Construction and Building Materials 187 (2018) 448–459

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Construction and Building Materials

journal homepage: www.elsevier.com/locate/conbuildmat

Enhancement of strength and durability of fly ash concrete in seawater

environments: Synergistic effect of nanoparticles
Sudha Uthaman a, Vinita Vishwakarma a,⇑,1, R.P. George b,1, D. Ramachandran a, Kalpana Kumari c,
R. Preetha c,1, M. Premila d, R. Rajaraman d, U. Kamachi Mudali e
a
Centre for Nanoscience and Nanotechnology, Sathyabama Institute of Science and Technology, Chennai 600 119, India
b
Corrosion Science and Technology Division, IGCAR, Kalpakkam 603 102, India
c
Civil Engineering Group, IGCAR, Kalpakkam 603 102, India
d
Materials Science Group, IGCAR, Kalpakkam 603 102, India
e
Heavy Water Board, Mumbai 400 094, India

h i g h l i g h t s

Fly ash concrete specimens were fabricated using TiO2 and CaCO3 nanoparticles.

Year-long studies in seawater showed synergistic effect nanoparticles.

Nano-TiO2 showed faster hydration with more filler effects and antibacterial.

Nano-CaCO3 contributed to high pH and compressive strength.

1:1 ratio of nano TiO2 and CaCO3 emerged with superior concrete properties.

a r t i c l e i n f o a b s t r a c t

Article history: Fly ash is used in concrete industry to reduce the amount of cement and to enhance the durability of con-
Received 26 March 2018 crete. Nuclear industry recently adopted fly ash concrete as a government initiative to reduce carbon
Received in revised form 24 July 2018 footprint and also to provide an impermeable skin for the several structures in the cooling water system
Accepted 27 July 2018
exposed to marine environment for enhanced durability. Earlier detailed studies on fly ash concrete has
shown that despite its superiority over conventional concrete with respect to strength and durability,
some concerns such as delayed setting and hydration, low early-age strength, and higher carbonation
Keywords:
may pose a problem for its wider application. The present work is an attempt to overcome these deficien-
Fly ash
Nanoparticles
cies by nanophase modification of concrete with the incorporation of nano-titania and nano-calcium car-
Strength bonate at 2% by weight of cement. Four different types of concrete mix were arrived and specimens of
Durability different sizes were cast in order to explore the various properties of concrete. After 28 days of curing
Antibacterial in potable water, the samples were exposed to seawater at Nuclear Desalination Demonstration Plant
(NDDP) sump at Kalpakkam and were withdrawn for testing at different ages like 56, 90, 180 and 365
days. Nanophase modification increased the pozzolanic activity resulting in faster hydration, early-age
strength and long-term compressive and split tensile strength, permissible electrical resistivity for corro-
sion, lower chloride ion penetration, carbonation depth biofilm formation and higher internal pH. Among
the different mixes, the synergy of 1% NC and 1% NT emerged superior with excellent concrete properties
related to mechanical properties, pore structure, durability and optimum antibacterial activity.
Ó 2018 Elsevier Ltd. All rights reserved.

1. Introduction and durability by pozzolanic action and filler effects [1]. The
desired properties can be achieved using high volume (>40%) of
Fly ash, a waste material from combustion of coal is used in fly ash in concrete [2]. Nuclear industry has a new mandate to plan
concrete as a partial cement replacement to upgrade the strength future nuclear power plants with a design life of 100 years to make
nuclear power more economical [3]. Hence, the durability of con-
⇑ Corresponding author. crete structures especially under marine exposure assumes great
E-mail address: vinitavishwakarma@sathyabama.ac.in (V. Vishwakarma). relevance. The sulphates and chlorides from the aggressive
1
Equal contribution to this paper.

