ACI MATERIALS JOURNAL
Title No. 115-M08
Thermal Effect on Micro Properties of Granite Aggregate
in Concrete
by Guruprasad Y. K., Ananth Ramaswamy, and K. Sajeev
Identification and selection of the type of rock used as coarse
aggregate in concrete exposed to high temperature is important
from a standpoint of strength and safety of existing concrete struc-
tures. The present work documents the microscale behavior of
granite coarse aggregates and its influence on strength parame-
ters of concrete, exposed to different temperatures ranging from
425 to 850°C (797 to 1562°F) for an exposure time of 2 to 4 hours.
Factors leading to decomposition of coarse aggregates in concrete
under thermal loads were obtained using petrographical scannign
electron microscopy (SEM) and electron probe micro analysis
(EPMA) techniques. At temperatures ranging from 425 to 550°C
(797 to 1022°F), the damage in concrete is gradual and is attribut-
able to mortar shrinkage and separation of mortar-aggregate inter-
face. Thermodynamic modeling results have shown that, beyond
the formation temperature (715°C [1319°F]), minerals in the rock
start to melt and migrate along the fracture planes, causing sudden
reduction in load-carrying capacity in concrete.
Keywords: coarse aggregate; concrete (high-temperature exposure);
melt identification; petrography and microanalysis; strength reduction;
thermodynamic modeling.
INTRODUCTION
Most of the present-day structures around the world
have concrete as an integral component. Concrete has a
wide range of applications in construction of buildings and
special structures, such as nuclear plants. High tempera-
ture (for example, due to fire) has a hazardous effect on the
strength and stability of a concrete structure. Studies on
strength and safety of concrete are thus an important sector
of materials research.
Caner and Boncu1 and Caner et al.2 studied and investigated
structural fire safety of circular tunnel linings and assessed
the reduction in service load due to degradation of the mate-
rial on account of temperature and duration in a tunnel fire.
Takeuchi et al.3 carried out experiments to develop a data-
base of material properties of concrete and steel reinforcing
bars exposed to high temperature, while Schneider4 presents
the properties of concrete (based on existing literature) and
analytical models employed for estimating the engineering
properties of concrete exposed to fire. Lee et al.5 studied
the transport and concrete’s mechanical properties, which
deteriorated due to heating and cooling processes. Iwankilo
et al.6 addressed issues faced during fire testing and identified
factors affecting structural aspects such as loading, strength,
mechanical properties, test termination, interpreting, and
repeatability of experiments.
Xin et al.7 studied the post-fire residual compressive
strength of high-strength concrete and used scanning elec-
tron microscopy (SEM) to capture the changes in durability
ACI Materials Journal/January 2018
TECHNICAL PAPER
and microstructure of high-strength concrete exposed to fire.
Georgali and Tsakiridis8 and Ingham9 carried out studies on
concrete exposed to fire to assess the color change and depth
of damage that has taken place in concrete using petrog-
raphy. Caner and Boncul and Annerel and Taerwe10 carried
out microscopic analysis on concrete exposed to fire and
studied the physicochemical changes in concrete using SEM
and investigated the influence of heat on the color change
of aggregate using petrography. Alonso11 carried out assess-
ment of reinforced concrete exposed to fire and identified the
heterogeneity in terms of distribution of damage and depth
of concrete that has been affected due to fire using SEM
and petrography techniques. Gillot and Soles12 investigated
concrete cores using petrography to correlate rock types (in
the maritime provinces of Canada) to alkali-reactive aggre-
gates used in concrete and pointed towards selection of
rocks for regional alkali reactivity tests. Broekmans’13 work
assesses the deterioration taken place due to poor quality
of concrete used and due to mechanical damage that has
taken place in concrete using petrography. Pešková et al.14
analyzed the products of chemical reactions in concrete
exposed to high-temperature (fire) using Raman spectros-
copy to identify and understand the structural changes taking
place during a fire. Machovic et al.15 studied the structural
changes taking place at the interfacial transition zone of
two different concretes that are reinforced using polypro-
pylene/polyethylene and basalt fibers using Raman micro
spectroscopy.
The aforementioned studies show that the effects of fire
or other high-temperature sources on concrete have received
some attention. Most of the recent research concentrates
on the properties and chemical structures of cements and
concrete and tend to overlook the behavior of the rock used
as coarse aggregate in concrete.
In the present work, petrography, Raman spectros-
copy, SEM, and electron probe micro analysis (EPMA)
were adopted to carry out the microanalysis of granite
rock used as coarse aggregate in concrete exposed to
high temperature. In addition to the aforementioned
analysis performed, thermodynamic modeling of the granite
rock used as coarse aggregate was carried out to determine
the formation temperature of the rock. Mineralogy of coarse
aggregate and its stability to temperature and exposure time
ACI Materials Journal, V. 115, No. 1, January 2018.
MS No. M-2017-047.R1, doi: 10.14359/51701004, was received March 7, 2017, and
reviewed under Institute publication policies. Copyright © 2018, American Concrete
Institute. All rights reserved, including the making of copies unless permission is
obtained from the copyright proprietors. Pertinent discussion including author’s
closure, if any, will be published ten months from this journal’s date if the discussion
is received within four months of the paper’s print publication.
77
Table 1—Gradation of coarse aggregates
Sieve No. Percent fine passing
80 mm 100.00
40 mm 100.00
20 mm 86.00
10 mm 1.00
4.75 mm 0.00
Residue 0.00
Residue 0.00
Note: 1 mm = 0.0394 in.
highlight the influence of formation temperature of the rock
on mechanical behavior.
RESEARCH SIGNIFICANCE
This study helps to establish the importance of selecting
suitable coarse aggregates to ensure their robustness and
their contribution to the mechanical strength of concrete
when exposed to high temperature. Choice of coarse aggre-
gates can influence the behavior and extent of damage occur-
ring in the concrete structures exposed to high temperature.
Results of this study point toward a need for a conscious
selection of coarse aggregates having a higher melting point,
which results in a concrete offering improved thermal resis-
tance and mechanical strength.
