J Therm Anal Calorim (2018) 131:949–968

https://doi.org/10.1007/s10973-017-6629-1

Thermal resistance, microstructure and mechanical properties

of type I Portland cement pastes containing low-cost nanoparticles
S. M. A. El-Gamal1 • S. A. Abo-El-Enein1 • F. I. El-Hosiny1 • M. S. Amin1,2 •

M. Ramadan1

Received: 4 April 2017 / Accepted: 9 August 2017 / Published online: 28 August 2017
Ó Akadémiai Kiadó, Budapest, Hungary 2017

Abstract This study aimed to utilize laboratory-prepared Introduction

nano-silica (NS) and nano-alumina (NA) as low-cost nano-
oxides additions for improving the mechanical properties Nano-technology applications have important roles in vari-
and thermal resistance of hardened ordinary Portland cement ous fields in our life, especially in science of concrete [1, 2].
(OPC) pastes. NS was synthesized from rice husk ash in the Utilization of nanoparticles (NPs) in the cementitious sub-
absence of any surfactant, while NA was synthesized from stances will generate specific concrete with high efficiency,
AlCl3 in the presence of CTAB as a surfactant. The average which is resistant to fire, acids and water permeability [3–7].
particle sizes of synthesized NS and NA were 30 and 40 nm, There are several reports on incorporation of metal
respectively. Nano-silica or nano-alumina was added to OPC oxides nanoparticles in concrete, in general, they focused
as a single phase with different ratios of 0.5, 1, 2 and 3 by on using SiO2 [8–22], Al2O3 [23–29], TiO2 [30–36], Fe2O3
mass % of OPC. The physico-chemical characteristics of [37–39] and ZnO nanoparticles [40–43]. The surface area
different OPC-NS and OPC-NA hardened pastes were of high value and good dispersion of nanoparticles causes it
studied after 1, 3, 7, 14, 28 and 90 days of hydration. The to act as binding centers for cement grains, as accelerators
resistance of the hardened composites for firing was evalu- for hydration reactions of cement particles, as nano-rein-
ated for specimens cured for 28 days under tap water and forcement, and as nano-filler in the pore space of cement
then fired at 300, 600 and 800 °C for 3 h. The fired specimens matrix thereby a more densified microstructure of low
were cooled by two methods: gradual cooling and rapid capillary porosity could be achieved [23].
cooling. The compressive strength test was performed for all Silica and alumina nanoparticles have an important role
mixes at each firing temperature. The compressive strength in the consumption of Ca(OH)2 via the pozzolanic reac-
results revealed that the optimum addition of NS is 1, tions. A secondary hydration products could be formed
whereas the optimum addition of NA is 0.5 by mass % of such as CSH, CAH and CASH, which contribute in the
OPC. XRD, TG/DTG and SEM results indicated that ill- mechanical properties development [27]. Nano-silica (NS)
crystalline and nearly amorphous C–S–H, C–A–S–H and C– particles possess high efficiency in concrete technology;
A–H were the main hydration products. this because of high surface area of these particles as well
as high pozzolanic reactivity [4].
Keywords Nano-silica
Nano-alumina
Thermal In the recent years, many researchers revealed the
resistance
Pozzolanic reaction
Compressive strength important roles of NS on the properties of cement-based
composites such as reducing setting times, increasing
hydration of heat, modifying the rheological properties of
& M. S. Amin cement pastes, increasing the mechanical behavior,
mohamedsamin@hotmail.com
decreasing the porosity and improving the durability factors
1
Chemistry Department, Faculty of Science, Ain Shams such as chlorine migration, sulfate resistance, water
University, Cairo, Egypt absorption, fire resistance, freeze–thaw resistance, diffusion
2
Chemistry Department, Faculty of Science, Taibah coefficient and conductivity [6, 42]. NS particles have
University, Medina, Saudi Arabia specific role in the fluidity of cement pastes. The small

123
950 S. M. A. El-Gamal et al.