https://doi.org/10.1016/j.conbuildmat.2018.07.214
0950-0618/Ó 2018 Elsevier Ltd. All rights reserved.
 S. Uthaman et al. / Construction and Building Materials 187 (2018) 448–459
seawater environment can penetrate and deteriorate the concrete
leading to its failure [4]. Many workers have reported that interac-
tion of seawater with cement paste leads to carbonation, sulphate
attack and chloride ion attack. It is reported that addition of min-
eral admixtures assures low permeability to aggressive anions
and offer excellent durability for concrete structures in seawater
[5]. Sandberg have studied the chloride binding of concrete
exposed in a marine environment and reported that the transport
of chloride ions in the concrete structure depends on the amount of
alkali hydroxide [6]. Permeability is the most important property
that determines the durability of concrete structures in seawater
[7]. When a structure is located in a marine environment, chloride
ions can penetrate the porous structure of concrete and reach the
steel leading to deterioration [8]. The holistic study conducted by
Lindvall [9] revealed that the concrete structures exposed to mar-
ine environment showed attachment of foulants on its surface and
the extent of marine growth facilitate the ingress of chloride ion
penetration. Nuclear Power Corporation of India Limited (NPCIL)
has also recently adopted fly ash concrete as a government initia-
tive to reduce carbon footprint and also to provide an impervious
skin for the concrete structures [10]. Ramachandran et al have
observed that flyash concrete exhibits superior strength and dura-
bility properties as compared to normal and modified concrete by
superplasticizer in sea water environments [11]. However, their
studies also brought into focus some drawbacks of fly ash concrete
like slower hydration, low early age strength and higher carbona-
tion depth [11,12]. The use of fly ash as a partial replacement of
cement is reported to reduce the tensile strength of concrete
[13]. Utilization of fly ash in concrete exposed to water involves
the potential leaching of some elements into water. This creates
a problem of secondary environmental pollution [14].
Recently, many researchers have started addition of different
nanoparticles to improve physical and chemical properties of con-
crete structures [15–26]. It has been reported that nanoparticles
can act just like fillers and densify the microstructure of concrete
or they can also form heterogeneous nuclei for accelerating cement
hydration; all contributing to reduction in porosity [24]. Several
nanoparticles were incorporated by different researchers, SiO2
[15–18], Al2O3 [19,20], TiO2 [21], Fe2O3 [22] and CaCO3 [23,24] in
the range of 0.5–5% of cement replacement which enhanced the
strength and other properties of the modified concrete compared
to conventional concrete without nanoparticles. It is found that
SiO2 nanoparticles up to 4% by wt. of cement acted as fillers and
also improved pore structure by decreasing harmful pores [16].
Ali Nazari et al., has also conducted an extensive study on the effect
of nano-Al2O3 and found that the 2% nano-Al2O3 particles blended
concrete, emerged with significantly higher compressive strength
[20]. The inclusion of 1% nano-Fe2O3 into the concrete matrix at
the early ages increased the percentage of water absorption and
later the mechanical strength [22]. The increased rate of water
absorption increases the number of capillary pores in concrete
which in turn reduces the desired performance of concrete [27].
Jayapalan et al. [25], investigated the effect of chemically non-
reactive anatase TiO2 nanoparticles on early-age hydration of
cement and found that addition of 5% TiO2 accelerated the rate of
Table 1
Mix proportion of concrete (kg/m3).
Sample designation Cement Fly ash Fine aggregates
River sand Crushed sand
FA 225.0 150 549 235
FAT 220.5
FAC 220.5
FATC 220.5
449
cement hydration by the heterogeneous nucleation effect. The
addition of TiO2 to cement is increased the heat of hydration, accel-
erated the rate of reaction at early stages of hydration and
enhanced the antimicrobial activity by the destructing the
microbes [26]. The CaCO3 nanoparticles was first considered as
only filler in cement to replace OPC, but later showed positive
effects in terms of strength and acceleration of hydration rate
[28]. All these studies refer to the nanoparticle modification con-
ventional concrete (100% OPC).
The main objective of this work was to overcome the drawbacks
of fly ash concrete by nanophase modification. In the fly ash con-
crete containing 40 wt% fly ash and 60 wt% OPC, 2 wt% of OPC is
replaced using nano-titania and nano-calcium carbonate individu-
ally and in combination. Based on our earlier screening studies
reported elsewhere [29] where a nanophase replacement of OPC
was studied in the range of 0.5–3 wt%, it was found that 2 wt%
replacement of OPC is the optimum level of nanoparticle substitu-
tion. Optimum workability and strength, very low RCPT values and
lowest reduction of pH was achieved with 2 wt% nanoparticle
replacement. Nazari et al. [30] and Xu et al. [31] have also reported
that enhancement of concrete properties by 2 wt% of CaCO3 TiO2
nanoparticle modification respectively. Hence it was decided to
select 2 wt% substitutions for the long-term exposure studies in
seawater environment. The various concrete properties related to
strength, durability and antibacterial characteristics were evalu-
ated by casting specimens of different shape and sizes for all the
four types of concrete mixes. The specimens were cured in potable
water at laboratory conditions for 28 days and thereafter exposed
to seawater for a year. Advanced characterization tools like SEM,
XRD and IR spectroscopy were used to get an insight into the role
of nanoparticles in improving the integrity of concrete.
2. Experimental methods and materials
2.1. Materials and mix proportion
Ordinary Portland Cement (43 Grade) conforming to IS 8112 – 1989 [32] was
used in this study. Black granite (Hard Blue Granite Rock Aggregate - Machine
