Cement and Concrete Composites 103 (2019) 331–338

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Cement and Concrete Composites

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New insights from reactivity testing of supplementary cementitious T

materials
Prannoy Suranenia,∗, Amir Hajibabaeeb, Sivakumar Ramanathana, Ying Wanga, Jason Weissc
a
Civil, Architectural and Environmental Engineering, University of Miami, Coral Gables, FL, 33146, USA
b
Ozinga Ready Mix Concrete Inc, Chicago, IL, 60616, USA
c
Civil and Construction Engineering, Oregon State University, Corvallis, OR, 97331, USA

ARTICLE INFO ABSTRACT

Keywords: Tests to determine the reactivity of supplementary cementitious materials (SCMs) by using isothermal calori-
Isothermal calorimetry metry and thermogravimetric analysis have been proposed. In one such test, the heat release and calcium hy-
Thermogravimetric analysis droxide consumption of SCMs mixed with calcium hydroxide (3:1 ratio of calcium hydroxide and SCM) at 50 °C
Pozzolan in a 0.5 M potassium hydroxide environment are measured. In this study, we show the results of such testing for
Supplementary cementitious materials
a large variety of SCMs and fillers, ranging from conventional materials such as fly ash, slag, silica fume, quartz,
and limestone, to alternative materials such as calcined clays, municipal solid waste incineration fly ash, basic
oxygen furnace slag, ground lightweight aggregates, ground pumice, ground glass pozzolan, and basalt fines. A
total of 54 SCMs are tested using this approach. Results show that even among SCMs of the same type, there is
considerable difference in the heat release and calcium hydroxide consumption, likely due to differences in
amorphous content, chemical composition, and fineness, leading to different reactivities. Based on the response
in the test, SCMs are classified into inert, pozzolanic, and latent hydraulic; the pozzolanic and latent hydraulic
materials are further classified into less reactive and more reactive. The relationship between heat release and
calcium hydroxide consumption depends on the chemical composition of the SCMs, and SCMs with high calcium,
high alumina, and high silica contents show different relationships (determined by the slope of the heat release
vs. calcium hydroxide plot).

1. Introduction
Supplementary cementitious materials (SCMs) are used in concrete
as they offer various benefits such as reduction in costs, reduction in
emissions, and an increase in concrete durability. Local and global
shortfalls of SCMs are being increasingly reported [1], necessitating the
identification and use of newer SCMs. Numerous alternative SCMs such
as calcined clays [2], natural pozzolans [3], zeolites [4], ground
lightweight aggregates [5], and steel slags [6], have been suggested,
and studied by various researchers. Before such materials can be used in
concrete, one must be able to determine if alternative SCMs are poz-
zolanic (SCMs that need calcium hydroxide and water to react), latent
hydraulic (SCMs that can react with water once activated, via high pH,
temperature, mechanical grinding, or other means; these SCMs do not
need calcium hydroxide to react), or inert material (materials that react
insignificantly in the aforementioned manners). Therefore, the re-
activity of SCMs, which is defined here as a) the extent that SCMs react
with calcium hydroxide and water (pozzolanic reactivity), and b) the
extent that SCMs react with water, once activated (hydraulic re-
activity), is an important parameter to determine. This reactivity,
however, is not necessarily the same as the degree of reaction of SCMs
in concrete as SCM effects in concrete are complex. The use of SCMs
contributes to the filler effect (an increase in the cement degree of re-
action due to the physical presence of the SCM [5,7,8]), but can also
result in the retardation of cement hydration due to release of alu-
minum as the SCM dissolves [9,10]. The reactivity of SCMs in concrete
depends on numerous factors including SCM fineness, replacement
level, water-to-cementitious materials ratio, and cement and SCM
chemistry [11,12].
Methods such the Chapelle test [12,13], the Frattini test [14–17],
the strength activity index test [14,15], and SCM dissolution tests [16]
have been used to study the reactivity of SCMs. While these methods
are useful, they are in general unable to distinguish pozzolanic and
hydraulic reactivity or provide information about both of these beha-
viors. A test that measures the heat release and calcium hydroxide
consumption of SCM-calcium hydroxide blends at 50 °C in a 0.5 M

∗
Corresponding author.
E-mail address: suranenip@miami.edu (P. Suraneni).

