Construction and Building Materials 307 (2021) 124761

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Construction and Building Materials

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Rheological behavior & modeling of calcined kaolin-Portland cements

Brandon Lorentz a, *, Natallia Shanahan b, A. Zayed b
a
Department of Chemical and Biomedical Engineering, University of South Florida, 4202 E. Fowler Ave, Tampa, FL 33612, USA
b
Department of Civil and Environmental Engineering, University of South Florida, 4202 E. Fowler Ave, Tampa, FL 33620, USA

A R T I C L E I N F O A B S T R A C T

Keywords: Low quality kaolins (LQK) were used as supplementary cementitious materials to investigate their influence on
Low quality kaolin paste rheological performance. Flow properties incorporating 20 wt% calcined clay with/without fine aggregate
Calcined clay were determined. Flow properties were significantly affected by metakaolin content rather than material particle
Rheological modeling
size, surface area or porosity. Accurately analyzing paste rheology following the Reiner-Riwlin procedure allows
Colloidal stability
Clay particle morphology
for the construction of a linear yield stress model based on all solids’ Particle size distribution (PSD) and raw LQK
kaolinite content. Models of this sort offer insight for mix design addressing the negative rheological influences
caused by LQK with mineralogical and microstructural heterogeneity.

1. Introduction the rheology of fresh cementitious systems are governed by their

The use of Low quality kaolins (LQK) as precursors for Supplemen­
tary cementitious materials (SCM) has gained significant interest in
recent years. Modern studies in countries including Argentina, Cuba,
Iran, India, Switzerland and Turkey have revealed that uncalcined LQK
containing as low as 30% kaolinite by mass can produce sustainable and
effective SCM on calcination [1–7]. In particular to Florida, LQK is
highly feasible as an alternative to fly ash where there are concerns with
its unsustainable supply as a performance enhancing SCM [8,9]. The
first part of this study showed that Central Florida contains a number of
raw LQK sources, which may produce suitable SCM upon calcination
[10]. It is established that structural performance of cementitious sys­
tems incorporating calcined LQK is high; however, research detailing
these systems’ flow behavior is sparse [11–13].
The rheological literature available on calcined clay cements has
predominantly focused on the flow behavior of cementitious mixtures
containing Metakaolin (MK), made from a precursor pure, high-quality,
kaolinite containing clay. It has been established that greater inclusions
of MK lead to reduced workability [12–20]. The authors attribute the
poor rheological performance of MK blended cements to the high surface
area of MK, platy particle geometry and Lewis basic character having an
affinity to adsorb water and flocculate with pore solution ions and
cement hydrates. Thus, greater MK content causes the cementitious
system to have poorer solid packing and colloidal stability when
compared to a cement system. This follows the fundamental ideologies
of Banfill, Hattori and Izumi and Talero et al. [21–24] who propose that
colloidal stability where the mechanisms of reversible coagulation and
flocculation of components are prevalent. Cassagnabère et al. [17]
published a comprehensive research article revealing that aside from
MK content, mortar rheology is affected by MK particle morphology,
surface area and porosity. The authors observed that mortar yield stress
and viscosity increased with the addition of greater quantities of platy
and elongated MK particles that are controlled by the nature and content
of clay impurities [17]. This influence is similarly expected when using
LQK, but mineralogy and structural disorder including isomorphic
substitutions vary widely from that found in MK. This heterogeneity
influences clay morphology and Lewis basic activity, which in turn is
influential on system rheology. Yet, the physical and mineralogical ef­
fects of naturally impure calcined LQK on system rheology have not been
addressed.
The most commonly used standardized techniques for analyzing the
flow performance of fresh cementitious systems is limited to slump and
the flow table which are simple and reliable tests [25,26]. Rheological
tools have gained much attention in modern research for accurately
evaluating the effects of various constituents and mixture proportions on
hydration kinetics, cement-admixture-aggregate interactions, and opti­
mizing flow performance. These parameters dictate system pumpability,
formwork filling and pressure decay, consolidation and self-compaction,
which are vital properties for industrial applications. However, the
published literature that has addressed the rheological performance of
calcined clay cementitious systems is limited and has ambiguity. Studies
to date do not commonly analyze rheological performance using raw

* Corresponding author.
E-mail address: bxl@usf.edu (B. Lorentz).

