as Example 1 to prepare fluidized solidified soil, the difference being that toughening fibers are used as toughening agents in this comparative example.
[0047] Compared to Example 1, the fluidity of the solidified soil in this comparative example decreased, and the strength loss was significant after soaking in water for 7 days and after soaking at 20°C and curing at 50°C.
[0048] Because of the poor solubility of fibers, they are prone to agglomeration during mixing, which reduces the fluidity of the solidified soil. Furthermore, the fibers and cementitious materials only have a physical interlocking effect, resulting in poor interfacial bonding, easy damage and peeling, and easy formation of microcracks and seepage channels. This leads to crack expansion, more serious water absorption and seepage, and increased strength loss.
[0049] Example of effect Following the methods in the "Technical Standard for Premixed Flowable Solidified Soil Filling" (T / CECS 1037-2022), the flowable solidified soil from the examples and comparative examples was prepared into standard specimens. The standard specimens were then treated and their performance was tested using the following methods: The unconfined compressive strength of the standard specimen was tested after curing for 28 days. The unconfined compressive strength of the standard specimens was tested after they were soaked in water for 7 days at 20℃. After soaking in water at 20℃ for 24 hours, the product is cured at 50℃ for 48 hours, and this process is repeated three times to test the unconfined compressive strength.
[0050] The test results are shown in Table 1.
[0051] Table 1 Performance Indicators of Fluidized Solidified Soil As can be seen from Table 1, the components of the high-durability fluidized solidified soil in Examples 1-3 work synergistically to form a dense and stable spatial network structure, resulting in a significant performance improvement.
[0052] The unconfined compressive strength after 28 days of curing was higher than that of comparative examples 1-3 and commercially available fluidized solidified soils, indicating that the fluidized solidified soil of the present invention has better physical and mechanical properties.
[0053] After soaking and curing in water for 7 days, the strength loss of the fluidized solidified soil of the present invention is about 5% to 6%, while the strength loss of comparative examples 1-3 reaches about 20%, which proves that the fluidized solidified soil of the present invention has significantly better water stability performance than comparative examples 1-3 and conventional commercially available fluidized solidified soil.
[0054] After soaking and curing in water for 7 days, the strength loss of the fluidized solidified soil in Examples 1-3 was only about 5%, which proves that it has strong resistance to water erosion, excellent internal structure and slow water penetration. Therefore, external water is not easy to enter the solid soil, which alleviates the pressure of ice expansion of the solid soil and is conducive to improving the freeze-thaw resistance of fluidized solid soil.
[0055] After a wet-dry cycle of soaking in water at 20℃ and curing at 50℃, the strength loss rate of the fluidized solidified soil of the present invention is about 10%, while the strength loss rate of the fluidized solidified soils in Comparative Examples 1-3 reaches more than 40%, indicating that the fluidized solidified soil of the present invention has good resistance to water erosion and environmental durability.
[0056] After a cycle of soaking in water at 20℃ and curing at 50℃, the strength loss of the fluidized solidified soil in Examples 1-3 was only about 10%. This indicates that the fluidized solid soil of the present invention can still maintain structural stability under drastic changes in temperature and humidity, and the water absorption and loss rates are effectively reduced, thereby reducing the risk of drying shrinkage and cracking.
[0057] Compared to Example 1, Comparative Example 1 lacks cementitious materials and cannot form a strong skeleton in the solidified soil, resulting in lower strength. Compared to Example 2, Comparative Example 2 lacks toughening agents, and its test results show a significant decrease in strength, water stability, and durability, indicating that the toughening agent has a good effect on enhancing the overall performance of the fluidized solidified soil of this invention. Compared to Example 3, Comparative Example 3 lacks oxime complexing agents and does not have multi-target synergistic effects. Its test results are similar to the performance indicators of commercially available conventional solidified soils, indicating that in the fluidized solidified soil of Example 3, the cementitious materials and toughening agents each play their roles, lacking intermediate substances for bridging, resulting in poor performance test indicators.
[0058] In summary, this invention optimizes the composition of fluidized solidified soil, promoting a synergistic enhancement effect among the components. This effectively improves the strength, water resistance, and environmental durability of fluidized solidified soil, expands its application scenarios, and enables it to meet more stringent engineering construction application requirements.
[0059] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.
Claims
1. A highly durable fluidized solidified soil and its preparation method, characterized in that: The fluidized solidified soil comprises, by weight, 60-80 parts soil, 12-30 parts cementitious material, 10-25 parts oxime complexing agent, 4-10 parts toughening agent, 3-8 parts stabilizer, and 8-24 parts water.
2. The high-durability fluidized solidified soil according to claim 1, characterized in that: The oxime complexing agent includes at least one of acetone oxime, cyclohexanone oxime, and propionaldehyde oxime.
3. The high-durability fluidized solidified soil according to claim 1, characterized in that: The soil in question is dry silty soil.
4. The high-durability fluidized solidified soil according to claim 1, characterized in that: The cementitious material comprises, by weight, 10-20 parts cement, 6-14 parts fly ash, 7-18 parts slag, and 4-8 parts phosphogypsum.
5. The high-durability fluidized solidified soil according to claim 1, characterized in that: The toughening agent includes at least one of lignin-grafted polylactic acid ester, lignin-grafted polycaprolactone, and lignin-grafted polybutylene succinate.
6. The high-durability fluidized solidified soil according to claim 1, characterized in that: The stabilizer includes at least one of tetrabutylammonium bromide, tetrabutylammonium chloride, and tetrabutylammonium iodide.
7. The method for preparing the high-durability fluidized solidified soil according to any one of claims 1-6, characterized in that: The preparation method includes the following steps: (1) Mix the soil, cementitious materials and toughening agent to obtain mixture A; (2) Add water, oxime complexing agent and stabilizer to mixture A and stir to obtain high-durability fluidized solidified soil.
8. The preparation method according to claim 7, characterized in that: In step (1), the stirring speed is 20~60 r / min and the stirring time is 2~5 min.
9. The preparation method according to claim 7, characterized in that: In step (2), the stirring speed is 50~100 r / min and the stirring time is 4~10 min.
10. The preparation method according to claim 7, characterized in that: In step (1), the specific preparation method of the cementitious material is as follows: cement, fly ash, slag and phosphogypsum are mixed and stirred evenly according to the following mass parts: 10-20 parts cement, 6-14 parts fly ash, 7-18 parts slag and 4-8 parts phosphogypsum.