https://doi.org/10.1016/j.cemconcomp.2019.05.017
Received 7 October 2018; Received in revised form 16 May 2019; Accepted 22 May 2019
Available online 23 May 2019
0958-9465/ © 2019 Elsevier Ltd. All rights reserved.
P. Suraneni, et al. Cement and Concrete Composites 103 (2019) 331–338

potassium hydroxide solution (water-to-solids ratio 0.9 and SCM: cal-

cium hydroxide mass ratio 1:3; pH of 13.5 at 23 °C) has been recently
proposed [18]. By measuring both heat release and calcium hydroxide
consumption, SCMs may be classified into inert, more hydraulic, poz-
zolanic, and highly pozzolanic [18]. This test is an alternative or
complement to the “rapid, relevant, and reliable” test method that uses
heat release or bound water to test the reactivity of SCMs [13,17]. The
main differences between the two test methods are the testing condi-
tions (elaborated on in Section 2) and the measured parameters (heat
release and/or bound water in the original version [13,17], heat release
and calcium hydroxide in the variant discussed here [18]).
In this paper, the results of the previous study, which examined only
a few SCMs [18], are expanded upon, and the results of reactivity
testing on 54 SCMs are presented. These include conventional and al-
ternative SCMs, and this large database being studied allows to draw
deeper conclusions about the reactivity of the studied SCMs.

2. Materials and methods

Twenty one fly ashes (FA including both Class C and Class F fly
ashes), nine ground granulated blast furnace slags (SL), eleven silica
fumes (SF), three calcined clays (CC), three ground lightweight ag-
gregates (GLWA), one quartz (Q), one ground limestone (LS), one basic
oxygen furnace slag (BOFS), one municipal solid waste incineration fly
ash (MSWIFA), one ground pumice (P), one ground glass (GG), and one
basalt fines (BF) were studied (Table 1). Some are commercially
available materials while some are materials being used for research.
The reactivity of a subset of these materials (four fly ashes, four slags,
two calcined clays, two silica fumes, quartz, and limestone) has been
reported elsewhere [18]. In addition, the heat release data of the
ground lightweight aggregates is also published [5]. The range and
average chemical compositions of the main oxides of these materials is
presented in Table 1. The chemical compositions of several materials
were tested using X-ray fluorescence (XRF) by using a device con-
forming to ASTM C114-15, Standard Test Methods for Chemical Ana-
lysis of Hydraulic Cement; while for other materials, chemical compo-
sition provided by the manufacturer is used. For the materials tested
using XRF, chemical composition determined using XRF generally clo-
sely matched that provided by the manufacturer. Compositional in-
formation was not available for seven silica fumes and one slag.
While average oxide composition is important, the tested materials
also showed clear differences in chemical composition even when they
were of the same type (for example, the fly ashes showed a broad range
of chemical compositions). Therefore, the individual compositions are
important and are represented in a ternary SiO2–Al2O3–CaO phase plot
in Fig. 1.
Fig. 1 and Table 1 provide valuable information about the SCMs
(and fillers); however, they do not provide the glass content, which
requires quantitative X-ray diffraction (XRD). Qualitative XRD showed
Fig. 1. Ternary phase diagram showing SiO2, Al2O3, and CaO amounts for
various SCMs.
the presence of crystalline phases in several SCMs, and these crystalline
phases and the glass content are likely to strongly impact the pozzo-
lanicity. Partial testing of SCM particle size distribution has been per-
formed and results show that these materials span a wide range of fi-
neness and mean particle size values (as an example, mean particle sizes
of two of the calcined clays are 12 μm and 24 μm) [18]. XRF, quanti-
tative XRD, and particle size distribution testing of several SCMs is
currently ongoing. In addition, the authors are also in the process of
determining the role that SCM fineness has on the response of SCMs in
this test for a smaller subset of materials.
The reactivity test was performed by mixing a 3:1 mass ratio of
reagent grade calcium hydroxide and SCM with solutions of 0.5 M re-
agent grade potassium hydroxide, maintaining a liquid-to-solid ratio of
0.9. As has been discussed elsewhere, the mixture design used here is
different from other variants of the test, which uses additional carbo-
nate and sulfate [13,17,18]. Sulfate and carbonate may result in
changes in the hydrate phase assemblage, and therefore, the response of
the materials in this test [13,17,18]. Additional sulfate and carbonate
are not considered here as the oxide compositions of all materials were
not known a priori [18]. The addition of sulfate and carbonate can
change the nature of the reaction products that are formed in this test.
Testing to determine the exact roles of sulfate and carbonate, including
measurement of bound water is currently ongoing.
The reactivity test was performed by mixing 40 g of material in a
plastic container using a spatula for 4 min [18]. After mixing, 6–7 g of
material was transferred into an ampoule, which was then placed in an
isothermal calorimeter (TAM Air, TA Instruments) that was