agglomerates act as filler in the void space to release free extracted from waste material (rice husk) according to the
water, while the large agglomerates absorb the original free method mentioned in previous publications [51–54].
water which contribute actually in the paste fluidity [44]. Gamma nano-alumina was prepared by sol–gel method
Pozzolanic activity and hydration acceleration effect of from aluminum chloride anhydrous, as precursor in the
both colloidal nano-silica and silica fume (SF) were presence of CTAB as a surfactant [57]. Full characteriza-
reported; excessive amount of high stiffness CSH gel was tions of the prepared nanoparticles (NA and NS) such as TG/
observed especially in the first ages of cement hydration in DTG, XRD, TEM and SEM techniques are shown in
case of colloidal nano-silica [14]. Rice husk (RH) is widely Figs. 1–4, respectively. The physical properties of both
used. This increases the fire risk and several pollution synthesized NS and NA are shown in Table 2. Superplas-
problems [45–49]. Recently efforts have been made to ticizer (SP) is used to give perfect dispersion of nano-oxides
extract low-cost amorphous NS from the waste (rice husk), and enhances the paste workability. In this investigation,
which has important environmental and economic impact polycarboxylate-based SP was used; it was supplied from
[50–54]. Nano-alumina (NA) also has a good pozzolanic Sika Company, Elobour City, Egypt; Table 3 shows some of
activity to produce additional hydration products such as the physical properties of SP admixture.
CASH and CAH gel, which contribute also in the devel-
opment of the mechanical characteristics. Methodology
Al2O3 nanoparticles possessing characterized surface
area can react with Ca(OH)2 produced from calcium alu- Different OPC pastes were prepared using various addi-
minate (C3A) hydration. The optimum level of NA parti- tions of NS or NA (by mass % of OPC). Table 4 indicates
cles content was achieved 1.0% to enhance mechanical the composition of the various cement composites and their
properties and decrease water absorption percentage of designation. The desired amounts of NS or NA were added
concrete specimens [25]. to an aqueous solution (using the whole mixing water)
The concrete workability was improved by superplasti- containing 0.3% of PC (by mass of OPC), and the resulting
cizers (SPs) addition [23]. The addition of NA up to 5% by suspensions were sonicated at 25 °C for 30 min; water/
mass enhanced the elasticity modulus without increasing in cement (W/C) ratio used to prepare different pastes is 0.27.
the compressive strength; the excessive amount of NA has a Each paste was made by mixing OPC with the desired
bad effect on the strength, due to agglomeration of NA [24]. amount of water containing the dispersed NS or NA for
It was concluded that alumina nanoparticles are used as about 5 min. The resultant paste was molded into cubic
an accelerator for belite phase dissolution mainly at the first specimens by using 1-inch cube molds.
ages of cement matrix hydration and it caused a decrease in The molds containing the specimens were cured
porosity of cement matrix [55]. Fire is natural problem and at *100% relative humidity for first 24 h to obtain the
has a dangerous effect on the building materials. Several
deteriorations occur for concrete exposure to elevated Table 1 Chemical oxide and mineralogical phase compositions of
temperature due to hydration products decomposition OPC
mainly as CH, CSH, CAH and CASH [56]. Oxides Mass/%
The resistance to fire is related to the type of substances
used on concrete. Addition of 1% NA particles can SiO2 19.40
improve the thermal resistance of cement matrix against Al2O3 4.65
fire [24, 27]. The aim of this study is to improve the Fe2O3 3.82
thermal resistance and mechanical properties of Type I CaO 64.11
Portland cement containing different additions of low-cost MgO 1.85
synthesized silica and alumina nanoparticles. SO3 3.16
Na2O 0.31
K2O 0.27
Experimental Cl- –
L.O.I 2.10
Materials LSF 99.37
Mineralogical phase composition, mass (%)
Type I Portland cement (OPC) was used in this study, sup- C3S 67.81
plied from Lafarge cement company, Suez, Egypt, with C2S 4.49
3320 cm2 g-1 surface area. Table 1 indicates the mass C3A 5.87
percentage of chemical oxides and mineral composition of C4AF 11.61
OPC. Amorphous NS particles used in this study were

123
Thermal resistance, microstructure and mechanical properties of type I Portland cement pastes... 951

0.01
18 140

16 0.00 120
14 88°C 483°C 100
381°C –0.01

DTG/mg min–1
12

Counts/s
TG/mg

10 16.4 % 80
–0.02
8
60
6 –0.03
40
4
310°C –0.04
2 20
0 –0.05
0 200 400 600 800 1000 0
(a) 0 10 20 30 40 50 60 70 80 90
50 2θ /°
0.005
(a)
45 0.000

–0.005 120
DTG/mg min–1
40
TG/mg

–0.010
441°C 100
16.73 %
35 –0.015
80
–0.020
Counts/s

30 138°C 60
–0.025
326°C

25 –0.030 40
0 200 400 600 800 1000
Temperature/°C 20
(b)
0

Fig. 1 TG/DTG of a RH and b synthesized Al(OH)3 0 10 20 30 40 50 60 70 80 90

2θ /°
final setting. After that, the specimens were cured under tap (b)
water at room temperature for various time intervals of 3,
Fig. 2 X-ray diffraction patterns of a synthesized nano-silica and
7, 14, 28 and 90 days. At each mentioned time, the com-
b synthesized gamma nano-alumina
pressive strength test is applied on 4 cubes and the average
value was recorded. This was done by using a Tonindustrie room temperature, while the others were soaked in tap
machine (West Germany). The resulting crushed speci- water (25 °C) for rapid cooling. The cooling periods var-
mens were ground, and the hydration reaction was stopped ied, depending on heating temperatures and cooling
[58]. The obtained samples were dried at 80 °C for 3 h and method. Finally, the compressive strength (FCompression)
maintained in a desiccator containing silica gel until the test is carried out on the cooled specimens.
time of testing. Phase composition and the morphology of hydrates
Chemically combined water content (Wn, %) and free formed were investigated by X-ray diffraction (XRD),
lime contents (CaO, %) are a good indicator for hydration thermal gravimetric analysis (TG/DTG) and scanning
kinetics which can be determined at various hydration ages. electron microscopy (SEM) techniques.
Wn, % and CaO, % can be determined via the method
mentioned in previous publications [5].
For thermal resistance test, the hardened cubic samples Results and discussion
were cured under tap water for 28 days, dried for 1 day at
80 °C, and then subjected to thermal treatment for 3 h at Compressive strength (FCompression)
300, 600 and 800 °C. The hot specimens were cooled by
two different ways. One group of specimens were left in a Figure 5a, b shows the FCompression values of hardened
closed desiccator for slow (gradual) cooling until reach the specimens made from control mix (neat OPC) and OPC

123
952 S. M. A. El-Gamal et al.

