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Cuifang Lu, Zuhua Zhang, Caijun Shi, Ning Li, Dengwu Jiao, Qiang Yuan
PII: S0958-9465(21)00130-X
DOI: https://doi.org/10.1016/j.cemconcomp.2021.104061
Reference: CECO 104061
Please cite this article as: C. Lu, Z. Zhang, C. Shi, N. Li, D. Jiao, Q. Yuan, Rheology of alkali-
activated materials: A review, Cement and Concrete Composites (2021), doi: https://doi.org/10.1016/
j.cemconcomp.2021.104061.
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2 Cuifang Lu a, b, Zuhua Zhang a, b*, Caijun Shi a, b*, Ning Li a, b, Dengwu Jiao a, c, Qiang
3 Yuan d
a
4 Key Laboratory for Green & Advanced Civil Engineering Materials and Application Technology of
6 b International Science and Technology Innovation Cooperation Base for Green Advanced Civil
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9 Ghent University, 9052 Ghent, Belgium
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d
10 National Engineering Laboratory for High Speed Railway Construction, School of Civil
11
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Engineering, Central South University, Changsha 410075, China
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12
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13 Abstract: Many alkali-activated materials (AAMs) exhibit poor workability in mixing owing to
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14 great viscosity of the paste and fast setting. Chemical admixtures commonly used in Portland
15 cement-based materials, such as rheology control additives and superplasticizers, show lower
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16 efficiency in AAM systems. Understanding the rheological features of various AAMs and their
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17 control can lead to a valuable guidance for their application in large-scale, especially in the field of
18 pumping and placement, grouting and 3D printing, etc. This paper aims to deliver a comprehensive
19 review of the effects of composition factors including activators, precursors, admixtures, additions,
20 aggregates and fibers on the rheology of AAMs, as well as models for describing their rheological
21 behavior. The current progress has shown that the large knowledge gap needs substantial research
22 from scientific mechanisms to robust formulations of paste, mortar and concrete to meet both
25 *Corresponding authors.
27
28 1. Introduction
29 In the past decades, alkali-activated materials (AAMs), including ‘geopolymers’[111], have been
30 accepted by both academic and industrial communities progressively as a family of effective and
32 manufactured by activation of a reactive solid aluminosilicate such as blast furnace slag [1, 2], fly
33 ash (Class-F fly ash in this paper unless otherwise stated) [3, 4], metakaolin [5, 6] and other
34 precursors [7-9] using an alkaline activator, which is usually a concentrated aqueous solution of
35 alkali hydroxide, silicate or carbonate. Properly designed AAMs can have denser microstructure than
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36 normal PCMs with superior engineering performances [10], particularly in aggressive environment
37 [11, 12]. Moreover, the manufacturing of AAMs avoids the energy consumption and CO2 emission
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38 -p
with respect to clinker production, endowing this kind of materials great potential to reduce adverse
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39 environmental impacts by a wide margin [13]. It should be noted that the use of sodium silicate leads
40 to a high CO2 emission and surface water acidification which can reduce the environmental benefit
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41 [112]. Hence a better mix design is required. However, the large-scale engineering application of
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42 AAMs progresses slowly. Regardless the regulation obstacles, there seems more because of the
43 technical challenges. Besides the shrinkage risk of AAMs [14, 15] and the inconsistent raw materials
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44 and alkali activators used [8], it is more likely due to the facts such as poor workability [16-18]. In
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45 addition, most commercial chemical admixtures for PCMs are incompatible in AAMs [19, 20].
46 Therefore, the effect of composition on rheological properties of AAMs must be fully understand so
48 In this paper, the effects of composition factor such as the nature and dosage of activators and
50 perspective to understand workability and rheology of AAMs, and a reference for future research
53 Rheology is the science that studies the deformation and flow of matter. Studies have shown that
54 slump value is an indicative but not a sufficient measurement to characterize the fundamental
55 rheological properties of PCMs, namely plastic viscosity and yield stress, which are respectively a
56 measure of the material resistance to flow after the material begins to flow and a measure of the
57 shear stress required to initiate flow [21]. The relationships between shear stress and shear strain rate
58 of fresh PCMs have been developed. The Bingham model, modified Bingham model and
59 Herschel-Bulkley (H-B) model are the most widely accepted for describing the rheological behavior
60 of PCMs [22].
61 The Bingham model has a linear relationship between shear stress (τ) and shear strain rate (𝛾̇ ) as
63 (1)
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τ = 𝜏0 + 𝜇𝛾̇
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64 where 𝜏0 is the yield stress (Pa) and 𝜇 is the plastic viscosity (Pa·s). This expression is the simplest
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65 one for non-Newtonian fluids. However, the addition of admixtures in PCMs can lead to the
66
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deviation of a linear relationship between shear stress and shear rate. Consequently, the modified
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67 Bingham model was proposed [24]:
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69 Compared to the Bingham model, the modified Bingham model introduced a quadratic term related
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70 to shear rate and its coefficient 𝑐 is the pseudoplastic constant. Feys et al. [25] applied rheological
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71 index 𝑐/𝜇 to depict non-linear behavior of the fluid which undergoes shear thinning when 𝑐/𝜇<0,
72 and shear thickening when 𝑐/μ>0. Besides, the Herschel-Bulkley (H-B) model was proposed in
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74 τ = 𝜏0 + 𝐾𝛾̇ 𝑛 (3)
75 where 𝐾 is the consistency coefficient and 𝑛 is the fluidity index that represents the degree of
76 deviation from the rheological behavior of Newton fluid [27]. When n<1, the fluid exhibits shear
78 Published literatures showed that the Bingham model, modified Bingham model and H-B model
79 are empirically adopted to the description of rheological behavior of AAMs. There is suitability
80 difference for various systems. It is widely accepted that the alkalinity of alkali activators controls
81 the dissolution behavior of precursor particles, and the alkali cations in activators work as charge
82 balancing cations. Moreover, the polymerization status and the adsorption on precursor surface of
83 anionic groups from activator solution, silicate species in particular, could influence particles
84 interaction. These mechanisms determine the effects of activators on the rheological behavior of
85 AAMs. Generally, Bingham model is recommended for NaOH-activated pastes [41, 135], while H-B
86 model suits better the sodium silicate-activated pastes [19, 25]. For example, as active silicates are
87 added in calcium-rich (slag) precursor suspensions, the initial and speedy formation of a primary
88 C,N-A-S-H gel and mixed N-A-S-H makes the alkali-activation reaction more complicated [113].
89 This primary gel may be destroyed and restructured by subsequent shearing, leading to a deviation
90 from Bingham fluid. However, sometimes adding admixtures/additions would change the
91 interactions between particles, so affect the rheological behavior of sodium silicate-based pastes, thus
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92 conforming to the Bingham model [37-40]. Furthermore, Bingham model seems to suit both NaOH
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93 and sodium silicate-activated mortar/concrete and this behavior is similar to PC based
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mortar/concrete [20, 31, 36]. Both Bingham model [41, 128] and H-B model [64, 129] were reported
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95 to be used in the systems activated by Na2CO3 (single or mixed with other activators). The modified
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96 Bingham model not only describes the non-linear behavior deviating from Bingham fluid, but also
97 avoids a variable dimension parameter like in H-B model without mathematical limitation in the low
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98 shear rate region [22, 25, 126]. However, it is rarely used in describing the rheological behavior of
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99 AAMs [49, 63]. The applicability of the modified Bingham model in different AAM systems needs
101 In addition to the activators used, the origin and composition of the starting aluminosilicates also
102 have great impact on the rheological behavior. Alkali-activated MK systems generally exhibit higher
103 viscosity and apparent yield stress due to their plate-like particles and large specific surface area [45,
104 74], which means that suitable activators and sufficient water are required to ensure good workability
105 [29, 47]. In the very early stage of Na-silicates activated MK pastes, the formation of a gel with
106 Si/Al<4.5, which strongly depends on the chemical composition of mixture, would be accounted for
107 the evolution of storage modulus, instead of colloidal interactions [34]. If Ca-rich precursors are used,
108 the chemistry of the system could be dramatically changed and the colloidal interactions between
109 grains could be enhanced as well [34]. As reported, alkali-activated fly ash pastes behaved like a
110 Bingham fluid [28, 37], while the rheological behavior of the fly ash-slag blended systems was more
111 consistent with H-B model [128, 136]. Besides, the area of thixotropy was significantly affected by
112 fly ash/slag ratio, although there were differences on its influence on thixotropy in different studies
113 [128, 138]. These rheological behaviors could not be separated from the differences of particle size,
114 dissolution behavior and reactivity of different precursor particles, as well as the initial precipitated
115 gels. The effects of composition factors on rheology of AAMs are discussed in detail in the following
116 sections.
118 It is known that alkaline nature and dosage significantly affect the reaction process, microstructure
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119 and properties of AAMs. Therefore, activator is a key composition controlling the rheological
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120 behavior of AAMs paste. According to Glukhovsky [50], chemical activators can be classified into
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six categories in terms of chemical composition: caustic alkalis, non-silicate weak acid salts, silicates,
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122 aluminates, aluminosilicates, and non-silicate strong acid salts. Among these activators, sodium
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123 based-activators are the most widely available and cost effective, such as Na2O·nSiO2, NaOH,
124 Na2CO3, Na2SO4 and a mixture of two or more. In addition, some potassium based-activators have
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125 been used in laboratory studies [51]. This section discusses the effects of Na/KOH, Na2O·nSiO2 and
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129 The most used alkali hydroxides in AAMs are NaOH and KOH. NaOH in particular, is usually
130 prepared into solution in advance in order to avoid the influence of dissolution heat on the reaction.