Table 1
Range and average (in parentheses) oxide compositions of the tested materials (in mass %). Range is provided only when multiple materials were tested and the
number of materials tested for each SCM is provided in parentheses after the SCM name. – indicates that the value was not provided by the manufacturer.
Na2O (%) MgO (%) Al2O3 (%) SiO2 (%) SO3 (%) K2O (%) CaO (%) Fe2O3 (%)

FA (21) 0.6–8.1 (1.92) 1.0–7.5 (3.79) 16.4–25.5 (20.59) 31.6–59.9 (44.50) 0.2–2.8 (1.19) 0.4–2.7 (0.97) 3.3–32.4 (17.08) 3.7–13.2 (6.40)
SL (9) 0.2–0.4 (0.32) 5.0–12.2 (8.47) 8.2–15.1 (11.02) 29.8–41.0 (35.06) 0.2–3.4 (1.38) 0.4–0.6 (0.45) 39.1–46.5 (41.69) 0.5–1.2 (0.76)
SF (11) 0.3–0.4 (0.31) 0.2–2.4 (1.34) 0.5–0.9 (0.69) 91.5–96.5 (93.26) 0.0–0.2 (0.13) 0.4–0.8 (0.56) 1.1–3.4 (2.24) 0.0–1.8 (0.91)
CC (3) 0.0–0.2 (0.13) 0.1–0.5 (0.34) 27.8–43.1 (35.86) 51.9–61.8 (57.15) 0.1–0.2 (0.16) 0.2–3.3 (1.38) 0.1–1.5 (0.64) 1.5–3.3 (2.44)
GLWA (3) 1.1–2.6 (2.11) 2.3–2.6 (2.48) 17.9–20.3 (18.73) 59.9–64.0 (62.41) 0.4–0.6 (0.55) 3.0–4.8 (3.59) 1.9–2.7 (2.18) 8.0–8.4 (8.26)
Q (1) – – 0.35 99.40 – 0.01 0.03 0.02
LS (1) 0.00 0.77 0.24 0.66 0.13 0.06 55.44 0.10
BOFS (1) 0.20 3.64 4.31 16.15 0.16 0.17 41.03 27.03
MSWIFA (1) 5.75 3.39 1.08 3.79 8.56 7.63 55.86 4.53
P (1) 1.60 0.05 13.50 76.20 – 1.80 0.80 1.10
GG (1) 13.00 4.00 1.00 72.00 – – 5.00 –
BF (1) 2.40 6.01 15.34 44.88 – 0.21 10.49 13.98

