Construction and Building Materials 262 (2020) 120738

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Construction and Building Materials

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

Experimental study on durability characteristics of composite fiber

reinforced high-performance concrete incorporating nanosilica and ultra
fine fly ash
Sujay H.M. a, Nishant A. Nair a, H. Sudarsana Rao b, V. Sairam a,⇑
a
School of Civil Engineering, Vellore Institute of Technology, Vellore, India
b
Department of Civil Engineering and Director (ICS), JNTU, Anantapur, India

h i g h l i g h t s

Investigated the effects of nanosilica and ultra-fine fly ash both individually and combined.

CFRHPC demonstrates superior resistance to an aggressive acidic environment.

The addition of nanosilica leads to reduced porosity and low permeability.

Nanosilica prevents the ingress of detrimental factors into concrete and improves durability.

Steel and polypropylene fibers marginally improved the durability of concrete.

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

Article history: This study is aimed at investigating the durability properties of Composite Fiber Reinforced High-
Received 8 April 2020 Performance Concrete. A 15% partial replacement of cement by weight was done with ultra-fine fly
Received in revised form 20 August 2020 ash. The addition of nanosilica was in fractions of 0%, 1.5%, 3.0% and 4.5% by weight of cement. For each
Accepted 25 August 2020
of the above combinations, 1.0% steel and 0.25% polypropylene fibers, respectively, by volume of the bin-
Available online 6 October 2020
ders were added. A constant aggregate binder ratio of 2.0 and varying water binder ratios of 0.275, 0.300,
0.325 were used in this investigation.
Keywords:
The sorptivity test was performed to assess the rate of absorption, and the rapid chloride permeability
High-performance concrete
Nanosilica
test (RCPT) was performed to assess the permeability of concrete. Test results revealed that all the mixes
Ultrafine fly ash attained low to very low chloride permeability. The decrease in chloride ion permeability for mixes with
Durability nanosilica and ultra-fine fly ash ranged from 53.83% to 71.45% for 28 days curing period and 55.88% to
Acid attack 74.27% for 56 days curing period, as against the reference mix.
Steel fiber ‘Residual Compressive Strength’ and ‘Percentage Weight Loss’ for 28 and 56 days of immersion in 5%
Polypropylene fiber concentrated solutions of HCl, H2SO4, and MgSO4 were evaluated to study the effects of aggressive ions
Hybrid fibers such as chlorides and sulfates on concrete. The weight loss observed ranged from 7.09% to 2.07% in
the case of HCl, from 7.96% to 2.86% in the case of MgSO4, from 17.93% to 11.02% in case of H2SO4 for
water binder ratio of 0.275 and 56 days of immersion. The percentage reduction in strength after 56 days
of immersion for mixes with water binder ratio of 0.275 ranged from 14.39% to 8.92% in HCl, from 14.53%
to 9.66% in MgSO4 and 14.81% to 10.92% in H2SO4.
The outcomes of the study showed that a combination of 15% ultra-fine fly ash and 3% nanosilica is the
optimum replacement level to achieve increased durability, reduced porosity and permeability due to
improved macro and micrometer densities of concrete. In addition, steel and polypropylene fibers have
also made a small contribution towards improving the durability of Composite Fiber Reinforced High-
Performance Concrete.
Ó 2020 Published by Elsevier Ltd.

1. Introduction
⇑ Corresponding author at: School of Civil Engineering, Vellore Institute of
Technology, Vellore 632014, India. Conventionally, people have given more importance to the
E-mail addresses: [email protected] (H.M. Sujay), [email protected] strength of concrete, ignorant of the fact that even weather attacks
(V. Sairam).

