4.1. Optimization of SCC mix design with the blend of CC and RHA
To optimize the blend of CC and RHA as partial replacement to PLC in SCC, the influence of CC and RHA on the amount of water confined by the binder was first considered. PLC without CC and RHA partial replacement confined approximately a volume of water equal to the volume of solid. A substitution by 10 vol-% CC showed no significant effect on the volume of water confined and increased to 11 vol-% of water at substitution ratio of 40 vol-%. RHA at 10 vol-% PLC substitution confined 20 vol-% additional water compared to the PLC, and the volume of water confined increased to 43 vol-% at RHA substitution ratio of 40 vol-%.
Figure 2 shows the V
w/V
p for CC, RHA and the ternary blends of CC and RHA.
However, the ternary blends of CC and RHA yielded no any reduction in the V
wΓo due to the high-water demand of RHA, for instance, the V
wΓo for 40 vol-% CC replacement is 1.15 and increased drastically to 1.37 when 5 vol-% of CC is replaced by RHA in the blend (35CC,5RHA).
Figure 2 shows the relationship between the water demand and the ratio of confined water by the binder systems. The ternary blends of CC and RHA appeared above the line of best fit, while the binary blends appeared on the line or below.
A possible explanation for this behavior of the ternary blends is the dominating influence of RHA on the properties of the blended binder. Even a small amount of RHA in the ternary blend leads to an increase in both, the water demand and the amount of water trapped by the binder compared to the binary CC mixes. It could also be due to improper mixing of the two materials, since CC has a heterogeneous surface morphology, while RHA contains an irregular, granular surface of isolated plate morphology as shown in
Figure 4, so the presence of CC in the mixture does not have a significant effect on reducing the water demand of ternary mixtures.
The design of SCC starts with the determination of the V
w/V
p required to impart on paste self-compactability. This V
w/V
p is calculated from the volume of water confined by the individual binder system, and the average of these values for the individual binder systems are shown in
Table 2. PLC requires an average of 0.87 V
w/V
p to achieve self-compactability. Partial substitution of CC up to 20 vol-% has minor effect on this value, CC partial substitution beyond 20 vol-% requires an adjustment of this value or an increase of the SP dosage to achieve similar deformability class as the PLC system, as previous investigation by [
48] achieved self-compactability using the same V
w/V
p and increasing SP dosage, with up to 40 vol-% CC in SC-M. On the other hand, the partial substitution of PLC with RHA requires an significant increase of V
w/V
p to achieve self-compactability. At 10 vol-% RHA partial replacement, V
w/V
p already increased to 1.1, which is 21 % higher than the value required for PLC. At 40 vol-% RHA partial replacement, the V
w/V
p increased by 42 %. In this case, the SP adjustment is not sufficient to achieve the required degree of deformability because of the higher water demand and specific surface area of the RHA compared to PLC. Therefore, urgent adjustment of the V
w/V
p of the RHA and the ternary blend of CC and RHA systems is required to achieve a deformability characteristic similar to that of PLC.
The SCP design in this section will later be used as a binder in SC-M and SCC. Therefore, the selection of the V
w/V
p will be done considering the intended final use of SCC. The following outlook is considered to justify the selection of V
w/V
p for the SCP design. In practice, the water-to-binder (w/b) and the strength of the binder determined the strength and durability class of the concrete and thus its application [
49,
50]. To achieve SCC with PLC, a V
w/V
p = 0.87 is required, corresponding to a w/p = 0.29; for CC replacement up to 40 vol-%, a w/p = 0.32 is required. For 10 vol-% RHA, w/p = 0.36 is required, increasing to 0.42, 0.45, and 0.50 for 20, 30, and 40 vol-% partial replacement, respectively. [
51] achieved self-compactability using a w/b = 0.26 with up to 20 wt-% RHA as partial replacement for cement in SC-M, and despite increasing dosages of SP, RHA increased the viscosity of the SC-M. It should be noted at this point that the deformability of the SC-M doesn’t necessarily indicate the deformability of SCC, because SCC contains a large volume of coarser aggregate in addition to SC-M, which has a significant impact on its deformability characteristics. [
52] achieved self-compactability using a low w/p = 0.28 and the same dosage of high range water reducers with RHA substation up to 20 wt-%, but the viscosity of 20 wt-% RHA binary blended SCC was 63 % higher than the control (viscosity = V-funnel time). The same deformability characteristic as the reference systems with higher RHA replacement ratios (≥ 20 wt-%) were achieved by increasing the w/p to 0.44 and above [
53,
54,
55]. Another factor that governs the selection of the w/b is the expected performance of the SCC after hardening. For chloride exposure under alternating wet and dry conditions, the maximum allowable w/b is 0.45 [
49].