EXPERIMENTAL AND ANALYSIS PROCEDURES
Casting, heat treatment, and uniaxial compression
testing of concrete cylinders
Grade 53 ordinary portland cement (OPC) (IS 12269-
198716) was used as binder; Grade II river sand (IS
383-197017) is used as fine aggregate; crushed granite stones
passing 20 mm (0.788 in.) IS sieve (IS 383-197017) are used
as coarse aggregate; and potable water is used to cast concrete
cylinders. Concrete mixtures having two different cylinder
compressive strengths—namely, 25 and 35 MPa (3625 and
5075  psi)—are used to cast concrete cylinders having a
diameter and height of 150 and 300 mm (5.91 and 11.82
in.), respectively. A concrete mixture having a 25 MPa (3625
psi) cylinder compressive strength has a mixture proportion
of cement:fine aggregate:coarse aggregate of 1:3.3:4.5 and
water-cement ratio (w/c) equal to 0.65. A concrete mixture
having a 35 MPa (5075 psi) cylinder compressive strength
has a mixture proportion of cement:fine aggregate:coarse
aggregate of 1:1.32:2.89 and w/c equal to 0.5. Gradation of
coarse aggregates (IS 383-197017) is shown in Table 1. The
concrete was mixed in a concrete mixer and was placed in
iron molds. The concrete was compacted with the help of a
needle vibrator while it was placed in the iron molds. The
concrete cylinders were demolded from the iron molds after
a period of 24 hours, and were placed in water for 28 days
of saturated curing. The concrete cylinders were removed
out of the water after 28 days and were allowed to dry for
a day at room temperature. The first set of concrete cylin-
ders having 25 and 35 MPa (3625 and 5075 psi) cylinder
compressive strengths were exposed to different tempera-
tures and exposure time by placing them in an electric
78
furnace. The internal temperature of the furnace was sensed
with the help of a thermocouple, which was fixed inside the
furnace and the temperature was displayed in an external
digital temperature indicator. The aforementioned concrete
cylinders were exposed to different temperatures and expo-
sure time in the electric furnace as follows: 425°C (797°F)
for 2 hours, 4 hours; 550°C (1022°F) for 2 hours, 4 hours;
715°C (1319°F) for 2 hours, 4 hours; and 850°C (1562°F)
for 2 hours, 4 hours. The time when the sample was placed
inside the furnace to the time when the steady-state tempera-
ture was attained inside the furnace was noted in each test.
This time duration to reach steady-state temperature was
approximately 5 minutes for temperature exposures up to
500°C (932°F) (2, 4 hours) and approximately 3 minutes for
higher-temperature tests (715°C, 850°C).
The concrete cylinders exposed to different tempera-
tures and exposure times were taken out of the furnace and
placed in ambient air condition for cooling until the cylin-
ders attained room temperature. Similarly, a second set of
companion concrete cylinders were exposed to the afore-
mentioned temperatures and exposure times and were placed
in ambient air condition for cooling until these cylinders
attained room temperature. Uniaxial monotonic compres-
sion loading was applied on the first set of concrete cylinders
that were exposed to different temperatures and exposure
time to ascertain the compressive strength and the stress-
strain behavior of the cylinders. The stress-strain response of
concrete cylinders having 25 and 35 MPa (3625 and 5075 psi)
cylinder compressive strengths, exposed to different
temperatures and exposure times, are shown in Fig.  1 and
Fig. 2, respectively. Axial strains of concrete cylinders
that were previously exposed to different temperatures and
exposure times were captured with help of electrical strain
gauges while carrying out monotonic compression tests in
a servo-hydraulic test system. For making thin sections of
concrete, concrete chunks were cut from the second set of
concrete cylinders exposed to different temperatures and
exposure time.
Thin section preparation and petrography
Petrography analysis of thin sections of concrete exposed
to different temperatures and exposure times was carried out
to study the changes taking place in the minerals present in
the coarse aggregate, degradation of the coarse aggregate,
and mortar. A diamond cutter was used to cut chunks of
concrete measuring approximately 20 x 40 x 25 mm (0.788 x
1.576 x 0.985 in.) around the top, middle, and bottom core
portions of concrete cylinders that were exposed to different
temperatures and exposure time to make thin sections. The
materials and equipment used to make the thin sections are
glass slides 25 x 50 mm (0.985 x 1.97 in.), 4 mm (0.16 in.)
in thickness. An electric grinder housed with a flat mild steel
(MS) disk approximately 300 mm (11.81 in.) in diameter,
having a rotating speed up to 600 rpm, was used to polish one
of the surfaces of the concrete chunks by using 80, 120, 400,
600, and 800 micron polishing powders to attain a smooth
and flat surface. Additionally, the concrete chunks were
polished on a glass plate, 8 mm thick, using 1200 micron
polishing powder to get an extra smooth and flat surface.
ACI Materials Journal/January 2018
Fig. 1—Stress-strain response of concrete cylinders having 25 MPa (3625 psi) cylinder compressive strength exposed over
range of temperature and exposure time: Control (without thermal exposure), 425°C (2, 4 hours), 550°C (2, 4 hours), 715°C
(2, 4 hours), and 850°C (2,4 hours). (Note: °F = 1.8°C + 32; 1 MPa = 145 psi.)

Fig. 2—Stress-strain response of concrete cylinders having 35 MPa (5075 psi) cylinder compressive strength exposed over
range of temperature and exposure time: Control (without thermal exposure), 425°C (2, 4 hours), 550°C (2, 4 hours), 715°C
(2, 4 hours), and 850°C (2, 4 hours). (Note: 1 MPa = 145 psi.)