Crushed) was used as coarse aggregate, with maximum size of 20 mm and 12.5
mm meeting the requirements of IS 383 [33]. High range water reducer type super-
plasticizer containing sulphonated naphthalene formaldehyde as base was used as
chemical admixture. Crushed sand and river sand with a maximum size of 4.75 mm
and meeting zone II requirements were used as fine aggregate. The partial replace-
ment of cement was 40% by siliceous type fly ash conforming to IS 3812 [34]. The
commercial grade anatase phase titanium dioxide (TiO2) and calcium carbonate
(CaCO3) with size ranging from 100 to 600 nm was purchased. To attain nano-
sized particles, TiO2 and CaCO3 powders were ground using ball mill (SPEX
8000M-230 dual mixer mill, 230 V/50 Hz) to achieve the size of the particles within
the range of 50–80 nm.
The total powder content which includes cement, fly ash and nanoparticles for
all the mixes was 375 kg/m3 and OPC was replaced with fly ash (40% by wt. of
cement). The nanoparticles were replaced at 2 wt% by cement. Concrete cube spec-
imens of 150 mm size were used for compressive strength test and cylindrical spec-
imen of 100 mm diameter and 200 mm height were used for RCPT and split tensile
strength test. Resistivity analysis was done on prism specimens of 350 mm length
and 100 mm depth with a thermo mechanically treated (TMT) rebar of 10 mm
diameter embedded in it. Mortar specimens of 35 mm diameter and 10 mm thick
were prepared to visualize the biofilms under epifluorescence microscope and
100 mm cube mortar specimens were cast to perform carbonation studies. The
mix proportion and casting details of the specimens are given in Table 1.
Coarse aggregates Superplasticizer Nano-TiO2 Nano-CaCO3
1130 4.5 – –
4.8 4.5 –
4.8 – 4.5
4.8 2.25 2.25
450 S. Uthaman et al. / Construction and Building Materials 187 (2018) 448–459
2.2. Specimen preparation
Four different types of concrete specimens were fabricated and named viz.
1. Fly ash concrete-FA (60 wt% OPC + 40 wt% fly ash)
2. Fly ash concrete with nano-TiO2 in which nanoparticles are replaced with 2 wt%
of OPC among 60 wt% (58 wt% OPC + 40 wt% fly ash + 2 wt% nano-TiO2)
3. Fly ash concrete with nano-CaCO3 in which nanoparticles are replaced with 2
wt% of OPC among 60 wt% (58 wt% OPC + 40 wt% fly ash + 2 wt% nano-CaCO3)
4. Fly ash concrete with 1:1 ratio of nano-TiO2 and nano-CaCO3 in which nanopar-
ticles are replaced with 2 wt% of OPC among 60 wt% (58 wt% OPC + 40 wt% fly
ash + 1 wt% nano-TiO2 and nano-CaCO3)
The fabricated specimens were demoulded after 24 h of casting and cured for
28 days in a curing tank at the concrete laboratory, Civil Engineering Group, Indira
Gandhi Centre for Atomic Research (IGCAR), Kalpakkam under ambient conditions
(temperature of 27 ± 2 °C). After curing for 28 days, all the specimens were exposed
to sea water at Nuclear Desalination Demonstration Project (NDDP) sump and with-
drawn at 56, 90, 180 and 365 days of casting. The concrete specimens were used for
thermogravimetry, pH measurement, compressive and split tensile strength tests,
chloride ion penetration test and microstructural characterization analysis.
For epifluorescence study, the cylindrical mortar specimens were withdrawn at
monthly frequency for a period of one year. The 100 mm cube mortar specimens
were withdrawn at 1 and 6 months of exposure to marine atmosphere for carbon-
ation test.
2.3. Characterization of concrete properties
2.3.1. Thermogravimetry and differential thermal (TG-DTA) analysis
Thermogravimetry and differential thermal (TG-DTA) analysis [35] was done for
28 days cured concrete specimens using Thermal Analysis SDT Q600 (USA make). In
this TGA test, proper weight loss was measured while the specimens were gradually
subjected to increasing temperatures. Specimens were broken into pieces and
ground into fine powder using agate mortar and pestle. The powder samples were
dried at 100 °C in oven and cooled at room temperature and kept in desiccator
before TG-DTA analysis. The powder sample of FA (17.67 mg), FAC (21.45 mg),
FAT (22.91 mg) and FATC (13.06 mg) were taken in a ceramic crucible and Al2O3
powder was used as reference material. The experiment was performed by heating
the samples from room temperature to 1000 °C at the heating rate of 10 °C per min-
ute under nitrogen gas dynamic atmosphere.
2.3.1.1. Calcium hydroxide content. The amount of calcium hydroxide (CH) was cal-
culated directly from the TG curves following the equation [36].
MWðCHÞ
CH ð%Þ ¼ WLðCHÞ  ð1Þ
MWðHÞ
where WL(CH) represents to the weight loss at the temperature range of 400–500 °C
attributable to CH dehydration and MW(CH) is the molecular weight of CH (74 g/mol)
and MW(H) is the molecular weight of water (18 g/mol).
2.3.1.2. Calcium carbonate content. The amount of calcium carbonate was calculated
directly from the TG curves following the equation [37].
MWðCaCO3 Þ
CaCO3 ð%Þ ¼ WLðCaCO3 Þ  ð2Þ
MWðCO2 Þ
where WL(CaCO3) represents to the weight loss at the temperature range of 501–900
°C attributable to decarbonation of CaCO3 and MW(CaCO3) is the molecular weight of
CaCO3 (100.0869 g/mol) and MW(CO2) is the molecular weight of CO2 (44.01 g/mol).
2.3.2. Crushed pH measurement
The crushed pH values of 28 days cured and sea water exposed (56, 90, 180 and
365 days) concrete specimens were measured. The specimens of FA, FAT, FAC and
FATC were crushed and powdered. 5 g of finely ground concrete powder was dis-
solved in 50 ml of distilled water and the suspension was mixed thoroughly for
15 min using a magnetic stirrer [38]. The pH of this suspension was measured by
portable flat surface electrode pH meter (SENTIX 3110, WTW GmbH). Minimum
three readings were measured to get the average value of the results.
2.3.3. Mechanical properties
The concrete specimens were withdrawn at different ages (56, 90, 180 and 365
days) of exposure in seawater and the various properties were analyzed. The com-
pressive strength test (IS 516) [39] and split tensile strength test (IS 5816) [40] were
performed using Servo Controlled Automatic Compression Testing Machine (AIMIL
make) of 3000 kN capacity. Three specimens from each mix were analyzed to get an