Partial replacement of PLC with CC even up to 40 vol-% yields the required deformability characteristics and has a wide applicability in different durability exposure classes, as previously reported by [
48,
56] while providing significant savings of production cost and reducing CO
2 emission. Higher PLC partial substitution with RHA up to 40 vol-% is also possible using a higher w/p of ≥ 0.5, this concrete could also have a wide range of applications, for instance in exposure classes X0, XC, and some classes of XD and XS exposure according to [
49]. Considering that RHA poses a challenge to deformability at higher PLC partial substitution due to its high-water demand, this study will limit the RHA replacement ration to 20 vol-%. For comparison, the binary blend with CC will also be kept at 20 vol-%, and the ternary blend will use 10 vol-%CC + 10 vol-%RHA. Therefore, V
w/V
p = 1.275 required to impart self-compactability to the 20 vol-% RHA binder system is considered as the V
w/V
p in the following and is used to established the SP dosages required to deform the SCP systems, as depicted in
Figure 5.
Based on the visual inspection, SC-P achieved deformability without segregation at a flow diameter of 220 to 265 mm. Therefore, the dosage of SP is established which is necessary for the individual binder systems to achieve a flow diameter 240 mm ± 20 and without segregation. The latter is assessed visually. PLC binder system (SC-P) requires an SP dosage of between 0.05 to 0.1 wt-% to achieve self-compactability. SC-P-20CC demands a slightly higher SP dosage as SC-P, while for the SC-P-20RHA system, the SP dosage already increases drastically to 0.3 wt-%, although this is reduced to 0.25 with the SC-P-10CC+10RHA blend. The increase in the SP demand is due to the higher water demand of RHA, which continues to trap water in its structure and requires more SP to achieve the required degree deformability. The final SCP mix design is shown in
Table 3 and were used as basis for SC-M design and to measure the portlandite over the period of 28 days of curing.
The SCP designed above were used in the next step as media to deform the SC-M and bind the fine aggregate. The SC-M mix designs are achieved by fixing the volume of the fine aggregate (V
s) at 44 vol-% of the total SC-M volume, based on the recommendation of (EFNARC 2002). SP dosages are adjusted to achieve the required degree of deformability.
Figure 6 shows the deformability and the rate of deformability of the individual SC-M systems.
With a slight adjustment of the SP dosage, SC-M-1-20CC achieved a similar deformability to SC-M-1, SC-M-1-20RHA and the blend SC-M-1-10CC+10RHA could achieved a similar deformability class to SC-M-1 but with an increased viscosity and higher SP dosages. For deformability assessment, (EFNARC 2002) guidelines were adopted. A range of 240 mm to 260 mm flow diameter and a viscosity class (V-funnel time) of 7 s to 11 s were used. Only SC-M-20RHA falls under these limits. The remaining mixtures exhibited a higher flow rate, indicating low viscosity. Therefore, mixtures that are stable (judged by visual assessment) between the flow diameter = 240 mm to 260 mm were considered for the production of the SC-M specimens.
Table 4 provides the final SC-M mix designs which were used to monitor the influence of CC and RHA on plastic and dry shrinkage strains.