Petrochemical epoxy was used to fix the polished and flat ened, the concrete chunk along with the glass slide was
surface of the thin sections to the glass slides. A hot plate allowed to cool up to room temperature. Precision cutting
was used to heat the concrete chunks adhered with the glass of the concrete chunk stuck to the glass slide was carried
slide at approximately 150°C (302°F) to solidify and harden out using a diamond cutter blade such that a thin layer
the petrochemical epoxy. After the epoxy completely hard- of the concrete chunk having a thickness of 2 to 3 mm

ACI Materials Journal/January 2018 79

(0.08 to 0.12 in.) was adhered to the glass slide. After the
precision cutting was done, the thin layer of the concrete
chunk stuck to the glass slide was polished on a rotating
disk of the electric grinder using 400, 600, and 800 micron
polishing powders. The polishing was carried out until the
thin layer of concrete attained a thickness of approximately
40  microns. Thereafter, the thin layer of concrete on the
glass slide was polished on the glass plate using 1200 micron
polishing powder so as to attain a thickness of 30 microns.
Thereafter, the thin layer of concrete adhered to the glass
slide was viewed in a petrography microscope to see if the
minerals appeared in their original color. This would imply
that the thin concrete layer adhered on the glass slide formed
into a thin section with a thickness of 30 microns. If the color
of the minerals seen under the microscope were different
from their original color, additional polishing was neces-
sary using 1200 micron powder until the true color of the
minerals appeared when the thin section was viewed in the
microscope. Diamond polishing of the thin sections using 8,
6, 3, and 1 micron diamond paste was carried out on a grinder
disk that has a rotating speed up to 600 rpm. After diamond
polishing, the thin sections were viewed in the petrography
microscope for identification of the minerals and capturing
the pictures (photomicrographs) of the thin sections in plane
and cross-polarized mode at different resolutions (2×, 4×,
10×, and 40×). Petrography analysis was also used to iden-
tify the melt and black glassy material observed along the
melt channels formed in coarse aggregates present in thin
sections of concrete exposed to high temperature and expo-
sure time (715°C, 2 hours and above).
Raman spectroscopy of thin sections of
concrete exposed to different temperatures and
exposure time
Raman spectroscopy18 was used to investigate the compo-
sition of the black glassy material seen in the melt channels
formed in the coarse aggregates present in thin sections of
concrete exposed to higher temperatures (715 and 850°C),
identified during petrography analysis. Raman spectroscopy
was carried out using a Raman microscope (at the Depart-
ment of Inorganic and Physical Chemistry, Indian Institute
of Science, Bangalore, India) having laser 514 and laser 785
at 10, 30, and 50 seconds scan time, to assess the composi-
tion of the mineral constituents in terms of the Raman shift.
This was especially important for assessing the composition
of the melt formed in the coarse aggregates present in thin
sections of concrete that were exposed to higher tempera-
tures (715°C, 2 hours and above) when compared to the thin
sections of concrete without thermal exposure.
EPMA and SEM study of thin sections of
concrete exposed to different temperatures and
exposure times
X-ray elemental mapping obtained from EPMA19 helps
to assess the minerals present in the area of interest in the
samples under consideration. In the present work, X-ray
elemental mapping obtained from EPMA was carried out
to ascertain the minerals present in the cement mortar and
coarse aggregate present in concrete exposed to different
80
temperature and exposure time. EPMA analysis was also
carried out to ascertain the possible contribution of cement
mortar (matrix) in the melting of coarse aggregates at higher
temperatures. Analytical conditions were 15 kV accelerating
voltage, a probe current of 15 nA, and a beam diameter of
3 microns for quantitative analysis; natural mineral oxides
were used as standards. The data were reduced using ZAF
correction procedures. SiO2, TiO2, Al2O3, Cr2O3, FeO, MnO,
MgO, CaO, Na2O, K2O, P2O5, and SO3 were analyzed for
all minerals. X-ray mapping and backscattered electron
(BSE) imaging of thin sections of concrete samples having
35 MPa (5075 psi) cylinder compressive strength without
thermal exposure and samples exposed to 850°C (4 hours)
was carried out using a field-emission hyper probe from the
Department of Materials Engineering, Indian Institute of
Science, Bangalore, India, and a super-probe at Okayama
University of Science, Okayama, Japan. For X-ray mapping,
a higher probe current of 240 nA, a beam size of 1 micron
diameter, and dwell time of 30 microseconds was used.
SEM19 imaging of the thin sections was carried out using a
field-emission hyper-probe at the Department of Materials
Engineering, Indian Institute of Science, Bangalore, India,
to study the microstructure of coarse aggregates, mortar, and
the melt present in the coarse aggregates used in concrete
exposed to different temperatures and exposure time. Back-
scattered and SEM images of the thin sections were captured.
Thermodynamic modeling of coarse aggregate
The thermodynamic modeling of the rock used as coarse
aggregate was carried out using PeRpLeX20 to assess the
pressure and temperature conditions prevailing in the forma-
tion of the rock. The formation temperature of the rock
obtained from this analysis indicates the initiation of melting
of the rock.
RESULTS AND DISCUSSIONS
This section presents the results and discussions of
the analysis performed on concrete exposed to different
temperature and exposure time using petrography, SEM,
Raman spectroscopy, EPMA, and thermodynamic modeling
of coarse aggregate.
Petrography analysis of concrete exposed to
different temperatures and exposure time
The stress-strain response of concrete cylinders subjected
to uniaxial compression and photomicrographs obtained
from petrography analysis of thin sections of concrete
having 25 and 35 MPa (3625 and 5075 psi) cylinder
compressive strengths exposed to different temperatures and
exposure time are shown in Fig. 1, Fig. 2, Fig. 3, and Fig. 4,
respectively. It is observed from the uniaxial compression
stress-strain response of concrete cylinders having 25 and
35 MPa (3625 and 5075 psi) cylinder compressive strengths
in Fig. 1 and Fig. 2, with increase in temperature and time of
exposure, both the strength (peak value) and stiffness (initial
slope) of concrete degrades. In particular, for temperatures
up to 550°C (425 and 550°C) and exposure duration up to
4 hours, the damage is gradual and the reduction in strength
is of the order of up to 30 to 50% when compared to the
ACI Materials Journal/January 2018
Fig. 3—Photomicrographs of thin sections of concrete having 25 MPa (3625 psi) cylinder compressive strength exposed to
different temperature and exposure time: (a) Control (without thermal damage); (b) 425°C (4 hours); (c) 550°C (2 hours); (d)
715°C (2 hours); (e) 715°C (4 hours); (f) 850°C (2 hours); and (g) 850°C (4 hours).
strength of the sample tested without thermal exposure. This
may be attributed predominantly to mortar shrinkage and
separation cracks at coarse aggregate mortar interface (Fig. 1
and Fig. 2). It was observed during the compression test that
coarse aggregates in concrete exposed up to 550°C for expo-
sure duration of 4 hours showed no signs of being crushed.