131 Published literatures have shown that paste suspensions containing NaOH solution usually exhibits
132 higher yield stress and plastic viscosity than KOH-based suspensions [28, 52]. As seen in Fig. 1, the
133 yield stress and plastic viscosity of fly ash paste activated by NaOH solutions are higher than those
134 of activated by KOH with the same dosage in terms of molarity [28]. This is due to the lower charge
135 density of K+, which gives lower ion-dipole forces and viscosity of solution [32]. Similarly,
136 irrespective of activator dosage, the Zeta potential value of KOH-activated slag system is higher than
137 that of NaOH-based system (Fig.2), due to lower concentration of Na+ cations adsorbed on the
138 surface of negatively charged particle [53]. More adsorption of K+ cations might reduce the van der
139 Waals forces and increase the repulsive force of double layer between charged particles, and thus
140 contributes to a decrease in yield stress. By contrast, Na+ cations would rather to combine with water
142
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143
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144 Fig. 1. The yield stress (a) and plastic viscosity (b) of fly ash paste activated by NaOH and KOH solutions of
146
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147
148 Fig. 2. Zeta potential of 3 wt.% slag suspensions with various dosages of NaOH, KOH activators [52].
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150 3.1.2 Concentration
151 Concentration is another important factor that impacts rheology of AAMs. Table 1 summarizes the
152 effects of NaOH concentration on the rheological properties of AAMs prepared with various
153 precursors. Rifaai et al. [49] raised NaOH concentration from 2 to 7 mol/L, and found a rise in yield
154 stress of alkali-activated slag pastes. However, Zhang et al. [54] found that higher NaOH
155 concentration (4.17~6.67 mol/L) of alkali-activated fly ash-slag blended pastes had shown lower
156 yield stress and plastic viscosity, thus increasing the fluidity of pastes (Fig. 3), which was similar to a
157 later study by the same group [135]. For the paste with high NaOH concentration, the value of Zeta
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158 potential is more negative (−7.28 mV) due to the high dissolution and ionization degree of
159 suspension [54]. The result is somewhat equivocal and unexpected. It is widely accepted that the
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dissolution of slag is faster than fly ash due to its higher reactivity. The ionic bond formed by
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161 modifier cations (such as Ca2+) and the non bridging oxygen in the calcium aluminosilicate glass
162 structure is more easily dissolved, resulting in the release of Ca2+ ions from slag in the early stage
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163 [124]. The Zeta potential become less negative due to the re-adsorption of Ca2+. However, silicate
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164 and aluminate may be partially replaced by low-charge cations. Therefore, the measured Zeta
165 potential is the result of the mutual compensation between this two mechanisms, which may be
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166 related to the dilution of suspension and the reaction time. Further, in the early stage, the
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167 water-binding ability of dominated N-A-S-H in fly ash-slag blended system was weaker than that of
168 C-A-S-H gels in slag system, thus the higher freedom of water in the mixed system [135]. But this
169 effect may be less significant than that of electrostatic repulsion. Therefore, different results were
170 obtained in the similar range of NaOH concentration [49, 54, 135], which may be related to the
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173 Table 1
174 Effects of NaOH concentration on the rheological properties of AAMs prepared with various precursors.
Critical
w/b or L/S NaOH concentration
Precursors concentration Main features Ref.
(by mass) (mol/L)
(mol/L)
Fly ash
τ0 and μ
(Mortar:
0.5-0.6 8; 10 - increased as concentration [31]
sand/binder
increased
=2:1)
Fly ash τ0 slighthly decreased as
0.25 8; 10 - [55]
concentration increased
τ0 and μ increased as
0.35 4; 8 - [28]
concentration increased
τ0 and G' increased as
concentration (< 7 mol/L)
increased; μ increased as
2; 3.5; 6; 6.5; 7; 7.5; concentration increased
0.4 7 [49]
8; 11; 14 until 3 mol/L, then
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decreased up to 8 mol/L,
and increased again
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afterwards
Slag
0.45 1; 2
-p -
τ0 increased as
concentration increased
[52]
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τ0 decreased as
concentration (< 3.37
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concentration increased
Slag + fly The growth rate of G'
0.83; 1.67; 2.5; 3.33;
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176 * In reference [31], τ0 and μ are calculated based on the speed-torque curve.
177
178
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179 Fig. 3. The yield stress (a) and plastic viscosity (b) of fresh fly ash-slag blended pastes activated by different
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182 Importantly, by reviewing the published works, there seems a critical value of NaOH
183 concentration alternating the rheological feature of AAMs, especially the development of
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184 viscoelasticity. OH- ions play a role as chemistry driven to stimulate solid aluminosilicate dissolution,
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185 and Na+ ions are necessary to house in the voids in tetrahedral coordination structure to compensate
186 for the electrical charge due to the substitution of Si4+ by Al3+ [107]. Hence, ion concentrations
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187 influence the competition between dissolution and polycondensation kinetics, thus affecting
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188 viscoelasticity [49, 56, 57]. A recent research (Fig. 4) reported that NaOH concentration of 7 mol/L
189 was a critical value, below which the yield stress, storage modulus (𝐺 ′ ) and rigidification rate of
190 alkali-activated fly ash (AAFA) pastes increased as concentration increased, while above which the
191 rheological properties showed a downward trend [49]. A reasonable explanation for this phenomenon
192 is the competition between dissolution and polycondensation. On the one hand, lower NaOH
193 concentration can accelerate both the dissolution and polycondensation kinetics. On the other hand,
194 the dissolution rate is more dominated in extremely alkaline environment, which induces more
195 negatively charged monomers leading to a remarkable repulsion between particles [49]. However,
196 the nature of precursors may also impact the critical value of NaOH concentration. For example, the
197 fly ash-slag blended suspension showed a critical value of 4.17 mol/L (the mass ratio of
198 NaOH/binder was 10%) for NaOH concentration, which might be related to the changed surface
199 charge of particles and initial dissolution behavior [56]. As discussed earlier, the higher CaO content
200 and lower degree of glass polymerization in slag are more conducive to dissolve, thus generating
201 higher reaction rate than FA [124]. This means that the introduction of slag can accelerate the
202 dissolution rate of overall raw materials, compared with the pastes containing FA as single precursor.
203 Hence, the alkalinity needed to achieve the equilibrium of dissolution and precipitation is reduced,
204 that is, the critical NaOH concentration is reduced. Furthermore, although an increase in NaOH
205 concentration promotes the formation of Si-O-Na bond, excessively high concentration is
206 unfavorable due to early hydration product precipitation on surfaces of particles. Xie et al. [57]
207 pointed out that 8.87 mol/L NaOH (the mass ratio of NaOH/phosphorous slag was 16%) was a
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208 threshold and the influence of NaOH concentration changed near this threshold on viscoelasticity.
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209 Below this value, the viscoelastic transition (the transition from the viscous behavior to the elastic
210
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behavior is the dominant feature) of alkali-activated phosphorous slag (AAPS) was delayed with the
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211 increase of NaOH concentration. Low hydration rate and good dispersion because of the enhanced
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212 electrostatic repulsive force may be responsible for this phenomenon. Above this threshold, the
213 viscoelastic transition accelerated with the increase of NaOH concentration, which was attributed to
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214 the rapid generation of cross-linked gels and the decreased electrostatic repulsive force [57].
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215 Unfortunately, no rheological research on metakaolin activated by NaOH solution has been reported
216 so far.
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217
218
219 Fig. 4. Effects of NaOH concentration on storage modulus and rigidification rate of alkali-activated fly ash pastes.
220 Data from Rifaai et al. [49].
223 AAMs activated with sodium silicates usually exhibits greater workability, i.e. with lower yield
224 stress, than that of PCMs and alkali hydroxide activated system due to plasticizing effect [31, 52, 55].
225 For example, Kashani et al. [52] reported that the initial Zeta potentials of Na/KOH-slag system and
226 sodium silicate-slag system are both negative due to the deprotonation of slag silanol groups.
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227 However, as activator concentration increase, the Zeta potential of Na/KOH-slag system changes
228 from negative to positive, which means that repulsive double layer forces decreases and then
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increases. By contrast, the Zeta potential of sodium silicate-slag system becomes more negative [52].
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230 This is due to that silicate oligomers adsorbing on the surfaces of slag particles, resulting in
231 insufficient dissolved Ca2+ in the solution and greater repulsive double layer forces. As expected,
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232 lower yield stress was also obtained in Na-silicate based fly ash pastes instead of NaOH-fly ash [28,
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233 55]. The overall negative surface charge of fly ash was increased by the adsorption of silicates from
234 activator solution, which enhanced inter-particle repulsive forces and reduce flocculation of particles
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235 [55]. The exact electric charge density of the surface of raw materials will depend on the polymer
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236 status of silicate oligomers, being monomers, dimers or trimmers, and the original surface charge.
237 The previous studies of sodium silicates-slag suspensions also showed obvious thixotropy feature
238 [19]. Thixotropy is usually observed in shear thinning fluids because that viscosity decreases with
239 time when a given shear rate is applied to the material at rest, and viscosity would recover once the
240 flow stops [114]. This process corresponds to the destruction and restruction of thixotropic materials,
241 respectively, which is strongly dependent on the flow history and rest time [23]. Thixotropy can be
242 described by a thixotropic hysteresis loop (qualitative) [23] and thixotropic index (quantitative) [114].
243 Fig. 5 shows the thixotropy of slag pastes activated with sodium silicates and NaOH, respectively. It
244 can be seen that sodium silicates-activated slag paste showed a larger area of the hysteresis loop and
245 a higher shear stress than that of NaOH system, especially at the first cycle [19]. This is mainly
246 attributed to the initial and rapid formation of primary C-A-S-H gels, which generate colloidal forces
247 between particles [58, 113]. It is important to note that this colloidal force can be interfered by
248 continuous shearing, thus a prolonged mixing will improve workability of sodium silicate
249 activated-slag concrete [20]. However, neither Na-silicate nor NaOH activated fly ash pastes showed
250 obvious thixotropic behavior [55, 128]. This may be attributed to the slower dissolution rate of fly
251 ash particles and lower precipitation rate geopolymeric gels (slower structure build-up) [128, 136].
252 On the other hand, the spherical particle feature of fly ash could be another important factor.
253 Interestingly, Poulesquen et al. [32, 73] conducted a strain sweep test to investigate the influence of
254 silicate activating solutions synthesized by Na/KOH and two types of silica on the viscoelastic
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255 parameters (storage modulus G’; loss modulus G’’ and tanδ=G’’/G’) of metakaolin (MK) systems
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256 during the polymerization process. Though Na-based activator shows weaker basicity, it can
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257 unexpectedly ensure a better dissolution of MK and exhibit faster geopolymerization. Smaller Na+
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258 with higher charge density strongly attract and retain their hydration layer of water molecules, while
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259 K+ show a weaker association with water [32, 137]. In other words, K + ions are more likely to
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260 combine with negatively charged silicates, exhibiting an interfering effect on the condensation
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261 process. However, compared to the Na-based system, smaller tanδ in K-based system was observed
262 due to stronger interactions between the dissolved Si and Al tetrahedral monomers, which indicated a
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263 more rigid structure [32, 137]. Additionally, the viscoelasticity of MK pastes in their study was not
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264 sensitive to the type of silica in synthetic silicate activation solution, but the activator synthesized by
265 smaller silica particles with NaOH reduced setting time evidently.
