In addition to the mechanical macroanalysis, a microanalysis should also be carried out. The hydration products, reaction mechanism, and micropores of clay cement and stone powder cement stone bodies were analyzed from the microscopic perspective. The microparameters of stone powder cement grouting hardened body are better. The combination of macro- and microanalysis further demonstrates that the stone powder cement slurry is more resistant to external loads, making the geotechnical reinforcement more stable and improving the bearing capacity.
3.4.2. Reaction Mechanism Analysis
The role of clay in cement hydration reaction: Under the heat released from the cement hydration reaction, a small amount of ferric oxide and magnesium oxide in clay components is converted into ferric hydroxide and magnesium hydroxide colloid with positive charge. Serum anion binding clouds cluster in the body, and clay adsorption by the electrostatic force between particles results in a low strength of the hardened body. A small amount of calcium oxide in the clay composition reacts with water to produce calcium hydroxide colloid with a positive charge and cement particles with a very weak charge exchange, providing crystal nucleus attachment points for cement particles, accelerating the hydration reaction of cement, clay, and cement hydration products by chemical bond force condensation, resulting in a hardened body with high strength. However, due to the low proportion of cement in the slurry and the reduction in cementing material after hydration, the overall strength of the hardened body is low.
The role of stone powder in the cement hydration reaction: The addition of stone powder inhibits the formation of monosulfur calcium sulphoaluminate hydrate (AFm), and the ettringite formed by the hydration reaction of cement clinker in the early stage of cement is more stable. Because the molar volume of ettringite is higher than that of AFm, the porosity of the hardened body is reduced, the pore structure of the hardened body is improved, and the strength is increased.
3.4.3. Analysis of Porosity Results
(1) Image-Pro Plus (IPP) porosity calculation method
To analyze the microscopic pores of the hardened body, SEM images were analyzed by IPP software with the help of binarization-related software and the Menger sponge model. The image obtained by scanning electron microscope was imported into IPP software, and the relationship between porosity and porosity obtained by mercury pressure test was calculated according to the gray threshold. When the gray threshold was set to 81, binarization was performed to reduce the test error. In the SEM scanning volume images, pixels are taken as units; 1 represents particles, and 0 represents pores. The porosity of the consolidated body can be calculated by counting the proportion of 0 and 1 images, as shown in
Figure 13.
In 3D space, based on the Menger sponge model, the expression of the micropore distribution density function can be derived as follows.
In the aperture area, [
] can be used to obtain the area between the microscopic pore volume for:
The microscopic porosity in the modified interval can be obtained as follows:
In summary, the microscopic pore volume of the hardened body can be expressed as:
Finally, taking the logarithm of both sides yields:
where
KV denotes the shape factor of microscopic pore volume,
V (≥
r) denotes the pore volume with a pore size is greater than or equal to the pore volume,
Va denotes the total pore volume of soil within the observation range,
L denotes the scale of observation range, and
D denotes the fractal dimension of the pore volume of the Menger sponge.
An electron microscope can magnify stone powder cement and clay cement hardened bodied by tens of thousands of times. The smaller the multiple, the larger the range of analysis and statistics and the more blurred the boundary between particles and pores, which affects the statistical error. The larger the multiple, the smaller the area of analysis and statistics, and the obtained data are one-sided and cannot be regarded as representative values. Therefore, it is necessary to select appropriate multiple images to study the porosity of the hardened bodies. Three electron microscopic scanning images of the mucinous hardened bodies with different magnifications (1500, 3500, and 5000) and different regions were selected, as shown in
Figure 14. According to calculations, the porosity of the three clay hardened body images was 26.2%, 37.3%, and 36.8%, respectively, with an average value of 33.43%. The porosity of the three images was 16.7%, 17.5%, and 20.3%, respectively, with an average of 18.16%.
