3.1 Determination of saturated superplasticiser dosing points
Fig. 2 illustrates the variations in the fluidity of red mud blended cement paste incorporating SR-PCE and WR-PCE at red mud concentrations of 0% and 20%. It was observed that at 0% red mud content, paste fluidity increased with higher dosages of the superplasticiser. The fluidity changes became negligible when the dosages exceeded 0.75% for SR-PCE and 0.5% for WR-PCE. Consequently, the saturation dosages were determined to be 0.75% for SR-PCE and 0.5% for WR-PCE. At a red mud content of 20%, the fluidity of the paste containing 0.75% SR-PCE improved by 98.4% compared to the paste without PCE, while the fluidity of the paste with 0.5% WR-PCE increased by 354.3%. This enhancement is attributed to PCE molecules dissociating into macromolecular anions in water, which then adhere to the surfaces of cement particles and their hydration products. This adsorption increases electrostatic repulsion between particles, disrupts and prevents the formation of flocculated structures in the paste, and increases the amount of free water, resulting in improved paste fluidity [22]. When the dosages of the superplasticiser and red mud were kept constant, the paste with WR-PCE consistently exhibited greater fluidity than that with SR-PCE. Thus, at a fixed red mud dosage of 20%, WR-PCE proved to be more effective than SR-PCE in enhancing the fluidity of red mud blended cement paste.
3.2 Rheological property analysis
3.2.1 Setting time of red mud blended cement paste
When the red mud admixture was maintained at 25%, the setting time of the reference group, SR-PCE (0.75%), and WR-PCE (0.5%) red mud blended cement paste was measured, as presented in Fig. 3. The initial setting time for SR-PCE and WR-PCE was 26.4% and 12.1% longer than the reference group, respectively, while the final setting time was 27.9% and 22.1% longer. These results indicate that PCE retards the setting time of red mud blended cement paste, with SR-PCE exhibiting a stronger retarding effect compared to WR-PCE. This is attributed to SR-PCE having longer and denser side chains than WR-PCE, which enhances spatial site resistance and thus more effectively delays cement hydration [23].
3.2.2 Influence of superplasticisers on the fluidity loss of red mud blended cement paste
Fig. 4 illustrates how SR-PCE and WR-PCE affect the fluidity loss of red mud blended cement paste with varying red mud dosages (0%, 12.5%, 37.5%, and 50%), while Table 2 details the impact of superplasticisers on the decrease rate of fluidity loss relative to a 0% red mud dosage. As the red mud dosage increased, the fluidity of the reference, SR-PCE, and WR-PCE groups exhibited a declining trend at both 30 and 60 minutes. The fluidity of the reference group fell below 100 mm, indicating excessive viscosity. For equal amounts of red mud, the SR-PCE and WR-PCE groups showed higher flow than the reference group, indicating that PCE enhances the initial flow of freshly mixed red mud blended cement paste. This improvement is attributed to the lubricating effect of PCE, which forms hydrogen bonds with water due to its hydrophilic carboxyl and other polar groups, and weakens van der Waals forces between red mud, cement, and PCE, thereby creating a hydration film that disperses red mud and cement particles [24].
Table 2 Impact of superplasticisers on the decrease rate of fluidity loss through time of red mud blended cement paste (compared to a 0% red mud dosage)
Red mud
PCE
|
Time (min)
|
12.5%
|
25.0%
|
37.5%
|
50.0%
|
SR-PCE
|
30
|
12.4%
|
27.1%
|
54.7%
|
58.8%
|
WR-PCE
|
30
|
39.6%
|
57.5%
|
65.8%
|
76.0%
|
SR-PCE
|
60
|
23.2%
|
35.0%
|
66.4%
|
69.2%
|
WR-PCE
|
60
|
34.2%
|
56.7%
|
67.5%
|
73.1%
|
At a red mud dosage of 12.5%, the SR-PCE red mud blended cement paste experienced the smallest fluidity loss compared to WR-PCE for both 30 and 60 minutes, showing reductions of 12.4% and 23.2%, respectively (Table 2). This is due to the ester groups in SR-PCE hydrolyzing in the alkaline environment of cement hydration, releasing carboxyl groups which significantly reduce the fluidity loss [19]. When the red mud dosage exceeded 12.5%, the fluidity loss for both SR-PCE and WR-PCE red mud blended cement paste increased by more than 25% at both 30 and 60 minutes. This occurs because the extensive specific surface area of red mud decreases the amount of free water in the paste. Additionally, red mud adsorbs PCE, diminishing its efficacy on the cement particle surfaces [25].