266
267
268
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Fig. 5. Hysteresis cycles for alkali activated slag pastes [19].
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269
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270 It is worth mentioning that activators in this paper are all added in the form of solutions, if not
271
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otherwise specified. Recently, there has been particular interest in one-part AAMs, which are
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272 produced by mixing solid activators and precursors [125]. Compared with liquid sodium silicate,
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273 there is a higher yield stress and plastic viscosity observed when solid sodium silicate is used. The
274 dissolution reaction of solid sodium silicate led to less free water acting as lubricant and the
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275 additional dissolution heat can improve the formation and size of gels in slag-fly ash system [38].
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276 Such rheological characteristics seem to make solid sodium silicate more suitable for preparing
277 extrusion-based 3D printing mortars than liquid sodium silicate [99]. Moreover, some studies have
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278 focused on the rheological behavior and fluidity of one-part AAMs with different raw materials [86,
279 106, 126-127]. Unfortunately, these studies did not specifically discussed the differences in rheology
280 properties between one-part AAMs prepared by solid activators and conventional two-part AAMs.
281 More research is therefore needed to explain rheology of one-part AAMs or the effect of adding
284 The addition of NaOH could raise the pH value and reduce modulus (the SiO2/Na2O molar ratio)
285 of sodium silicate activator solution, affecting the distribution of different ions in the solution and
286 thus the rheological properties of AAM suspensions. This is directly related to the immediate
287 viscosity of activator solution. When the alkali content (in oxides form) is constant, adjusting the
288 modulus should consider more about effects of the polymerization degree of silicate oligomers and
290 Mehdizadeh and Kani [35] found that the yield stress of AAPS declined as the modulus of sodium
291 silicate activator increased at constant Na2O/Al2O3 ratio of 1.0, which may be explained by the
292 plasticizing effect of silicates [52], though this molar ratio showed a negligible effect on the
293 shear-thinning parameter. Some similar results were reported in 3D printing pastes based on
294 alkali-activated blast furnace slag/steel slag [63]. It was observed that increasing modulus could
295 decrease the yield stress and its thickening rate, as well as plastic viscosity of fresh pastes. Therefore,
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296 for example, for 3D printing AAM concrete based on slag, to obtain satisfying thixotropic property,
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297 reduced modulus is more favorable to ensure the stability between the layers of the printed materials.
298
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However, some recent researches reported that increasing the modulus of sodium silicates resulted in
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299 an increase in apparent viscosity and yield stress of alkali-activated fly ash pastes [28]. Wen et al. [59]
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300 found that the viscosity of metakaolin-based AAMs increased dramatically with modulus when the
301 sodium silicates was in SiO2 polymerized zone (the modulus>2.2). In the high-ionized zone (the
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302 modulus<1.8), however, the viscosity of suspensions showed insignificant responses to modulus
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304 In slag-fly ash blended pastes (fly ash/slag=5:5), the yield stress and the area of thixotropy
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305 decreased by approximately 76% and 83%, when modulus increased from 0.4 to 1.6 [136]. Similar
306 results were reported in a grout of fly ash-slag (fly ash/slag=9:1) blended system, plastic viscosity
307 decreased as modulus increased from 1.4 to 1.8 [46]. This might be attributed to the high alkalinity
308 and high degree of ionization in suspensions of lower modulus (1.4) at high liquid-solid ratio, which
309 promoted the dissolution and consequent polymerization, thus resulting in higher plastic viscosity.
310 Additionally, Dai et al. [136] found that the effects of low modulus (0<Ms≤0.4) and high modulus
311 (0.4<Ms≤1.4) on evolution of structure build-up were quite different. As shown in Fig. 6, mixtures
312 with lower modulus behaved a higher initial G’, and subsequently structure build-up rate increased
313 slowly, while high modulus led to a delay in structure build-up, followed by a rapid increase [136].
314 Low modulus activator, by contrast, showed higher alkalinity and promoted the early
315 dissolution-precipitation in mixtures, resulting in higher initial G’. Consequently, precipitated gels on
316 the surface of precursor particles might hinder further reactions [136]. Moreover, Hasnaoui et al.
317 [140] reported that increasing modulus (from 1.0 to 2.0) induced a rise of viscosity in alkaline
318 solution, which led to increase of the yield stress and the plastic viscosity of slag-MK mortars, thus
319 reducing workability. This effect is pronounced in the mixture with more MK, which is partly due to
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321
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322 Fig. 6. Effect of n(SiO2)/n(Na2O) molar ratio on normal scale(a) and log scale (b) storage modulus evolution of
323
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alkali-activated slag-fly ash pastes (slag/fly ash=1) using small amplitude oscillatory shear test at strain of 0.005%,
325
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326 Based on these findings, the relationship between the modulus and yield stress and plastic
327 viscosity of AAMs in different literatures is shown in Fig. 7. In general, the increase of modulus is
328 helpful to reduce yield stress of AAMs thanks to the plasticizing effect when the modulus of
329 activator is below around 1.2 with a relatively high degree of ionization. However, higher modulus
330 (>1.4) seems not conducive to the reduction of yield stress (Fig. 7a). In addition to the strong
331 increase of ion-dipole forces, a rise of modulus also induced more colloidal HO-Si-OM complexes in
332 activator solution forming clusters with several nanometers, and thus the polymerization degree of
333 silicate anions raises. Further, it must consider the effect of early C-(A)-S-H gels precipitate by Ca2+
334 ions and silicate species on rheology in calcium-containing systems [113]. Higher modulus induced
335 more active [SiO4]4- react with dissolved Ca2+ ions, producing more hydration products [46].
336 Therefore, the viscosity of suspension increased [60] and the complex network structure of highly
337 polymerized silicates is not easy to be damaged by shearing [46]. Theoretically, the viscosity of
338 interstitial fluid (silicates) has immediate impact on the viscosity of AAMs. The plastic viscosity
339 would ordinarily increase as modulus, due to more colloidal clusters (Fig. 7b). It should be noted that
340 plastic viscosity is the embodiment of internal friction between substances in suspensions, and also
341 depends on liquid-solid ratio and the structure of gel network (the precipitation of gels or
343
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344
345 Fig. 7. Effect of n(SiO2)/n(Na2O) molar ratio of sodium silicate activator on yield stress (a) and plastic viscosity
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346 (b) of AAMs at the first shear cycle [35, 41, 46, 59, 61, 62, 63, 136, 140].
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347
349 To provide a guidance for the application requiring better workability and fluidity, some studies
350 have focused on the effect of sodium silicate concentration on the rheology of high-calcium AAMs.
351 At constant modulus of 1.0, Vyšvařil et al. [42] observed that the increase of dosage (higher
352 concentration) of sodium silicates could allow activated-brick powder pastes to flow more easily, but
353 unexpectedly, the long term strengths of hardened pastes were slightly reduced at the highest dosage
354 of activator. Surprisingly, Kashani et al. [52] noticed that higher concentration of sodium silicate
355 induced greater negative Zeta potential, which does not always mean lower yield stress value of slag
356 based suspension, as can be seen in Fig. 8. The yield stress is lower (12.5 Pa-17.5Pa) when the
357 square of Zeta potential is between 40-80 mV2, which means that this sodium silicate concentration
358 was conducive to disperse particles compared with the blank group. Surprisingly, the yield stress
359 increases although the square of Zeta potential are further increased to 150 mV2, which indicates that
360 the attraction and flocculation increases at higher sodium silicate concentration. Fig. 9 well illustrates
361 this phenomenon: in the case of lower concentration of sodium silicates (2.2 and 4.4×10-4 mole
362 Na2O/g slag), the increase of repulsive forces reflects the plasticization and deflocculation effects of
363 [SiO4]4- groups (Fig. 9b). However, a further increase in the amount of Na2O brings about a rise in
364 yield stress (6.6×10-4 mole Na2O/g slag), which indicates that the electric double layer force could
365 exhibit a sign of attractiveness, promoting flocculation and leading to higher yield stress [52, 55]
f
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366 (Fig. 9c). The effect of Na2O% on yield stress was complex in sodium silicates-slag systems. With
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367 relatively low modulus (<0.8) (Fig. 10), the fact that the rise in Na2O% led to an increase in pastes
368
-p
yield stress was consistent with the discussion above. Suspensions, however, did not show the similar
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369 behavior when increased Na2O% at higher modulus (>1.2) of Na-silicates (Fig. 10). This might be
lP
370 ascribed to the fact that modulus needed for primary C–(A)–S–H gel to form and breakdown in
371 dynamic shearing conditions declined as Na2O% rose [41]. More detailed explanations are needed in
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373 For some blended systems and calcium-free systems, the effects of Na/K-silicate concentration
374 (Na/K2O%) on the rheological properties, especially the viscoelasticity (structural build-up kinetics),
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375 have been studied. Dai et al. [136] reported that increasing sodium silicate dosage (3%-6% of N2O%)
376 in slag-fly ash paste caused a delayed structural build-up followed by an abrupt increase, which was
377 related to the longer initial setting time. Interestingly, they observed humps in loss factor evolution
378 curve during the rapid increasing structural build-up stage with higher Na-silicate concentration,
379 which indicated that the loss modulus (G’’) increases faster than the storage modulus (G’) for a given
380 time. This phenomenon could be explained by the release of extra water from the condensation of
381 Si(OH)4 species, leading to an increase of loss factor and a more liquid-like behavior [136]. These
382 humps were also related to the gelation [137]. Furthermore, the dynamic yield stress, thixotropy and
383 the shear-thickening response decreased as Na-silicate dosage increased, and even behaved like a
384 Bingham fluid. In a system of calcined shale (CS) as a metakaolin source, the complex viscosity
385 (obtained by small amplitude oscillatory) for describing hardening rates of pastes activated by
386 different amount of K-silicate was measured [138]. The results showed that increasing activator
387 resulted in a delay of saturation-polycondensation stage and reducing hardening rate and matrix
389
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390
391
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Fig. 8. Yield stress of sodium silicate activated slag suspensions with a water-binder ratio of 0.45 as a function of
392 the square of Zeta potential at different activator dosages (0, 2.2, 4.4 and 6.6×10-4 mole Na2O/g slag) [52].