Microstructural analysis of the clay cement slurry hardened body and the stone powder cement slurry hardened body revealed many hydration products in the stone powder cement slurry hardened body. The strength of the hardened body was improved as the cement particles encapsulated the stone powder particles to provide an attachment point for the cement reaction, accelerating the cement hydration reaction and producing a large number of hydration products that effectively filled the pores of the hardened body. However, due to the small size of the clay particles, the clay particles wrapped the cement particles and prevented the cement hydration reaction. As a result, the clay cement slurry hardened body had fewer hydration products, a simpler structure, and larger pores. Comprehensive comparative analysis shows that the microstructure of stone powder cement slurry is dense.
(2) Mercury Intrusion Porosimeter (MIP) porosity calculation method
The prepared stone powder cement slurry hardened body and clay cement slurry hardened body samples were dried (three for each group), processed into 10 mm × 10 mm × 10 mm squares with fine steel wire, and placed in a dilatometer under a pump vacuum to ensure that the pore pressure in the samples was close to zero. Then, mercury was injected for mercury injection analysis. The pore parameters of the samples were collected. The MIP test operation is shown in
Figure 15.
Analysis of the data obtained from the mercury intrusion test, allowed for calculation of the porosity of the samples, the maximum volume of mercury injection, and other parameters. As shown in
Table 9, the mercury inflow volume of stone powder cement slurry hardened body is 0.12–0.18 mL, and that of clay cement slurry hardened body is 0.23–0.31 mL. Other parameters measured in the mercury injection test are listed in
Table 9.
After data processing and analysis, the distribution curves of pore diameter and accumulated mercury volume of the samples were obtained according to the accumulated mercury volume and pore diameter data obtained in the mercury intrusion test, as shown in
Figure 16. The curve value of sample 2-3 is the highest among all samples, indicating that it has the highest mercury intake and porosity. The curve value of sample 1-1 is the lowest, indicating that it has the lowest mercury intake and porosity. The mercury content of stone powder cement slurry (sample 1) at mutation point 1 increased, indicating that the pore diameter of stone powder cement slurry hardened body is concentrated in the range of 10–50 nm. When the pore diameter is greater than 50 nm, the cumulative mercury content of the pore volume changes minimally, indicating that there are few pores larger than 50 nm in the sample. The mercury content of clay cement slurry (sample 2) at mutation point 2 increased, indicating that the pore diameter of the clay cement slurry hardened body is concentrated in the range of 100–150 nm. When the pore diameter is greater than 150 nm, the cumulative mercury volume change of the pore is minimal, indicating that there are few pores larger than 150 nm in the sample.
Mutation point 1 is on the right side of mutation point 2, indicating that the average pore diameter of the stone powder cement slurry hardened body is smaller than that of the clay cement slurry hardened body, whereas the curve height of sample 1 is lower than that of sample 2, indicating that the porosity of the stone powder cement slurry hardened body is smaller than that of the clay cement slurry hardened body because when the stone powder cement slurry hydration reaction occurs, because the stone powder particle size is larger than the cement particle size, the stone powder particles are surrounded by cement, providing an attachment point for the cement reaction and accelerating the cement hydration reaction, generating a large number of hydration products, effectively filling the voids of the hardened body and resulting in a small pore size in the stone powder cement slurry hardened body. However, when the hydration reaction occurs in the clay cement slurry, owing to the small size of the clay particles, the clay particles surround the cement particles, hindering the hydration reaction of cement and resulting in few hydration products, so the gaps of the hardened body cannot be effectively filled, resulting in high porosity and a large pore diameter of the clay cement slurry hardened body.
The average porosity of stone powder cement slurry produced using the MIP method is 19.53%, and the error of IPP calculation is 7%. The average porosity of the clay cement slurry hardened body is 33.77%, and the error of IPP calculation is 1%. The calculation results are similar between the two methods, indicating that the combination of SEM and IPP is an effective porosity calculation method.
Analysis of the hydration reaction products, hydration mechanism, and pore structure of the slurry hardened body show that the stone powder slurry hardened body has many hydration products, a sufficient hydration reaction, and low porosity. These microstructures are conducive to improving the strength of the stone powder slurry hardened body and strengthening the bearing capacity of the geotechnical reinforcement, indicating that the microstructure of the stone powder cement slurry is superior to that of the clay cement slurry.