https://doi.org/10.1016/j.conbuildmat.2021.124761
Received 3 March 2021; Received in revised form 30 August 2021; Accepted 31 August 2021
Available online 24 September 2021
0950-0618/Published by Elsevier Ltd.
B. Lorentz et al.
Fig. 1. Photographs of Florida LQK a) A, b) F, c) G and d) D.
rheometer data, such as angular velocity and torque, and do not exploit
analytical fluid momentum conservation equations for quantifying fluid
properties, namely yield stress and viscosity [18,27–37]. One reason for
this is due to the complexity of cementitious systems’ rheological
behavior, which is highly dependent on the measurement techniques
and methods of data interpretation. These complexities arise as a direct
result of the rheometer’s programmed mathematical limitations, being
geometry dependent, and on the intrinsic properties of cementitious
systems such as thixotropy, structural breakdown, particle segregation,
yield stress, plug flow and hydration reactions [38,39]. The majority of
rheological studies make use of the tools provided as a black box without
consideration of the possible errors due to these factors [38,39]. Wal­
levik et al. [38] state that “the only 2 rheometer geometries that offer
analytical transformation equations that are suitable for cement-based
materials are the concentric cylinders and the parallel rotating plates”.
All other non-conventional geometries result in fluid profiles and sub­
sequent transformation equations without analytical solutions, offering
only an approximation of the true rheological behavior. An accurate and
widely known method for assessing the rheological behavior of
cementitious systems using concentric cylinders is the Reiner-Riwlin
procedure. The raw torque and angular velocity data recorded from
the rheometer is used to determine system fluid properties by fitting to
an integrated fluid model. Since most cementitious rheological studies
overlook the more complex methods of data analysis and typically use
the rheometer’s program, rheological behavior is not absolute. Further
rheological study with calcined clay cements making use of the more
rigorous and accurate data analysis techniques is needed for detailing
the flow controlling parameters. The current study aims to provide an
insight into the rheological behavior of cementitious mixtures incorpo­
rating calcined LQK by using clays with varying kaolinite contents ob­
tained across the state of Florida [10]. Their mineralogy posed
promising as potential materials for calcination and use in concrete as
SCMs. After calcination, these calcined clays are expected to have a
negative influence on concrete and mortar workability as supported by
studies on mixtures incorporating MK [11–13,15–20]. The current study
examines the influence of calcined Florida LQK on paste’s rheological
performance using rotational rheometry. The underlying parameters
controlling flow behavior are detailed using physical, chemical and
electro-chemical material characterization techniques. The results ob­
tained provide for unaddressed research on the rheological influence of
calcined LQK considering their heterogeneous material properties.
Furthermore, the use of accurate analytical procedures for interpreting
rheometry data leads to the construction of a yield stress model, offering
rheological insight for mixture design.
2. Materials and methods
Seven LQK samples were used in this study. Four samples (A, D, F and
G) were used to develop a yield stress prediction model for ordinary
Portland cement (OPC)-calcined LQK mixtures and threes additional
samples (1, 2 and 3) were used for model validation. Raw LQK samples
2
Construction and Building Materials 307 (2021) 124761
A, D, F and G were obtained from clay mines in Central Florida regis­
tered by Florida’s Department of Environmental Protection Agency’s
Integrated Habitat Network (IHN) [40]. The IHN considers these sam­
ples as clay for containing fine-sized phyllosilicate minerals including
1:1 structured clay minerals such as those of the kaolinite group:
kaolinite, dickite and nacrite in addition to absorbable 2:1 structured
clay minerals such as illite and those of the smectite group [41–43].
However, despite the IHN’s classification of these LQK as clays, a pre­
vious study showed that they coexist in mines with large quantities of
sand and small quantities of metal oxides, hydroxides and alumino-
silicate gels [10]. Material finer than 45 μm (clay fraction) has poten­
tial to have pozzolanic properties. Clay fraction mineralogy including
structural disorder was characterized in the previous study using a
multi-technique procedure proposed using X-ray fluorescence (XRF),
Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD),
and Thermogravimetric analysis (TGA) [10]. Although ten raw LQK
were characterized in the previous study, four samples were selected for
this investigation to represent a range of kaolinite contents observed in
the raw clays in Central Florida. The kaolinite content of clay fractions
A, F, G and D was determined by TGA to be 94, 86, 80, and 74 wt%,
respectively. The uncalcined clay fractions are shown in Fig. 1 and ar­
ranged by decreasing kaolinite content and increasing structural disor­
der from left to right.
The elemental oxide composition of the selected clay fractions re­
ported in the previous study [10] and of Type I/II Portland cement (PC)
used in all paste mixtures are provided in Appendix A (Table A-1) for the
reader’s convenience. All clay fraction samples met the ASTM C618 [44]
requirements for class N natural pozzolans.
Characterization of LQK in this study focused on their particle size
characteristics. The LQK were separated into the clay fraction (finer than
45 μm) and the fine aggregate fraction (coarser than 45 μm) by wet-
sieving through sieve No. 325 (45 μm mesh) in totality following
ASTM C117 [45] except sieve No. 325 was used instead of No. 200 (75
μm mesh). Both the passing and retained fractions were collected and
dried in a laboratory box furnace, model BF51894C-1, manufactured by
Lindberg/MPH at 110 ◦ C until a constant mass was achieved. Clay
fractions were ground in a rotary ball mill until passing sieve No. 100
(150 µm) to simulate the processing of these materials when used as
SCM. Their particle morphologies and surface characteristics were then
imaged using a field emission Hitachi S800 Scanning electron micro­
scope (SEM).
The two raw and one calcined LQK used for model validation were
obtained from various sources and ranged in metakaolin content and
filler mineralogy (quartz and metal oxides). Raw LQK samples 1 and 2
were obtained from Georgia and Central Florida, respectively. Calcina­
tion of these samples is discussed below. Calcined LQK sample 3 was
calcined in a rotary cement kiln at a pilot clay calcination plant in
Columbia at a temperature of 850 ◦ C. The kaolinite content of LQK 1 and
2 was determined to be 89% and 38%, respectively, using XRD. Kaolinite
content of LQK 3 was estimated from XRF analysis to be 50%.
Clay fractions A, F, G and D and raw LQK sample 1 were calcined for
B. Lorentz et al. Construction and Building Materials 307 (2021) 124761