Fig. 4 SEM images of a synthesized NS and b synthesized gamma NA

Fig. 3 TEM images of a synthesized NS and b synthesized gamma NA

Besides, NS undergo pozzolanic reactions with port-
landite formed from the hydration process of Portland
pastes blended with different amounts of NS. In general, cement (PC), giving additional amount C–S–H, which
the FCompression values show a continuous increase with the leads to the compressive strength development [27].
hydration age for all the tested mixes, Fig. 5a. This However, addition of excessive amount of NS (3 mass %)
increase is a mainly due to the progress of hydration leads to a notable decrease in the FCompression values as
reaction and formation of calcium silicate hydrates (CSHs), compared to other NS-OPC composites (mixes S1–S3), but
calcium aluminate hydrates (CAHs) and calcium aluminate the compressive strength values still comparable to that of
silicate hydrates (CASHs) as a main hydration products. the control (mix S0); actually, this decrease is mainly due
These hydration products act as the main binding centers to the agglomeration of NS particles [15, 16, 29]. Figure 5b
between the remaining unhydrated cement particles [3, 4]. shows the relative FCompression values of the hardened
Obviously, the addition of NS up to 2 mass % enhances specimens made from mixes S1–S4. The results indicated
the FCompression values of OPC pastes during nearly all that the hardened specimens made of mixes S1, S2, and S3
periods of hydration, especially after 7 days of hydration. give higher relative compressive strength values as com-
This result is explained in terms of the high specific surface pared to those of mixes S0 and S4, indicating the
area of NS (195 m2 g-1), its filling effect and the good enhancing effect of the well-dispersed NS particles.
dispersion of NS particles, which act as nucleation sites for Obviously, the specimens made from mix S2 (containing
cement hydration. 1% NS) present the highest relative strength values.

123
Thermal resistance, microstructure and mechanical properties of type I Portland cement pastes... 953

Table 2 General physical properties of nano-silica and nano-alumina

Property Diameter/nm BET surface area/m2 g-1 Density/g cm-3 Purity/%

NS 30 ± 5 195 \0.14 [97

NA 40 ± 5 173 \0.1 [99

Table 3 Physical properties of polycarboxylate superplasticizer (SP)

120
Appearance Yellow–brown liquid

Solid residue/% Approximately 39.9%

100

Compressive strength/MPa
pH 7.51–7.53
Specific gravity/g mL-1 Approximately 1.08%
80

S0
60
Table 4 Mix compositions of the prepared composite cements, S1
mass % S2
S3
Mix OPC NS NA 40
S4

S0 100 – –
20
S1 100 0.5 – 1 10 100
S2 100 1 – Age of hydration/days
S3 100 2 – (a)
S4 100 3 –
A1 100 – 0.5
Relative strength to the mixes without NS %

S1 S2 S3 S4
A2 100 – 1
140
A3 100 – 2
A4 100 – 3 120

100

The FCompression values of these specimens increased by 80

10, 12, 14, 42, 10 and 14% (relative to blank) after 1, 3, 7,
14, 28 and 90 days, respectively. This increase is mainly 60

due to the good dispersion of NS particles and the filler 40

effect between the formed hydration products which by its
role has a large effect in reducing the total porosity of the 20
hardened cement matrix, causes an observed increase in the 0
values of FCompression for the hardened specimens. 1 3 7 14 28 90

The effect of addition 0.5, 1, 2, 3 mass % of NA on the Age of hydration/days

values of FCompression of OPC hardened pastes is given in
(b)
Fig. 6a. Evidently, addition of 0.5 and 1% NA (by mass of
OPC) enhances the compressive strength values of OPC Fig. 5 Effect of NS addition on a compressive strength values and
hardened pastes, during all periods of hydration (especially b relative compressive strength values for different OPC-NS hardened
pastes
during the first 14 days), while addition of 2 and 3 mass %
NA gives higher and/or comparable values to that of con-
trol (mix S0), during nearly all age of hydration. Evidently,
these results are a mainly due to the high specific surface the hardened cement matrix [24]. Finally, NA undergoes a
area of NA (173 m2 g-1), good dispersion of NA. Besides, pozzolanic reaction with the free lime produced from
NA accelerates the OPC hydration by acting as nuclei for cement hydration, resulting in the formation of excessive
the hydration process of cement particles, as well as the amounts of hydration products (mainly as C–A–H and
nano-filler effect of NA, which densifying the microstruc- C–A–S–H), which produces a highly dense matrix with
ture, thereby causing a net reduction in the total porosity of low porosity and high strength [27].

123
954 S. M. A. El-Gamal et al.

120 21
20
Compressive strength/MPa

100 19
18
17
80
16
S0

Chemical combined water contents/Wn,%

15 S1
S0 14 S2
60
A1 S3
13 S4
A2
A3 12
40
A4 11
10
1 10 100
20
1 10 100 Age of hydration/days
Age of hydration/days (a)
(a)
20