During petrographic study of the microphotographs of
thin sections shown in Fig. 3 and Fig. 4, it was observed
that granite coarse aggregates present in concrete exposed to
425°C up to 4 hours (Fig. 3(b) and Fig. 4(b)) do not have any
significant differences when compared to a similar sample
not exposed to high temperature (control sample) (Fig. 3(a)
and Fig. 4(a)). In the case of coarse aggregates present in
concrete exposed to 550°C (4 hours) shown in Fig. 3(c) and
Fig. 4(c), minor development of fractures along the mineral
boundaries are observed; however, no major changes such
as melting or degradation are seen in comparison with corre-
sponding samples without thermal exposure (Fig. 3(a) and
Fig. 4(a)). Previous studies have shown that concrete samples
heated up to 350°C (662°F)8,10 develop slight pink or red
discoloration of coarse aggregates caused by oxidation of
iron compounds, which commences at approximately 300°C
(572°F). Visual examination of the concrete cylinder samples
exposed to 425°C for durations of 2 to 4 hours showed very
few cracks on the surface, and there was not much change in
the exterior color of the concrete cylinders when compared
to the concrete samples that were not exposed to temperature
(control samples). Further, a slight pinkish-red discoloration
of the coarse aggregates and a powdery surface texture with
ACI Materials Journal/January 2018
microcracks caused by the loss of bound water in the cement
matrix was observed. Concrete cylinder samples exposed to
550°C for durations of 4 hours were slightly pinkish in color
on the exterior and had moderate number of cracks on the
surface. It is observed in the thin section of concrete exposed
to 550°C for durations of 4 hours in Fig. 3(c) and Fig. 4(c),
the cement matrix exhibits a slight beige color in cross-po-
larized light with radial cracking pattern around the quartz
grains in the coarse aggregates. In the case of concrete cylin-
ders exposed to 715°C for durations of 2 to 4  hours, the
coarse aggregates were pinkish/red in color while the mortar
exhibited a light whitish gray color on the exterior. There
were numerous cracks developed on the surface of these
cylinders with severe microcracking of the cement matrix.
Concrete cylinder samples exposed to 850°C for durations
of 2 to 4 hours were completely whitish gray in color with a
very slight tinge of pink with large number of wide cracks on
the surface with severe microcracking of the cement matrix.
The coarse aggregates in the concrete samples exposed to
850°C for durations of 2 to 4 hours had also turned pinkish
with slight whitish gray in color. The coarse aggregates in
concrete exposed to 850°C (2 to 4 hours) were easily broken
and crushed with the application of a small amount of pres-
sure by hand when compared to the coarse aggregates in
concrete samples exposed to 715°C, which were compar-
atively harder and could not be broken or crushed easily.
On the whole it is observed, at temperatures ranging from
425 to 550°C, damage is gradual and reduction in strength
(30 to 50% of the control value) may be attributed to mortar
81
Fig. 4—Photomicrographs of thin sections of concrete having 35 MPa (5075 psi) cylinder compressive strength exposed to
different temperature and exposure time: (a) Control (without thermal damage); (b) 425°C (4 hours); (c) 550°C (2 hours); (d)
715°C (2 hours); (e) 715°C (4 hours); (f) 850°C (2 hours); (g) 850°C (4 hours); and (h) 850°C (4 hours) BSE image.
shrinkage due to loss of free and bound water, and slight increases up to 400°C. In contrast, the compressive strength
expansion of coarse aggregates. No melt in aggregate or of OPC cement pastes27 increases with temperature up to
separation at aggregate mortar interface was seen. Whereas 200°C (392°F) and then their strengths drop with increase in
at a higher temperature exposure of 715 to 850°C, there is temperature above 200°C. Degradation of mortars exposed
severe cracking in concrete followed by high loss in strength; to high temperature is attributed to a buildup of water vapor
this is attributed due to complete drying of the mortar and pressure within the pores of the matrix, resulting in the
initiation of melt in the coarse aggregate, too. Studies have development of tensile microcracks. Polypropylene fibers
shown that behavior of normal OPC mortars and blended embedded in these mortars melt at high temperatures and
cement mortars containing fly ash, silica fume, or metaka- offers a channel for the water vapor to escape from the mortar,
olin-based mineral additives21-23 with polypropylene/steel mitigating the pressure buildup and consequent spalling of
fibers24-26 introduced into the matrix exhibit an increase in mortar. This makes mortars with blended cements impreg-
the thermal resistance when exposed to high temperatures nated with fibers an attractive option, as they are more stable
when compared to the normal OPC mortars, which do not and robust when exposed to high temperatures in compar-
contain the polypropylene/steel fibers. The degradation in ison to the normal OPC mortars. Thus, at high temperatures,
the strength of blended cement mortars exposed to high the microstructure of coarse aggregates introduced into a
temperature initiates at a temperature range of approximately modified mortar matrix dominates the overall mechanical
400 to 500°C (752 to 932°F), as the compressive strength response of concrete. In the present work, as observed from
of blended cement pastes increases when the temperature petrographic analysis (Fig. 3 and Fig. 4) and the BSE image

82 ACI Materials Journal/January 2018

Fig. 5—BSE images and EPMA X-ray mapping of thin sections of concrete having 35 MPa (5075 psi) cylinder compressive
strength exposed to different temperature and exposure time: (a) BSE image: control (without thermal damage); (b) BSE
image: 850°C (4 hours); (c) BSE image: 850°C (4 hours): close-up of melt channel; (d) Raman shift of melt formed in coarse
aggregate in concrete exposed to higher temperatures (715 to 850°C).