1 h in ceramic crucibles in the box furnace at 600 ◦ C. LQK was calcined Table 1
for 1 h at 850 ◦ C. After calcination the samples were cooled to room Helical Ribbon Rheology Mix Designs.
temperature under ambient conditions, and their crystallinity and Mix ID PC (wt. Calcined Clay Fine Aggregate Fraction Clay:
mineralogy were assessed using XRD to ensure dehydroxylation and %) (wt.%) (wt.%) Sand
complete conversion of kaolinite to metakaolin. XRD scans were Control 100 – – –
collected with a Phillips X’Pert PW3040 Pro diffractometer equipped B20 80 20 – –
with X’Celerator Scientific detector and a Cu-Kα x-ray source. Tension T19 80 19 1 19:1
and current were set to 45 kV and 40 mA, respectively; 5 mm divergence T18 80 18 2 9:1
T16 80 16 4 4:1
and anti-scatter slits were used in the automatic mode. Scans were T20 76 20 4 5:1
collected in the 4–70◦ (2Θ) angular range, and the sample was rotated at
30 rpm during data collection. The external standard method with
corundum was selected for determining the amorphous/unidentified
Table 2
content of the calcined clay samples. The mass absorption coefficient
Rheology shearing routines.
(MAC) of corundum was 30.91 cm2/g. MAC values for the clays were
calculated based on their respective chemical oxide compositions (Ap­ Helical Ribbon Concentric Cylinders

pendix A). Phase identification and Rietveld refinement were performed
using the Panalytical Highscore Pus 4.5 software. The following pa­
rameters were refined during Rietveld analysis in the current study:
scale factors, lattice parameters, zero shift, 5th order regular polynomial
for background fitting, preferred orientation for kaolinite, dickite and
nacrite structures. A comprehensive XRD, XRF and Fourier Transform
Infrared Analysis of kaolinite crystallinity including analysis of iron
isomorphic substitution and both qualitative and quantitative analysis
of structural disorder was determined following the technique proposed
by Vaculikova et al. (2011) [10,46]. The structural disorder for the 4
LQK used in this study was been detailed in Appendix B.
The Particle size distribution (PSD) of the ground calcined clays and
PC was determined using HORIBA’s LA-950 laser scattering particle size
analyzer utilizing the wet method. The dispersing liquids used for PC
and calcined clays were ethanol and deionized water, respectively.
Approximately 250 mL of liquid and 1 g of dry sample was used for
analysis. The tests were conducted in triplicate, and the averaged dis­
tributions, mean particle size and span (Eq. (1)) are reported here.
D90 − D10
Span = (1)
D50
where D90, D50, and D10 are the particle sizes where 90, 50, and 10% of
all particles are smaller than using a volume-based distribution.
A combined PSD was calculated for each calcined clay-PC mixture
using the following equation:
∑
n
yb = yi xi (2)
i=0
where yb is the property of interest, yi is the measured property for ith
component of the mixture, xi is the fraction of the ith component, and n
is the total number of components in the mixture. For a binary mixture n
= 2, for a ternary mixture n = 3. A fitted parameter n, which describes
the breadth of a PSD, was then determined for mixture using the Rosin-
Rammler model as described in [47].
The surface area and porosity of PC and calcined clay fractions A, D,
F and G were assessed using Quantachrome’s Autosorb-1 instrument
with nitrogen as the adsorbate. The samples were outgassed under
vacuum at 110C immediately prior to analysis in order to remove any
moisture or contaminants from the sample surface. Specific surface
areas (SSA) of calcined clays were computed using the multi-point
Brunauer-Emmett-Teller (BET) technique [48,49]. Sample porosity
was assessed using the Barrett-Joyner-Halenda (BJH) method making
use of the desorption isotherm at relative pressures between 0.4 and
0.967 to assess mesoporosity [49,50].
Fresh paste rheological behavior of calcined clay-PC mixtures was
assessed using a TA Instrument Discovery hybrid rotational rheometer,
model HR-2. Preliminary rheological studies were conducted using a
helical ribbon geometry where a constant mass of solids and water-to-
solids ratio of 50 g and 0.5, respectively, were used such that the total
volume was kept nearly constant for all mix designs and workability was
1. 2 min. shear at 50 s− 1 1. Sample conditioning at 10 s− 1 for 10 s
2. 2 min. rest 2. Shear at 70 s− 1 for 1 min.
1
3. Increasing strain sweep 0.5–50 s− 3. Decreasing strain sweep 70–0.1 s− 1
sufficient for rotational rheometry. Six mixtures were analyzed with the
helical ribbon geometry: a neat cement paste (Control), a binary blend
using a 20% cement replacement with ground calcined clay (B20), three
ternary blends where 20% of cement mass was replaced with variable
amounts of calcined clay and its respective sand fraction (T-19, T-18 and
T-16) and one ternary blend (T-20) where 20% of cement mass was
replaced by calcined clay and an additional 4 % of cement mass was
replaced by the sand fraction (Table 1). The T-20 mix was used to make
direct comparisons with B-20 and T-16 in order to evaluate the effect of
sand fraction on rheology of the cement-calcined clay mixtures.
These mixtures were used to infer which system parameters control
rheological behavior but were limited by the use of a complex and non-
analytical procedure for data transformation, i.e. using the helical rib­
bon stress–strain fluid profile. In an effort to avoid these errors and
attempt rheological modeling, studies were also conducted using the
concentric cylinders geometry following the Reiner-Riwlin procedure
[38,51].
The mixtures used for model development were designed identically
to the B20 pastes (Table 1) with the exception that a homogenous and
standardized Ottawa sand (OS) passing sieve No. 30 was added to in­
crease system mass in intervals of 5 wt% up to 30 wt% without adjust­
ment to the proportions of cementitious materials. The OS was first
passed through sieve No. 30 to avoid rheometry measurement artifacts
due to particle sizes larger than 10% of the programmed geometry gap.
OS was implemented in these mixtures as a solid addition to observe and
isolate the rheological influences due to particle filler effects and
calcined clay content. The rheological model developed is purely
dependent on these 2 individual parameters and was validated using 3
independent pastes prepared with 20 wt% calcined clay-PC blends with
LQK 1, 2, and 3 without separation of their clay and sand fractions.
Pastes containing calcined clay 1 may be considered as binary systems,
most closely related in mineralogy to the designed B20 pastes. The
pastes containing calcined LQK samples 2 and 3 may be considered as
ternary systems with a significant portion of the LQK being present as
filler materials. All fresh pastes under rheological study were prepared
by mixing in an IKA WERKE low shear mixer for 3 min. Immediately
after mixing the sample was transferred into the rheometer testing cup
and isothermally at 23 ◦ C exposed to programmed shearing routine
(Table 2).
The pseudoplastic flow behavior of cementitious systems has been
described using a variety of fluid models with a comprehensive review
presented by Talero et al. [23]. However, very commonly they are
treated as Bingham plastic fluids exhibiting a characteristic yield stress
and a linear viscoelastic behavior when subject to shear
[11,21,39,52,53]. For both rheology geometries, the linear Bingham
fluid model (Eq. (3)) was fitted to each mixture’s collected stress–strain