332
P. Suraneni, et al.
preconditioned at 50 ± 0.05 °C [18]. Data for the first 45 min was not
recorded as the signal was not stable due to temperature differentials.
The heat flow from the samples was recorded for 240 h, after which
samples were removed. Approximately 30–50 mg of material was taken
from the sample and thermogravimetric analysis was performed on it
(Q50, TA Instruments) by heating from 23 to 500 °C, at a rate of 10 °C/
minute in a nitrogen purged atmosphere [18]. Thermogravimetric
analysis was generally done within 6 h after removing the samples from
the isothermal calorimeter, and additional reactions that occur in this
short time are negligible [18]. The testing was done very quickly
(generally within 5 min) after material was removed from the calori-
meter ampoule in order to minimize risk of carbonation. Other variants
of this test are performed with the calorimeter at 40 °C [13,17]. The
lower temperature provides better control of the calorimeter, but the
higher temperature will lead to a greater extent of reaction of the SCM,
which is useful for less reactive SCMs. While this variant of the re-
activity test provides more information (pozzolanic and hydraulic be-
havior), it does require additional cost and effort for the thermogravi-
metric analysis, which may need to be justified. Both isothermal
calorimetry and thermogravimetric analysis results had less than 5%
coefficient of variability in replicate testing.
3. Results
3.1. Fly ash
Fig. 2 shows the cumulative heat release plotted against the calcium
hydroxide consumption for the tested fly ashes. The calcium hydroxide
consumption ranges from 43 to 81 g/100 g SCM, with an average value
of 60 g/100 g SCM. The heat release ranges from 192 to 351 J/g SCM,
with an average value of 294 J/g SCM. These ranges are larger than
previously reported values of 56–69 g/100 g SCM and 309–347 J/g
SCM for the calcium hydroxide consumption and the heat release, re-
spectively [18]. While the heat release increases as the calcium hy-
droxide consumption increases, the correlation is poor, because of data
scatter. As the data points move further from the origin, the fly ashes
corresponding to these data points have greater heat release and cal-
cium hydroxide consumption. This is explained by a greater extent of
SiO2 and Al2O3 from these fly ashes reacting with the calcium hydro-
xide. In addition, for the calcium-rich fly ashes, a greater extent of CaO
from the fly ashes has reacted with the alkaline medium. Therefore, as
the distance of the points from the origin increases, the reactivity of the
fly ashes increases [19]. Differences in reactivity in fly ash and other
SCMs under these conditions can be explained by differences in
Fig. 2. Heat release plotted against calcium hydroxide consumption for tested
fly ashes.
333
Cement and Concrete Composites 103 (2019) 331–338
Fig. 3. Heat release plotted against calcium hydroxide consumption for tested
slags.
fineness, amorphous content, and chemical composition [1,11–15]. As
the CaO content of the fly ash increases, the calcium hydroxide con-
sumption decreases (not shown here), because fly ashes with greater
CaO contents are relatively more hydraulic. There is no clear re-
lationship between the CaO content and the heat release, presumably
because the heat release depends on several factors including amor-
phous content and fly ash fineness.
3.2. Slag
Fig. 3 shows the cumulative heat release plotted against the calcium
hydroxide consumption for the slags. The calcium hydroxide con-
sumption ranges from 21 to 47 g/100 g SCM, with an average value of
31 g/100 g SCM. The heat release ranges from 377 to 519 J/g SCM,
with an average value of 436 J/g SCM. These ranges are larger than
previously reported values of 23–40 g/100 g SCM and 377–448 J/g
SCM for the calcium hydroxide consumption and heat release, respec-
tively [18]. No obvious relationship between the calcium hydroxide
consumption and the heat release was observed, because slags are la-
tent hydraulic, and reactions apart from those with calcium hydroxide
also contribute to the heat release. These results show that slag does
consume calcium hydroxide, however, slag consumes much less cal-
cium hydroxide than fly ash, while having a greater heat release (as can
be seen by comparing Figs. 2 and 3). Other results in literature also
show calcium hydroxide consumption of slag, both in model systems
[18] and in cement pastes [20,21].
3.3. Silica fume
Fig. 4 shows the cumulative heat release plotted against the calcium
hydroxide consumption for the silica fumes. The calcium hydroxide
consumption ranges from 61 to 176 g/100 g SCM, with an average
value of 121 g/100 g SCM. The heat release ranges from 324 to 613 J/g
SCM, with an average value of 478 J/g SCM. These ranges are sig-
nificantly larger than previously reported values of 104–176 g/100 g
SCM and 398–604 J/g SCM for the calcium hydroxide consumption and
the heat release, respectively [18]. However, it should be noted that
only two silica fumes were tested earlier [18] and several of the silica
fumes tested here are not commercial products, so their fineness and
performance may be lower than expected from a conventional silica
fume. In addition, the hand mixing may not have led to complete dis-
persion of some of the densified silica fumes. The differences in fineness
and dispersion could lead to differences in the extent of reaction of the
different silica fumes, which is reflected in lower heat release and cal-
cium hydroxide consumption. A strong linear relationship between the
calcium hydroxide consumption and the heat release was observed, if
P. Suraneni, et al.