140 A1 A2 A3 A4
Relative strength to the mixes

18
120
16
100 S0
without NA %

14 A1
80 A2
A3
60 12 A4

40
10
20 1 10 100
0 Age of hydration/days
1 3 7 14 28 90
(b)
Age of hydration/days
(b) Fig. 7 Chemical combined water contents of a OPC-NS and b OPC-
NA hardened pastes
Fig. 6 Effect of NA addition on a compressive strength values and
b relative compressive strength values for different OPC-NA
hardened pastes
progress of the hydration reaction, and the accumulation
of excessive amounts of hydration products, which pre-
cipitated in the available open pores system of the hard-
Figure 6b shows the relative FCompression values of OPC- ened cement pastes [5].
NA hardened composites (mixes A1–A4). The results Evidently, the values of Wn % obtained for all OPC-NS
indicated that the specimens made from OPC admixed with and OPC-NA hardened pastes are higher than those of
0.5% NA (mix A1) has the highest relative compressive control (mix S0), (Fig. 7a, b). The higher values of com-
strength values among all other tested mixes. The com- bined water obtained for the specimens admixed with dif-
pressive strength values for these specimens increased by ferent amounts of NS or NA are mainly due to the higher
6, 23, 32, 28, 11 and 11% after 1, 3, 7, 14, 28 and 90 days, pozzolanic activity of NS or NA nanoparticles, which
respectively (relative to mix S0). result in the formation of additional hydration products
[4, 27]. Besides, the presence of NS or NA particles
Hydration characteristics accelerates the hydration process of OPC grains by acting
as nucleation centers for hydration process [16, 24].
Chemically combined water contents (Wn %)
Free lime content (FL %)
The results of chemically combined water content (Wn %)
for hardened specimens made from OPC, OPC-NS and The values of the free lime content (FL %) of the hardened
OPC, OPC-NA mixes are given in Fig. 7a, b, respectively. specimens made from OPC, OPC-NS, and OPC, OPC-NA
Obviously, the Wn values increase with the age of mixes are represented in Fig. 8a, b, respectively. The val-
hydration for all the tested mixes up to the final age of ues of (FL %) obtained for specimens made from neat OPC
hydration (90 days). This increase is a main result of the (mix S0) showed a continuous increase with the age of

123
Thermal resistance, microstructure and mechanical properties of type I Portland cement pastes... 955

S0 25 °C 300 °C 600 °C 800 °C

10
S1 120
S2
8 S3 100
S4

6 80

4 60

40
2
Free lime contents/CaO,%

20

Compressive strength/MPa
1 10 100
Age of hydration/days 0
(a) S0 S1 S2 S3 S4
Type of cement composite
S0
10 A1 (a)
A2
A3 120 25 °C 300 °C 600 °C 800 °C
A4
8

80
6

4
40

1 10 100
Age of hydration/days
(b) 0
S0 S1 S2 S3 S4
Fig. 8 Free lime contents of a OPC-NS and b OPC-NA hardened Type of cement composite
pastes
(b)

hydration up to the final ages of hydration, indicating the Fig. 9 Compressive strength values of hardened composites made
from OPC-NS after firing at different temperatures and cooled
continuous liberation of free portlandite (CH) from the a gradually in air, b suddenly cooled in water
hydration of OPC. FL contents for hardened OPC pastes
blended with different amount of NS (mixes S1–S4)
showed a continuous slight increase up to 14 days, fol- S4), Fig. 8b. These results are explained in terms of the
lowed by a marked decrease up to the final age of hydration same reasons mentioned previously in case of NS-OPC
(90 days), Fig. 8a. Evidently, the free lime values obtained composites.
for these hardened composites are a net result of two
opposite processes, namely (1) an increase in the amount of Effect of firing temperature on the compressive
free lime produced from OPC hydration and (2) the con- strength values of neat OPC, OPC-NS and OPC-NA
sumption of these liberated lime via the pozzolanic reaction hardened pastes
with NS to produce additional amount of C–S–H as a main
hydration products. As a net result of these two opposite The results of compressive strength values of the speci-
processes, the values of free lime contents obtained for all mens made from mixes S0–S4 after firing at 300, 600 and
OPC-NS hardened pastes are lower than those of mix S0. 800 °C for 3 h and cooled gradually in the air are presented
Also, increase in the percentage addition of NS to OPC in Fig. 9a. All fired mixes showed an observed increase in
pastes is accompanied by a large decrease in the values of the values of compressive strength upon heating at 300 °C.
FL content [5, 8]. This increase is followed by subsequent decrease upon
FL contents for OPC-NA hardened composites (mixes firing at 600 and 800 °C. The residual compressive strength
A1–A4) are lower than those of neat OPC hardened paste, for fired specimens made from mix S0 increased by 3%
during all period of hydration and also indicated the same (relative to its compressive strength value recorded at
trend as that of NS-OPC hardened composites (mixes S1– 28 days of hydration) after heating at 300 °C, while mixes

123
956 S. M. A. El-Gamal et al.