3
B. Lorentz et al. Construction and Building Materials 307 (2021) 124761

Fig. 2. SEM images of Florida kaolins a) A, b) F, c) G and d) D.

profile.
90 0.4
τ = τ 0 + μγ (3) 80 0.35

Pore Volume (cm3/g)

70 0.3

BET SSA (m2/g)

where τ is an applied shear stress, τ0 is the fluid’s characteristic yield 60 0.25
stress, µ is the fluid’s plastic viscosity and γ is an applied shear rate. The 50
0.2
fitted constants, yield stress and viscosity, were found using the linear 40
R² = 0.8394 0.15
30
viscoelastic region of the stress–strain profile and reported in this study 0.1
20
as characteristic system fluid properties. It is emphasized that when R² = 0.7603 0.05
10
computing fluid properties using the Reiner-Riwlin procedure, rheom­ 0 0
eter torque and angular velocity profiles should be fitted to the strain 70 75 80 85 90 95 100
rate integrated Bingham fluid model (Eq. (4)) [38,51]. Kaolinite content (wt.%)
R BET SSA Pore Volume
4πLbob lnRbob
cup
4πLbob μ
T=[ ]τ 0 + [ ] (4) Linear (BET SSA) Linear (Pore Volume)
1 1 1 1
R2bob
− R2cup R2bob
− R2cup Fig. 3. BET SSA and pore volume of calcined clays.

where T is the measure torque, Lbob and Rbob are the length and radius of
the inner cylinder bob, Rcup is the radius of the outer cylindrical cup,
τ0 and µ are the fitted system yield stress and viscosity parameters. No
such data transformation techniques are possible using the helical rib­
bon geometry, and a compromise in using the rheometer’s programmed
stress–strain output must be made. Bingham fluid properties reported in
this study for all mixtures were computed using an average of three
replicated mixtures.
The colloidal stability of the calcined clay pastes used for helical
ribbon rheometry was analyzed using electro-kinetic and packing den­
sity measurements. A Malvern Instrument nano-series Zetasizer was
used to measure the zeta potential following Smoluchowski’s expression
and ionic mobility of these pastes. Methods used for paste analysis were
similar to those reported by Safi et al. [19] and Talero et al. [24,54]
where fresh paste as prepared for rheological study was analyzed in a
diluted aqueous solution. Paste packing density was measured using
methods proposed by Lecomte et al. [55] using the water required for
normal consistency (W.N.C.) as described in ASTM C187 [56]. This
model assumes the free voids between particles are full of water and
does not take into account any entrained air [57].
3. Results and discussion
3.1. Uncalcined clay fraction characterization
SEM images of sample A, which had the highest kaolinite content,
showed the pseudo-hexagonal, platy, and layered stacking fault particle
geometry of the kaolinite minerals (Fig. 2a). The rest of the clays with
lower kaolinite contents, greater iron and amorphous content show less
of a layered structure if at all and present greater degrees of agglomer­
ation and particle coarseness (Fig. 2b-d). Iron oxides have been reported
to exist in natural kaolin deposits not only as discrete phases but also as
deposited hematite and goethite coatings on kaolin particles which
contributes to particle coarseness [58–60]. According to Cassagnabère
et al. [17], it is expected that the more coarse, rounded, and structurally
disordered kaolin particles will facilitate system flow more readily than
the higher quality clays. This suggests calcined clay A will have a more
negative influence on paste rheology compared to the more coarse and
rounded samples D, F and G. It should be noted that the SEM image of
clay D was taken at a lower magnification than the other samples due to
issues with resolution attributed to its higher Fe2O3 content distorting
the imaging electron beam. Although these images were taken of the
pre-calcined clays, their particle shapes and size distributions will be
similar to their calcined counterparts if calcination is performed at a
temperature ≤ 600 ◦ C where no sintering takes place [61–64].
3.2. Calcined clay fraction characterization
The BET SSA of the calcined clays were well above that of the PC (0.4
m2/g) ranging from 25–80 m2/g with the highest kaolinite content clay
(A) being at the lower bound. The values of SSA and pore volume
appeared to decrease with increasing kaolinite content (Fig. 3).
Although relatively high coefficients of determination (R2 values) were
observed between these parameters and uncalcined kaolinite content,
sample D with the highest amount of Fe2O3 and structural disorder
(Appendix B) as determined by Lorentz et al. [10] does not appear to
follow the trend of the other clay samples. Stacking faults, isomorphic
substitution, oxide mineral coatings and auxiliary crystalline and
amorphous minerals have been shown to contribute to high SSA and
porous kaolin particles [65–72].
Higher SSA SCMs are typically reported to reduce system fluidity
[11,16–20,47,73]. In addition, increased particle porosity has been
shown to increase water demand and is also expected to have a negative
effect on flow [74,75]. SSA and porosity values suggests that clay D
would contribute most negatively to paste flow, which contradicts no­
tions made prior based on its particle morphology compared to that of A.