average value of the results.
2.4. Durability properties
2.4.1. Rapid chloride penetration test (RCPT)
RCPT was conducted by using 8 cells RCPT Apparatus-DAQ system (ASTM C
1202-97) [41] for the 28 days cured and sea water exposed (56, 90, 180 and 365
days) concrete specimens. A cylindrical specimen (200  100 mm) was typically
cut as a slice (50  100 mm) and was used for this test. The RCPT apparatus consists
of two reservoirs. The specimen was fixed between two reservoirs using an epoxy
bonding agent to make the test setup leak proof. One reservoir (connected to the
positive terminal of the DC source) was filled with 0.3 N NaOH solution and the
other reservoir (connected to the negative terminal of the DC source) with 3% NaCl
solution. The terminals were then connected to the 60 V DC power supply and the
current reading in mA was recorded for every half an hour upto 6 hrs. The total
charge passed during this period was calculated in terms of coulombs using the
trapezoidal rule as given in ASTM C 1202-97 [41].
2.4.2. Resistivity analysis
The resistivity test was conducted on 28 days cured and sea water exposed con-
crete prism samples. The resistivity test was carried out to know the electrical resis-
tance of the concrete [42]. This test was used to assess the probability or likelihood
of corrosion of the reinforcement bar. The equipment used for this test was a bat-
tery operated, portable, four probe device which measures concrete resistivity.
The set of four probes were fitted with super conductive foam tips to ensure full
contact on irregular surfaces. The probes were kept in contact with the concrete
surface and the LCD display indicated the resistivity value directly on the screen.
2.4.3. Carbonation test
The carbonation test was done for all the four types of mortar specimens
exposed to marine atmosphere for 1 and 6 months. After exposure, the mortar spec-
imens were cut into two halves and sprayed with 1% phenolphthalein in 70% ethyl
alcohol solution to a freshly fractured surface of concrete [43]. Researchers have
reported that the dark aggregates in concrete creates an obstacle in the measure-
ment of carbonation depth by making a visual illusion, when sprayed over by the
phenolphthalein solution in the carbonation affected areas [44]. Hence, in order
to assess the depth of carbonation, mortar specimens were used as it does not con-
tain aggregates [45,46]. Non-carbonated areas turn purple while carbonated areas
remain colorless. Then the depth of penetration was measured using Vernier caliper
(Mityuto Digital Vernier Caliper).
2.5. Microstructural properties
2.5.1. X-ray diffraction studies
The powder samples of 28 days cured and 365 days sea water exposed FA, FAT,
FAC and FATC specimens were used for XRD analysis. The analysis was carried out
using Inel – EQUINOX 2000 diffractometer with a X-ray source of Co- Ka radiation
(k = 1.7889 Å) over a 2 h range of 10°–80° at a scan step size of 0.05°. The unknown
crystalline compounds were analyzed and identified by Brag Brentano method. The
standard JCPDS database for XRD pattern was used for crystalline phases and quan-
tification of cementitious materials [47].
2.5.2. Scanning electron microscope (SEM) studies
The SEM analysis of 28 days cured and 365 days sea water exposed FA, FAT, FAC
and FATC specimens was carried out for comparative morphological studies. All the
specimens were coated with gold for electrical conduction for SEM imaging [48].
The specimens were examined under Desktop mini SEM, Korea to observe the mor-
phological changes.
2.5.3. Infrared spectroscopy (IR) studies
The concrete specimens cured for 28 days and exposed to seawater for 365 days
are used for this study. IR measurements were carried out using Bruker make
(Model- Vertex 80 V) IR spectrophotometer in the range 400–5000 cm1 with a res-
olution of 4 cm1 [49] using a combination of globar source, KBr beam splitter and
DLaTGS detector. Measurements were done on powdered samples dispersed in KBr
matrix in the transmission mode.
2.6. Evaluation of antimicrobial properties
2.6.1. Total viable count technique (TVC)
The antibacterial studies were carried out by TVC for FA, FAT, FAC and FATC
specimens for the cubical concrete specimens which were exposed in sea water
for 56 and 365 days. TVC was performed to evaluate the bacterial density of aerobic
bacteria using sea water agar (SWA) (Hi Media-M592). Pseudomonas agar (PSA),
manganous agar (MnA), cyanophycean agar (CA), Czapek Dox Agar (CDA) to know
the density of different types of microbes such as Pseudomonas, Manganese-
oxidizing bacteria, algae and fungi. The withdrawn concrete specimens from the
sea water were gently washed and the attached biofilm were removed using sterile
brush and dispersed into 500 ml of sterile phosphate buffer (0.0425 g KH2PO4, 0.19
g MgCl2 per litre). Serial dilutions of the bacterial cell suspension were prepared.
 S. Uthaman et al. / Construction and Building Materials 187 (2018) 448–459
0.1 ml of each dilution was plated onto respective media. The plates were incubated
for 24–48 h at 37 °C and the bacterial density was estimated according to APHA
standards [50].
2.6.2. Epifluorescence microscopic studies
Mortar specimens (35  10 mm) of all the mixes which were cured for 28 days
and exposed in sea water from 1 day to 365 days were withdrawn for microscopic
analysis. It was used for visualizing biofilms under epifluorescence microscope
(Nikon Eclipse E600, excitation filter BP 490; barrier filter O515). The specimens
were stained with 0.1% acridine orange (AO) which is a fluorescent dye. This stain
differentiates the single stranded RNA and double stranded DNA. The stained sam-
ples were observed under the epifluorescence microscope [51].
3. Results and discussion
3.1. Thermogravimetry analysis
Thermogravimetric analysis of 28 days cured specimens gave
details on the mass loss due to free moisture, decomposition of
calcium silicate hydrate (CSH), decomposition of CH and
decarbonation of CaCO3 at 25–123 °C, 123–420 °C, 400–500 °C
and 501–900 °C respectively. Fig. 1(a–d) shows the TG results of
weight loss percentage. In the first endothermic reaction at