https://doi.org/10.1016/j.conbuildmat.2020.120738
0950-0618/Ó 2020 Published by Elsevier Ltd.
H.M. Sujay et al. Construction and Building Materials 262 (2020) 120738

on concrete can deteriorate strength over time. Whereas resisting glass fibers on the mechanical, rheological and durability proper-
the change in climate and retaining the designed strength of the ties of concrete. In this study, the addition of nanosilica was varied
concrete throughout its service life is more important. What hun- in fractions of 0%, 2%, 4% and 6% by weight of cement. From the
dreds of years did not do to the structures, the past three decades outcomes of this study, a 4% addition of nanosilica imparts better
of abuse of material and environment have wreaked havoc, causing filling and pozzolanic effects in the contact area between fibers
rapid deterioration of heritage structures. and cement matrix. Durability performance of concrete incorporat-
Durability refers to retaining the original form and quality of ing 0.3% and 0.9% of nanosilica was studied by [16]. Results from
concrete throughout its service life. The deterioration of concrete’s this study confirmed the refined pore size distribution, which
original form and quality is caused by chemical and physical reduces water permeability and improvement in chloride attack
changes in its internal structure due to the transport of substances resistance [17] concluded that a reduction of chloride ion perme-
such as liquids and gases from the surrounding environment. This ability was achieved by using 1% of nanoparticles per cement mass.
chemical and physical decay of concrete can be controlled in its Very few studies, if at all, are done to highlight the efficacy of a
microstructure, preventing water movement and transportation multi-admixture system using UFFA and nanosilica in augmenting
of ions in concrete. Aggressive ions such as chlorides, sulfates, durability performance. Nanomaterial incorporated HPC, and the
and water, etc. which penetrate the concrete are essential factors effects of fibers on such systems are not studied extensively. Hence
that determine the durability of concrete [1]. there is a wide gap in the available research material. Furthermore,
Conventional efforts of replacing cement in concrete with new Indian Standard Codes are silent on the tests to be performed for
components and industry by-products have paved the way for evaluating the durability of high performance concretes and the
High-Performance Concrete (HPC), one that is intentionally created guidelines required for designing the concrete mix to meet durabil-
to achieve specific goals in building concrete structures. Composite ity in addition to strength requirements. The results of this study
Fiber Reinforced High-Performance Concrete (CFRHPC) is HPC are intended as an effort to contribute towards evolving the codes
added with a combination of two or more fibers, such as to account for such needs in the future.
Polypropylene Fibers (PPF), Steel Fibers (SF), etc. In order to gener-
ate HPC for better concrete performance, mix design is supple-
mented with an important component ‘admixtures.’ Mineral 2. Materials and mix design
admixtures such as fly ash, Ground Granulated Blast-furnace Slag
(GGBS), silica fume, metakaolin, rice husk ash etc. are extensively The objective of the present investigation is to evaluate the
researched and have found their place in the industry [2–5]. durability of Composite Fiber Reinforced High-Performance Con-
Recently, the research on nanotechnology and nano-scale mate- crete (CFRHPC) produced by adding UFFA and nanosilica as mineral
rials has proven its immense applications in many fields, including admixtures. The mix design was carried out by absolute volume
building materials. Currently, research focusing on the nano-scale method. Aggregate-to-binder ratio was kept at 2.0, and varying
matter to get extraordinary performing multifunctional materials water binder ratios of 0.275, 0.300, 0.325 are used in this investi-
is in the limelight. With the incorporation of nano-scale admix- gation. It is to be expected that, using such a low water-to-