Fig. 4. Heat release plotted against calcium hydroxide consumption for tested
silica fumes.
one data point is considered as an outlier. This is because of the high
SiO2 content in the silica fumes, because of which the heat release arises
from the reaction between calcium hydroxide and SiO2, without sig-
nificant contributions from reactions between calcium hydroxide and
Al2O3 or hydraulic reactions. As with the fly ash, the silica fume degree
of reaction increases as the distance of the corresponding points from
the origin in Fig. 4 increases. If one assumes that in the silica fumes, the
SiO2 reacts with 1.5–1.8 mol of Ca(OH)2 [22] and that the amorphous
SiO2 content is on average 93% by mass (Table 1), then based on
stoichiometry, it can be calculated that for full reaction, the silica fume
would have a calcium hydroxide consumption of between 172 and
206 g/100 g SCM. This enables the calculation of a silica fume degree of
reaction in the reactivity test ranging from approximately 30–90% (on
average 65%). The factors that limit the degree of reaction are unclear
at present and are being investigated.
3.4. Alternative SCMs
Fig. 5 shows the cumulative heat release plotted against the calcium
Fig. 5. Heat release plotted against calcium hydroxide consumption for alter-
native SCMs.
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Cement and Concrete Composites 103 (2019) 331–338
hydroxide consumption for alternative SCMs. The calcium hydroxide
consumption and the heat release range from 0 to 131 g/100 g SCM and
21–711 J/g SCM, respectively. Some of these materials seem to be inert
(low calcium hydroxide consumption and low heat release), while some
are hydraulic (but to lesser extent than slag), while some are pozzolanic
or highly pozzolanic. As extremely different responses for different
SCMs are observed from this test, it is suggested that this test is able to
classify SCMs depending on their response in this test. The difference in
responses for the various SCMs is discussed further in the next section.
3.5. SCM classification
Fig. 6 shows the response of all SCMs in the reactivity test; this
response may be used to classify the SCMs. Previously, SCMs were
classified into inert, pozzolanic, highly pozzolanic, and more hydraulic,
based on the response to the pozzolanic test [18]. An updated classi-
fication is proposed here based on Fig. 6: inert; pozzolanic, less reactive;
pozzolanic, more reactive; latent hydraulic, less reactive; and latent
hydraulic, more reactive. Whether the SCMs are latent hydraulic or
pozzolanic is decided by the ratio of the heat release and the calcium
hydroxide consumption (which is the slope of the curve; discussed
further in Section 3.7). The reactivity increases as the distance from the
origin increases, although the exact difference between less reactive
and more reactive SCMs is clearly somewhat subjective.
Quartz, limestone, municipal solid waste fly ash, and basalt fines are
classified as “inert” in this test. The inert behavior of quartz and
limestone is expected [7,18], although the quartz does have significant
calcium hydroxide consumption due to the high temperature and pH,
which accelerate quartz dissolution [18,23]. The behavior of the mu-
nicipal solid waste incineration fly ash is explained by its high CaO
content (55.9%) and low SiO2 and Al2O3 contents (the sum of which is
less than 5%). These results are consistent with results from literature
showing low pozzolanic activity of municipal solid waste incineration
fly ash [24]. While compositionally basalt fines are similar to fly ash
(Table 1 and Fig. 1), XRD showed that it was almost completely crys-
talline, which explains its inert behavior.
The basic oxygen furnace slag is latent hydraulic, but less reactive
than the slag (“latent hydraulic, less reactive”), as it has lower heat
release (and calcium hydroxide consumption) compared to the slag.
This is likely because of its high Fe2O3 content (27.0%), and low SiO2
and Al2O3 content (the sum of which is 20.4%). The sum of the SiO2 and
Al2O3 contents is higher than the municipal solid waste incineration fly
ash, therefore, some reactivity can be expected. The basic oxygen fur-
nace slag has very low calcium hydroxide consumption as it has high
CaO content (41.0%). These results are consistent with literature
showing very poor or low hydraulic activity of basic oxygen furnace
slag [25,26].
All slags are classified as “latent hydraulic, more reactive”; however,
two slags have higher heat release than the others (> 500 J/g SCM);
this could be due to the composition (for example, the addition of
calcium sulfate phases could activate the slag [27–29]), or due to higher
fineness [30].
Ten silica fumes and two calcined clays are classified as “pozzolanic,
more reactive”. There is a significant scatter in the highly pozzolanic
silica fume and calcined clay results, due to differences in fineness and
densification for the silica fumes [31] and differences in fineness and
chemical composition for the calcined clays [16,32].
The fly ashes, one silica fume, and one calcined clay, ground
lightweight aggregates, ground pumice and ground glass pozzolan are
classified as “pozzolanic, less reactive”. One silica fume and calcined
clay are significantly lower in their reactivity than other silica fumes
and calcined clays, likely due to chemical composition, fineness, and
densification [16,31,32]. This suggests that testing the reactivity of
SCMs would be valuable not only in identifying alternative SCMs and
their reactivity or lack thereof, but also to identify less/more reactive
conventional SCMs. However, caution should be exercised with some
P. Suraneni, et al. Cement and Concrete Composites 103 (2019) 331–338