S1, S2, S3 and S4 showed an increase in the residual that showed by OPC-NS admixed hardened pates upon
compressive strength by 8, 9, 14 and 12% (relative to their firing at the different temperature, Fig. 10a. The residual
compressive strength values recorded after 28 days of compressive strength of mixes A1, A2, A3 and A4
hydration), respectively. increased by 15, 18, 5 and 3%, respectively, after firing at
This increase in percentage residual strength is mainly 300 °C. This increase in percentage of residual strength is
due to the internal autoclaving process, besides, enhancing mainly due to the internal (self-autoclaving) effect result
the pozzolanic interaction between NS and free lime from flow of the steam production from the elimination of
formed from OPC hydration. These two factors produce capillary and/or physically adsorbed as well as bound water
excessive amounts of nearly amorphous and microcrys- in NA-OPC pastes at high temperature. This internal
talline C–S–H, which is filling up the pores, producing a autoclaving reaction produces additional amounts of
highly dense and closely packed structure, with higher hydration products (mainly as CSH); besides it enhances
residual compressive strength values [4, 24]. the pozzolanic reaction between NA and CH leading to the
However, the residual compressive strength values of formation of additional amounts of C–A–H and C–A–S–H
mixes S0, S1, S2, S3 and S4 decreased by 49, 23, 25, 36, [4, 34].
37%, respectively, after firing at 600 °C. This decrease is However, the compressive strength decreased by about
explained in terms of the decomposition of the cementi- 15, 21, 21, and 21% after firing at 600 °C, for mixes A1,
tious materials and the free Ca(OH)2, which loses its A2, A3, and A4, respectively. This decrease is due to the
combined water after 500 °C [3]. decomposition of nearly all formed hydration products.
Increasing the heating temperature up to 800 °C leads to
140
the reduction in compressive strength values by 69, 65, 65, 25 °C 300 °C 600 °C 800 °C
64 and 68% for mixes S0, S1, S2, S3 and S4, respectively;
120
the great loss in the strength for the hardened pastes fired at
800 °C is mainly due to the formation of new cracks inside 100
the fired specimens. In addition, the complete thermal
decomposition of the binding hydration products, such as 80
CSH, leads to an enlargement in the micro-cracks. On
conclusion, the addition of NS to OPC enhances the 60
resistance of the OPC hardened pastes toward firing at
different temperatures. 40

Figure 9b shows the compressive strength values of the

Compressive strength/MPa

hardened pastes made of mixes S0–S4 fired at 300, 600 and 20

800 °C and suddenly cooled in water. Obviously, the val-

0
ues of compressive strength obtained for suddenly cooled S0 A1 A2 A3 A4
specimens were lower than those of their corresponding Type of cement composite
samples gradually cooled at the same firing temperature. (a)
Evidently, all mixes showed a continuous decrease in
120 25 °C 300 °C 600 °C 800 °C
the compressive strength values with increasing the heating
temperature from 300 to 600 °C till reached to zero at
800 °C. The degree of loss in compressive strength values
for OPC-NS nanocomposites is lower than that of mix S0. 80
The notable great loss in strength for suddenly cooled
specimens can be explained, besides the effects of high
temperatures, in terms of the thermal shock that occurred
40
by sudden cooling (using cooled water) of the fired spec-
imens. This leads to an enlargement in the micro-cracks,
besides the formation of new cracks inside the fired spec-
imens. Increasing the heating temperature increases the 0
effect of thermal shock, and this explains the great decrease S0 A1 A2 A3 A4

in the residual strength in all specimens fired at 600 and Type of cement composite
800 °C [59]. (b)
The compressive strength values of the hardened com-
Fig. 10 Compressive strength values of hardened composites made
posites made from mixes A1–A4 fired at 300, 600 and from OPC-NA after firing at different temperatures and cooled
800 °C and gradually cooled in air indicated similar trend a gradually in air, b suddenly cooled in water

123
Thermal resistance, microstructure and mechanical properties of type I Portland cement pastes... 957

Fig. 11 XRD diffraction CH Quartz

patterns of hardened pastes CSH β -C2S
made of mix S0 CaCO3 C 3S

90 days

Intensity
28 days

3 days

10 20 30 40 50 60
2θ /°

Fig. 12 XRD diffraction CH Quartz

β -C2S
patterns of hardened pastes CSH
C3 S
CaCO3
made of mix S2
90 days
Intensity

28 days

3 days

10 20 30 40 50 60
2θ /°

Fig. 13 XRD diffraction CH Quartz

patterns of hardened pastes CSH β -C2S
CaCO3
made of mix A1 C3S

90 days
Intensity

28 days

3 days

10 20 30 40 50 60
2θ /°

123
958 S. M. A. El-Gamal et al.

Fig. 14 TG/DTG curves of 74

hardened pastes made of mix S0 0.000
at different ages of hydration 72

70 –0.002

DTG/mg min–1
8.43 %
68

TG/mg
19.19 % –0.004
66 770°C
162°C 6.02 % –0.006
64

62 6.74 % –0.008

60
90 days 500°C –0.010
58
0 200 400 600 800 1000
64
0.000
62

DTG/mg min–1
60 –0.002
6.71 %
TG/mg

58 16.43 %
–0.004
135°C 4.33 % 767°C
56
–0.006
54 5.39 %

52 498°C –0.008
28 days

0 200 400 600 800 1000

94

92 0.000
5.18 %
90
–0.002

DTG/mg min–1
88
3.15 % 14.21 %
86
TG/mg

–0.004
84
132°C
5.88 % –0.006
82

80
3 days 502°C –0.008
78
0 200 400 600 800 1000
Temperature/°C

Upon firing these hardened composites at 800 °C, the specimens were lower than those of their corresponding
reduction in compressive strength values reaches 60, 62, specimens gradually cooled specimens after firing at the
67 and 73% for mixes A1, A2, A3, and A4, respectively. same temperature. In addition, for all tested specimens,
Obviously, addition of NA to OPC enhances the resis- there is a continuous decrease in the compressive strength
tance of the hardened OPC pastes toward firing; besides, values with increasing the firing temperature from 300 to
the results indicated that OPC hardened paste admixed 600 °C and reached 800 °C, but the degrees of loss in the
with 0.5% of NA presented the highest residual com- compressive strength values for mixes containing NA is
pressive strength values upon heating at different tem- lower than that of control (mix S0).
peratures, as compared with neat OPC and all OPC-NA
admixed mixes. X-ray diffraction
Figure 10b shows the compressive strength values of the
pastes made of mixes S0, A1–A4 after firing at 300, 600 X-ray diffraction patterns obtained for the hardened spec-
and 800 °C and suddenly cooled in water. Obviously, the imens made from neat OPC (mix S0), OPC containing 1%
compressive strength values obtained for suddenly cooled NS (mix S2), and OPC containing 0.5% NA (mix A1) after