3.2.3 Influence of PCE on the shear stress of red mud blended cement paste
Fig. 5 presents the hysteresis curves for red mud blended cement paste with red mud contents of 0%, 25%, and 50% under the influence of superplasticisers. Table 3 details the yield stress values for these paste. When no red mud was incorporated (0%), the shear stress of the red mud blended cement paste increased with the shear rate in both the reference group and the groups containing SR-PCE and WR-PCE. However, the increase in shear stress was notably smaller for the WR-PCE group. The Bingham model was used to characterize the rheological behavior [26]. At 0% red mud, both the reference group and the SR-PCE incorporated paste behaved as standard Bingham fluids, whereas the WR-PCE incorporated paste exhibited properties closer to a Newtonian fluid. At a red mud content of 25%, the shear stress of the SR-PCE and WR-PCE incorporated paste also increased with the shear rate. The WR-PCE incorporated paste behaved similarly to a Newtonian fluid, while the reference group and SR-PCE incorporated paste continued to act as Bingham fluids. The WR-PCE incorporated paste showed the lowest yield stress, approaching zero. When the content reached 50%, the overall shear stress rose linearly with the shear rate. Both the reference group and the PCE-incorporated paste remained Bingham fluids, with the WR-PCE incorporated paste consistently exhibiting the lowest yield stress.
Table 3 Yield stress of red mud blended cement paste with various red mud dosages under the action of different superplasticisers
|
Yield stress/Pa (red mud 0%)
|
Yield stress/Pa (red mud 25%)
|
Yield stress/Pa (red mud 50%)
|
Ref
|
69.678
|
327.730
|
1026.300
|
SR-PCE
|
26.193
|
136.780
|
612.500
|
WR-PCE
|
0.015
|
1.811
|
112.660
|
3.2.4 Influence of superplasticisers on the apparent viscosity of red mud blended cement paste
Fig. 6 illustrates how PCE affects the apparent viscosity of red mud blended cement paste with red mud contents of 0%, 25%, and 50%, while Table 4 presents the impact of PCE on these paste' plastic viscosity. When the red mud content was 0% or 25%, the apparent viscosity of the reference group and the SR-PCE incorporated paste increased with the shear rate. In contrast, the WR-PCE incorporated paste showed minimal fluctuation in apparent viscosity. Once stabilized, the viscosities of all three paste approached 0, representing the plastic viscosity, with the order of magnitude being: reference group > SR-PCE > WR-PCE. When the red mud content was 50%, the apparent viscosity of the reference group, SR-PCE incorporated paste, and WR-PCE incorporated paste decreased with increasing shear rate. Upon stabilization, the viscosities of all three paste again approached 0, indicating the plastic viscosity, with the same order of magnitude: reference group > SR-PCE > WR-PCE. This observation aligns with the findings in Section 3.2.3.