tures into concrete, tremendous changes in the microstructure of binder ratio will have increased durability. Contrary to this, when
concrete, both in fresh and hardened conditions, have resulted in concrete with UFFA and nanosilica are mixed at low water content,
enhanced mechanical properties and durability, contributing to the mix has insufficient workability. Here, adding more water has
longer service life [6] studied the effect of iron oxide nanoparticles to be done with compromise on strength and durability. Hence, the
by using 4% nano Fe2O3 and 45% partial replacement of cement use of superplasticizer is necessitated to avoid further addition of
containing 4% nano TiO2 by GGBFS per cement mass the results water. The added percentages of nanosilica were 1.5, 3.0 and 4.5
showed a reduction in the permeability of the concrete [7,8], in by weight of cement.
their investigation, studied the mechanical and the durability From the literature [18–26], it was noted that the maximum
parameters of concretes containing 1.5% of nano-ZrO2, nano-TiO2, strengths were observed for the range 10% to 20% partial replace-
nano-Al2O3, and nano-Fe3O4 individually. They concluded that ment of cement by UFFA. In this study, the substitution of UFFA
the use of nano-Al2O3 resulted in better performance. Among nano was a 15% partial replacement of cement by weight. The test
admixtures, the use of which is being researched currently, the results from [27–29] showed that the optimum values for the addi-
researchers tend to favor the use of nano-silica because of its high tion of steel fibers are usually between 1% and 2% of the cement
silica content leading to higher pozzolanic activity [9–12]. The volume. Synthetic fibers are generally used in lower proportions
nanosilica addition reduces the pore amount and makes the con- when compared to steel fibers. Synthetic fibers are added between
crete denser in the microstructure level, which in turn increases 0.1% and 0.5% of the cement volume [15,30] revealed that increas-
the strength and durability [13]. ing the addition of fibers results in fiber balling, and the efficiency
Concrete mixes, when modified with ultra-fine fly ash (UFFA) in of the mixture reduces due to which more pores appeared in the
addition to nanosilica, offer a well-graded improved particle size concrete. In this study, a combination of steel (1.0%) and
distribution in the micro to the nano-scale. As a result, with their polypropylene fibers (0.25%) at a total fiber volume fraction of
fine size, the voids are filled extensively, lowering the porosity 1.25% of total cementitious material were added. Polypropylene
and effectively blocking the ingress of detrimental substances from Fiber (PPF) of 12 mm length and 30–35 mm in diameter obtained
the outside environment. The addition of nanosilica to cementi- from Reliance Industries under the trade name RecronÒ 3S and
tious composites further accelerates both the amount and time of crimped steel fibers of 30 mm length and 0.5 mm diameter were
C-S-H gel produced by acting as nucleation sites and promoting used to produce CFRHPC in the laboratory. Table 1 gives the per-
pozzolanic reactions. Together, these two factors act to produce centage of dosage used in this study.
more hydration products at an early age, bridging the gaps, thus Cement: Ordinary Portland Cement (OPC) of 53 grade conform-
densifying the microstructure and obstructing water absorption, ing to standard IS 12269:2013 and of specific gravity 3.10 of Ultra-
capillary absorption, and distribution of chloride and sulfate ions Tech brand was used.
resulting in a new generation of concrete that is both strong and Fine aggregate: The locally available river sand with a specific
durable [14]. gravity of 2.60 conforming to IS 383:2016 was used as fine aggre-
Beigi et al. [15] investigated the effects of nanosilica with differ- gate. The weight fraction of fine aggregate was 40% of the total
ent concrete reinforcing fibers, including steel, polypropylene and aggregate, which was maintained constant throughout the study.
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H.M. Sujay et al. Construction and Building Materials 262 (2020) 120738