Fig. 6. Heat release plotted against calcium hydroxide consumption for all SCMs.

densified silica fumes, as they may not be adequately dispersed by the Table 3
hand mixing adopted in this study, but may be better dispersed when Average and ranges of calcium hydroxide consumption and heat release for
added to concrete. The ground lightweight aggregates are approxi- different SCMs.
mately as reactive as the fly ashes, on average; and therefore, they can SCM type Calcium hydroxide consumption (g/100 g Heat release (J/g SCM)
be used as SCMs [5]. Further discussion about these ground lightweight SCM)
aggregates (which are compositionally similar to fly ash and calcined
Range Average Range Average
clay) can be found in Ref. [5]. Ground pumice and ground glass are also
pozzolanic, with the pumice showing greater reactivity. Others have FA 43–81 60 192–351 294
discussed the reactivity of pumice [33,34] and ground glass [35,36]. SL 21–47 31 377–519 436
SF 61–176 121 324–613 478
CC 80–131 104 366–711 531
3.6. Boundaries and ranges of SCM classification GLWA 53–72 60 215–300 260
Q* – 46 – 62
LS* – 0 – 21
Table 2 shows suggested ranges of calcium hydroxide consumption
BOFS* – 5 – 217
and heat release for the classification of SCMs from this test. MSWIFA* – 1 – 113
In the classification scheme, the following boundaries are P* – 98 – 268
used: < 120 J/g SCM – inert; 120 J/g SCM to 370 J/g SCM – less GG* – 67 – 211
reactive; > 370 J/g – more reactive, all in terms of heat release. It is BF* – 13 – 19

unlikely that there is anything “fundamental” about these numbers, as

changing the system in terms of the SCM: calcium hydroxide value, or
the temperature, will result in different values. However, these are
boundaries where clear and separate data clusters are observed. As a
large number of SCMs (50+) have been tested, these classifications
seem reasonable. The regions identified for the classifications generally
span a large range of heat release and calcium hydroxide consumption
values. In addition, they have a significant number of SCMs associated
with them, which lends confidence to the proposed classification
scheme. The only exception is the classification latent hydraulic, less
reactive, which is quite narrow and only has one point lying in it.
Further study of steel slag and related materials is ongoing [37].
Table 3 shows average and ranges of calcium hydroxide
* Only one specimen was tested, therefore range is not provided, and the
average is simply the value of the tested specimen.
consumption and heat release for different SCM types. SCMs ordered by
increasing order of average calcium hydroxide consumption are LS <
MSWIFA < BOFS < BF < SL < Q < GLWA = FA < GG < P <
CC < SF. The corresponding order of heat release is BF < LS <
Q < MSWIFA < GG < BOFS < P < GLWA < FA < SL < SF <
CC. These orders are not the same because hydraulic material rank low
for calcium hydroxide consumption, but not for heat release. Due to the
large variation in results from SCMs of the same type, the average va-
lues and such ordering have limited significance. As only a single

Table 2
Calcium hydroxide consumption and heat release ranges for SCM classification.
Classification Reactivity Calcium hydroxide consumption (g/100 g SCM) Heat release (J/g SCM) SCM examples

Inert Not reactive 0–50 0–120 Q, LS, MSWIFA, BF

Pozzolanic Less reactive 40–100 200–370 FA, SF, CC, GLWA, P, GG
More reactive 100–180 400–750 SF, CC
Latent Hydraulic Less reactive 0–20 150–250 BOFS
More reactive 20–50 370–550 SL