Table 4 Impact of PCE on the plastic viscosity of red mud blended cement paste with red mud contents of 0%, 25%, and 50%
|
Plastic viscosity/Pa·s
(red mud 0%)
|
Plastic viscosity/Pa·s
(red mud 25%)
|
Plastic viscosity/Pa·s
(red mud 50%)
|
Ref
|
4.499
|
13.228
|
31.548
|
SR-PCE
|
3.2541
|
7.966
|
20.288
|
WR-PCE
|
0.172
|
1.697
|
12.050
|
3.3 Compressive strength analysis
Fig. 7 displays the specimens' compressive strength at 1, 3, 7, and 28 days, with superplasticisers added at 0%, 25%, and 50% red mud content. The data reveal that the compressive strength of the PCE-enhanced paste was marginally greater than that of the reference group across all red mud contents (0%, 25%, and 50%). This suggests that the addition of PCE not only does not compromise the compressive strength of red mud blended cement paste but also has a slight strengthening effect. The enhancement can be attributed to the disruption of the flocculation state among cement particles by PCE. The anionic PCE molecules attach to the surfaces of red mud and cement particles, creating electrostatic repulsion. The spatial resistance effect of PCE's long side chains further disperses the cement particles, freeing up water, which then participates in the hydration process, resulting in more hydration products [27].
Additionally, the carboxylic acid groups in PCE easily complex with Ca2+ in the red mud blended cement paste, which reduces the pore size distribution, fills internal pores, and enhances the overall strength of the specimens [28]. The early and late strengths of the WR-PCE samples were greater than those of the SR-PCE samples. This might be because the dispersion properties of WR-PCE in red mud blended cement paste are superior, further promoting the hydration reaction [11].
When the red mud content was increased to 50%, the overall compressive strength decreased significantly compared to the 0% and 25% red mud content paste. This reduction could be due to the high alkalinity of the paste at higher red mud dosages, which destabilizes the PCEs in such highly alkaline environments [29].
3.4 Mineral composition analysis
Fig. 8 presents the X-ray diffraction (XRD) plots of red mud blended cement paste with red mud contents of 0%, 25%, and 50% at various ages. At both 7 and 28 days, with a red mud content of 0% (Fig. 8(a)), no significant difference was observed in the type of hydration products between the reference group and the paste incorporated with SR-PCE and WR-PCE. This indicates that PCE doping does not alter the hydration product types in the red mud blended cement paste but enhances its physical properties by reducing the water/cement ratio while maintaining its strength. Moreover, compared to the 7-day samples, the 28-day samples exhibited higher peak intensities of C-S-H gel and Ca(OH)2, along with decreased peaks of C2S and C3S. This suggests that SR-PCE and WR-PCE accelerate the hydration process, depleting C2S and C3S and generating more C-S-H hydration products.
For red mud contents of 25% and 50% (Figs. 8(b) and (c)), the 28-day samples with SR-PCE and WR-PCE showed higher peak intensities of C-S-H and Ca(OH)2 compared to the samples without water reducers. This indicates that SR-PCE and WR-PCE enhance the hydration degree of C2S and C3S over time, producing more C-S-H and hence improving strength. Additionally, the presence of aqueous calcium aluminum garnet peaks is due to the red mud addition. The intensity of hydrogrossular peaks decreased in the 28-day samples compared to the 7-day samples, suggesting that red mud participates in the hydration reaction, which is not complete [30].
3.5 Micro-morphological analysis
Fig. 9 presents the SEM images at 28 days (magnifications of ×5000 and ×20000) for the hardened red mud blended cement paste from the reference group, SR-PCE, and WR-PCE with a 25% red mud dosage. Figs. 9(a) and (b) show a substantial formation of fibrous C-S-H gels and flaky Ca(OH)2 crystals. The fibrous C-S-H gels not only adhered to the flaky Ca(OH)2 but also effectively filled the pores, densifying the matrix structure. At a magnification of ×5000 (Fig. 9(c)), numerous uniformly distributed flocculated structures were observed, adsorbed on the cement particle surfaces and evenly distributed across the cement paste.
At ×20000 magnification (Fig. 9(d)), it was noted that the SR-PCE molecules displayed fewer surrounding C-S-H gels than the reference group. This difference is attributed to the adsorption and dispersion of SR-PCE molecules on the C-S-H gel surface, encapsulating the gel. Fig. 9(e) at ×5000 magnification revealed that the hydration products in the WR-PCE incorporated red mud blended cement paste were more uniformly distributed than in the SR-PCE incorporated paste, further supporting the better dispersion properties of WR-PCE. Finally, Fig. 9(f) at ×20000 magnification showed that the C-S-H gel in the WR-PCE incorporated paste exhibited a network structure, differing from the fibrous structure observed in the reference group.