Table 1 Table 2
Percentage of dosage used in this study. Nomenclature of mixes studied.

SL. Material Dosage S. Designation of Mix Details

NO No mix
1 Ultra-Fine Fly Ash 15% partial replacement by weight of cement 1 NS 0 Reference mix with 0% UFFA, 0% Nanosilica, 0% SF
2 Nanosilica 1.5%, 3.0% and 4.5% addition by weight of and 0% PPF
cement 2 NS 1.5 Mix designed with 0% UFFA, 1.5% Nanosilica, 0% SF
3 Polypropylene Fibers 0.25% addition by the total volume of binder and 0% PPF
4 Steel Fibers 1.0% addition by the total volume of binder 3 NS 3.0 Mix designed with 0% UFFA, 3% Nanosilica, 0% SF and
5 Super Plasticizer up to 1.20% of the total weight of 0% PPF
cementitious material is used 4 NS 4.5 Mix designed with 0% UFFA, 4.5% Nanosilica, 0% SF
and 0% PPF
5 NS 0 F Mix designed with 0% UFFA, 0% Nanosilica, 1% SF and
0.25% PPF
6 NS 1.5 F Mix designed with 0% UFFA, 1.5% Nanosilica, 1% SF
Coarse aggregate: The locally available aggregates from a stone and 0.25% PPF
crusher quarry with 40% passing through a 12.5 mm sieve and 7 NS 3.0 F Mix designed with 0% UFFA, 3% Nanosilica, 1% SF and
retained on 10 mm sieve and 60% passing through a 20 mm sieve 0.25% PPF
8 NS 4.5 F Mix designed with 0% UFFA, 4.5% Nanosilica, 1% SF
and retained on 12.5 mm sieve were used. The total weight fraction
and 0.25% PPF
of the coarse aggregate was 60% of the total aggregate. 9 UF NS 0 Mix designed with 15% UFFA, 0% Nanosilica, 0% SF
Ultra-Fine Fly Ash (UFFA): UFFA, namely SUPPERPOZZ P500TM and 0% PPF
obtained from Ashtech India Pvt.Ltd compliant with IS 3812 Part 10 UF NS 1.5 Mix designed with 15% UFFA, 1.5% Nanosilica, 0% SF
1, BS EN 450 – S and ASTM C618 Class F was used in the present and 0% PPF
11 UF NS 3.0 Mix designed with 15% UFFA, 3% Nanosilica, 0% SF
project. According to the manufacturer, the procured batch had a and 0% PPF
mean particle size of 3.9 – 5.0 mm. 12 UF NS 4.5 Mix designed with 15% UFFA, 4.5% Nanosilica, 0% SF
Nanosilica (NS): Powdered nanosilica having a surface area of and 0% PPF
200 – 220 m2/g from Astra Chemicals, Ahmedabad was used in 13 UF NS 0 F Mix designed with 15% UFFA, 0% Nanosilica, 1% SF
and 0.25% PPF
the investigation. These nanosilica particles are approximately
14 UF NS 1.5 F Mix designed with 15% UFFA, 1.5% Nanosilica, 1% SF
1000 times smaller than the average cement particles making and 0.25% PPF
them highly active particles, improving the overall strength, 15 UF NS 3.0 F Mix designed with 15% UFFA, 3% Nanosilica, 1% SF
microstructure, and durability of concrete. and 0.25% PPF
Water: Potable fresh water available in the laboratory, with a 16 UF NS 4.5 F Mix designed with 15% UFFA, 4.5% Nanosilica, 1% SF
and 0.25% PPF
pH of 8.1 that is free from the concentration of acid and organic
substances, was used for mixing the concrete.
Superplasticizer: superplasticizer by the name CONPLAST SP 430
with a specific gravity of 1.18, manufactured by FOSROC, Banga- imen, resulting from absorption of water as a function of time,
lore, complying with IS: 9103 – 1999, BS 5075, BS: EN 934–2 and when only one surface of the specimen is exposed to water. In gen-
ASTM C494 (Type A and Type F), depending on the dosage used. eral, the rate of absorption of concrete at the surface differs from
In the present investigation, superplasticizer was used only to that of a sample taken from the interior, since the exterior surface
improve the workability of the concrete. is often subjected to less than the intended time of curing and is
exposed to the most potentially adverse conditions. This test
method is used to measure the water absorption rate of both the
2.1. Test program surface and interior of the concrete [31].
The standard test specimen is a 100 mm diameter disc, with a
In order to study the durability of CFRHPC and also to under- length of 50 mm. These specimens were pre-conditioned for 3 days
stand the influence of mineral admixtures such as UFFA and in a hot air oven. The mass was measured to the nearest 0.01 g
nanosilica, 16 mixes for each of W/B ratios 0.275, 0.300 and within 15 sec of removal from the pan, immediately replacing
0.325 have been tried. In all the mixes, the same type and batch the specimen on the support device and restarting the timing
of aggregates and river sand have been used. The same proportion device. The schematic diagram and the actual experimental setup
of sand and aggregate was maintained for all mixes. OPC 53 grade is shown in Fig. 1.
cement of UltraTech make from a single batch has been used. For The absorption, I, is the change in mass divided by the product
W/B 0.275 and 15% UFFA, the quantity of cement used was of the cross-sectional area of the test specimen and the density of
622 kg/m3, and the quantity of UFFA used was 109 kg/m3. water. For this test, the temperature dependence of the density of
The experiments were carried out for 28 and 56 days of curing water is neglected, and a value of 0.001 g/mm3 is used. The units of
age. For each of the mix design adopted, three specimens were I are mm.
tested for each curing age. Mixes were cast and tested in the labo-
ratory to evaluate sorptivity and RCPT. Further, weight loss and mt
residual strength were evaluated by immersion in HCl, MgSO4, I¼
ad
and H2SO4. The mix designs and the proportion of ingredients are
tabulated in Table 2.
where,
I = the absorption,
3. Sample preparation, curing and testing mt = the change in specimen mass in grams, at time t,
a = the exposed area of the specimen, in mm2, and
3.1. Sorptivity test d = the density of the water in g/mm3
The absorption (I) is plotted against the square root of elapsed
This test was carried out with adherence to ASTM C 1585-04, time. The slope of the line of best fit of these points (ignoring the
which is used to determine the rate of absorption (sorptivity) of origin) is reported as sorptivity. The results are discussed in
water by concrete, by measuring the increase in the mass of a spec- Section 4.4.
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H.M. Sujay et al. Construction and Building Materials 262 (2020) 120738