123
Thermal resistance, microstructure and mechanical properties of type I Portland cement pastes... 959

Fig. 15 TG/DTG curves of 84

hardened pastes made of mix S2 0.000
82
at different ages of hydration
80
0.002
78
10.06 %

DTG/mg min–1
76 19.17 % 0.004

TG/mg
74 820°C
220°C 2.97 % 0.006
72 115°C
176°C
70 6.15 % 0.008
68
90 days 520°C 0.010
66

0 200 400 600 800 1000

56

54 0.000
8.93 %
52

DTG/mg min–1
–0.002
TG/mg

50 18.84 %
230°C 2.98 %
48
173°C 820°C –0.004
118°C
46 6.93 %

44 28 days 513°C –0.006

0 200 400 600 800 1000

76

0.000
74

72 –0.002
6.52 %

DTG/mg min–1
70 14.93 %
TG/mg

–0.004
131°C 3.11 %
68
792°C
–0.006
66 5.3 %
497°C –0.008
64
3 days

0 200 400 600 800 1000

Temperature/°C

3, 28 and 90 days of hydration are presented in Figs. 11– characterized for calcium silicate hydrates (CSHs) and CH
13, respectively. The main hydration products obtained increases with increasing age of hydration up to the final
from neat OPC hydration are calcium silicate hydrates age of hydration (90 days), Fig. 11, because of the progress
(CSH) and portlandite (CH), Fig. 11. Also, the peaks of hydration reaction.
characteristics for unhydrated parts of C3S and b-C2S For the hardened specimens made from OPC admixed
grains could also be distinguished, besides quartz (Q) and with 1% of NS and 0.5% NA (mixes S2 and A1), indicated
calcium carbonate. Obviously, the intensities of the peaks the same diffraction patterns as blank, and the same trend,
characterizing C3S and b-C2S decrease with increasing age with a notable decrease in the intensity of the main peak
of hydration; meanwhile, the intensities of the peaks characteristic for CH and subsequent increase in the

123
960 S. M. A. El-Gamal et al.

Fig. 16 TG/DTG curves of

86 0.000
hardened pastes made of mix
A1 at different ages of hydration 84
–0.002
82
80 9.78 % –0.004

DTG/mg min–1
19.08 %
78

TG/mg
118°C –0.006
825°C
76 3.19 %
–0.008
74
72 6.11 % –0.010
70 520°C
90 days –0.012
68
0 200 400 600 800 1000

96
0.000
94
–0.002
92
90 8.84 % –0.004

DTG/mg min–1
88 17.54 %
TG/mg

222°C 815°C –0.006

86 175°C
120°C 3.91 %
84 –0.008

82 4.79 % –0.010
80
524°C
78 28 days –0.012

0 200 400 600 800 1000

54
7.08 % 0.000

52

DTG/mg min–1
15.43 % –0.002
TG/mg

50 223°C
2.61 %

173°C 812°C
116°C –0.004
48
6.74 %

46 3 days 519°C
–0.006

0 200 400 600 800 1000

Temperature/°C

intensity of the peak characteristic for CSH, Figs. 12 and NS cement paste containing 1% NS (mix S2), and OPC-
13, respectively. These results are attributed to the poz- NA cement paste containing 0.5% NA (mix A1), after 3, 28
zolanic reaction between NS or NA and the released and 90 days are shown in Figs. 14–16, respectively. The
portlandite during OPC cement hydration [3, 5]. TG/DTG curves of the hardened neat OPC paste indicate
the presence of three endothermic peaks located at tem-
Differential thermogravimetric analysis (TG/DTG) perature ranges of 100–150, 450–520 and 650–800 °C,
Fig. 14.
The results of the differential thermogravimetric analysis The first endothermic peak located at 100–150 °C is
obtained for the hardened neat OPC paste (mix S0), OPC- due to the dehydration of the amorphous part of

123
Thermal resistance, microstructure and mechanical properties of type I Portland cement pastes... 961

Fig. 17 SEM micrographs of cement pastes made of mix S0: a1, a2 after 3 days, b1, b2 after 28 days and c1, c2 after 90 days

calcium silicate hydrates (CSH) and calcium sulphoa- The main endothermic peak observed in the temperature
luminates hydrates (ettringite and monosulphate) [60]. range of 450–520 °C, with a maximum at 500 °C, is attrib-
The values of percentage mass loss of this endotherm uted to the thermal decomposition of Ca(OH)2, [61]. The
are 5.18, 6.71 and 8.43% after 3, 28, and 90 days of values of percentage mass losses of this endotherm are 3.15,
hydration, respectively. The observed increase in the % 4.33 and 5.02% after 3, 28 and 90 days, respectively. The
mass loss with hydration age is an evidence of observed increase in the percentage mass loss with increas-
increasing the amount of the formed hydration products ing age of hydration is due to increase in the amount of the
(mainly as CSH and calcium sulphoaluminate hydrates) formed CH as a result of the progress of hydration of OPC.
as a result of the progress of hydration reaction. These Furthermore, it is evident that a part of the hydrated
results agree with the results obtained from compressive product was carbonated during handling of the specimens
strength test. as demonstrated by endotherm at 650–800 °C. The mass

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962 S. M. A. El-Gamal et al.