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B. Lorentz et al. Construction and Building Materials 307 (2021) 124761

100
90
80

Cumulative % Passing
70
60
50
40
30
20
10
0
0.1 1 10 100 1000
Diameter (μm)
A D F G PC
A FA F FA G FA D FA
Fig. 4. Cumulative PSD for PC, calcined clay fractions and LQK sand fraction (FA).

Table 3 90 0.900
PC and calcined clay mean particle size and span. 80 a)
Sample ID Mean particle size (μm) Span 70 R² = 0.9499 A 0.800
Yield Stress (Pa)

Viscosity (Pa*s)
PC 9.75 2.03
60
0.700
A 17.57 2.11 50 F
F 33.31 1.44 40 G
G 34.80 1.27
0.600
30
D 34.13 1.24 R² = 0.9128
20 D 0.500
1 61.92 2.39
2 61.95 2.76 10
3 20.64 1.81 0 0.400
70% 80% 90% 100%
Kaolinite Content (wt.%)
All calcined clay PSD were coarser than that of cement. No signifi­
Yield Stress Viscosity
cant differences were observed in the PSD and mean particle size of
calcined clays D, F and G, while A was notably finer and is therefore 90 0.8
expected to have a more negative effect on rheology (Fig. 4, Table 3). 80 b) 0.75
It is widely reported that as SCM PSD becomes broader, packing 70 0.7
Yield stress (Pa)

Viscosity (Pa*s)
60
increases and system workability improves [64,73]. Although the PSD 0.65
50
span was highest for primary sample A, it was remarkably similar for F, 40 R² = 0.9493
0.6
G and D (Table 3). This suggests that calcined clay A should yield a more 30 0.55
workable paste than the other clays. It is clear that based on the particle 20 0.5
R² = 0.869
10 0.45
characteristics of the selected clays there are a number of parameters
0 0.4
that are expected to have contradictory effects on rheology. 0 20 40 60 80 100
BET SSA (m2/g)
3.3. Rotational rheometry Yield stress Viscosity

After assessing the mineralogy of each clay and comparing their 90 0.8
calcined counterparts’ microstructural properties (surface morphology, 80 c)
0.75
surface area, porosity, PSD), the control, binary and ternary fresh paste 70 0.7
Yield stress (Pa)

Viscosity (Pa*s)

mixtures were prepared for rheological study. A clear increase in fresh 60

0.65
paste yield stress and viscosity was observed upon replacement of PC 50
0.6
with calcined clay. This phenomenon is expected as all calcined clays 40 R² = 0.8922
0.55
exhibited SSA that were two orders of magnitude higher than that of PC, 30
20 0.5
resulting in a paste with a greater water demand. The A-B20 mixture had R² = 0.7917
10 0.45
the highest viscosity and yield stress among all the binary mixes, which
0 0.4
may be attributed in part to the finer PSD of calcined A relative to the 0 0.1 0.2 0.3 0.4
other calcined clays (Fig. 4). While the PSD of calcined clays F, G, and D Pore volume (cm3/g)
were nearly identical to one another (Fig. 4), clear differences were
observed in their flow parameters. Higher SSA and porosity clay frac­ Yield stress Viscosity
tions with lower PSD span values yield a proportional reduction in paste Fig. 5. Binary paste yield stress and viscosity with a) LQK kaolin content, b)
fluid properties, contradicting their expected influence as SCMs calcined clay SSA, c) calcined clay pore volume.
following the published literature [11,16–20,47,73]. The yield stress

5
B. Lorentz et al. Construction and Building Materials 307 (2021) 124761

90
R² = 0.9945
80

Paste Yield Stress (Pa)

70 R² = 0.9695
R² = 0.9499
60 R² = 0.9679
50
40
30
20
10
0
0.55 0.65 0.75 0.85 0.95
Kaolinite Content (wt.%)
B20 T19 T18 T16
Fig. 6. B20, T19, T18, T16 yield stress with LQK kaolin content (D, G, F, A from left to right).