Fig. 1. Schematic representation of Sorptivity test setup (left) and actual experiment setup (right).

3.2. Rapid chloride permeability test (RCPT) I0 = current (amperes) immediately after voltage is applied, and
It = current (amperes) at t min after voltage is applied.
The durability of concrete is determined by its resistance to RCPT was conducted on specimens of 50 mm in height and
chloride ion penetration, which is related directly to low perme- 100 mm in diameter for each CFRHPC mix after 28 days and 56 days
ability, which dominates the process of deterioration. This study of curing. As per the classification system in ASTM C-1202, the con-
was conducted as per ASTM C 1202-19 [32], which is economical crete resistance to chloride permeability is classified as shown in
and time-saving. RCPT apparatus is shown in Fig. 2. In the test, Table 3. The results are discussed in Section 4.1.
chloride ions from the NaCl solution cell are driven towards the
NaOH solution cell, through the pore network present in the con-
crete placed in between the cells. An ammeter in the test setup
measures the intensity of the electric current, which is propor-
3.3. Effect of HCl, H2SO4 and MgSO4 on CFRHPC mixes
tional to the movement of chloride ions.
The test is carried out for a total duration of 6 h and the current
In the absence of a standard test procedure for measuring the
is measured at 5-minute intervals. The chloride ion permeability
resistance of CFRHPC to acid attack, this resistance was tested by
was computed as the total electric charge passing through the
immersion of concrete specimens in solutions containing 5% con-
specimen, given by the formula below.
centration of acids HCl, MgSO4 and H2SO4.
Chloride ion permeability, in Coulombs
To determine the weight loss, a series of conventional concrete
cubes of 100 mm side were cast and cured in fresh water for
Q = 900(I0 + 2I30 + 2I60 +......... + 2 I300 + 2I330 + I360 ) coulombs
28 days. The initial weights of all the cubes were recorded after
28 days of curing, after which they were kept immersed for 28
where, and 56 days more in separate tanks containing solutions of 5% con-
Q = charge passed (coulombs), centrations of HCl, MgSO4 and H2SO4. The immersion medium was
replaced with fresh solutions at the end of every week to maintain
the same concentration throughout the acid immersion. After the
specified period, the cubes were removed from the acid solution
and allowed to dry under shade. The specimens were again
weighed at the end of 28 and 56 days of acid immersion to deter-
mine the percentage weight loss. The results are discussed in
Section 4.2.
To evaluate the compressive strength and residual compressive
strength of concrete, the concrete cubes of 100 mm side were
tested in a 3000 kN Aimil digital compression testing machine,
adhering to BIS IS 516:1959 (Part 1) [33] before acid immersion
and after 28 and 56 days of acid immersion. The compressive
strength after acid immersion is known as residual compressive
strength. Also, the percentage loss of compressive strength was
calculated. The results are discussed in Section 4.3.

Table 3
Classification of permeability as per ASTM C-1202.

Charge passed (coulombs) Permeability

>4000 High
2000–4000 Moderate
1000–2000 Low
1000–100 Very Low
<100 Negligible
Fig. 2. Cross-sectional view of RCPT Apparatus.

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H.M. Sujay et al. Construction and Building Materials 262 (2020) 120738

Table 4
Chloride ion permeability test results of CFRHPC mixes.