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P. Suraneni, et al.
Fig. 7. Effect of SCM chemical composition on reactivity test response.
sample type was tested with some materials, caution should be ex-
ercised in generalizing results, as variations in compositions and fine-
ness can occur in SCMs of the same type. However, it is evident that the
general testing regime and classification outlined here are applicable
for all SCMs and inert materials.
3.7. Effect of chemical composition on heat release and calcium hydroxide
consumption
From Fig. 6, it is apparent that SCMs with high CaO content have
lower calcium hydroxide consumption, whereas SCMs with high SiO2
content have higher calcium hydroxide consumption. The ratio of the
heat release and the calcium hydroxide consumption (the slope of the
curve), also depends on the SCM chemical composition. This is plotted
for various SCMs as shown in Fig. 7. In Fig. 7, a different grouping of
SCMs is used – SCMs are grouped as High CaO (39–55%), High Al2O3
(15–43%), and High SiO2 (72–96%). Straight lines are then fit to the
data for each of the three SCM groups. In general, SCMs may be
grouped in these categories, and the best-fit lines show a moderate to
strong correlation. The correlations and the slopes of the fits are shown
in Fig. 7 and Table 4.
The highest value of the slope, 13.19 is found in high calcium SCMs
(slag, limestone, basic oxygen furnace slag, and municipal solid waste
incineration fly ash). As these SCMs have high calcium, they are inert or
latent hydraulic. Whether the materials are inert or latent hydraulic
depends on the SiO2 and Al2O3 amounts, and other factors, such as glass
content [24,26,37]. As these materials show some value of heat release
but have low calcium hydroxide consumption, they have a high value of
the slope. The heat release for these materials is more from hydraulic
reactions and not from calcium hydroxide consumption alone. The
large number of slag data points could potentially bias the determined
value of the slope and the R2 value; however, it is clear that these SCMs
behave in a different manner from the rest of the SCMs.
SCMs which have high values of SiO2 (silica fume, quartz, pumice,
Table 4
Slope of heat release vs. calcium hydroxide consumption plot for various SCMs.
Group CaO (%) SiO2 (%) Al2O3 (%)
High CaO 39–55 1–41 0–15
High Al2O3 0–33 31–64 15–43
High SiO2 0–4 72–96 0–13
Cement and Concrete Composites 103 (2019) 331–338
ground glass) show the lowest value of the slope (3.78). These materials
have high silica amounts and are inert or pozzolanic. Quartz is inert as
the silica is crystalline instead of amorphous. The difference between
the different silica fumes (in terms of reactivity) is explained by dif-
ferences in fineness, densification, and dispersion, and other factors, as
discussed earlier. Pumice and ground glass have high SiO2 contents,
although their fineness is likely to be much lower than silica fumes. For
these SCMs, the heat release is due to the reaction between calcium
hydroxide and SiO2, as they have very low Al2O3 amounts. The value of
the slope, 3.78, corresponds favorably to the theoretically generated
slope from reaction of SiO2 with Ca(OH)2 in 0.5 M potassium hydroxide
solution, which is 3.60 [19].
SCMs which are high Al2O3 are inert or pozzolanic and show an
intermediate value of the slope (fly ash, calcined clay, ground light-
weight aggregates, basalt fines), equal to 4.93. Basalt fines is inert as it
is highly crystalline and crystalline materials do not usually behave as
SCMs. For the other SCMs, the heat release is due to reactions between
calcium hydroxide with both SiO2 and Al2O3. Al2O3 releases a greater
amount of heat than SiO2 when it reacts with calcium hydroxide [18].
The theoretical slope of the reaction of Al2O3 with Ca(OH)2 in 0.5 M
potassium hydroxide solution is 9.30 [19]. As different SCMs are being
considered, the amounts of Al2O3 and SiO2 vary, but if one assumes that
the ratio of reactive Al2O3 and SiO2 is 2:3 (based on a rough approx-
imation of high Al2O3 SCMs from Table 1), then the theoretical slope
would be 5.88, which is somewhat higher than the slope obtained in
this work (4.93). Further developing such relationships may be valu-
able, as it could allow for the prediction of one of the two parameters
(calcium hydroxide consumption and heat release) given one parameter
and the SCM XRF and XRD data, which would reduce experimental
effort.
3.8. Reactivity, classification, and the ternary phase diagram
Another way of visualizing the effect of chemical composition is
shown in Fig. 8. This figure shows the same data points as Fig. 1;
however, these points have been grouped by the classifications sug-
gested earlier. The points which are highest in CaO, and therefore
closest to the CaO vertex of the triangle (limestone, municipal solid
waste incineration fly ash) are inert. The rest of high CaO materials
(basic oxygen furnace slag, slag) are hydraulic, with reactivity in-