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393
394 Fig. 9. A schematic sketch of electrostatic inter-particle forces with different dosages of sodium silicate in slag
396
397
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398 Fig. 10. Effect of Na2O% and n(SiO2)/n(Na2O) molar ratio on 11-min (for the second shear cycle) yield stress in
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400 -p
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401 3.3 Other activators
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402 In addition to the widely used activators discussed above, there are some unconventional
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403 activators, such as carbonate, sulphate and phosphate. In a calcium-free MK based system, Wang et
404 al. [131] used orthophosphoric acid and liquid monoaluminum phosphate to prepare different Al/P
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405 molar ratios (0, 0.1 and 0.3) of phosphate activating solution. It was observed that more aluminum
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406 species from phosphate activating solution favors to reduce the yield stress of MK based pastes due
407 to a faster sol/gel transition. Similarly, in a low-calcium paste with fly ash/slag ratio of 4, the yield
408 stress and viscosity of the control group (without borax) can be effectively reduced by partially
409 replacing borax for sodium silicate solution owing to partial structural breakdown of flocs [139]. In
410 addition, borax composite behaved like a Bingham fluid while the rheological behavior of control
411 group is more consistent with the H-B model. For now, though, more studies on the rheology of
412 high-calcium systems activated by other activators were reported. When using a combination of
413 NaOH, Na2CO3 and waste glass (SiO2, Na2O, CaO, etc.) to activate slag, Torres-Carrasco et al. [64]
414 observed that the rheological behavior of AAS pastes was similar to that of sodium silicates-activated
415 slag pastes, which can be characterized by the H-B model. The other important finding in their work
416 is that “false setting” arose in both systems. This can be attributed to the rapid precipitation of
417 primary C-(A)-S-H gels. It should be noted that longer time is required for activating the solution
418 containing waste glass to generate primary C-(A)-S-H gels because of the difference of silicon
419 source and environment, where the potential retarding effect of the mixed activator bearing waste
421 Recently, Mehdizadeh et al. [65] reported the rheological behavior and fluidity of phosphorus slag
422 activated by two mixed activators (Na2CO3+ Ca(OH)2, Ca(OH)2+Na2SO4). The presence of CO32-
423 ions and concomitant formation of AFm and calcium sodium carbonate-type compounds in
424 alkali-activated slag pastes would like to intensify the interactions between flocs and thus generated
425 higher shear stress [41, 129]. In addition, when the ‘designed’ NaOH concentration increases from 3%
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426 to 5%, the measured shear stress and yield stress values increased. For the phosphorous slag pastes
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427 activated by Ca(OH)2 and Na2CO3 (PS/CNC), as shown in Fig. 11a, the concentration of main
428
-p
elements, especially Si, increased significantly in the first 35 min, indicating that the reaction
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429 between Ca(OH)2 and Na2CO3 enhanced the alkalinity of solution and promoted the dissolution of
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430 phosphorous slag. Hence, the high yield stress of the PS/CNC was attributed to the formation of
431 more early gels as Ca2+ reacted with dissolved silicates (the yield stress started to increase after 15
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432 min of mixing in Fig. 12). This can be confirmed by the decreased concentrations of these ions after
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433 35 min. Nevertheless, a lower yield stress in the Ca(OH)2 and Na2SO4 activated phosphorous slag
434 pastes (PS/CNS) pastes was detected (Fig. 12), which was probably caused by the weak reaction of
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435 Na2SO4 and Ca(OH)2. As shown in Fig. 11b, concentrations of the leached Si and Al in PS/CNS were
436 very low compared to those in the PS/CNC. Therefore, it can be deduced that lower alkalinity and
437 presence of SO42− mean low activation capability, which also leads to less early gels. This provides
438 an approach for designing a robust formula of AAMs with good fresh performance. For Na2CO3-slag
439 pastes, increasing activator concentration from 6% to 10% showed no significant effect on yield
440 stress and plastic viscosity because of its long setting time [129]. The addition of Ca(OH)2 can
441 accelerate reaction effectively by consuming free CO32− ions. By contrast, it is a good method to
442 replace Na2CO3 with a small amount of NaOH (20 wt.%) by which setting time could be shorten and
443 the rheological parameters yield stress and plastic viscosity only slightly increased [129].
444 Furthermore, Alrefaei et al., designed a slag-fly ash paste activated by one-part Ca(OH)2/Na2SO4
445 exhibited a higher fluidity, but rather the conventional Na2SiO3-anhydrous activator [132]. This
446 one-part Ca(OH)2/Na2SO4 has also been used to activated fiber-reinforced AAS composite, and
448
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449
450 Fig. 11. Concentration variation of main ions in the leached solutions from (a) Ca(OH)2 + Na2CO3 activated
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451 phosphorous slag paste (PS/CNC) and (b) Ca(OH)2 + Na2SO4 activated phosphorous slag paste (PS/CNS) [65].
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452
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453
454 Fig. 12. The yield stress of phosphorus slag activated by Ca(OH)2 + Na2CO3 (PS/CNC) and Ca(OH)2 + Na2SO4
456
457 4. Effect of precursors on rheology of AAMs
458 AAMs cover a wide variety of materials whose differences depend on the physical and chemical
459 properties of the starting aluminosilicates. Extensive researches have been focused on the
460 understanding of the alkali-activation reaction with various precursors under various curing
461 conditions and their products. Inspired by these achievements, a few studies have been carried out
462 about rheological behavior with different precursors, such as slag, fly ash and their blends [40, 65,
463 66]. According to the calcium concentration of precursors [95], AAMs can be divided into three
464 categories: ① low-calcium system, generated from those precursors like metakaolin (CaO%<1%)
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465 or calcium-poor fly ash (usually Class F, 1%≤CaO<10%), is dominated by highly cross-linked
466 aluminosilicate geopolymeric gels (N-A-S-H); ② high-calcium system based on calcium rich
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467
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precursors such as blast furnace slag (10%≤CaO) with tobermorite-like calcium aluminosilicate
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468 hydrate gels (C-A-S-H) as the dominant products; ③ alkali-activated blended system with
470 geopolymeric gels and C-A-S-H products [8, 67, 68]. With a constant Al/Si of 0.5, N-A-S-H were
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471 found to coexist with C-A-S-H gels when Ca/Si<0.6, but only C-A-S-H gels were formed when
472 Ca/Si≥0.6 [96]. The rheological behavior and parameters of AAMs are substantially different when
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475 For calcium-rich precursors such as blast furnace slag, phosphorous slag and Class C fly ash, they
476 are usually used as a single precursor alone in AAM manufacturing because of their high content of
477 reactive components. Gonzalez et al. [70] used 0.25 M NaOH solutions to activate a modified
478 basic-oxygen-furnace slag incorporated by 13 wt.% Al2O3 (reactive amorphous: 55.5 wt.%) and
479 found that the plastic viscosity of the paste was about 2 times higher than that of the modified slag
480 induced by 11 wt.% Al2O3 and 5 wt.% SiO2 (reactive amorphous: 65.5 wt.%). The results mean that
481 the total amount of reactive component of a specific calcium-rich precursor cannot determine its
482 reactivity. The chemistry of the reactive component seems more important. In a Class C fly
483 ash-waste brick powder blended high-calcium system, it was found that increasing content of
484 calcium-rich waste brick powder tended to increase yield stress and consistency coefficient of pastes
485 activated by Na-silicate [43], due to the fact that more divalent cations (Ca2+) could lead to attractive
486 ion correlation forces and more primary gels [42]. Poor dispersion of brick powder (contained some
487 concrete powder) also led to higher solid volume fraction in the suspension, which induced the
488 increase of rheological responses [43]. Moreover, it was reported that the AAPS pastes (PS was
489 almost completely amorphous, and mainly composed of 45.16 wt.% CaO, 38.39 wt.% SiO2 and 7.66
490 wt.% Al2O3) exhibited as a shear thinning behavior where flow index (n, can be determined by Eq. (3)
491 in section 2) and thinning index (TI, the ratio of the apparent viscosity at low rotational speed to that
492 at rotational speed ten timer higher according to ASTM D2196) were independent upon the chemical
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493 composition of activator, implying that such shear thinning mechanism was more associated with the
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494 characteristics of phosphorous slag [35].
495
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Class-F Fly ash (FA) is common used as calcium-poor precursor, and their reactivity lies on
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496 content and composition of vitreous phase(s). In the alkali-activated blended system dominated by
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497 low-calcium fly ash, the spherical and fine fly ash particles exhibited beneficial impacts on the
498 rheological properties. Aboulayt et al. [47] studied the alkali-activated metakaolin-fly ash (MK-FA)
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499 blended system. The maximum packing volume fraction (𝜙𝑀 ) of MK-FA blended AAMs grout
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500 increased with the replacement level of MK by FA, which was due to dense packing model of
501 spherical FA particles. Furthermore, the specific surface areas of FA is usually much lower than MK,
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502 and the replacement by FA makes more surface wetting water being free. Thus, in overall, the
503 viscosity (consistency) was tested to be reduced and the setting time as well as the risk of bleeding
504 increased. Yang et al. [40] proposed to use fly ash microspheres (FAM) as a novel inorganic
505 dispersant based on its “ball-bearing” effect. The SEM image in Fig. 13 shows the morphology of
506 nanoscale FAM particles with smooth surface and high sphericity. This morphologic feature
507 facilitates the usage as dispersing agent. When the fly ash replacement ratio by FAM increased, the
508 plastic viscosity for all samples declined, irrespective of the modulus (Ms) of sodium silicate (in
509 Fig.14a). This phenomenon was ascribed to the “ball-bearings” effect, together with the lubricating
510 effect of FAM particles which breaks down the interlocking between flocs and fragmentation [40,
511 71]. Apart from the packing density, the yield stress appeared to be more susceptible to the activator
512 modulus (in Fig.14b). In the Ms=1.4 system , only 40% FAM reduced the yield stress of suspensions,
513 which could be inferred that the ‘ball-bearings’ of FAM destroyed the interlocking between fly ash
514 and slag particles to resist the increased particle packing [40]. By contrast, ‘ball-bearings’ effect in
515 the Ms =1.8 system seems less important, since more colloidal silicate species might react with Ca2+
516 released from slag to produce more primary gels, and thus increasing the attraction between
517 suspended particles. Again, it should be noted that particles with larger specific surface area need to
518 consume more water, therefore, there is a balance between the three effects of packing density,
520
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521
522 Fig. 13. The SEM image of fly ash microspheres used as inorganic dispersant in AAMs [40].
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523
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524
525 Fig. 14. The plastic viscosity (a) and yield stress (b) of the alkali-activated fly ash-slag blended pastes prepared by
526 Ms=1.4 and 1.8 sodium silicate solutions. At constant slag content of 40 wt.%, the 60 wt.% fly ash is replaced by 0,
527 10, 20, 30 and 40 wt.% fly ash microspheres, denoted as AM0, AM10, AM20, AM30 and AM40, respectively (data
529
530 Effects of fly ash/slag ratios on rheology of alkali activated slag-fly ash composite systems have
531 always been a research hotspot. Introducing different contents of slag directly affects the initial
532 dissolution behavior, and higher calcium content leads to changes of the precipitated gel systems.