The final SCC mix design is achieved with a fixed CA content of 33 vol-% and assuming an air content (V
a) of 2 vol-% of the total SCC volume according to (EFNARC 2002), while the SC-M designed above complete the remaining SCC volume. The SP dosages were adjusted until an acceptable deformability is achieved as shown in
Figure 7(a). Criteria for assessing the deformability of SCC in the absence of obstacles (filling ability) include the slump-flow, V-funnel and t
500 times as an indication of viscosity, while the use of J-ring can give an estimation of the deformability in the presence of obstacle (passing ability). The combination of these assessments was used as the basis for the selecting the appropriate mixes to produce the final SCC. By adjusting the SP dosages, SCC-1 achieved a deformability class SF2 and viscosity class VS1 and VF1 according to [
50]. With a slight increase in the SP dosage, SCC-1-20CC achieved similar deformability to the SCC-1, with viscosity classes of VS2 and VF1. SCC-1-20RHA exhibited higher viscosity than SCC-1 and requires an increased SP dosage to attain deformability class SF2 and viscosity classes VS2 and VF1. The ternary blended, SCC-1-10CC+10RHA, exhibited a deformability and viscosity behavior somewhat in-between that of binary CC and RHA SCC. The increased viscosity with RHA substitution is due to the higher water demand of RHA compared to PLC and CC as depicted in
Table 1. A relationship between the V-funnel time (VF) and the t
500 (VS) measured together with the slump-flow is observed with a high correlation [
57] as shown in
Figure 7 (b).
Similarly, by adjusting the SP dosages, the blocking tendency of the SCC decreases and its possible to bring all the SCC mixtures to a passing ability class PJ2, classified according to [
50] (
Figure 8).
The reference mixture (SCC-1) exhibits with an SP dosage of 0.3 good passing ability, but the viscosity (V-funnel time) falls below 6 s, the minimum recommended by (EFNARC 2002) (
Figure 7 (b)). The tendency of segregation is high with this mixture, and therefore it was not considered for the production of final SCC. The viscosity of the SCC depends largely on the w/p: The higher the w/p the higher the rate at which the SCC will flow, as previous investigations obtained VF time ≤ 6 s using w/p ≥ 0.5 [
4,
58]. When the w/p is < 0.4, SCC have a VF time ≥ 6 s [
53,
56]. SCC-1 with 0.25 SP dosage is at the limit for both the filling and passing ability values, but is considered suitable for the final SCC mix design. The selection criterion for the final SCC mix design is therefore based on SF ≥ 650 mm, VF ≥ 6 s and PJ ≤ 10 mm and the proportions of the final SCC mix designations are presented in
Table 5 and
Table 6, and are used to determine the influence of CC and RHA on the segregation resistance, rheology, time dependent workability, compressive strength and chloride migration resistance of SCC.
The reference system (SCC-1) required a V
w/V
p = 0.87, corresponding to w/p = 0.29, for self-compactability, similar to that previously used by [
48,
52] to achieve high-strength SCC. Both CC and RHA have a water demand greater than that of PLC, the water demand of CC is one third higher than that of PLC (see
Table 1) but required only an adjustment of SP to achieve a degree of deformability comparable to SCC-1, although with an increased viscosity and SP demand as previously investigated by [
48,
59]. The increase in viscosity is not only due to the higher water demand of the CC compared to PLC but also due to its different particle shape [
31,
60] leading to an increased resistance to flow and hence higher SP demand to deform the SCC-1-20CC system. The use of RHA as partial replacement to PLC in SCC is more critical due to its more than three time high water demand (see
Table 1). Unlike the SCC-1-20CC system, SP adjustment is not sufficient to deform SCC-1-20RHA and even the SCC-1-10CC+10RHA system. Therefore, V
w/V
p adjustment is urgently needed to achieve self-compactability. When substituting high proportion of PLC with RHA (20 % and above), higher w/p, from 0.44 and above will be required to properly deformed the RHA-SCC system. This affects the concrete porosity and limits its applications [
49]. Therefore, this study limits the content of RHA to 20 vol-% and uses a Vw/Vp = 1.275 (0.42 w/p equivalent) for all PLC-, CC-, and RHA-SCC systems.