Fig. 18 SEM micrographs of cement pastes made of Mix S0: a1, a2 after firing at 300 °C and b1, b2 after firing at 800 °C

loss values of this endotherm are accounted for the dif- represents the decomposition of hydrogarnet, mainly as
ferent degrees of carbonation of the hydrated specimens C3ASH4, [62–66].
[27, 58]. The sixth endothermic peak observed at about
Figure 15 illustrates the TG/DTG curves obtained for 450–520 °C, with the maximum at 513 °C, is due to the
OPC-NS hardened pastes containing 1% NS (mix S2). The thermal decomposition of Ca(OH)2. The last two
curves indicate the same three endothermic peaks as that of endothermic peaks appear at 780 and 890 °C represent the
control (mix S0) after 3 days of hydration, while, after 28 decomposition of CaCO3 with different degree of crys-
and 90 days of hydration, the TG/DTG curve shows eight tallinity, [67–70]. Evidently, the appearance of additional
endothermic peaks. The first endothermic peak located at four endothermic peaks at 160–200, 200–280, 300–350,
about 100–150 °C characterizes the dehydration of the and 380–410 °C is mainly due to the presence of nano-
amorphous part of calcium silicate hydrates, mainly as silica which acts as nucleation center enhances the for-
CSH-I and CSH-II, as well as calcium sulphoaluminate mation of additional hydration products mainly as C–A–H
hydrates (ettringite and monosulfate hydrates). and C–A–S–H, Fig. 15.
The second endothermic peak observed at about The values of the total mass loss for the formed
160–200 °C represents the decomposition of the calcium hydration products increase from 14.93, 18.84 and 19.17%
aluminate hydrate, mainly as C4AH13 and/or the gehlenite after 3, 28 and 90 days of hydration, respectively. These
hydrate, mainly as C2ASH8. The third endothermic peak results account for increase in the amount of the formed
observed at about 200–280 °C represents the dehydration hydration products as a result of the continuity of the
of hexagonal phase of calcium aluminate hydrate, mainly hydration process. The values of the mass loss of the
as C2AH8. The fourth endothermic peak located at about endothermic peak characteristic for the decomposition of
300–350 °C characterizes the decomposition of calcium portlandite are 3.11, 2.98 and 2.97% after 3, 28 and
aluminate hydrate of cubic shape mainly as C3AH6. The 90 days of hydration, respectively. These values are
fifth endothermic peak observed at about 380–410 °C attributed to the formation of CH from OPC hydration and

123
Thermal resistance, microstructure and mechanical properties of type I Portland cement pastes... 963

Fig. 19 SEM micrographs of cement pastes made of Mix S2: a1, a2 after 3 days, b1, b2 after 28 days and c1, c2 after 90 days

its subsequent consumption of it via the pozzolanic reac- loss values for the formed hydration products increase from
tion with the NS particles. 15.43, 17.54 and 19.08% after 3, 28 and 90 days of
The TG/DTG curves obtained for the hardened speci- hydration, respectively. These results are explained in
mens made from OPC paste containing 0.5 mass % NA terms of the progress of hydration reaction.
(mix A1) are present in Fig. 16. The TG/DTG curves of The values of the mass loss of the endothermic peak
these specimens indicated the same eight endothermic characteristic for decomposition (located at 520 °C) are 2.61,
peaks mentioned previously in case of mix S2 after 3, 28 3.91 and 3.19% after 3, 28 and 90 days of hydration, respec-
and 90 days of hydration. The formation of additional four tively. These values are explained in terms of the formation of
peaks 160–200, 200–280, 300–350 and 380–410 °C is CH due to OPC hydration and its subsequent consumption via
mainly due to the presence of NA particles. The total mass the pozzolanic reaction with the NA particles.

123
964 S. M. A. El-Gamal et al.

Fig. 20 SEM micrographs of cement pastes made of mix S2: a1, a2 after firing at 300 °C and b1, b2 after firing at 800 °C