533 Compared with FA paste activated by a composite activator (NaCO3 and Na-silicate), a replacement
534 of slag to fly ash (fly ash/slag = 3:1; 4:1) reduced the yield stress of pastes. Similar to this finding,
535 Dai et al. [136] increased the replacement amount of slag to fly ash to 70wt.% in Na-silicate based
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536 pastes, the yield stress and consistency coefficient were reduced by 51% and 81%, respectively. This
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537 is attribute to a reduction of flocculation caused by fine FA particles and a faster dissolution of slag
538
-p
resulting in low solid content [128, 136]. Besides, the AAFA pastes behaved like a Bingham fluid,
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539 while the rheological behavior of the composite pastes was more consistent with H-B model. Dai et
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540 al. [136] observed the hysteresis area increased as the slag/fly ash ratio in the composite pastes. The
541 other study, however, reported opposite results in the hysteresis area, and the yield stress of blending
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542 paste with fly ash/slag ratio of 2 was almost doubled the AAFA [128]. Different w/b ratios and
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543 particle sizes may be responsible for these differences. Dai et al. [136] designed the w/b ratios to
544 decrease with the increase of FA content, and the fly ash used was finer than slag. This enhances
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545 attractive inter-particle forces leading to more flocculation structures that are more difficult to be
546 disturbed by shearing. Similarly, Na-silicate based fly ash-slag mortars with copper slag as fine
547 aggregate, higher yield stress and consistency were obtained in the mixture containing more FA due
548 to a higher specific surface area FA [72]. On the contrary, it must be considered that the introduction
549 of more slag means faster dissolution and higher structure build-up rate, which was characterized by
550 shorter percolation time, faster storage modulus growth [136] and flow loss [141]. These results are
552 The MK-based AAMs generally have higher rheological response because very high specific
553 surface area of MK [45, 74], which indicates that suitable activators [123], dispersing agents [74] and
554 sufficient water [29] are required to achieve good workability. As a calcium free precursor, sodium
555 silicate-MK pastes have been demonstrated that the formation of primary gels with Si/Al<4.5,
556 instead of colloidal interaction between grains, could be accounted for the evolution of early
557 mechanical properties (storage modulus) [34]. As discussed previously, it is very different from
558 Ca-containing systems: the presence of calcium causes a dramatic change of systemic chemistry and
559 the colloidal interactions between grains could be enhanced as well [34]. Moreover, compared to
560 cement-based suspensions, MK-based pastes usually exhibit high viscosity due to the fact that
561 plate-shape MK grains have low 𝜙𝑀 . In the sodium silicate based-suspension with a volume fraction
562 of MK around 0.25, the small volume of solid grains prevented the contact between grains though
563 the 𝜙𝑀 of MK was small, and thereby the suspension viscosity was nearly exclusively controlled by
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564 the viscosity of interstitial fluid [33]. Interestingly, the plastic viscosity of alkali-activated MK-based
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565 suspensions could be reduced by increasing the replacement of MK by waste red brick powder [74].
566
-p
Similar results were also reported in MK-slag mortars activated by sodium silicate solution [64, 140],
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567 as shown in Table 2. In addition to the negative effect of irregular spiny plate-shape particles of MK,
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568 the viscosity-enhancing effect of MK was attributed to the larger specific area, requiring more
569 mixing water for wetting. Moreover, MK with distorted aluminum layer structure had higher
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570 reactivity than brick powder, hence, the suspensions containing more MK led to faster growth of
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571 yield stress and storage modulus due to rapid gelation [74]. Table 2 summarizes the effects of
572 precursor nature on the rheological properties of alkali-activated blended systems. It can be seen that
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573 the physical properties of precursors, morphology in particular, jointly affect the surface water
574 absorption and packing density to alter the rheological properties of AAMs. In PCMs system, many
575 studies have been demonstrated that the combined effects of these factors could be well evaluated by
576 the water (paste or mortar) film thickness [108-110] whereas correlation between these film
577 thickness and rheological properties of AAMs has not been quantitatively proposed. Furthermore,
578 rheological parameters were also affected when precursors with different reactivities was mixed with
579 various proportions, due to changes of polymeric structure and polymer-particle interactions.
580
581 Table 2
582 Effects of precursor nature on the rheological properties of sodium silicate-activated blended systems.
Precursors L/S ratio (by Controlling Rheological parameters Decisive factors Refs.
/mass ) Pa*s)
fly ash (Grout) 0.75 0:10; 2:8; Decreased Increased from surface area of MK;
0.02
f
w/b SF/FA ratio Higher specific [75]
oo
fume
0.75 0:10; 1:9; Increased Increased from surface area and
(Grout)
r
2:8; 3:7; 4:6 from 1.81 to 0.0105 to 0.066 reactivity of SF
-p
9.51
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lP
fly ash 0.5 6:0; 5:1; 4:2; Increased Decreased effect, dense packing
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microspheres 3:3; 2:4 from 2.51 to from 1.05 to and higher specific
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40 wt.%) 2.35
9.8
Class C fly ash w/b FA/waste brick powder ratio Waste brick powder [43]
powder 0.3 1:8; 3:6; 4:5; Decreased Decreased surface area and
(All Pastes 5:4; 6:3; 7:2 from 4.42 to from 7.2 to reactivity of glass
f
containing 10 1.8 2.95 powder
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wt.% calcium
r
aluminate
cement)
-p
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Metakaolin + L/S The brick powder/MK ratio Higher specific [74]
lP
slag 0.45 3:7; 5:5; 7:3 Increased Increased from surface area of MK
binder:sand 120
ratio of 0.33)
Metakaolin + L/B MK/slag ratio
slag 1 3:7; 5:5; 7:3 Increased Increased from Higher specific [140]
binder:sand 118
ratio of 0.25)
(Mortar with 0.55 5:5; 8:2 Increased Increased from surface area of FA
f
ratio of 0.5 ) 29.5
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583 * L/S = liquid/solid ratio; w/b = water/binder ratio; L/B = liquid/binder ratio.
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584
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585 4.2 Content of precursors
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586 According to the Krieger-Dougherty formula [76] and the“YODEL” model [77], the apparent
587 viscosity (𝜂) and the yield stress (𝜏0 ) of suspension can be evaluated in accordance with Eq. (4) and
na
𝜙 −[𝜂]𝜙𝑀
𝜂 = 𝜂0 (1 − ) (4)
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𝜙𝑀
𝜙(𝜙 − 𝜙0 )2
𝜏0 = 𝑚1 (5)
𝜙max (𝜙max − 𝜙)
589 where 𝜂0 is the viscosity of interstitial fluid; 𝜙 is the actual solids packing fraction (by volume);
590 𝜙𝑀 is the maximum packing fraction (by volume); and [𝜂] is the intrinsic viscosity of the
591 suspension, which is related to the effect of individual particles on the viscosity. In Eq. (5), 𝜙0 is the
592 lower limit solid volume fraction (percolation threshold) at which the disperse phase behaves as a
593 three dimensional network structure; 𝑚1 represents the effects independent of solid volume fraction,
594 depending on the particle size distribution and interparticle force parameter. Based on the theory
595 from Eq. (4) and Eq. (5), the viscosity and yield stress of suspensions increase as the solid content
596 increases. It can be explained by the following two aspects: 1) more solid particles will induce the
597 particles-cluster effect; 2) less water added would increase the solids concentration, the inter-particle
598 friction and thereby the mortar is more reluctant to flow [23]. In other words, a high water to binder
599 ratio (w/b) leads to good dispersion of grains and low interparticle friction in the suspension [78],
600 and consequently reducing in shear stress and viscosity. As shown in Fig.15, the yield stress and
601 plastic viscosity of alkali-activated fly ash-silica fume blended grouts increased as w/b decreased [75,
602 79]. Similarly, the yield stress of MK suspensions activated by sodium silicate increased significantly
603 with the increase of precursor content (57 wt.% ~ 62 wt.%) under different curing time [45]. Even
604 more interesting is that the flow index (n) of MK-suspensions was reported to increase with the
605 solid/liquid content, regardless of curing time [45]. This was due to the change of particles
606 distribution (Brownian movement) and inter-particle structure when different shear rates were
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607 applied.
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608
-p
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609
610 Fig. 15. The yield stress (a) and plastic viscosity (b) of alkali-activated fly ash-silica fume blended grouts prepared
612 As expected, Alonso et al. [31] observed that the static yield stress value declined by 96.65% when
613 the liquid to binder (L/B) ratio of sodium silicate-activated slag mortars (the aggregate/binder=2:1)
614 increased from 0.45 to 0.65. This is in line with a report on one-part sodium silicate activated
615 slag/glass powder pastes [126]. Increasing w/b from 0.275 to 0.350, the yield stress and plastic
616 viscosity of pastes were reduced by 64.14% and 91.48%, respectively [126]. Fig. 16 is a typical shear
617 rate-shear stress curve of pastes with different w/b ratios. In the low shear rate region, the measured
618 shear stress of sodium silicate-fly ash/slag (2:1) pastes decreased with the increase of w/b ratios, for
619 suggesting greater fluidity. This is due to strong hydrodynamic forces that seriously disturb the
621
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623 Fig. 16. Shear rate-shear stress curve of fly ash/slag (2:1) pastes with different w/b ratios [128].