25–123 °C, the evaporation of surface absorbed water was found
to be more on FA followed by FATC, FAC and FAT (Fig. 1a). In the sec-
ond endothermic reaction which was at 123–420 °C, the weight
loss due to the dehydration of CSH was found to be more on FAT
(Fig. 1b) followed by FA, FATC and FAC specimens. The third
endothermic reaction attributed to the decomposition of CH
Fig. 1. TG results of weight loss percentage on 28 days cured FA, FAT, FAC and FATC concrete specimens (a) Dehydration of surface absorbed water (b) Dehydration of CSH (c)
Decomposition of calcium hydroxide (d) Decarbonation of calcium carbonate.
451
(420–600 °C) was more on FAT (Fig. 1c). FAC followed by FATC
and FA showed minimum weight loss attributed to the decomposi-
tion of CH. The final endothermic reaction explaining the decarbon-
ation of CaCO3 at 600–730 °C shows least weight loss on FATC
specimen and maximum was on FAT (Fig. 1d).
3.1.1. CH content
Fig. 2 shows the percentage of CH content present in FA and
modified FA concrete specimens cured for 28 days. These results
show that at 28 days of hydration, CH content was found to be
more on FAT and least on FAC. However, in the case of FA and FATC
concrete specimens, the CH content was found to be in-between
FAT and FAC. At early age two predominant reactions are poz-
zolanic activity where CH is consumed to form additional CSH
gel, while second is nucleation effect, where hydration is acceler-
ated leading to additional CH formation. Hence net effect depends
upon the kinetics of these reactions, which need larger data base.
3.1.2. CaCO3 content
The amount of CaCO3 calculated from TG curves of 28 days fresh
water cured concrete specimens is shown in Fig. 3. The percentage
of CaCO3 was observed in the decreasing order of FAT (14.98) > FAC
(11.14) > FA (10.91) > FATC (8.86). The CaCO3 content was found to
be more on FAT and it was least on FATC concrete specimens.
Results showed that hydration products like CH, CSH and CaCO3
were highest in FAT showing faster hydration in the presence of
TiO2 nanoparticles which is also reported by earlier workers [25].
452 S. Uthaman et al. / Construction and Building Materials 187 (2018) 448–459
Fig. 2. CH content calculated from TG curve of FA and nanophase modified FA
concrete specimens cured in fresh water for 28 days.
Fig. 3. CaCO3 content calculated from TG curve of FA and nanophase modified FA
concrete specimens cured in fresh water for 28 days.
In FAC concrete the CH content was least due to the higher reactiv-
ity of CaCO3 nanoparticles leading to the consumption of CH by
pozzolanic reaction [24]. However, CSH content was lesser in FAC
compared to FAT confirming the combined effect of nucleation
and pozzolanic activity by TiO2 nanoparticles. FATC with 1% NT
and 1% NC showed optimum hydration with values in between
FAT and FAC. The content of CaCO3 was also least on FATC com-
pared to FAT and FAC showing better concrete properties.
3.2. Crushed pH measurement
pH is an important parameter for studying the properties of
concrete. Fig. 4 illustrates the crushed pH of different concrete
mixes (FA, FAT, FAC and FATC) before (28 days cured) and after
exposure to seawater for 56, 90, 180 and 365 days. Nanophase
modified FA concrete specimens showed higher crushed pH com-
pared to FA concrete. FAC showed highest pH. With exposure pH
value decreased in all the concrete specimens. However, when
compared to FA, all the modified concrete of FAT, FAC and FATC
Fig. 4. Crushed pH of powdered concrete specimens.
is found to be still alkaline even after exposure to an aggressive
environment for 365 days. The pH reduction was seen in the order
of FA (8.57) > FAT (9.75) > FAC (9.89) > FATC (10.25). Among all the
nanophase modified concrete specimens, FATC showed least
reduction in pH value under sea water exposure.
All the nanoparticles added FA concrete, showed higher pH for
28 days cured specimens, which confirmed nucleation effects of
nanoparticles wherein additional CH is formed. The FAT specimen
with highest CH content showed the highest pH [52]. During sea-
water exposure pH of the all the specimens decreased due to the
environmental effects, i.e. ingress of free carbon-di-oxide, chloride
ions and hydrogen sulphide present in the seawater [53]. However
after 365 days exposure all nanophase modified FA specimens
showed higher pH compared to FA. FAC showed consistently
higher pH upto 180 days indicating acceleration of hydration reac-
tion of Portland cement to form CH in the presence of NC [54].
After 180 days exposure, pH of FAT and FAC decreased whereas
pH of the FATC specimens stabilized and was highest among the
modified concrete specimens.
3.3. Mechanical strength
The compressive strength results of 7 and 28 days cured and 56,
90, 180 and 365 days seawater exposed concrete specimens of FA,
FAT, FAC and FATC are given in Table 2. In order to get a clear pic-
ture about variations in compressive strength among the different
mixes after long term exposure in seawater, the compressive
strength of 365 days seawater exposed FA, FAT, FAC and FATC
specimens are separately plotted in Fig. 5. Comparing the early
age for all the mixes, FATC and FAC showed highest values at 7
and 28 days respectively. After seawater exposure upto 90 days,
all the specimens showed progressive increase in strength and
FAC showed the highest strength. However, FAC specimens
showed a decline in compressive strength after six month expo-
sure. Among all the specimens, FATC specimens showed a progres-
sive increase in strength even after exposure to seawater for 365
days.
Many workers have reported improvement of mechanical prop-
erties by addition of nanoparticles [55,56]. Compared to FA con-
crete, the compressive strength of the 7 days cured FATC and FAT
increased by about 12.4% and 7.2% respectively. FAC showed com-
parable strength with respect to FA. Thus early age strength
improved by addition of NT. At 28 days, the compressive strength
of FAC increased marginally by 2.6% compared to FA. Further,
 S. Uthaman et al. / Construction and Building Materials 187 (2018) 448–459 453