Sl. No Designation of mix Chloride ion permeability (Coulombs) % Decrease

28 Days 56 Days 28 Days 56 Days
1. NS 0 1555 1446 – –
2. NS 1.5 718 638 53.83 55.88
3. NS 3.0 611 515 60.71 64.38
4. NS 4.5 596 502 61.67 65.28
5. NS 0 F 1375 1268 11.58 12.31
6. NS 1.5 F 676 585 56.53 59.54
7. NS 3.0 F 568 472 63.47 67.36
8. NS 4.5 F 535 449 65.59 68.95
9. UF NS 0 824 743 47.01 48.62
10. UF NS 1.5 612 527 60.64 63.55
11. UF NS 3.0 483 406 68.94 71.92
12. UF NS 4.5 461 392 70.35 72.89
13. UF NS 0 F 786 690 49.45 52.28
14. UF NS 1.5 F 578 482 62.83 66.67
15. UF NS 3.0 F 458 385 70.55 73.37
16. UF NS 4.5 F 444 372 71.45 74.27

4. Results and discussion From Table 4, it can be observed that all the mixes attained low
to very low chloride permeability range as per ASTM C-202 criteria
The proportion of all the components of the mix have been tab- (See Table 3), with total charge passed in coulombs well below
ulated in Table 2. Durability test results of various mix proportions 2000. It can be observed that the chloride ion permeability of all
are discussed in the following Sections 4.1–4.4. CFRHPC mixes are considerably lower (approximately 50%) than
that of reference mix concrete. The decrease in chloride ion perme-
ability for CFRHPC mixes with nanosilica ranged from 53.83% to
4.1. Rapid chloride permeability test (RCPT)
71.45% for 28 days curing period and 55.88% to 74.27% for 56 days
curing period, as against the reference mix.
Consolidated results of the chloride ion permeability test
Thus, it can be concluded that the chloride ion permeability val-
obtained from the present investigation are presented in Table 4.
ues of CFRHPC mixes are significantly less when compared to cor-
responding plain concrete due to the high reactivity of nanosilica
4.1.1. Effect of UFFA on chloride ion permeability because of its higher specific surface. The nanosilica reacts with
The effect of the percentage of mineral admixture on chloride available calcium hydroxide leading to the formation of additional
ion permeability for UFFA based nanosilica HPC mixes are depicted C-S-H gel resulting in a denser morphology. Hence, HPC produced
in Fig. 3 and Fig. 4. From Fig. 3, it can be observed that the addition with UFFA and nanosilica mineral admixtures has low permeabil-
of UFFA has a considerable effect on the chloride ion permeability ity, indicating high durability.
of CFRHPC. For 15% replacement of cement with UFFA, the decrease
in chloride ion permeability observed at 28 days curing age was
47.0% in the absence of fibers (UF NS 0) and 49.45% with the addi-
tion of 1.25% composite fibers (UF NS 0F) in comparison to the ref-
erence mix. A similar trend can be observed for specimens of
56 days curing age, and the reduction in percentage is 48.62% for
the mix UF NS 0. When composite fibers were added to the same
mix, the reduction in chloride ion permeability is 52.28%. Thus, it
can be concluded that the addition of mineral admixture UFFA is
beneficial in reducing the permeability of CFRHPC.

4.1.2. Effect of nanosilica on chloride ion permeability

From Table 4, Fig. 3, and Fig. 4 it can be observed that with the
increase in the percentage of nanosilica, the chloride ion perme-
ability decreases. For a mix with 0% UFFA and W/B ratio of 0.275
for 28 days, it is observed that as the percentage of nanosilica
increased from 0% to 4.5%, the chloride ion penetration decreased
from 1555 C to 596 C. With the addition of steel and polypropylene
fibers to the above mix, the chloride ion penetration decreased
from 1375 C to 535 C as the percentage of nanosilica increased.
A similar such trend was observed for specimens tested after
56 days of curing, and the charge passed decreased from 1446 C
to 502 C, a 65.28% decrease in chloride ion permeability.
Clearly, there is a decrease in the amount of charge passed with
an increase in the percentage of nanosilica in concrete. From the
above results, it is seen that the decrease in percentage is high
up to 3% addition of nanosilica, and at 4.5% addition, the decrease
in percentage is very less (61.67%) than at 3% (60.71%), hence the
Fig. 3. Chloride ion permeability of CFRHPC mixes at 28 Days.
optimum replacement of nanosilica can be restricted to 3%.
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H.M. Sujay et al. Construction and Building Materials 262 (2020) 120738

Fig. 4. Chloride ion permeability of CFRHPC mixes at 56 Days.