624
lP
627 As is well known, water-reducing admixtures are widely used to improve the rheology and
631 their compatibility with Portland cement has been well explained in massive literature, where
632 inter-particle electrostatic repulsion and steric hindrance are induced by the effective adsorption of
633 admixtures on cement particles surface (Fig. 17), and consequently avoiding the formation of flocs
634 [80]. Thus, to some extent, such admixtures can reduce the water demand and improve durability and
635 mechanical properties [81, 82]. Encouraged by their early success of the application in PCMs,
636 researchers attempted to use these chemical admixtures to modify the rheology of AAM systems.
637 Table 3 summarizes and compares effects of various water-reducing admixtures with different
638 dosages on the rheological properties of AAMs in literatures.
639
640
641
f
Fig. 17. The schematic diagram of function mechanisms of superplasticisers on cement particles [83].
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642
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643 Table 3
644
-p
The comparison of effects of various water-reducing admixtures with different dosages on the rheological
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645 properties of AAMs.
lP
Lignosulphonate (LS);
The minimum μ and
Melamine-derived
𝜏0 from mixtures with M
ur
synthetic polymers
0.80% Fly ash (paste) and M-PCE, respectively; [83]
(M); Modified
segregation in mixtures
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polycarboxylic ethers
with LS
(M-PCE)
f
naphthalene-formaldeh
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yde (SNF); LS; PCE;
PCE; melamine Effects of all
r
formaldehyde Slag (paste and
derivative (M); 0.3%; 0.5%;
-p
mortar)
plasticizer-admixtures are
negligible
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naphthalene 1.0%; 1.5%; [19]
NaOH
formaldehyde 2.0% Slag (paste and Mixtures with NF
lP
647 The suitability of commercial water-reducing admixtures to control the rheological properties of
648 AAS have been studied by many researchers. In NaOH-AAS system, proper dosage plasticizers
649 exhibited certain plasticizing effect in the early stage, but they might become unstable afterwards,
650 which was depending on the molecular structure at high pH conditions. Palacios et al. [19]
651 investigated the influences of four different high-range water-reducing admixtures (HRWRAs) on the
652 rheological behavior of NaOH-activated slag pastes/mortars. Only the naphthalene-based HRWRA
653 could lower the yield stress prominently due to its chemical stability in the alkaline environment.
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654 Though the lower molecular weight fragments of the polycarboxylate-based, melamine-based and
655 vinyl copolymer HRWRAs may be still adsorbed on the particles surface and induce an electrostatic
r
656 -p
repulsion, the steric contribution is not noticeable [19, 87]. It is worth noting that the presence of
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657 melamine-based superplasticizer caused much higher yield stress in the suspension activated by
658 NaOH and the reason for this phenomenon was not clear [87].
lP
659 The authors also reported similar behavior of these admixtures in their subsequent experiments on
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660 the 13.6-pH NaOH-AAS pastes [66]. As shown in Fig. 18, the yield stress and plastic viscosity of
661 AAS pastes with different amounts of the melamine-based admixture were all higher than those of
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662 the blank control group, when the shearing regime was implemented for at least 10 minutes. The
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663 plasticizing effect of vinyl copolymer seems less prominent in AAS pastes. Only the
664 naphthalene-based superplasticizer with 1.26 mg substantially reduced both yield stress and plastic
665 viscosity in NaOH-AAS pastes (in Fig. 18c-d). This is due to the fact that the adsorption-mediated
666 decrease in size and number of agglomerated particles, which further supports the chemical stability
667 of this admixture. These results revealed the suitability and plasticizing effectiveness of different
669
670
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671
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672
673 Fig. 18. The yield stress and plastic viscosity evolution in 13.6-pH NaOH-AAS pastes containing three types of
674 superplasticizers: melamine-based, naphthalene-based and vinyl copolymer at different dosages. Data from
675 Palacios et al. [66].
676
677 In the AAS suspensions activated by sodium silicates, Palacios et al. [19] observed that all
678 water-reducing admixtures were useless. Actually the yield stress even increased in the case of using
679 vinyl copolymer HRWRA. However, Luukkonen et al. [86] pointed out that the first- and
680 second-generation plasticizers were more efficient than the commonly used third-generation
681 superplasticizers, particularly when adding 0.5 wt.% lignosulfonate-based superplasticizer could
682 decrease the yield stress and viscosity of AAS mortars to 56% and 27% at 40 min, respectively.
683 Palacios and Puertas [87, 88] reported functional groups changed (as indicated by the shifts in the
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684 infrared spectra) when the naphthalene-based HRWRA was mixed in sodium silicates activated slag
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685 systems. These changes (modified or released) in the sulphonates might be account for the failure of
686
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naphthalene-derived admixtures. Nevertheless, they did not provide a detailed description of exact
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687 structural alterations taking place for this admixture. Interestingly, Ren et al. [89] suggested that the
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688 addition of lignosulfonates and sodium silicates separately could reduce the likelihood of failure.
689 Compared to simultaneous addition method, adding the lignosulfonates 3 minutes prior to or after the
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690 sodium silicates both led to a great reduction on both yield stress and plastic viscosity, thus obtained
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691 the increased mini-slump spreads. They also observed shear thickening behaviour when the
692 lignosulfonates and the activator were added separately in the sodium silicate activated slag.
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693 The effective adsorption of admixtures on precursor particles is very important for their
694 plasticizing efficiency. Nevertheless, the results from Palacios et al. [66] showed that the adsorption
695 of the three superplasticizers (melamine-based, naphthalene-based and vinyl copolymer) on slag
696 particles in AAS pastes was much lower than on PC particles, and variation of pH of the alkaline
697 solution seemed less important for the adsorption behavior. This may be partially due to the
698 difference of adsorption mechanisms in the two suspensions, since the initial Zeta potential of the
699 11.7-pH NaOH AAS paste was negative (about −2 mV) owing to deprotonation whereas that of PC
700 paste was positive (about +0.5 mV). Generally, with the increasing adsorption of anionic
701 superplasticizer moleculars (admixtures containing sulfonic groups) on the particles surface, the Zeta
702 potential values of blast furnace slag and fly ash suspensions gradually decrease (more negative),
703 which indicated that electrostatic repulsion may play a role in the dispersion mechanism [53]. The
704 working mechanism of these superplasticizers in NaOH-AAS were further studied by Palacios et al.
705 [115] later and they turned out that that steric hindrance was dominant in the working mechanisms of
706 both the sulfonate and polycarboxylate superplasticizers in NaOH-AAS. Melamine admixtures
707 induced the highest contribution (only around 26%) to the electrostatic repulsion, and the
708 naphthalene derivative admixture with the lowest molecular weight presented the smallest range of
709 steric repulsion. Compared to the melamine derivative and vinyl copolymer, polycarboxylate
710 superplasticizer with lower molecular weight showed the highest steric hindrance, which might be
711 attributed to different adsorption conformations related to molecular structures [115-116]. In addition,
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712 Kashani et al. [30] noticed that the addition of polycarboxylates in sodium silicates-AAS pastes
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713 reduced the flow index in the H–B model with shear thinning behavior. A dramatic yield stress
714
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reduction was found in the mixture with higher density of long side chains in the lower molecular
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715 weight polymers. Side chains were assumed to work as a steric effect supplier to disperse particles
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716 after polycarboxylate ethers molecular was adsorbed on particles surface. Because of this, a bridging
717 effect may occur to provide partial protection of the backbone charges against attachment of one
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718 admixture molecule to two or more slag particles, thereby enhancing the plasticizing efficiency.
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719 Interestingly, the plasticizing mechanisms are similar despite the different charge signs of molecules,
720 which indicates that both anionic and cationic adsorption sites are available on slag particle surface
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722 In addition to the chemical stability, the solubility in alkaline media [120-121] and the competitive
723 adsorption between the anionic species of activators and anionic superplasticizers [121-122] also
724 affect the adsorption efficiency and dispersion effect of these superplasticizers in AAMs. Conte et al.
725 [120] reported that the solubility difference of PCEs with different molecular structures in NaOH and
726 Na2CO3 solutions induced different dispersing efficiency. All the PCEs tested in the study had no
727 important impact on improving the flow of Na2CO3-slag paste, due to the extremely low solubility in
728 Na2CO3 solution. Moreover, allyl ether based PCEs with a high molecular weight (Mw > 30000 Da)
729 and a short side chain (nEO = 7) exhibited the best dispersing performance in NaOH-slag system,
730 which might be attributed to their good solubility in NaOH solution and stronger chelating ability
731 with Ca2+ ions. It should be noted that better solubility of these polymers in alkaline solutions does
732 not always mean superior dispersing ability. Lei et al. [121] synthesized a series of PCEs with
733 different anionic charge density or side chain lengths, based on α-methallyl-ω-hydroxy poly
734 (ethylene glycol) ether (HPEG). As shown in Fig. 19, even 23HPEG15 (Mw = 42000 Da; nEO = 23)
735 showed higher solubility (4.50 mol/L) in NaOH solutions than 23HPEG7(a) (Mw = 410000 Da; nEO
736 = 23; 2.96 mol/L NaOH), it presented poor dispersing performance in NaOH-slag pastes. Therefore,
737 the solubility of PCEs is a limit factor of dispersing efficiency of such polymers in AAMs, but not
739
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740
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741 Fig. 19. NaOH concentrations (a) needed to achieve the cloud point of different HPEG PCEs, and
742 spread flow (b) of NaOH-slag pastes containing 0.05 wt% of different HPEG PCEs [121].
743
744 It is well known that many commercial anionic superplasticizers improve adsorption efficiency by
745 the strong chelation with Ca2+ ions. Due to the deprotonation of hydroxyl, the negatively charged
746 slag particles attract some Ca2+ ions in alkali-activated slag system, which provides a possibility for
747 the adsorption of anionic superplasticizers on slag particles surface. However, current research shows
748 that the adsorption capacity of superplasticizers on slag surface is still far less than that in PCMs. To
749 some extent, the low adsorption efficiency might be generically grouped under competitive
750 adsorption between such polymer molecules and anionic species in activators [120-122]. Marchon et
751 al. [122] considered that the fast flow loss of PCEs in alkali-activated system was probably due to a
752 competitive adsorption between PCE molecules with the hydroxyls. As previously discussed, the low
753 adsorption performance of PCEs in Na2CO3-slag pastes could also be accounted for the almost
754 complete removal of Ca2+ ions in solutions resulting from precipitation by the CO32- ions [120]. It
755 could lead to an insufficient adsorption of Ca2+ ions on slag particles, lowing adsorption efficiency of
756 PCEs. Similarly, Palacios et al. [88] found that all the superplasticizers tested in sodium silicate-slag
757 pastes failed to provide any dispersing effect. To a certain extent, this could be attributed to the
758 preferential adsorption of silicate species with Ca2+ ions dissolved from slag.