and viscosity of binary pastes were directly proportional to the kaolinite

0.530
content of the uncalcined clay which is equivalent to the metakaolin D
content of the calcined clay, SSA and pore volume of their respective 0.525 R² = 0.9658
LQK (Fig. 5). The yield stress and viscosity increased with increasing
Packing Density, Ø
0.520 R² = 0.9988
kaolinite content, decreasing SSA and decreasing pore volume. These D
parameters could not be individually isolated in this study. However, the 0.515 G
G
highest R2 values were observed between yield stress and kaolinite
F
content and viscosity and kaolinite content (Fig. 5a). 0.510 F
The increase in yield stress and viscosity with higher kaolinite con­ 0.505
tent in the uncalcined LQK precursors was not surprising as published A A
research has conveyed higher MK content leads to reduced paste fluid 0.500
50 60 70 80 90 100
properties [13,15,16,18,20,76]. The decrease in yield stress and vis­
cosity with increasing porosity and SSA is contrary to the expected Kaolinite Content (wt.%)
trends, which indicates that the rheological parameters for the binary B20 T16
pastes are dictated by the quantity of metakaolin in a given calcined
Fig. 7. Packing density relationship with LQK kaolinite content.
clay, outweighing the expected effects of SSA and porosity. Broadness of
the PSD also does not appear to influence rheology of cement-calcined
inclusion of fine aggregate. These packing effects facilitate the flow of
kaolin blends as clay A with the highest span value had the highest
fresh paste by breaking down agglomerated particles, enhancing the
yield stress and the rest of the clay had variable yield stress and viscosity
lubricating effect of water during mixing and improving system colloidal
values despite similar span values. Unclear relationships between the
stability [77,78]. However, these electrostatic and solid packing effects
PSD span and flow properties are attributed to confounding chemical
challenge the development of unanimous and predictive rheological
and physical interactions which are dictating system flow performance.
models applicable to calcined LQK-PC pastes.
Calcined clay replacement with fine aggregate reduced yield stress in
ternary pastes due to dilution of the kaolinite content. The highest
3.4. Packing density
decrease in yield stress was observed in T16 pastes with greater incor­
poration of fine aggregate as calcined clay replacement. It is noted that
A decreasing linear trend in packing density with increasing raw clay
the T20 pastes showed similar flow performances to those of the T19 and
kaolinite content was observed when pastes were considered individu­
T18 mix designs. Thus, replacing cement with each clay’s fine aggregate
ally (Fig. 7). A low packing density implies lower amounts of mixing
in T20 mixtures did not improve flow performance as significantly as
water acting as a lubricating fluid between solid particles resulting in
equivalent replacement of calcined clay (T16 mixtures). This is consis­
higher yield strength and viscosity [79]. This is consistent with experi­
tent with the observation that LQK kaolinite content dictates flow per­
mental results reported by Vance et al. [16] where greater MK content in
formance (Fig. 5a). Following this idea, any sand added as calcined clay
portland cement pastes caused greater degrees agglomeration and paste
replacement dilutes its reactive metakaolin content and should improve
de-watering with corresponding reductions in packing density and
paste yield stress and viscosity.
flowability [16,34,80]. It is important to note that similar to the
The yield stress and viscosity of both binary and ternary pastes were
dependence of yield stress on kaolinite content, a unanimous trend be­
proportional to the raw clay kaolinite content. However, a continuous
tween kaolinite content and all packing densities was not found. Hence,
trend was developed when only comparing pastes with a given calcined
LQK kaolinite content is insufficient to fully describe packing density of
clay and aggregate at the chosen replacement levels or when comparing
calcined low quality metakaolin-PC pastes. The bimodal packing effects
different calcined clay fractions incorporating equivalent replacement
caused by calcined clay and fine aggregate particles must be also be
levels of fine aggregate (Fig. 6). Despite the observed improvements in
considered.
flow performance, an overall direct linear relationship between
Additionally, calcined clay replacement with fine aggregate for A, F,
kaolinite content and yield stress and viscosity of all the binary and
and G pastes did not have a significant influence on packing density.
ternary pastes could not established. This limitation is attributed to the
Talero et al. [24] reported similar observations when investigating the
inability of kaolinite content to account for the unique bimodal particle
effect of a quartz filler of similar size on paste packing properties. A
packing effects caused by the differing clay particle morphologies and
maximum increase in packing density of 1.5% was observed between D-

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B. Lorentz et al. Construction and Building Materials 307 (2021) 124761

Table 4
Zeta potential and ionic mobility of paste.
Calcined Clay PC

A F G D

Mix Design B20 T16 B20 T16 B20 T16 B20 T16 Control

Zeta Potential (mV) 1.35 2 1.83 2.1 2.21 2.33 2.65 2.68 2.89
Ionic Mobility (µmcm/Vs) 0.1 0.15 0.14 0.16 0.17 0.18 0.2 0.2 0.22

3.00 0.25
0.23
R² = 0.9064

Ionic Mobility (μmcm/Vs)

2.50 D D 0.21
Zeta Potential (mV)

R² = 0.9973
G 0.19
2.00 F G
A 0.17
1.50 R² = 0.9081 F 0.15
0.13
1.00 R² = 0.9973 A
0.11
0.50 0.09
0.07
0.00 0.05
55% 65% 75% 85% 95%
Kaolin Content (wt.%)
B20 ZP T16 ZP B20 IM T16 IM
Fig. 8. B20 and T16 zeta potential and ionic mobility with LQK kaolinite content.