creasing as the distance from the CaO vertex increases. As the distance
increases further from the CaO vertex, materials become either high
Al2O3 or high SiO2. Two of these materials are inert – one is basalt fines
and the other is quartz; mostly because of the lack of reactive amor-
phous aluminosilicate phases. Several of these materials are pozzolanic,
highly reactive – these are silica fumes (which lie almost exactly at the
SiO2 vertex) or calcined clays (which lie on the SiO2 − Al2O3 edge).
Some silica fumes and calcined clays are less reactive than the rest,
however, why this is not so is not obvious in Fig. 8. The rest of the
materials (fly ash, ground lightweight aggregates, pumice, ground
glass) are pozzolanic, less reactive.
One way to improve the value of a representation such as Fig. 8
would be to use amorphous oxide content instead of bulk oxide content
or to use some sort of an adjustment factor for amorphous oxide con-
tent. Such changes will likely resolve issues with the inert nature of
municipal solid waste incineration fly ash, basalt fines, and quartz,
however, they may not explain the difference in behavior between the
Examples Classification Slope R2
SL, LS, BOFS, MSWIFA Inert, latent hydraulic 13.19 0.50
FA, CC, GLWA, BF Inert, pozzolanic 4.93 0.87
SF, Q, P, GP 3.78 0.75
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P. Suraneni, et al.
Fig. 8. Ternary phase diagram showing SiO2, Al2O3, and CaO amounts for SCMs
of varying reactivities.
different silica fumes (or calcined clays). Such differences may be
caused by differences in SCM fineness. While it is clear that increasing
fineness increases SCM reactivity [38,39], it is not completely obvious
how fineness affects reactivity test response for a range of SCMs. While
the authors are investigating fineness effects, such a discussion is out of
the scope of this work.
Regardless of some of the limitations highlighted here, it is evident
that the tests developed here clearly distinguish different types of re-
active SCMs from inert materials. The ability to make such distinctions
offers significant advantages over tests such as ASTM C311/311M − 18
and ASTM C618-19 which rely on bulk oxide content and strength gain
measurements to classify SCMs, as finely ground inert materials can
provide false positives in such testing [40,41].
One concern when using heat release and calcium hydroxide con-
sumption as measures of reactivity is that interlaboratory variability
values (as compared to single operator, single laboratory measure-
ments) can be rather high. As an example, values of approximately 20%
coefficient of variation for interlaboratory variability have been mea-
sured [42]. A potential way in which calcium hydroxide consumption
variability could be reduced would be for calcium hydroxide to be
measured on the SCM and calcium hydroxide mixture at the time of
mixing, and for calcium hydroxide consumption to be quantified using
the initially measured calcium hydroxide value, instead of the initially
calculated calcium hydroxide value. Regardless, these are fairly com-
plex tests, and high coefficient of variation values are an inevitable
challenge for standardization.
4. Conclusions
A reactivity test that measures the heat release and calcium hy-
droxide consumption of SCMs mixed with calcium hydroxide (3:1 ratio
of calcium hydroxide and SCM) at 50 °C and 0.5 M potassium hydroxide
was performed on 54 SCMs. These SCMs range from conventional SCMs
(fly ash, slag, and silica fume) to alternative SCMs (calcined clays,
municipal solid waste incineration fly ash, basic oxygen furnace slag,
ground lightweight aggregates, ground pumice, and ground glass), and
filler material (quartz, limestone, and basalt fines).
Based on the results, information about SCM behavior and reactivity
is obtained, and SCMs are classified into inert; pozzolanic, less reactive;
pozzolanic, more reactive; latent hydraulic, less reactive; and latent
hydraulic; more reactive. Even among SCMs of the same type, there is
considerable difference in the heat release and calcium hydroxide
consumption. The relationship between heat release and calcium
337
Cement and Concrete Composites 103 (2019) 331–338
hydroxide consumption, determined by the slope of the heat release vs.
calcium hydroxide curve, depends on the composition of the SCMs, and
SCMs with high calcium, high alumina, and high silica contents show
different relationships.
Acknowledgements
Brian Jeppsen (Hess Pumice), Chul-Woo Chung (Pukyong National
University), Jedadiah Burroughs (U.S. Army Engineer Research and
Development Center), John Horton (SGI), and Dr. Tyler Ley (Oklahoma
State University), are thanked for providing material for testing. Ladi
Famodu (Ozinga, Inc.) is thanked for help with XRF testing. The authors
would also like to thank insightful comments from two anonymous
reviewers which helped improve this manuscript.
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