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760 The effects on rheology of the three generations of water-reducing agents also have also been
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761 studied in AAFA pastes and concretes. Compared to the blank control pastes, the AAFA containing
762
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the tested water-reducing admixtures (including lignosulphonates, melamines and polycarboxylates)
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763 all showed reduced yield stress and plastic viscosity after mixing and the effectiveness was only in
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764 the early age [83, 84]. As discussed earlier, the chemical stability and solubility of superplasticizers
765 in alkali solution, and the adsorption degree on particles should be considered as possible reasons for
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766 low plasticizing efficiency. Interestingly, Laskar and Bhattacharjee [84] pointed out that the
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767 concentration of 4 M for NaOH solution was a critical value, below which increasing dosages of
768 both lignosulphonate-based and polycarboxylate-based admixtures could improve workability of fly
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769 ash paste activated by sodium silicate. However, it still unclear why the addition of
770 lignosulphonate-based admixture is more likely to induce segregation in fly ash based-suspensions
771 [83, 84]. Furthermore, unlike in AAS suspensions, Criado et al. [83] reported that polycarboxylate
772 superplasticizers in AAFA systems showed the most effective plasticizing properties among these
773 three types of water-reducing agents. Most admixtures including the third-generation
774 supersuperplasticizer are designed to form complexes with the dissolved Ca2+ in the early hydration
775 of Portland cement [85]. Slag and high-calcium (Class C) fly ash can also release large amounts of
776 Ca2+, yet hardly any calcium is dissolved in low-calcium fly ash (Class F) systems. Therefore, the
777 steric-hindrance effect is prohibited or not trigged in Class-F fly ash systems. As reported by Montes
778 et al., the polycarboxylate-based admixture only slightly reduced the viscosity of fly ash paste
779 activated by Na-silicate [130]. In another study, however, polycarboxylates were more effective to
780 induce apparent drop of shear stress and viscosity in sodium silicate-Class C fly ash, and this higher
781 adsorption efficiency was attributed to the presence of positively charged Ca2+ [119]. In contrast to
782 PC, the drop in the plastic viscosity and yield stress of AAFA pastes containing plasticizers is not
783 always accompanied by the improvement of fluidization performance. There was hardly correlation
784 between slump and the rheological parameters in the research by Criado et al. [83]. This is adverse to
785 the report from Laskar and Bhattacharjee [84] who concluded that good correlation between
786 rheological parameters and slump test results in AAFA concretes containing different plasticizers. It
787 is evident that the properties of fly ash, the interaction between water-reducing admixtures and fly
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788 ash, and the type of activator and the addition method should be considered in the future research for
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789 different AAM systems.
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790 5.2 Other chemical admixtures
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791 In addition to water-reducing admixtures, other commonly used admixtures, such as shrinkage
792 reducing agents, retarders, deflocculants, etc., have also been studied for their impacts on rheological
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794 shrinkage reducing agent on AAS was investigated by Palacios et al. [19]. Although these authors
795 have proved that this admixture was stable in highly alkaline solutions [88], it did not improve the
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796 fluidity of NaOH-activated slag pastes, and even increased the yield stress of sodium silicates-slag
797 pastes. A recent publication showed that fluidity of AAS pastes with polypropylene glycol
798 (PPG)-based shrinkage reducing agent could be increased (PPG1000), reduced (PPG400), or
799 maintained (PPG2000) at a similar level (Fig. 20), which depended on the dosages and molecular
800 weight of PPG [118]. The difference in fluidity can be attributed to the effect of PPG on the viscosity
801 of suspensions and the dissolution process of slag grains [118]. Hence the chemical stability and
802 rheological properties of shrinkage reducing agents with different structure and molecular weight in
803 high alkaline-AAMs need more research. Xu et al. [90] found that citric acid can work not only as a
804 setting retarder, but also a potential plasticizer in AAMs. As shown in Table 4, the NaOH activated
805 fly ash (Class C)-lime kiln dust paste (marked as AAFA-LKD) with addition of 3 wt.% citric acid
806 showed a low plastic viscosity and a comparable yield stress to Portland cement (PC), and these
807 rheological parameters could be maintained at viable levels in the first 1h. The introduction of citric
808 acid reduces the alkalinity of suspension and thus delay the dissolution process. In addition, the
809 formation of carboxylate complexes between the carboxylic acid groups of citric acid and Ca2+ ions
810 released from calcium-containing precursors would also affect the gelation process, then reducing
811 yield stress. Similarly, Wang et al. [61] also reported that the introduction of a retarder was effective
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813
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814 Fig. 20. Fluidity of the AAS pastes after adding different dosages of polypropylene glycol (PPG)-based shrinkage
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816
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Table 4
817 Plastic viscosity and yield stress of Portland cement (PC) paste and alkali-activated fly ash (Class-C)-lime kiln dust
818 (marked as AAFA-LKD) pastes without and with 3 wt% citric acid at different times after reaction [90].
819 * In the table of Ref [90], the unit of yield stress is (MPa). This might be wrong, so here it is
821 Sodium polyacrilate with low molecular weight (Mw=2000 au) was used to work as a deflocculant
822 to reduce the yield stress and shear viscosity of aqueous suspensions of kaolinite [45,117]. However,
823 the sodium polyacrylate has limited effect on reducing yield stress and viscosity of metakaolin-based
824 AAMs, or even for the aqueous suspensions of metakaolinite [45]. Therefore, the admixture in this
825 case behaves more like a flocculant than deflocculant. Grout materials usually require a good balance
826 between flowability and stability. Viscosity modifying agents or stabilizers are usually added to
827 prevent segregation and bleeding. Aboulayt et al. [47] applied polysaccharide-based stabilizer
828 (xanthan gum) in metakaolin-fly ash blended AAM grouts and found the beneficial effect on the
829 stability. For a given fly ash ratio, both the yield stress and plastic viscosity at different shear rates
830 increased with the increase of stabilizer dosage. Similarly, excellent pumpability at high temperature
831 is vital for drilling fluid in oil well cementing engineering. A novel self-degradable temporary sealing
832 material based on sodium carboxymethyl cellulose-modified alkali-slag-fly ash (Class C) material
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833 was developed, and the addition of 2 wt.% polylactic acid could enhance the pumpability and reduce
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834 the viscosity [91].
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835 6. Effects of mineral additions on rheology of AAMs
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836 Whether inert or latent hydraulic mineral additions with small particle size, they all have physical
837 filling effect in the hydration process, not only in PCMs but also AAMs. The high surface area of the
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838 fines can provide abundant nucleation sites for the hydration. Accordingly, both the fresh and
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841 Silica fume (SF) is a frequently-used pozzolanic addition, and it also can be used as a precursor in
842 AAMs to mix with slag or fly ash. Here, in order to better explain the influence of SF, it will be
843 discussed in this part. The rheological modification of AAMs by SF is closely linked with the water
844 to binder ratio (w/b) and its physicochemical properties. The amount of SF that caused significant
845 increase in the yield stress and plastic viscosity of AAFA grout decreased as w/b ratio (Fig.15). For
846 example, the critical content of SF in the suspension with w/b of 0.75 is 20%, while 50% is the
847 critical content of SF in the suspension with w/b of 1.25 (Fig.15). Beyond this critical content, it was
848 observed that the yield stress and plastic viscosity of AAFA grout increased with the increasing of SF
849 proportion [75]. This is similar to the impact of adding SF in the conventional grouts [92, 93]. The
850 influence of higher specific surface (21080 m2/kg for SF, in comparison with 379 m2/kg for FA) [75]
851 and reactivity of SF under the interaction of alkaline activators must be taken into account [92, 94,
852 126]. The use of SF above the critical content means that there is insufficient water to wet and react,
853 leading to a pronounced increase in the yield stress and plastic viscosity. On the other hand, the “ball
854 bearing” effect of this spherical ultra-fine powder (the passing rate of 0.01mm is 93% for SF, while
855 18% passing for FA) could play a role as lubricators [40, 75]. Below this critical content, the
856 lubricating effect of SF was dominant due to spherical particles. In a recent study, ultra-high
857 performance concrete based on alkali-activated slag with a very low w/b ratio of 0.175 retained good
858 workability by incorporating with 12.5 wt.% SF [97]. Similarly, Liu et al. [98] reported that the
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859 workability of alkali-activated ultra-high strength concrete increased when used less than 10 wt.% SF,
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860 since the lubricating effect of SF was more important in this case.
861
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It is well understood that a high thixotropy characterized by shear thinning and large viscosity
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862 recovery is more favorable for printable materials. Fig. 21 illustrates the viscosity recovery of AAS
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863 system with different amounts of thermal treated nanoclay (NC) [99]. It shows that NC content has
864 little effect on the initial apparent viscosity, but more NC addition yields larger viscosity recovery as
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865 a result of a more rigid AAS through the flocculation effect of clay. As shown in Fig. 22, the initial
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866 static yield stress of mixtures with 0.2% NC was around triple that of NC free mixtures. This
867 indicates that the flocculation effect of NC is far greater than that of the plasticizing and
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869 significant static yield stress. It is important to note that structural rebuilding rate (the rate of change
870 of static yield stress with time) is not sensitive to the presence of NC. Steel slag (SS) is a
871 metallurgical slag containing a large number of low reactive or inert ingredients and its pozzolanic
872 reactivity is low [100]. Increasing the replacement ratio of SS in AAS-based 3D printing resulted in
873 the reduction of thixotropy [48]. Raising SS content reduces the degree of hydration, and therefore
874 the connection between particles is weakened due to fewer intial gels formed after mixing, thus
875 reducing the reversible connection of particles [48]. Besides, the addition of SS reduced the plastic
876 viscosity of AAM due to the smaller specific surface area of SS [101].
877
878
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879 Fig. 21. Effect of the nanoclay (NC) on the viscosity recovery of 3D printing-AAS mixtures [99].