(Fig. 5(a), (b), and (c)) of the thin sections indicate the pres- as they pass through the minerals and cuts across the grain
ence of quartz, plagioclase, K-feldspar, and biotite. Through boundaries. It is also important to note the fractures within
a pointwise identification of the minerals carried out during the coarse aggregate in these samples are filled with a black
thin section studies, the percentages per unit volume of the glassy material. Interestingly, hydrous mineral, biotite,
minerals present in granite coarse aggregate was found to be becomes dark and degraded when exposed to high tempera-
approximately 70 to 85% quartz, 20 to 65% plagioclase, and ture (715 and 850°C).
approximately 10 to 20% biotite. These values of mineral
composition present in granite have also been reported in the SEM, Raman spectroscopy, and EPMA of
literature.28 This implies that coarse aggregates comprising concrete exposed to different temperatures and
of a larger percentage of minerals such as quartz that has exposure times
a higher melting temperature is desired for high-temperature The BSE images of thin section samples of concrete having
applications. It must also be noted that natural rock samples 35 MPa (5075 psi) cylinder compressive strength not exposed
are highly heterogeneous in mineral distribution and quanti- to temperature (control sample) and thin section samples of
fying mineral percentage will also include a factor of uncer- similar concrete exposed to 850°C (4 hours) are shown in
tainty. In concrete cylinder specimens exposed to higher Fig. 5(a) and (b), respectively. The close-up of the melt channel
temperatures ranging from 715 to 850°C for exposure dura- containing a black glassy material, mainly silica rich melt/glass
tions up to 2 to 4 hours, degradation in the strength and formed in the coarse aggregate present in concrete exposed to
stiffness is substantial (70 to 80% degradation in strength) 850°C (4 hours), is shown in Fig.  5(c). Raman spectroscopy
when compared to the strength of samples without thermal was carried out to determine the composition of black glassy
exposure (Fig. 1 and Fig. 2). The petrographic observation material present in the melt channel formed in coarse aggre-
shows that the granite coarse aggregates in concrete exposed gates present in concrete exposed to higher temperatures
to temperatures of 715 and 850°C for exposure durations of (715 and 850°C) by Raman shift value (1499 cm–1) is shown
2 to 4 hours were substantially fractured, and this can be in Fig. 5(d) and as inset in Fig. 1. Figures 6 and 7 show the
observed in Fig. 3(d), (e), (f), and (g) and Fig. 4(d), (e), X-ray mapping of the cement matrix and coarse aggregates in
(f), and (g), respectively. The degree of fracturing escalates thin sections of concrete having 35 MPa (5075 psi) cylinder
in samples exposed to 850°C when compared to samples compressive strength: without thermal exposure (Control) and
exposed to 715°C. The fractures are clearly late fractures exposed to 850°C (4 hours), respectively, obtained from EPMA.

ACI Materials Journal/January 2018 83

Fig. 6—X-ray mapping of cement matrix and coarse aggregates in thin section of concrete having 35 MPa (5075 psi) cylinder
compressive strength without thermal exposure (Control), obtained from EPMA shows no melting in coarse aggregate.

Fig. 7—X-ray mapping of cement matrix and coarse aggregates in thin section of concrete having 35 MPa (5075 psi) cylinder
compressive strength exposed to 850°C (4 hours), obtained from EPMA.
Figure 8 shows the X-ray mapping of the melt present in the (plagioclase-Pl; K-feldspar-Kfs, biotite-Bt) in the granite coarse
coarse aggregates in thin section of concrete (having 35 MPa aggregate, and the melt in oxide (in weight percentage [Wt %]).
[5075 psi] cylinder compressive strength) exposed to 850°C Based on the Raman spectroscopy, Raman shift value
(4 hours), obtained EPMA. Table 2 shows the chemical anal- (Fig.  5(d) and inset in Fig. 1), and EPMA results, it was
ysis of OPC,16 granite whole-rock chemistry,29 major minerals confirmed the glassy material in the melt channels has

84 ACI Materials Journal/January 2018

Fig. 8—X-ray mapping of melt present in coarse aggregates in thin section of concrete having 35 MPa (5075 psi) cylinder
compressive strength exposed to 850°C (4 hours), obtained from EPMA.
Table 2—Chemical analysis of OPC,16 granite whole-rock29 chemistry, major minerals (plagioclase-Pl;
K-feldspar-Kfs, biotite-Bt) in granite aggregate, and melt (in oxide Wt %)
Granite aggregate in control sample
without thermal damage Sample exposed to 850°C (4 hours)
Granite Calculated granite
OPC whole-rock whole-rock* Pl Kfs Bt Crystallized melt Glass in melt
SiO2 21.00 70.21 70.21 65.22 64.70 36.28 43.53 95.02
TiO2 0.00 0.31 0.00 0.03 0.03 2.56 0.29 0.00
Al2O3 5.10 15.86 15.88 21.50 18.16 15.82 3.99 0.08
Cr2O3 0.00 0.00 0.00 0.00 0.00 0.04 0.98 0.00
MgO 2.50 1.08 1.08 0.03 0.01 6.10 1.13 0.02
MnO 0.00 0.05 0.00 0.00 0.03 0.64 0.04 0.00
FeO 0.00 1.28 1.28 0.09 0.02 25.48 5.56 0.04
Fe2O3 3.10 0.84 0.00 10.27 0.42 0.00 0.00 0.00
Na2O 0.30 3.82 3.99 3.06 0.06 0.01 1.96 0.20
CaO 64.10 1.82 1.98 0.06 16.08 0.10 12.40 0.26
K2O 0.70 4.46 4.99 0.00 0.01 9.25 0.93 0.03
P2O5 0.00 0.11 0.00 0.01 0.00 0.00 0.06 0.00
SO3 2.20 0.00 0.00 0.00 0.00 0.00 0.14 0.00
Chlorides 0.03 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Insolubles 0.30 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Loss on ignition/H2O 0.60 0.59 0.59 0.00 0.00 3.72 29.00 4.35
Free lime 0.80 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Total 100.73 100.43 100.00 100.26 99.51 100.00 100.00 100.00
*
Granite bulk chemical composition calculated/estimated from mineral modes for thermodynamic modeling.