Table 2
Compressive strength of unexposed and seawater exposed concrete specimens.

Type of specimen Compressive strength (N/mm2)

7 days 28 days 56 days 90 days 180 days 365 days
cured cured seawater exposed seawater exposed seawater exposed seawater exposed
FA 18.99 36.98 43.97 48.52 48.27 54.48
FAT 20.36 30.18 39.40 47.40 42.46 56.27
FAC 18.85 37.95 43.98 50.45 52.10 50.50
FATC 21.35 34.94 40.62 42.76 45.70 57.25

Fig. 6. Resistivity of seawater exposed concrete specimens in comparison with

unexposed concrete specimens.
Fig. 5. Compressive strength of concrete specimens exposed to sea water for 365
days.

during exposure to seawater FAC maintained highest strength upto

180 days compared to other modified concrete showing the
enhanced pozzolanic effect of NC with time. At 365 days of expo-
sure the strength gain of FAC ceased whereas FATC and FAT
showed 5% and 3.2% higher strength respectively compared to FA
concrete.
Table 3 illustrates the split tensile strength of concrete speci-
mens before and after exposure to seawater. After 28 days of cur-
ing, FATC and FAC specimens showed more tensile strength
compared to FA and FAT specimens. After exposure to seawater,
tensile strength of FA, FAC and FAT increased upto 90 days and
then started declining. However, FATC specimens did not show this
decline split tensile strength.
Variation of split tensile strength with respect to nanophase
addition for 28 days cured and 365 days exposed specimens
showed an increase compared to FA concrete. FATC followed by
FAC showed the highest values of split tensile strength, indicating
Fig. 7. RCPT of 28 days cured and seawater exposed concrete specimens.

Table 3
contribution of NC. Optimum substitution levels of NC need to be
Split tensile strength of unexposed and seawater exposed concrete specimens.
further investigated with respect to split tensile strength as it
Type of Split tensile strength (N/mm2) decreased at 2% level.
specimen
28 days 56 days 90 days 180 days 365 days
cured seawater seawater seawater seawater 3.4. Resistivity analysis
exposed exposed exposed exposed
FA 2.64 3.78 3.92 3.84 3.28 Resistivity depends on the porosity of the concrete specimens.
FAT 2.40 3.87 3.30 3.42 3.33
Generally addition of fly ash increases the density and thereby
FAC 2.93 3.47 3.9 3.6 3.56
FATC 2.95 3.75 3.67 3.69 4.06 increases the resistivity. Resisvity measurements were conducted
for an year on prism specimens and the results are shown in
454 S. Uthaman et al. / Construction and Building Materials 187 (2018) 448–459

Fig. 6. In this study all the nanophase modified and FA concrete

showed more than 30 KXcm which is well above the limit of
12 KXcm below which corrosion is likely [57]. The resistivity of
28 days cured specimens showed the same trend of TGA results
where FAT with faster hydration showed the highest resistivity
(52.47 KXcm). FAC with lowest CH and CSH content showed lower
resistivity (36.73 KXcm). With exposure in seawater resistivity of
all the specimens increased. It is to be noted that after 180 days of
exposure resistivity of FA (106.65 KXcm) and FAT (107.95 KXcm)
appears to be stabilized. In contrast FATC (142.41 KXcm) and FAC
(142.24 KXcm) showed exponential increase in the resistivity
clearly indicating the evident role of NC in enhancing the hydration
and thereby providing a dense microstructure.

3.5. Rapid chloride penetration test (RCPT)

RCPT results give us an insight into the performance of concrete

in chloride environments. If the total charge passing through the
specimen is less than 2000 Coulombs the concrete is considered
Fig. 8. Depth of CO2 penetration into the mortar specimens exposed to marine as having low chloride penetrability [41]. The chloride penetrabil-
atmosphere for 6 months. ity values of 28 days cured and 365 days seawater exposed