B20 and D-T16 pastes. It is crucial to note that determination of paste
packing density following Lecomte et al. [55] makes use of a mixture’s
water content required for normal consistency (WNC). However, the
Vicat apparatus and procedure used for WNC measurements in ASTM
C187 [56] is quite robust and limits paste packing density from being
notably influenced by the small additions of fine aggregate used in this
study.
3.5. Electro-kinetic study
All LQK pastes possessed a lower zeta potential and ionic mobility
than the control paste (Table 4). This was anticipated from trends
developed during rheological investigations and implies that the addi­
tion of calcined clay results in paste agglomeration with a reduction in
colloidal stability and workability when compared to the control. Most
interestingly, both electro-kinetic parameters in the B20 and T16 pastes
were found to be linearly proportional to LQK kaolinite content when
assessed individually (Fig. 8).
The observed trends are synonymous to those developed during
rheological and packing density investigations where a unanimous
relationship between the measured properties and kaolinite content was
not observed. This phenomenon is again attributed to the inability of the
independent variable to adequately account for the bimodal particle
packing effects caused by inclusion of calcined low quality metakaolin
and fine aggregate with varying particle morphologies. Nonetheless, an
increase in zeta potential and ionic mobility is clearly observed in binary
and ternary mix designs including calcined clays of lower kaolinite
content. Thus, as LQK metakaolin content decreases in a given mixture,
a more stable and deflocculated paste is obtained with progressively
lower viscosity and yield strength. The direct relationship between
kaolinite content of the raw clay and electro-kinetic parameters re­
inforces the notion that the enhanced Lewis basic properties of calcined
low quality metakaolin clays result in elevated levels of particle
agglomeration [11,13,15–18,20,81]. Recalling the differences in rheo­
logical performance properties of corresponding binary and ternary
mixture designs, these electro-kinetic trends reveal that each clay’s fine
aggregate not only dilutes the reactive metakaolin content in each
mixture but also aids in the breaking and dispersion of agglomerates
formed immediately after mixing. This in turn yields pastes with a more
stable colloidal suspension. A direct dependence of flow properties on
system zeta potential and ionic mobility was observed for all the pastes
(Fig. 9).
The relationships developed in Fig. 9 show a nearly linear depen­
dence of stress and viscosity on zeta potential and ionic mobility. These
results indicate that system colloidal stability is controlling the LQK-PC
paste flow properties as proposed by Banfill [21], Hattori and Izumi [22]
and Talero et al. [24] who investigated cementitious systems other than
those including calcined LQK.
Clay replacement with fine aggregate increased zeta potential and
ionic mobility in all the T16 pastes compared to B20, with the largest
effect observes with clay A. Incorporation of fine aggregate in pastes
with lower metakaolin content had a lower effect on system electro-
kinetic properties, and the effect appeared to decrease with decreasing
raw clay kaolinite content. This suggests that lower purity kaolins
contribute to rheological performance as fillers more so than reactive
colloids. Additionally, kaolinite structural disorder as analyzed using
several techniques such as XRD, and FTIR (Appendix B), increased in
LQK with lower uncalcined kaolinite content and more impurities. These
results suggest that the presence of greater amounts of impurities
correspondingly aids in the formation of kaolinite with greater struc­
tural disorder, which after calcination will not influence rheology as
strongly as a well-ordered and high purity kaolinite clay.
3.6. Yield stress model development
Raw LQK kaolinite content and all assessed calcined clay and
aggregate particle properties were insufficient in describing the differ­
ences in rheological performance of binary and ternary mix designs
using the helical ribbon. However, both electro-kinetic properties were
shown to capture the compounded influence of metakaolin content and
particle interactions of the calcined LQK pastes. Rheological models
incorporating system zeta potential are expected to be accurate but

7
B. Lorentz et al. Construction and Building Materials 307 (2021) 124761

0.8
120 a)
R² = 0.8545 0.7
B20A
Yield Stress (Pa) 100 0.6

Viscosity (Pa*s)
80 B20F T16A
B20G 0.5
T16F 0.4
60 R² = 0.9149 T16G
B20D
0.3
40 T16D
Control 0.2
20 0.1
0 0
1.20 1.70 2.20 2.70
Zeta Potential (mV)
Yield Stress Viscosity
120 0.8
b) R² = 0.8556 0.7
100
Yield Stress (Pa)

B20A

Viscosity (Pa*s)
0.6
80 B20F T16A
B20G 0.5
60 R² = 0.9159 T16F
T16G
0.4
B20D
0.3
40 T16D
Control 0.2
20
0.1
0 0
0.09 0.11 0.13 0.15 0.17 0.19 0.21 0.23
Ionic Mobility (μmcm/Vs)
Yield Stress Viscosity
Fig. 9. B20 and T16 yield stress and viscosity dependence on a) zeta potential and b) paste ionic mobility.

Table 5
Yield stress model validation.
Paste LQK ID Predicted (Pa) Experimental (Pa) Model Error (Pa)

1 14.8 15.6 − 0.8

2 10.8 9.9 0.9
3 9.9 9.2 0.7

LQK-PC mixtures.
Based on the concentric cylinder measurements, a model for paste
yield stress, τ0, was developed using the parameter n and raw clay
kaolinite content, X in wt.% (Eq. (5), Fig. 10):
τ0 = 136n + 0.78*X − 215.61 (5)

3.7. Model validation

The model was validated by using 20 wt% calcined clay-PC pastes

Fig. 10. 3D plot of model yield stress dependence on materials properties.
prepared with LQK 1–3 without separation of their fine aggregate. These
LQK ranged in kaolinite content, filler mineralogy (quartz and metal
require testing that is not normally carried out in cement and concrete
oxides) and particle characteristics, resulting in mixture characteristics
testing laboratories. A simpler model is needed that utilizes routinely
both within and outside of pastes used for the model’s development.
measured material properties to predict rheological behavior of calcined
Despite the vast mineralogical heterogeneity and particle characteristics