ACI Materials Journal/January 2018 85

Fig. 9—Thermodynamic modeling (P-T phase diagram) of rock (without thermal damage) used as coarse aggregate. (Compar-
ison with calculated and analytical data for granite sample is given in Table 2. Solution model used for calculation is provided
in Table 3).
silica-aluminium-calcium-sodium-potassium composition
(silica rich melt/glass), which is attributed to the result of
granite coarse aggregate melting. The composition also
pointed out the melt channels could not be the result of
cement melting; however, they may have a potential contri-
bution. This significant observation warranted detailed analysis
and discussion of these melts, as it may have direct implica-
tion on the degradation of concrete strength when exposed to
high temperature in the event of a fire. Petrographic analysis
showed no evidence of melting in the granite coarse aggre-
gates for concrete exposed to temperatures up to 550°C.
However, traces of melting and extensive fracturing started
in coarse aggregates for concrete samples exposed to 715°C
for 2 hours. Extensive melting is clearly evident from the
photomicrographs of thin sections of concrete exposed
above 715°C (850°C) (Fig. 3(d), (e), (f), and (g); Fig. 4(d),
(e), (f), and (g); and Fig. 5(b) and (c)). Figure 4(h) shows
the BSE image of the melt in K-feldspar group (plagioclase)
mineral present in the coarse aggregate in concrete, which
was exposed to 850°C (4 hours). It is also observed from
Fig. 4(h), the melt traverses along the grains of the K-feldspar
group mineral in the coarse aggregate.
Dense fissures filled predominantly with silica rich melt/
glass along the fractures or cracks in coarse aggregates are
86
widely distributed in the region associated with hydrous
minerals (biotite), shown in Fig. 5(c).
The X-ray elemental mapping results obtained from EPMA
analysis help to assess the mineral melting as well as the
contribution of cement mortar (matrix) in the melt at higher
temperatures. The mapping results can primarily detect the
presence and percentage of elements such as calcium (Ca),
iron (Fe), phosphorous (P), and sulfur (S) in the coarse
aggregate and in the cement mortar (matrix) portions, so as
to assess the constituents in concrete that contribute to the
formation of the melt in coarse aggregates when the concrete
is exposed to high temperature.
The results of the EPMA X-ray mapping related to both
thin section samples—that is, control sample (Fig. 6) and the
one exposed to 850°C (4 hours) (Fig. 7) indicates calcium
(Ca) is present in both the cement mortar (matrix) and in
coarse aggregate. Traces of iron (Fe) are seen along the melt
channels in the coarse aggregate present in concrete exposed
to 850°C (4 hours) in Fig. 7, whose origin is basically from
ferro-magnesium hydrous minerals such as biotite and partly
from cement. The X-ray mapping in Fig. 6 and 7 shows the
elements phosphorus (P) and sulfur (S) are predominantly
present in the cement mortar (matrix) portion, as these two
elements exist in cement only. X-ray mapping results of the
melt (fracture fills) in the coarse aggregate shown in Fig. 8
ACI Materials Journal/January 2018
Table 3—Solution notation, formulas, and model sources for phase diagram calculation
Symbol Solution
Pl Feldspar KyNaxCa1-x-yAl2-x-ySi2+x+yO8, x + y ≤ 1
Bt Biotite K[MgxFeyMn1–x–y]3–u–v–wFe3+wTiuAl1+vSi3–vO10(OH)2-2u, x + y ≤ 1, u + v + w ≤1
Melt Melt Na-Mg-Al-Si-K-Ca-Fe hydrous silicate melt
Note: Unless otherwise noted, compositional variables x, y, and z may vary between zero and unity and are determined as function of computational variables by free-energy
minimization.
indicates phosphorus (P) and sulfur (S) are absent in the melt
and along the melt channels. It is inferred from the EPMA
results and chemical analysis of cement, whole granite rock
chemistry, major minerals in granite coarse aggregate, and
the melt (expressed in oxide weight percentage) shown in
Table 2 that the melt formation in the coarse aggregate is
contributed predominantly due to the melting of the minerals
such as biotite and feldspars in the granitic coarse aggre-
gate alone and the cement has no direct contribution to the
melt composition.
Thermodynamic modeling of the coarse aggregate
Figure 9 shows the thermodynamic modeling of the
rock (without thermal exposure) used as coarse aggregate.
Figure  9 shows the phase diagram that indicates the crys-
tallization temperature of the granite rock used as coarse
aggregate in this study. Table 3 shows the solution notation,
formulae, and model sources for phase diagram calculation.
In Table 3, unless otherwise noted, the compositional vari-
ables x, y, and z may vary between zero and unity and are
determined as a function of the computational variables by
free-energy minimization. The crystallization temperature of
a rock can be estimated using traditional thermos-barometric
studies or through thermodynamic modeling methods—
an approach widely used by geologists. Here, isothermal
pressure temperature (P-T) phase diagram is used, which
is obtained through thermodynamic modeling methods
to estimate the mineral stability as well as the crystalliza-
tion temperature of the granite rock used as coarse aggre-
gate. The phase diagram sections were computed using free
energy minimization30 as shown in Table 3, with end member
thermodynamic data from Holland and Powell.31 The phase
diagram results in Fig. 9 indicate the formation temperature
of granite rock used as the coarse aggregate to be at approx-
imately 700°C (1292°F) at a pressure of approximately 4 to
5 kbar. These results were also crosschecked with the feld-
spar thermometry that indicated a formation temperature of
689 ± 30°C (1272.2 ± 54°F) at 4 to 5 kbar pressure.
It is observed from this study for the first time the role
of crystallization temperature on the capacity of concrete to
withstand high temperature. On cross verification of the ther-
modynamic modeling results with the experimental results
of concrete, it is clear that the rock starts melting34 once the
temperature crosses the melting temperature (solidus) of
the granite.