Fig. 9. Mineralogical changes of unexposed (28 days cured) and 365 days seawater exposed (a) FA (b) FAT (c) FAC and (d) FATC concrete specimens SiO2-Quartz, CAS- Calcium
aluminium silicate, CSH- Calcium silicate hydrate, CASHH- calcium aluminum sulfate hydroxide hydrate (Ettringite).
 S. Uthaman et al. / Construction and Building Materials 187 (2018) 448–459
concrete specimens are shown in Fig. 7. After 28 days of curing, all
the specimens showed RCPT value less than 500 Coulombs con-
firming low chloride penetrability. Nanophase modification of FA
concrete enhanced its resistance to chloride penetrability. FATC
followed by FAC showed least RCPT values. After exposure in sea
water, RCPT values further decreased due to higher pozzolanic
activity. However, after 180 days RCPT value started
increasing for all specimens though the values were still far below
2000 Coulombs. This trend needs further investigation. FATC
showed least chloride penetrability even after 365 days seawater
exposure.
3.6. Carbonation depth measurement
The depth of CO2 penetration into the mortar specimens
exposed to marine environment for 6 months is shown in Fig. 8.
The depth of CO2 penetration was found to be higher on FA
(0.53 mm) compared to nanophase modified FA mortar specimens.
Among all the nanophase modified mortar specimens, FATC (0.17
mm) showed least depth of CO2 penetration further confirming the
role of NC in providing the dense microstructure.
3.7. Microstructural properties
3.7.1. Mineralogical characterization studies
Fig. 9 shows the X-ray diffraction spectra of the 28 days cured
and 365 days seawater exposed FA, FAT, FAC and FATC specimens.
After 28 days of curing all the FA and nanophase modified FA con-
crete specimens were found with conventional peaks of hydration
[58] like SiO2 (2h = 24.1°, 31.09° and 50.01°; JCPDS 01-072-1088),
CSH (2h = 32.6°, 37.7°, 42.7°, 46.2° and 71.4°; JCPDS 01-089-
7639) and calcium aluminium silicate (CAS) (2h = 10.1°, 34.4°,
59.27°, and 64.38°; JCPDS 01-083-1278). However, FA showed
comparatively lesser number of hydration peaks and intensity.
Fig. 10. SEM surface micrographs of 28 days cured concrete specimens (a) FA (b) FAT (c) FAC (d) FATC.
455
FAC showed highest intensity peaks of SiO2 and CAS. FAT showed
highest intensity peaks of CSH. FATC had good intensity peaks of
SiO2, CAS and large number of CSH peaks.
After seawater exposure for 365 days, the intensity of quartz
peaks increased in FA, FAT and FATC specimens. FATC and FAT
showed more number of CSH peaks with high intensity. However
in FAC, intensity of CAS decreased with sea water exposure and a
predominant peak of ettringite (calcium aluminum sulfate hydrox-
ide hydrate) was found corresponding to a decrease in compressive
strength as well.
3.7.2. Morphological analysis
Figs. 10 and 11 shows the comparison morphology of different
concrete specimens cured for 28 days and exposed to seawater for
365 days respectively. Scanning electron microscopic analysis of
the nanophase modified concrete specimens at the age of 28 days,
showed a comparable morphology with FA concrete. However,
after exposure to seawater for 365 days, SEM micrographs showed
distinct morphology for each type of specimen. Surface deteriora-
tion was exhibited by FA concrete in the form of microsized pits
and grooves. In the case of FAC needle shaped crystals of ettringite
formation corresponded with reduction in calcium aluminate
phase decrease in XRD spectra. It is well known that gypsum and
other sulphate in concrete or in the environment can react with
calcium aluminate phase to form ettringite [59]. This ettringite for-
mation can explain some detrimental properties of FAC like
decrease in compressive strength and increase in chloride penetra-
bility compared to other nanophase modified FA concrete speci-
mens. Literature also shows that ettringite is more soluble in the
presence of chlorides [60]. However, FATC clearly showed colloidal
CSH morphology as reported by earlier workers [61] and was free
of ettringite, voids and cracks. Though FAT also showed homoge-
neous morphology of hydration products, it did not show colloidal
CSH morphology.
456 S. Uthaman et al. / Construction and Building Materials 187 (2018) 448–459

Fig. 11. SEM images of concrete specimens exposed to seawater for 365 days (a) FA (b) FAT (c) FAC (d) FATC.

3.7.3. Infrared spectroscopy studies
The structural changes in the main hydrated phases of all the
concrete specimens were recorded with IR spectroscopy technique.
Fig. 12 shows the infrared (IR) spectroscopy of as cast 28 days
cured FA concrete along with FAT, FAC and FATC. IR measurements
revealed expected phonon features for FA concrete. The most
intense feature at 1091 cm1 corresponds to the SiAO stretching
frequency of the major cementitious product, the CSH gel. The
mode at 462 cm1 can also be attributed to the SiAO bending
mode of the CSH gel, while the mode at 1464 cm1 arises due to
the CAO stretching of the carbonate species in the concrete. The
broad absorption feature between 3000 and 4000 cm1 arises
due to the presence of bound water in cement. The absence of
sharp features 3616 cm1 characteristic of Portlandite (crystalline
CH – the major hydration product of OPC concrete) in FA concrete
provides excellent proof of the fact that alumino-siliceous rich poz-
zolans (fly ash) participates in reactions with CH producing various
calcium aluminate and calcium alumino-silicate hydrates. Since
the IR spectra of all the four 28 days cured and nanophase modified

Fig. 12. IR spectra of 28 days cured FA and nanophase modified FA concrete Fig. 13. IR spectra of 28 days cured and 365 days seawater exposed FA and FATC
specimens. concrete.
 S. Uthaman et al. / Construction and Building Materials 187 (2018) 448–459 457

samples are identical, it can be readily inferred that nanophase
modification of FA concrete does not significantly affect the overall
chemical composition/structure of the concrete samples.
Fig. 13 shows the area normalized set of IR spectra of the as cast
unexposed samples (FA and FATC) along with the 365 days sea
water exposed samples. It can be observed from the figure that
FA and FAT (not shown in Fig) concrete samples remain more or
less unaffected even after 365 days of exposure to sea water, while
both FATC and FAC (not shown in figure) are observed to exhibit
significant changes with respect to the IR peak at 1091 cm1 corre-
sponding to the CSH mode. It is also very surprising to note that the
modified structure of both FAC and FATC samples after 365 days of
sea water exposed are identical.
In particular, the intensity of the major CSH mode at 1091 cm1
is drastically reduced while the shoulder at 1020 cm1 evidently
picks up on sea water exposure. This clearly indicates a change
in the calcium/silica (C/S) ratio of the CSH gel that could have
caused the above shift in CSH modes [62]. Since both FAC and FATC
contain NC, we immediately infer that the observed structural
change could be associated with NC. According to Scherer [63],
CSH paste of cement is a colloidal precipitate of sol–gel nature.
The condensation reaction that drives the sol–gel transition can
continue with time leading to polymerization of silicate network
due to ageing [64]. According to Kumar et al. [65], nanoparticles
can increase polymerization of silicate chains in silica gel leading
to formation of colloidal CSH and thereby accelerate the effects
of ageing. Campillo et al. [61] reported that colloidal silica is more
effective than agglomerated silica and contribute to strength. Thus
this study shows that NC contributed to this colloidal formation
thereby increasing gel porosity and reducing capillary porosity
which can explain the resistivity increase in FAC and FATC even
after 365 days exposure [66].