3.6 Thermal analysis
Fig. 10 presents the thermogravimetric analysis (TG) and differential scanning calorimetry (DSC) plots for the reference group, SR-PCE, and WR-PCE red mud blended cement paste with a 25% red mud admixture. Table 5 details the mass loss of hydration products for 7 and 28-day samples from the reference group, SR-PCE, and WR-PCE red mud blended cement paste across three stages: C-S-H gel dehydration [31], Ca(OH)2 crystal dehydration [32], and CaCO3 decomposition [33]. The TG and DSC plots (Figs. 10(a) and (b)) showed mass loss up to 100 ℃, primarily due to the free and adsorbed water's natural evaporation in the paste [34]. From 100 to 300 ℃, mass loss is mainly attributed to C-S-H gel dehydration, with WR-PCE incorporated samples exhibiting greater C-S-H dehydration, indicating more C-S-H formation. Between 400 and 500 ℃, the mass loss corresponds to the Ca(OH)2 crystal dehydration, and from 600 to 750 ℃, it is caused by CaCO3 decomposition. Additionally, the mass loss of Ca(OH)2 crystals in the 28-day
Table 5 Mass loss of 7 and 28-d hydration products of the reference group, SR-PCE, and WR-PCE hardened paste at each hydration stage
|
Curing time (d)
|
Stage I
|
Stage Ⅱ
|
Stage Ⅲ
|
Total loss
|
Ref
|
7
|
2.7%
|
5.7%
|
5.2%
|
18.4%
|
SR-PCE
|
7
|
3.3%
|
4.8%
|
5.4%
|
19.0%
|
WR-PCE
|
7
|
4.7%
|
4.3%
|
5.3%
|
19.5%
|
Ref
|
28
|
3.5%
|
5.2%
|
5.5%
|
19.6%
|
SR-PCE
|
28 d
|
4.4%
|
4.6%
|
5.0%
|
20.2%
|
WR-PCE
|
28 d
|
5.2%
|
4.0%
|
4.1%
|
20.9%
|
hydration products of the reference group, SR-PCE, and WR-PCE red mud blended cement paste was lower than in the 7-day samples. This indicates that more Ca(OH)2 crystals are consumed as samples age, leading to increased generation of C-S-H gels.
3.7 Mechanistic analysis
The results from the rheological property experiments, compressive strength experiments, XRD, SEM, and TG-DSC analyses reveal the underlying mechanisms in the early stages of the red mud blended cement paste reaction with WR-PCE and SR-PCE. The hydration of tricalcium aluminate (C3A) and tetracalcium ferroaluminate (C4AF) in the cement imparts a positive charge on the surface of cement particles. This enhances the adsorption of hydrolyzed PCE molecules, which generate carboxylate and other anions. The hydration product Ca(OH)2 and the alkaline nature of red mud favor the PCE adsorption on the red mud and cement particle surfaces [35].
As numerous PCE molecules adsorb onto the surfaces of red mud and cement particles, these surfaces become negatively charged. This leads to electrostatic repulsion between red mud and cement particles [10], dispersing them and extending the red mud blended cement paste's initial and final setting times [36]. The hydration products in the WR-PCE incorporated red mud blended cement paste were more evenly distributed compared to those with SR-PCE. This is primarily due to the complexation of SR-PCE with Ca2+ in the paste and the cross-linking between SR-PCE molecules, which diminishes its dispersibility [37]. Consequently, the apparent viscosity and shear stress of the WR-PCE red mud blended cement paste are lower, resulting in greater fluidity.
Moreover, SR-PCE molecules possess longer and denser side chains compared to WR-PCE, which enhances their spatial site resistance effect, thereby more effectively retarding cement hydration [23]. This results in a lower rate of time-dependent loss and better retardation and slump retention effects.