CONCLUSIONS
From this study, it is inferred that selection of coarse aggre-
gates for concrete plays a very important role, where expo-
sure to fire or other high-temperature sources is an important
ACI Materials Journal/January 2018
Formula Source
Fuhrman and Lindsley32
Tajcmanová et al.33
Holland and Powell31; White et al.34
safety criterion from a strength and stiffness point of view.
Coarse aggregates for concrete structures are generally
selected based on their local availability. The present results
suggest that the load-carrying capacity of the concrete struc-
tures when exposed to fire (to withstand high temperature
for a particular exposure time) will vary with respect to the
formation temperature or melt temperature of the rock used
as the coarse aggregate in concrete.
Hydrous minerals tend to degrade when exposed to high
temperature causing fissures or cracks due to their lower
melt point. Therefore, for high-temperature applications,
coarse aggregates composed of minerals having a high melt
point and high mechanical strength is desirable.
AUTHOR BIOS
Guruprasad Y. K. is a Researcher and former PhD research scholar in the
Department of Civil Engineering at the Indian Institute of Science, Banga-
lore, India, where he received his PhD. His research interests include repair
and retrofit of reinforced cement concrete structures subjected to earth-
quakes and high temperature, fracture mechanics, structural analysis and
mechanics, nondestructive testing, and microanalysis of concrete exposed
to high temperature.
Ananth Ramaswamy is a Professor in the Department of Civil Engi-
neering at the Indian Institute of Science. He received his BTech from the
Indian Institute of Science in 1985; his MS from the University of Cali-
fornia, Davis, Davis, CA, in 1986; and his doctorate degree from Loui-
siana State University, Baton Rouge, LA, in 1992. His research interests
include analysis and design of reinforced concrete structures, prestressed
and fiber-reinforced concrete; bridge engineering; structural and shape
optimization; fiber-reinforced polymer composites; and smart materials
and vibration control.
K. Sajeev is an Associate Professor at the Centre for Earth Sciences,
Indian Institute of Science. He received his PhD from Okayama University,
Okayama, Japan. His research interests include lower-crustal processes,
tectonics, role of fluids along regional structures, high-grade metamor-
phism, microscale geochronology, and geochemistry with emphasis on the
high-temperature/high-pressure paleotectonic activity on the lower crust
of Gondwana.
ACKNOWLEDGMENTS
The authors are thankful to S. V. Kailash (Dept. of Mechanical Engi-
neering, Indian Institute of Science), S. Umapathy (Dept. of Inorganic
and Physical Chemistry, Indian Institute of Science), A. Paul and Vandana
(Dept. of Material Engineering, Indian Institute of Science), Dept. of Civil
Engineering & Centre for Earth Sciences, Indian Institute of Science,
Banglaore, India, for the facilities; and T. Itaya of Okayama University of
Science for the facilities. The authors gratefully acknowledge the financial
support received from CiSTUP, IISc project: CIST010 and BRNS project:
2012/36/38-BRNS/1676. This work is a contribution to both the projects.
REFERENCES
1. Caner, A., and Boncu, A., “Structural Fire Safety of Circular Concrete
Railroad Tunnel Linings,” Journal of Structural Engineering, ASCE, V. 135,
No. 9, 2009, pp. 1081-1092. doi: 10.1061/(ASCE)ST.1943-541X.0000045
2. Caner, A.; Zlatanic, S.; and Munfah, N., Quantitative Assessment of
Structural Fire Endurance of Concrete and Shotcrete Tunnel Liners. Under-
ground Space Use: Analysis of the Past and Lessons for the Future, Erdem
and Solak, eds., Taylor & Francis, London, UK, 2005, pp. 585-590.
87
 3. Takeuchi, M.; Hiramoto, M.; Kumagai, N.; Yamazaki, N.; Kodaira,
A.; and Sugiyama, K., Material Properties of Concrete and Steel Bars at
Elevated Temperatures, K. Kussmaul, ed., SMiRT– 12; Elsevier Science,
Amsterdam, the Netherlands, 1993, pp. 133-138.
4. Schneider, U., “Concrete at High Temperatures—A General
Review,” Fire Safety Journal, V. 13, No. 1, 1988, pp. 55-68. doi:
10.1016/0379-7112(88)90033-1
5. Lee, J.; Xi, Y.; and Willam, K., “Properties of Concrete after High
Temperature Heating and Cooling,” ACI Materials Journal, V. 105, No. 4,
July-Aug. 2008, pp. 334-341.
6. Iwankiw, N.; Beyler, C.; and Beitel, J., “Testing Needs for Advance-
ment of Structural Fire Engineering,” Structures in Fire, 2008, pp. 334-343.
7. Xin, Y.; Li, H.; and Wong, Y. L., “Assessment and Repair of Fire-
Damaged High-Strength Concrete: Strength and Durability,” Journal of
Materials, ASCE, V. 19, No. 6, 2007, pp. 462-469.
8. Georgali, B., and Tsakiridis, P. E., “Microstructure of Fire-Damaged
Concrete—A Case Study,” Cement and Concrete Composites, V. 27, No. 2,
2005, pp. 255-259. doi: 10.1016/j.cemconcomp.2004.02.022
9. Ingham, J., “Application of Petrographic Examination Techniques
to the Assessment of Fire-Damaged Concrete and Masonry Structures,”
Materials Characterization, V. 60, No. 7, 2009, pp. 700-709. doi: 10.1016/j.
matchar.2008.11.003
10. Annerel, E., and Taerwe, L., “Revealing the Temperature History
in Concrete after Fire Exposure by Microscopic Analysis,” Cement and
Concrete Research, V. 39, No. 12, 2009, pp. 1239-1249. doi: 10.1016/j.
cemconres.2009.08.017
11. Alonso, C., “Assessment of Post-Fire Reinforced Concrete Struc-
tures: Determination of Depth of Temperature Penetration and Associated
Damage,” Concrete Repair, Rehabilitation And Retrofitting II, Alexander
et al., eds., Taylor & Francis, London, UK, 2009, pp. 471-477.