Fig. 5. Percentage Weight Loss Due to immersion in HCl for mix designs with W/B
0.275.
4.2. Behavior of CFRHPC when subjected to acid attack

In the present section, the durability of CFRHPC has been stud-

ied by conducting acid immersion test on concrete cubes. Residual
compressive strength and percentage weight loss of all the mixes
after acid immersion have been measured. Based on the results
of this investigation, a discussion is presented in the following
sections.

4.2.1. Percentage weight loss on acid immersion

In the present section, the percentage weight loss of CFRHPC
due to acid immersion has been determined as a parameter of
durability. The percentage weight loss due to acid immersion in
acids HCl, H2SO4 and MgSO4 of all CFRHPC mixes tried in this
investigation are presented.

4.2.2. Effect of added mineral admixtures on percentage weight loss

The effect of percentage replacement of cement by nanosilica
and UFFA on the percentage of weight loss is presented in Figs. 5–
13.

4.2.3. Effect of age of acid immersion on percentage weight loss

It can be observed from the results that the percentage weight
loss increases with an increase in the age of acid immersion. This is
true for all the acids tried in this investigation. The percentage of
weight loss is higher at 56 days of immersion in acid. For example,
for UF NS 0 F mix and 0.275 W/B ratio, the percentage weight loss Fig. 6. Percentage Weight Loss Due to immersion in HCl for mix designs with W/B
has increased from 4.18 to 5.11 as the age of HCl acid immersion 0.300.
increased from 28 to 56 days. Similarly, for the same mix, on
immersion in H2SO4, the percentage weight loss increased from
8.01 to 16.07, and on immersion in MgSO4, the percentage weight H2SO4 acid immersion, and minimum percentage weight loss
loss increased from 5.06 to 6.86 for the increase in age of acid was observed for HCl acid immersion.
immersion from 28 to 56 days. For example, for UF NS 0 F mix, the weight loss due to 56 days of
immersion in HCl is 5.11%, whereas, for the same mix with immer-
4.2.4. Effect of type of acid on percentage weight loss sion in H2SO4, the weight loss is 16.07% which indicates the sever-
In the present investigation, all the composite fiber nanosilica ity of H2SO4 on CFRHPC. Also, it is observed that for the same mix
and UFFA mixes have been exposed to 5% concentration of acids of immersion in MgSO4, the percentage weight loss at 56 days is
HCl, H2SO4 and MgSO4. From Figs. 5–13, it can be observed that 6.86. Thus, it can be observed that the MgSO4 attack is severe when
the maximum percentage weight loss has occurred in the case of compared with that of HCl and the attack of H2SO4 is most severe

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H.M. Sujay et al. Construction and Building Materials 262 (2020) 120738

Fig. 9. Percentage Weight Loss Due to immersion in H2SO4 for mix designs with W/
B 0.300.
Fig. 7. Percentage Weight Loss Due to immersion in HCl for mix designs with W/B
0.325.

Fig. 10. Percentage Weight Loss Due to immersion in H2SO4 for mix designs with
W/B 0.325.

Fig. 8. Percentage Weight Loss Due to immersion in H2SO4 for mix designs with W/
B 0.275.
porous resulting in additional ingress of acids. This causes volume
increase in concrete resulting in spalling and weight loss. Further-
more, it can be noticed that the percentage weight loss of all
on CFRHPC mixes. Similar trends are observed for all W/B ratios CFRHPC mixes were considerably lower when compared to the ref-
and at all replacement levels. erence mix. Hence, it can be concluded that concrete with 15%
The severity of the sulphuric acid is due to its combined action UFFA and 3% nanosilica with and without fibers very well resist
of acid attack and sulfate attack. The visual observation of the con- the acid attack in comparison to conventional concrete.
crete cubes tested after 56 days of immersion (Fig. 14) indicated
the signs of severe deterioration due to sulfate attack. The corners 4.3. Behavior of CFRHPC cubes under compression after subjecting to
were the first to fall off because, near the corners, the intrusion is acid attack
from the two adjacent faces of the cube.
The reason for increasing weight loss at higher W/B ratios is In the present section, the percentage strength loss of CFRHPC
that, with increase in water content, the transition zone becomes due to acid immersion has been determined as a parameter of
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H.M. Sujay et al. Construction and Building Materials 262 (2020) 120738