8
B. Lorentz et al. Construction and Building Materials 307 (2021) 124761

of these three calcined LQK, the model was validated by predicting all Table A
pastes’ yield stress to an accuracy of less than 1 Pa (Table 5). XRF elemental oxide composition of portland cement and uncalcined clay
An analysis of variance (ANOVA) including the F-test, an evaluation fractions.
of the variance of input parameters to that of the model’s residual Clay ID A D F G PC
variance, showed that both kaolinite content and n with 95% confidence Analyte wt.%
have F values over four orders of magnitude greater than their critical F-
SiO2 45.99 38.47 42.63 43.84 20.5
distribution values, which indicates that the developed model can
Al2O3 37.7 31.29 34.94 32.52 4.9
accurately predict yield stress of LQK-PC mixtures. This is a direct result Fe2O3 0.9 8.91 4.55 5.48 3.1
of employing the concentric cylinders rheometer geometry and trans­ CaO <.01 0.12 <.01 <.01 64.0
forming raw data collected into defined Bingham fluid properties using MgO 0.16 0.49 0.21 0.22 0.7
the Reiner-Riwlin procedure. It is noted that the value of n according to SO3 <.01 <.01 <.01 <.01 3.2
Na2O 0.05 0.05 0.02 0.02 -
the Rosin-Rammler model is limited to fine particles, whose value does K2O 0.24 0.23 0.12 0.3 -
not vary far from 1, and the kaolinite content of raw LQK is typical to TiO2 0.27 1.39 1.13 1.18 -
that employed in the field, ranging from 30 to 100 wt%. P2O5 0.05 1.26 0.21 0.81 -
Mn2O3 <.01 0.01 <.01 0.01 -
SrO <.01 0.16 0.04 0.23 -
Cr2O3 0.03 0.02 0.01 -
3.8. Model limitations & potential extensions
<.01
ZnO <.01 <.01 <.01 <.01 -
BaO <.01 0.09 0.01 0.16 -
The model was developed using a specifically designed experimental Total Alkali (Na2O + 0.658 K2O) 0.21 0.2 0.1 0.22 0.24
plan where an LQK content of 20 wt%, additions of a standardized fine L.O.I (950˚C) 14.17 16.6 15.39 14.41 2.2
Total 99.53 99.08 99.27 99.21 98.84
aggregate, a constant water content and no chemical admixtures were
SiO2 + Al2O3 + Fe2O3 85.6 78.7 80.3 81.8 28.5
used. This allowed for observation of quantifiable differences in yield
stress attributed to LQK kaolinite content and PSD of all solids upon the
addition of sand. Calcined clay cements used in the field are expected to
vary compared to conducted experiments with respect to the cement Table B
Kaolinite degree of disorder based on FTIR.
used, water content, clay addition level, chemical admixtures, time and
temperature of placement. Additionally, the experiments conducted Clay ID Classification by Vaculikova et al. (2011)
were performed using cement paste whereas in the field mortar and A Well-ordered
concrete designs are typically employed. Further development of the D Poorly-ordered
proposed model to incorporate more fine and coarse aggregates such as F Well-ordered
G Partially-ordered
those used in mortar and concrete would require manipulation of the
Rosin-Rammler PSD model or use of another model that allows for
particles of such size. Importantly, rheological analysis of cementitious CRediT authorship contribution statement
systems using concentric cylinders and the Reiner-Riwlin procedure may
be scaled up for application in larger concrete and mortar rheometers. Brandon Lorentz: Conceptualization, Validation, Formal analysis,
Although the flow mechanisms would become more complex, intro­ Investigation, Resources, Writing – original draft, Writing - review &
ducing measurement artefacts due to plug flow, particle migration, editing, Visualization, Supervision, Project administration. Natallia
thixotropy, and structural breakdown among others [38]. Shanahan: Conceptualization, Methodology, Validation, Formal anal­
Despite all the fore-mentioned limitations, comprehensive and ysis, Writing – original draft, Writing - review & editing, Visualization,
robust model extensions may be made to account for expected differ­ Supervision. A. Zayed: Conceptualization, Methodology, Validation,
ences in calcined LQK systems’ mix designs other than those addressed Supervision, Project administration, Funding acquisition.
in this study. Overall, the developed model offers insight into the ex­
pected yield stress of any given 20 wt% calcined LQK PC cement paste Declaration of Competing Interest
using clay with or without additions of inert filler materials. It may be
used to make decisions on how a given LQK and auxiliary minerals are The authors declare that they have no known competing financial
processed, whether ground or separated, and how much of a particularly interests or personal relationships that could have appeared to influence
sized aggregate admixture may be required to ensure that the calcined the work reported in this paper.
LQK blended cement has the desired flow properties. In turn, models
such as those reported in this study alleviate the concern of the unan­ Acknowledgments
ticipated negative rheological influences caused by calcined LQK with
vast mineralogical heterogeneity and microstructural characteristics. The University of South Florida Chemical and Biomedical Engi­
neering Department, as well as the Civil and Environmental Engineering
4. Conclusions Department is given sincere acknowledgment for contributing funds and
resources for accomplishing all the work described here-in. Dr. Kyle
The flow performance properties such as yield stress, viscosity, Riding with the University of Florida is given acknowledgment for his
packing density, zeta potential and ionic mobility of pastes incorpo­ expertise advice throughout this research and development.
rating calcined LQK were found to be mostly influenced by their raw
LQK kaolinite content rather than by their calcined particle character­ Appendix A
istics. Most significantly, this study revealed that the zeta potential and
ionic mobility of calcined LQK pastes unanimously describes rheological
performance accounting for the effects of both metakaolin content and
all solids physical bimodal interactions as filler materials. Based on these Appendix B
observations, a model based on total solids PSD and raw LQK kaolinite
content was developed to predict the yield stress of calcined LQK-PC
mixtures. This model provides a pathway for predicting flow perfor­
mance of pastes with mineralogically heterogeneous LQK.

9
B. Lorentz et al. Construction and Building Materials 307 (2021) 124761

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