Table 4
TVC of concrete specimens exposed to seawater.

Total Viable Count (cfu/cm2)

Type of agar used 56 days seawater exposed concrete 365 days seawater exposed concrete
Type of specimens Type of specimens
FA FAT FAC FATC FA FAT FAC FATC
5 3 6 4 9 7 9
Seawater agar 3.9  10 6.2  10 5.7  10 7.2  10 2.7  10 5.3  10 1.5  10 6.1  107
Pseudomonas agar 2.7  105 4.7  103 6.9  105 5.7  104 6.8  108 2.7  105 8.7  107 3.8  106
Manganese agar 0.9  105 1.2  103 1.1  105 2.2  104 2.1  106 5.2  103 8.5  105 6.7  103
Czapek Dox agar 1.7  103 2.5  101 3.9  103 2.6  103 7.5  105 7.1  103 5.7  105 2.1  104
Cyanophycean agar 0.4  101 – – – 5.1  104 3.1  103 1.9  104 4.2  103

Fig. 14. Epifluorescence images of seawater exposed FA and nanophase modified FA mortar specimens.
458 S. Uthaman et al. / Construction and Building Materials 187 (2018) 448–459
3.8. Biofilm characterization studies
3.8.1. Bacterial enumeration
The TVC of aerobic bacteria on the 56 days exposed cube con-
crete specimens was highest on FAC (5.7  106 cfu/cm2) and least
on FAT (6.2  103 cfu/cm2) whereas by 365 days bacterial density
was lesser on all nanophase modified concrete compared to FA
concrete specimens. FAT and FATC showed least TVC values
(Table 4).
3.8.2. Epifluorescence micrographs of biofilms
Epifluorescence micrographs (Fig. 14) showed gradual increase
in biofilm formation as indicated by increase in the intensity of
orange fluorescence of RNA on all the specimens. After 365 days
of exposure FAC showed maximum intensity of orange fluores-
cence indicating thick biofilm formation. FAT and FATC showed
least fluorescence indicating antibacterial activity.
4. Conclusions
1. Thermogravimetric analysis of 28 days cured specimens
showed weight loss due to the dehydration of CSH was more
on FAT and decarbonation of CaCO3 was least on FATC due to
the enhanced rate of hydration provided by the synergistic
effect of 1 wt% nano-TiO2 and 1 wt% nano-CaCO3.
2. All the nanophase modified FA concrete specimens showed
higher crushed pH values compared to FA concrete with
highest values for FAC.
3. FATC specimens showed least reduction in pH even after
365 days exposure in seawater.
4. Early age compressive strength of 7 and 28 days cured spec-
imens was highest for FATC and FAC respectively due to the
strong accelerating effect of nano-CaCO3 at early ages.
5. Post exposure compressive strength of FATC specimens pro-
gressively increased and was the highest at 365 days seawa-
ter exposure.
6. Split tensile strength of FATC was the highest for the 28 day
cured and 365 days seawater exposed specimens.
7. Resistivity of FAC and FATC specimens continuously
increased upto 365 days of seawater exposure.
8. RCPT values showed least chloride penetration for FATC
specimens even after 365 days of seawater exposure.
9. All the nanophase modified FA concrete showed lesser car-
bonation depth compared to FA concrete with least on FATC.
10. Mineralogical phase identification in nanophase modified
concrete by XRD showed large number of high intensity
CSH peaks in FATC and transformation of CAS into deleteri-
ous ettringite in FAC at 365 days of seawater exposure.
11. SEM micrographs confirmed absence of detrimental phases,
voids and cracks and presence of colloidal CSH in FATC
specimens.
12. Infrared Spectroscopy analysis clearly confirmed that overall
structure of FA concrete remained unaffected by nanoparti-
cle substitution. Further the spectra indicated a change in
C/S ratio of CSH gel in FATC and FAC probably signaling col-
loidal CSH formation.
13. Evaluation of antibacterial activity of nanophase modified
concrete by culture and microscopic techniques clearly
showed enhancement in FAT and FATC.
Thus, for the first time a systematic study on holistic effects of
nanophase modification of fly ash concrete on properties, durabil-
ity and antibacterial activity brought out the ability of nanoparti-
cles to eliminate the concerns regarding FA concrete and enhance
its superiority for practical applications. Studies using IR spec-
troscopy also gave confidence by confirming absence of any new
deleterious phases and nanoparticles was found to enhance only
the amount of useful hydration products like CSH and CAS. Titania
nanoparticles helped in early hydration by filler effects and poz-
zolanic activity and also enhanced antibacterial activity. However
calcium carbonate nanoparticles by providing more C/S ratio con-
tributed to several advantages like high pH, both early age strength
and increase in compressive strength with seawater exposure, den-
ser microstructure and higher resistivity. However, after 180 days
of exposure, the higher concentration of CAS in FAC with 2% NC
turned into deleterious ettringite that resulted in increase of chlo-
ride penetrability and reduced strength. Thus, Synergistic combi-
nation of 1% NC and 1% NT helped FATC to emerge superior with
least decarbonation, reduction in pH, penetrability of chloride,
highest early age and post exposure strength, split tensile strength,
resistivity and optimum antibacterial activity.
Acknowledgments
Financial support from Board of Research in Nuclear Sciences,
Mumbai (2013/36/33-BRNS/2355) is greatly acknowledged. Sin-
cere thanks to Chancellor Sathyabama Institute of Science and
Technology, Chennai and Director, IGCAR, Kalpakkam for guidance,
encouragement and motivation.
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