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880
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881 Fig. 22. Effect of the nanoclay (NC) dosage on the apparent viscosity and static yield stress of 3D printing-AAS
883
885 The addition of a proper amount of inert mineral additions, such as limestone (LS) powder, can
886 improve rheological properties by working as fillers to optimize the particle packing model of blend
887 system, and more water for lubrication. This can compensate for the negative effects of high specific
888 surface area and nucleation effect. According to the study by Xiang et al. [38], the incorporation of 5
889 wt.%-20 wt.% LS powder in sodium silicate-activated slag-fly ash blended grout did not alter the
890 rheology model (Bingham model), but showed a positive effect on reducing yield stress and plastic
891 viscosity (Fig. 23), especially for the grouts activated by solid sodium silicate. As shown in Fig. 24,
892 the particle size range and d50 of LS are lower than those of slag and fly ash. To a certain extent, LS
893 can therefore play a filling role and reduce the wetting water demand. Similarly, to modify the very
894 sticky AAFA binders for 3D printing purpose, Alghamdi et al. [102] used 15 wt.%-30 wt.%
895 limestone powder (d50 =1.5 μm) to replace fly ash (d50 =17.9 μm). As expected, a partial
896 replacement by limestone powder can effectively address this issue and improve print quality, due to
897 the consistency and water retention. Moreover, it was [29] also found that a similar positive effect
898 could be achieved in sodium silicate-activated MK grout by replacing MK with different percentages
899 of Fuller-fine sand powders (by10, 20, 30 and 40 wt.%). For example, in the sample group
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900 synthesized with 70 wt.% MK (specific surface area=16646 m2/kg) and 30 wt.% Fuller-fine sand
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901 (specific surface area=8886 m2/kg), the yield stress was reduced by 73% at the first shear cycle.
902
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However, it should be noted that adding different volume fraction (10%, 30% and 60 wt.%) of fine
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903 silica sand as filler to Na-silicate based MK pastes caused an increase in viscosity, but less than if the
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904 water content of pastes was reduced to obtain the same solid volume fraction [134].
905
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906
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907
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908 Fig. 23. The 27 min yield stress (a) and plastic viscosity (b) of the alkali-activated slag-fly ash (AASF) grouts
909
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using liquid waterglass and solid waterglass as activator, after adding 0-20 wt.% limestone (LS) [38].
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910
911 Fig. 24. Particle size distribution of slag, fly ash and limestone powder [38].
912
914 Currently, most research efforts are being focused on the rheology AAM paste while only very few
915 studies regarding the rheology of AAM mortar/concretes have been reported. For AAMs paste,
916 Bingham model is normally recommended to describe the rheological behavior of NaOH
917 activated-pastes, and H-B model is more suitable for sodium silicate-activated pastes [19, 41].
918 However, for alkali-activated mortar/concrete, Bingham model suits both two systems and this
919 behavior is similar to PC based mortar/concrete [20, 31]. Furthermore, compared with PC mortars, it
920 was reported that the workability of both alkali-activated fly ash and alkali-activated slag mortars
921 was more sensitive to changes of liquid/solid ratio [31]. You et al. [72] found that using copper slag
922 (CS) as fine aggregate to replace natural sand (NS) could alter rheological characteristic of the
923 alkali-activated fly ash-slag mortar. It was observed that a low replacement by 20% and 40% (by
924 volume) CS resulted in higher yield stress and consistency, due to the characterics of CS by more
925 irregular shape and containing higher amounts of fine powders [103]. Higher replacement (60%) led
926 to undesiable rheological responses, such as undergoing segregation and bleeding, which might
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927 thanks to a relatively higher density of CS than NS [104].
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928 8. Effect of fibers on rheology of AAMs -p
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929 Though AAMs have been shown to possess more compact microstructure than PCMs in numerous
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930 literature, and good mechanical properties, the large shrinkage property, particularly for sodium
931 silicate activated systems, remains a big challenge, particularly for potential application in aggressive
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932 environments. This is because excessive shrinkage can cause microcracks. Therefore, in order to
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933 address this problem, adding fibers to AAMs becomes an approach and this leads to recent
934 innovation of high-performance and ultra-high-performance AAM concrete (UHPC) have been
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935 conducted in recent years. As expected, the flowability of AAM-based UHPC decreased as steel fiber
936 volume fractions increased from 1%, 2% and 3% [98, 105]. The mixtures with hooked-end fiber
937 showed the best fluidity at high fiber content while the effect of fiber shapes was negligible at low
938 fiber content (Fig. 25). Moreover, Liu et al. [105] investigated effects of various aspect ratios
939 (length/diameter: 6/0.12, 8/0.12,13/0.12, 13/0.2) of straight steel fiber on the flowability. They
940 reported that the aspect ratio of 6/0.12 is the most optimal choice to ensure good flowability when
941 the steel fiber volume fraction increased to 3% (Fig. 26). The increase of the polyvinyl alcohol (PVA)
942 fiber volume also can give rise to high viscosity and yield stress of the AAS composite due to its
943 poor dispersibility. Even so, Choi et al. [106] have successfully produced AAS based-composite with
944 high ductility, low plastic viscosity and yield stress, at the proportion of w/b of 0.4, superplasticizer
945 of 0.27% and PVA fibers of 1.3 vol.%.
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947
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Fig. 25. Flowability of fresh AAM-based UHPC with different steel fibers [105]. Note: “D&L” means “diameter
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949 and length”.
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950
951 Fig. 26. Flowability of fresh AAM-based UHPC with different aspect ratios of straight steel fibers [105].
952
955 This paper has reviewed the progresses in the the rheology of AAMs influenced by composition
956 factors including activators, precursors, admixtures and additions. Based on these discussions, the
958 1) Current models for PCMs can also describe the rheological behavior of AAMs though there
959 is suitability difference for various systems. The type of activator seems to be the
960 predominant factor that control the rheological model. Generally, Bingham model is
961 recommended for NaOH-activated pastes, while H-B model suits better the sodium
962 silicate-activated pastes. And other component factors such as precursors and chemical
963 admixtures also have important effects on rheological parameters, for example, Na-silicate
964 activated fly ash pastes behaved like a Bingham fluid in some reports, while the rheological
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965 behavior of a fly ash-slag composite was more consistent with H-B model.
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966 2) The polymerization status of silicate species from activator solution and their adsorption
967
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mechanism on precursor surface plays an important role affecting rheological properties of
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968 AAMs. Furthermore, due to the different ion sizes, Na-based activators usually induce
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969 higher yield stress, higher viscosity and faster viscoelastic evolution of suspensions
970 compared to K-based activators. Silicates-based activators at proper doses can have an
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972 (modulus and Na2O%), which can reverse the trend of rheological properties by affecting
974 3) The physical properties of precursors affect their surface water absorption and packing
975 density, whereas the chemical properties change dissolution behavior of precursor particles
976 and types of precipitated gels, both altering rheology of AAMs. In alkali-activated blended
977 systems, the content of precursor with high specific surface area (such as MK) is usually the
978 predominant factor that increases the yield stress and plastic viscosity.
979 4) Nowadays most of the common chemical admixtures for PCMs show lower dispersion
980 efficiency in AAMs, which can be explained by three aspects: chemical stability in the
981 extremely alkaline environment, the solubility in alkaline media, and the competitive
982 adsorption between the anionic species of activators and anionic chemical admixtures. All
983 these aspects depend on the rational design of polymers molecular structure and charge. A
984 few candidates show effectiveness for some specific systems: HPEG PCEs with high
985 anionicity, high molecular weight and short side chain length showed a good dispersion in
987 5) The addition of inert mineral additions, such as fine sand and limestone power, have
988 exhibited a positive effect on improving rheological properties due to better particle dense
989 packing model, which can compensate for the negative effects of high specific surface area
990 and nucleation effect. On the other hand, the impact of reactive mineral additions on the
991 rheology of AAMs is complex, depending on their physicochemical characteristics and the
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993 6) Bingham model could well describe the rheology behavior of AAMs mortar/concrete.
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994 Furthermore, the flowability of AAMs mortars is proportional to liquid/solid ratio and
995
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significantly affected by the type of aggregate. For fibre reinforced AAMs, like in PCMs,
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996 the shape and aspect ratio of fiber are two vital factors.
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998 Although a great effort has been made in the field, there is still a large gap between recent progress
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999 and full understanding of rheology of AAMs and facilitation of engineering application. In future
1001 1) More in-depth studies on the relationship between the composition factors and inter-particle
1002 forces, as well as hydration kinetics in the AAMs. This will provide a deeper understanding
1003 of the interaction mechanisms and a full picture of effects of various components.
1004 2) More efforts should be paid with regard to some research gaps and limited research,
1005 including the way of adding activator, NaOH-MK based systems or systems applying a
1007 3) Robust formulations and relevant chemicals to meet rheological and mechanical
1008 requirements of AAMs. For instance, the development of organic plasticizers tailored for
1009 AAMs or the appropriate addition of inorganic plasticizers to improve the poor workability
1012 concrete study is limited, especially the effect of fibers and additives on rheology.
1013 Establishing empirical formulas to quantitatively describe the relationship between these
1014 materials and the rheological properties of AAMs are necessary, and thus promotes
1016
1017 Acknowledgements
1018 The authors are grateful to the financial support by the National Natural Science Foundation of
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1019 China projects 51878263, U 2001225 and 51638008.
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1021 References
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1024 [2] C. Shi, D. Roy, P. Krivenko, Alkali-activated cements and concretes, CRC press, 2003.
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1025 [3] P. Chindaprasirt, T. Chareerat, V. Sirivivatnanon, Workability and strength of coarse high calcium
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1030 gel chemistry in advancing geopolymer technology, Chem. Eng. Res. Des. 83 (2005) 853-860.
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1034 [7] C. Shi, Characteristics and cementitious properties of ladle slag fines from steel production, Cem.
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1037 Res. 78 (2015) 110-125.
1038 [9] Z. Zhang, Y. Zhu, T. Yang, L. Li, H. Zhu, H. Wang, Conversion of local industrial wastes into
1039 greener cement through geopolymer technology: A case study of high-magnesium nickel slag, J.
1041 [10] D.M. Roy, W. Jiang, M.R. Silsbee, Chloride diffusion in ordinary, blended, and alkali-activated
1042 cement pastes and its relation to other properties, Cem. Concr. Res. 30 (2000) 1879-1884.
1043 [11] E. Douglas, A. Bilodeau, V.M. Malhotra, Properties and durability of alkali-activated slag
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Statement of Conflict of Interest
We have no conflict financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
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