12. Gillott, J. E., and Soles, J. A., “Petrography of Concrete Cores
from New Brunswic, Relating to the Durability Problem,” Cement
and Concrete Composites, V. 15, No. 1-2, 1993, pp. 101-114. doi:
10.1016/0958-9465(93)90041-7
13. Broekmans, M. A. T. M, “Petrography as an Essential Complemen-
tary Method in Forensic Assessment of Concrete Deterioration: Two Case
Studies,” Materials Characterization, V. 60, No. 7, 2009, pp. 644-654. doi:
10.1016/j.matchar.2008.12.017
14. Pešková, S.; Machovic, V.; and Procházka, P., “Reed Spectroscopy
Structural Study of Fired Concrete,” Ceramacis – Silikáty, V. 55, No. 4,
2011, pp. 410-417.
15. Machovic; V.; Kolár; F.; Procházka, P. P.; Pešková, S.; and Kuklík,
P., “Raman Spectroscopy Study of Interfacial Transition Zone in Cement
Composite Reinforced by Pp/Pe and Basalt Fibres,” Acta Geodyn. Geoma-
terials, V. 3, No. 2-142, 2006, pp. 63-67.
16. IS 12269, “Specification for 53 Grade Ordinary Portland Cement,”
Bureau of Indian Standards, New Delhi, India, 1987, 26 pp.
17. IS 383, “Specification for Coarse and Fine Aggregates from Natural
Sources for Concrete (Second Revision),” Bureau of Indian Standards, New
Delhi, India, 1970, 19 pp.
18. Vašková, H., “A Powerful Toolf Material Identification: Raman
Spectroscopy,” International Journal Mathematical Models and Methods
In Applied Science, V. 5, No. 7, 2011, pp. 1205-1212.
19. Reed, S. J. B., Electron Microprobe Analysis and Scanning Elec-
tron Microscopy in Geology, Cambridge University Press, Cambridge, UK,
2005, 212 pp.
88
20. Connolly, J., “PeRpLeX: A Tutorial,” ETH Zurich, Zurich, Switzer-
land, 1995, 90 pp., http://www.perplex.ethz.ch/perplex/tutorial/tutorial.pdf.
(last accessed Jan. 2, 2018)
21. Morsy, M. M.; Shebland, S. S.; and Rashad, A. M., “Effect of Fire
on Microstructure and Mechanical Properties of Blended Cement Pastes
Containing Metakaolin and Silica Fume,” Asian Journal Civil Engineering,
V. 9, 2008, pp. 93-105.
22. Tanyildizi, H., and Coskun, A., “An Experimental Investigation of
Bond and Compressive Strength of Concrete with Mineral Admixtures at
High Temperatures,” Arabian Journal Science, V. 33, 2008, pp. 101-109.
23. Demirel, B., and Keles-Temur, O., “Effect of Elevated Temperature
on the Mechanical Properties of Concrete Produced with Finely Ground
Pumice and Silica Fume,” Fire Safety Journal, V. 45, No. 6-8, 2010,
pp. 385-391. doi: 10.1016/j.firesaf.2010.08.002
24. Zeiml, M.; Leithner, D.,; Lackner, R.; and Mang, H. A., “How Do
Polypropylene Fibers Improve the Spalling Behavior of In-Situ Concrete,”
Cement and Concrete Research, V. 36, No. 5, 2006, pp. 929-942. doi:
10.1016/j.cemconres.2005.12.018
25. Ezziane, M.; Molez, L.; Jauberthie, R.; and Rangeard, D., “Heat
Exposure Tests on Various Types of Fibre Mortar,” EJECE, V. 15, No. 5,
2011, pp. 715-726. doi: 10.1080/19648189.2011.9693360
26. Park, S. J., and Tanigawa, Y., “Estimation of Fire Damage in High-
Strength Mortar Mixed with Polypropylene Fibers by Ultrasonic Tomog-
raphy,” Fire Science & Technology, V. 26, No. 4, 2007, pp. 351-359. doi:
10.3210/fst.26.351
27. Mendes, A.; Sanjavan, J.; and Collins, F., “Phase Transformations
and Mechanical Strength of OPC/Slag Pastes Submitted to High Tempera-
tures,” Materials and Structures, V. 41, No. 2, 2008, pp. 345-350. doi:
10.1617/s11527-007-9247-8
28. Le Maitre, R. W., Igneous Rocks—A Classification and Glossary of
Terms, second edition, Cambridge University Press, Cambridge, UK, 2002,
256 pp.
29. Divakara Rao, V.; Subba Rao, M. V.; and Murthy, N. N., “Granite
Forming Events and Their Role in Crustal Formation of the Indian Shield,”
Revista Brasileira de Geociencias, V. 29, 1999, pp. 33-40.
30. Connolly, J. A. D., “Computation of Phase Equilibria by Linear
Programming: A Tool for Geodynamic Modeling and Its Application to
Subduction Zone Decarbonation,” Earth and Planetary Science Letters,
V. 236, No. 1-2, 2005, pp. 524-541. doi: 10.1016/j.epsl.2005.04.033
31. Holland, T., and Powell, R., “Calculation of Phase Relations
Involving Haplogranitic Melts Using an Internally Consistent Thermody-
namic Dataset,” Journal of Petrology, V. 42, No. 4, 2001, pp. 673-683. doi:
10.1093/petrology/42.4.673
32. Fuhrman, M. L., and Lindsley, D. H., “Ternary-Feldspar Modeling
and Thermometry,” The American Mineralogist, V. 73, 1988, pp. 201-215.
33. Tajcmanová, L.; Connolly, J. A. D.; and Cesare, B. A., “Ther-
modynamic Model for Titanium and Ferric Iron Solution in Biotite,”
Journal of Metamorphic Geology, V. 27, No. 2, 2009, pp. 153-165. doi:
10.1111/j.1525-1314.2009.00812.x
34. White, R. W.; Powell, R.; and Holland, T. J. B., “Calculation of
Partial Melting Equilibria in the System Na2O-CaO-K2O-FeO-MgO-Al2O3-
SiO2-H2O(NCKFMASH),” Journal of Metamorphic Geology, V. 19, No. 2,
2001, pp. 139-153. doi: 10.1046/j.0263-4929.2000.00303.x
ACI Materials Journal/January 2018