4.3. Rheological and time dependent workability retention of SCC
The time-dependent rheological assessment of SCC begins with determining the influence of CC and RHA on the torque required to initiate and maintain displacement of SCC based on the applied shear rate measured with a viscometer as depicted in
Figure 12. At 15 min of testing, SCC-1 recorded a torque of 66 Nmm at a lower velocity of 1 rpm, and 109 Nmm at the maximum applied velocity of 12 rpm. After 90 min of testing, the torque increased to 133 and 228 Nmm, respectively. SCC-1-20CC required lower torque to achieve and maintained displacement compared to SCC-1, both at lower and higher velocities and at all test times. Although CC has a higher water demand than PLC, the decreased torque could be due to the higher dosage of SP applied to deform the SCC-1-20CC system, despite both binder systems required almost similar V
w/V
p to achieve self-compactability as shown in
Table 2. For the RHA binder system, on the other hand, at 15 min of testing, a torque of 102 Nmm was measured at lower velocity and 180 Nmm at higher velocity. These values increased significantly after 30 min of testing due to the stiffening of the SCC-1-20RHA mixture as a result of higher water demand of RHA (see
Figure 10). The ternary blend with CC and RHA behaved somewhat in between the SCC-1-20CC and SCC-1-20RHA, the presence of the CC in the blend decreased the torque required to achieve displacement at 90 min of testing by 53 and 59 % at lower and higher velocities, respectively, compared to RHA-SCC system.
Establishing the dynamic yield stress of SCC is important to determine the extent of energy required to maintain SCC flow; this is important to ensure uniform deformability of SCC across formwork sections. The time-dependent yield stress and plastic viscosity of SCC were established from the measured torque values induced by the applied velocity using a Bingham model as presented in
Figure 13. SCC-1 has a yield stress of 60 Nmm and a plastic viscosity of 3.9 Nmm*min at 15 min of testing, which gradually increased to 120 Nmm and 8.2 Nmm*min, respectively, after 90 min of testing. SCC-1-20CC showed a similar increasing tendency in yield and viscosity values as SCC-1. The gradual increase of the yield stress and plastic viscosity could be due to the loss of water from the surfaces of SCC caused by evaporation, or due to the chemical reaction between the binder and mixing water leading to the initial formation of ettringite [
62]. SCC-1-20RHA had a yield stress of 88.5 Nmm and a plastic viscosity of 6.2 at 15 min of testing, which are 47 and 59 % higher than SCC-1, respectively. This yield stress and plastic viscosity values increased rapidly up to the 90 min of testing unlike the SCC-1 and SCC-1-20CC systems. The rapid increase of both yield stress and plastic viscosity values is due to the increase plastic stiffening caused by the continues absorption of the mixing water by the RHA particles. The ternary blend of CC and RHA had both, lower dynamic yield, plastic viscosity values and smaller rate at which they increased compared to SCC-1-20RHA. In all cases, SCC mixtures containing RHA exhibited higher yield stress and plastic viscosity values, due to their higher water demand.
The workability retention of SCC is monitored by comparing the flow resistance of the SCC mixes over a period of 90 minutes. The flow resistance is determined as the area under the curve of the torque plotted against the velocity values from
Figure 12. The flow resistance of SCC-1 measured 15 min after water addition is 933 Nmm/min and increases to 1900 Nmm/min after 90 min (
Figure 14). SCC-1-20CC mixture exhibits similar flow resistance to SCC-1 up to 90 min of testing. SCC-1-20RHA, on the other hand, had a flow resistance value of 1388 Nmm/min at 15 min, which is 30 % higher than SCC-1 and increased to 8205 Nmm/min at 90 min of testing. SCC-1-10CC+10RHA showed similar flow resistance to SCC-1-20RHA up to 30 min of testing, after which it increased less compared to SCC-1-20RHA. The decrease in flow resistance of SCC-1-10CC+10RHA is due to the presence of CC in the blend, which reduces the water demand and SSA of the system.
Generally, by increasing the SP dosage, PLC partial replacement with 20 vol-% CC has no effect on time dependent workability retention of SCC up to 90 min and therefore, SCC-1-20CC can be used to produce both in-situ, precast and ready-mix SCC. However, the use of 20 vol-% RHA and the ternary blend 10CC+10RHA developed high flow resistance and exhibited rapid loss of workability after 30 min of mixing. Therefore, their workability retention needs to be improved for applications beyond 30 minutes.