Morphology and microstructure This result is attributed to the internal autoclaving of the
remaining parts of unhydrated OPC particles, leading to a
The SEM micrographs of hardened specimens made from massive structure with relatively higher compressive
neat OPC pastes (mix S0) after 3 days of hydration are strength. After firing neat OPC at 800 °C and gradually
shown in Fig. 17a1, a2, the SEM images of these speci- cooling in the air, the SEM images present microstructure
mens indicate the formation of small amount of nearly which possesses various micro-cracks, which have a neg-
amorphous and microcrystalline particles of tobermorite- ative effect on the porosity and the compressive strength
like calcium silicate hydrates (C–S–H) as well as hexago- values of OPC cement pastes, (Fig. 18b1, b2).
nal crystals of CH; besides small amount of calcium car- The SEM micrographs of hardened OPC pastes con-
bonates was observed in the cement matrix due to the taining 1% NS (mix S2) after 3 days of hydration reveal
partial carbonation of the specimens during handling. the formation of nearly amorphous and ill-crystalline cal-
After 28 and 90 days of hydration, the SEM images of cium silicate hydrate (C–S–H) as a main product of OPC
these specimens indicate dense cement matrix consists of hydration intermixed with small amount of hexagonal
excessive amount of dominant hydration products mainly crystals of CH and calcium sulfoaluminate hydrate (et-
as needle crystals as well as fibers of C–S–H intermixed tringite), Fig. 19a1, a2. After 28 days of hydration, SEM
with well-developed CH crystals, but there are pore spaces micrographs show well-developed crystals of CH as thin
still available for the deposition of further hydration plates of hexagonal symmetry with the presence of micro-
products Fig. 17b1, b2, c1, c2, respectively. fibrous and amorphous particles of CSH, Fig. 19b1, b2.
Figure 18a1, a2 presents the SEM images of hardened After 90 days of hydration, SEM images indicate the for-
OPC cement pastes (mix S0) after firing at 300 °C and mation of an excessive amount of hydration products
gradually cooled in air. The micrographs reveal a highly mainly as needle crystals of C–S–H.
dense and compact microstructure due to the formation of This excessive amount of C–S–H is attributed to the
an excess amount of nearly amorphous and microcrys- pozzolanic reaction of nano-silica with free lime liberated
talline C–S–H as the dominant hydration products. from OPC hydration reaction, Fig. 19c1, c2. Figure 20a1,

123
Thermal resistance, microstructure and mechanical properties of type I Portland cement pastes... 965

Fig. 21 SEM micrographs of cement pastes made of mix A1: a1, a2 after 3 days, b1, b2 after 28 days and c1, c2 after 90 days

a2 shows the SEM micrographs of hardened specimens from OPC hydration. The microstructure of S2 specimens
made from mix S2 after firing at 300 °C and gradually after firing at 800 °C and gradual cooling in air reveals the
cooled in air. The micrographs reveal the formation of an presence of different micro-cracks as a result of high-
excess amount of hydration products mainly as needle and temperature effect as well as the decomposition of the
microcrystalline calcium silicate hydrate (C–S–H) and formed hydrates; this leads to obvious depression in the
well-developed crystals of hydrogarnet phase (C–A–S–H) values of compressive strength for these specimens,
as well as small amount of hexagonal crystals of CH. Fig. 20b1, b2. The SEM micrographs of hardened speci-
This excessive amount of the formed hydration products mens made from mix A1 (OPC ? 0.5% NA) after 3 days
is attributed to the internal autoclaving of the remaining of hydration indicate the formation of nearly amorphous
parts of unhydrated OPC particles as well as the pozzolanic and microcrystalline hydration products mainly as C–S–H
reaction of nanoparticles (NS) with free lime produced and calcium sulfoaluminate hydrate (ettringite), as well as

123
966 S. M. A. El-Gamal et al.

Fig. 22 SEM micrographs of cement pastes made of Mix A1: a1, a2 after firing at 300 °C and b1, b2 after firing at 800 °C

small amount of CH crystals dispersed in the matrix, of CH with the presence of excess amount of CAH and
Fig. 21a1, a2. CASH crystals.
After 28 days of hydration of these specimens, the SEM After firing these specimens at 800 °C, several micro-
images reveal the formation of the dense microstructure of cracks appeared in the matrix as well as the decomposition of
hydration products mainly as needle crystals of C–S–H and the formed hydration products was observed, leading to the
hexagonal crystals of calcium sulfoaluminate mono-hy- destruction of the binding forces as represented by very low
drate as well as hydrogarnet phase (C–A–S–H); also some compressive strength for these specimens, Fig. 22b1, b2.
hexagonal crystals of CH were still present, Fig. 21b1, b2.
After 90 days of hydration, SEM micrographs indicate
the formation of highly compact microstructure with low
degree of porosity due to the formation of excessive Conclusions
amount of hydration products (CASH and CAH) as result
of pozzolanic interaction between NA and CH formed from Based on the results obtained in this study, the following
OPC hydration; these hydration products fill up the present conclusions could be derived:
pore as well as the filling effect of the NA particles for the 1. All the OPC hardened pastes admixed with different
nanopores present in the hardened paste, Fig. 21c1, c2. As amounts of NS or NA have high compressive strength
a result, these specimens present high compressive strength values, as well as fire resistance than that of neat OPC
values as compared with neat OPC (mix S0). hardened paste.
The SEM micrographs of the hardened specimens made 2. The compressive strength values of OPC-NS hardened
from mix A1 (OPC ? 0.5% NA) after firing at 300 °C and cement pastes increase with increasing the NS content up
gradually cooled in the air are shown in Fig. 22a1, a2. As to 2% (by mass of OPC), while in the case of OPC-NA
indicated from the SEM images, the microstructure com- hardened cement pastes it continues to increase with NA
posed of a dense structure of microfibers and amorphous content up to 1% (by mass of OPC). The compressive
CSH intermixed with a small amount of hexagonal crystals strength values, as well as the fire resistance test indicated

123
Thermal resistance, microstructure and mechanical properties of type I Portland cement pastes... 967

that the optimum addition of NS is 1 mass % (mix S2). 14. Hou P, Kawashima S, Kong D, Corr DJ, Qian J, Shah SP.
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4. The free lime content of nanocomposites containing elevated water curing temperature and regular room air curing
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