The relationship between the flow resistance time-dependent workability measurement and the sedimentation analysis conducted by plunger method is valid in the case of SCC-1 and SCC-1-20CC up to 75 min of testing, while for the SCC-1-20RHA and SCC-1-10CC+10RHA, the relationship is valid only up to 30 min of testing (
Figure 15). The penetration of the plunger is not possible in the SCC mixes containing RHA after 45 min of testing due to the stiffening of SCC surface which hinders the plunger penetration.
The differences between the two methods of time-dependent workability assessment could be explained from the mechanism of time-dependent workability loss due to structural build up (thixotropy), that can easily be reversed during the viscometer rotation in the flow resistance assessment method, while for the sedimentation analysis, the plunger is only guided and allowed to penetrate the concrete on its own weight, the SCC remained undisturbed and structural build ups unreversed.
4.4. Formation of hydrate phases from the hardened SCP
The formation of SCP hydrates phases was determined at 2, 7 and 28 days of hydration (
Figure 16). The mass loss between 50 °C to 140 °C is due to dehydration of the ettringite (E) and calcium silicate hydrates (C-S-H) [
63] and increases with an increase in the hydration time for all the SCP specimens. The second mass loss is observed between 140 °C and 190 °C due to the dehydration of the monophases (AFm) [
64] and is more pronounced in the SCP with RHA partial replacement in all hydration stages. Portlandite decomposition occurs between 400 °C to 450 °C for all SCP specimens, while calcium carbonate (CaCO
3) decomposition takes place between 600 °C to 800 °C (
Figure 16). The pattern of the formation of the hydrate phases is similar to was observed previously by [
48] when CC was used as partial replacement to PLC in SC-P.
The partial replacement of PLC by CC and RHA has a noticeable effect on the formation of hydrate phases, especially in the ranges of mass loss between 140 °C and 190 °C and between 400 °C and 450 °C. At 2 days of hydration, the DTA peak due to the dehydration of carbonate AFm phases is not evident in the SC-P and SC-P-20CC systems by TG measurements due to the increase of the Vw/Vp ratio used in this study, as the previous study by [
48] noticed the formation of these phases in SC-P and SC-P-CC systems at the same age of hydration using a V
w/V
p = 0.875. The reaction between the LP and CC enhanced the formation of the carbonate AFm phases at 7 and 28 days of hydration. This increased the volume of the hydration products in the SCP-CC system and densified its microstructure, as previously reported by [
48]. RHA and the ternary blend of CC and RHA enhanced the precipitation of theses phases even at 2 days of hydration and continue to increase up to 28 days of hydration.
Figure 17 shows the influence of CC and RHA on the portlandite (CH) consumption. SC-P has the highest CH content at each test age, while SC-P-20RHA exhibits the lowest CH content. SC-P had a CH content of 9.4 g at 2 days, 12.3 g at 7days and 14 g at 28 days. The CH content of SC-P-20CC at 2 days 7.9 g and increased to 10.2 g and 10.6 g at 7 and 28 days, respectively. SC-P-20RHA had a CH content of 5.8 g at 2 days, which increased to 6.8 g at 7 days and decreased to 5.8 g at 28 days. The CH content of SC-P-10CC+10RHA is half way-between that of SC-P-20CC and SC-P-20RHA at all test ages.
The CH content of SC-P increases over the experimental period due to the continued hydration of C
3S and C
2S in the clinker portion of PLC. The use of CC and RHA as SCM reduced at 2 days of hydration the CH content, mainly due to the dilution effect. Simultaneously, CC and RHA provide more nucleation sites for precipitation of hydration products at this stage of hydration, as previously observed by [
48,
65]. The relative decrease in CH content at 7 days of hydration is due to the dilution effect and the initiation of the pozzolanic reaction of CC and RHA, which consumes CH. At 28 days of hydration, CH consumption is significant, especially in SCPs with RHA as a partial substitute for PLC. This is indeed expected and attributed to the pozzolanic effect of CC and RHA, which consumed the CH and produced more C-S-H, which densified the SCP microstructure and thus increased the strength of the SCC, as can be seen later in Figure 20.