Fig. 11. Percentage Weight Loss Due to immersion in MgSO4 for mix designs with Fig. 13. Percentage Weight Loss Due to immersion in MgSO4 for mix designs with
W/B 0.275. W/B 0.325.

Fig. 14. Concrete cubes after 56 days of immersion in H2SO4.

ent acids. From these figures, it can be observed that the percent-
age decrease in residual compressive strength increases with an
increase in the age of acid immersion. This is true for all the acids
tried in this investigation. The percentage decrease in residual
Fig. 12. Percentage Weight Loss Due to immersion in MgSO4 for mix designs with
compressive strength is higher at 56 days of immersion in acid.
W/B 0.300.
For example, for UF NS 0 mix, the percentage decrease in compres-
sive strength is 5.91 to 4.90 for immersion in HCl acid after 28 days
durability. The percentage strength loss due to immersion in acids of acid immersion. As the nanosilica addition increases from 0% to
HCl, H2SO4 and MgSO4 of all CFRHPC mixes tried in this investiga- 4.5%, there is a decrease in percentage residual compressive
tion are presented in Figs. 15–23. strength. The same trend is observed for other W/B ratios of 0.3
and 0.325.
In H2SO4 acid immersion, at 28 days for W/B 0.275, the percent-
4.3.1. Effect of age of acid immersion on percentage decrease in age residual compressive strength decreases from 7.09% to 6.18%.
compressive strength The higher the nanosilica content more is the residual compressive
The effect of the age of acid immersion on percentage decrease strength. A similar trend is seen for 56 days of immersion. The
in compressive strength is depicted in Figs. 15–23 for three differ- decrease in residual compressive strength varies from 13.99% to
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H.M. Sujay et al. Construction and Building Materials 262 (2020) 120738

Fig. 17. Percentage Strength Loss Due to immersion in HCl for mix designs with W/
Fig. 15. Percentage Strength Loss Due to immersion in HCl for mix designs with W/
B 0.325.
B 0.275.

Fig. 18. Percentage strength Loss Due to immersion in MgSO4 for mix designs with
Fig. 16. Percentage Strength Loss Due to immersion in HCl for mix designs with W/
W/B 0.275.
B 0.300.

10.92%. The same trend is observed for other W/B ratios of 0.3 and
The primary cause of a reduction in compressive strength with
0.325. Also, For MgSO4 acid immersion, the trend is the same. The
increasing W/B ratio can be attributed to the fact that higher water
percentage decrease in residual compressive strength for W/B
content permits deeper penetration of acids resulting in deteriora-
0.275 was from 6.41% to 5.25% for 28 days, and for 56 days of
tion of C-S-H gel. The maximum loss of compressive strength was
immersion, the decrease was from 11.80% to 9.66%.
noticed after 56 days of acid immersion. This decrease in residual
compressive strength was due to the increased formation of ettrin-
gite in the concrete microstructure with an increase in the age of
4.3.2. Effect of type of acid on percentage decrease in compressive acid immersion. The presence of admixtures UFFA and nanosilica
strength causes a decrease in residual compressive strength as the packing
From the results, it is clear that there was a maximum decrease density in the matrix increases resulting in a reduction of capillary
in residual compressive strength for cubes immersed in H2SO4. pores and formation of gel pores responsible for resistance against
Thus, it can be concluded that H2SO4 has a severe effect on CFRHPC acid attacks. Hence, it can be concluded that 15% replacement of
mixes. Whereas MgSO4 has a moderate effect, and HCl has a mild cement by UFFA and 3% addition of nanosilica is optimum for
effect comparatively on the CFRHPC mixes. CFRHPC in resisting acid attacks.
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H.M. Sujay et al. Construction and Building Materials 262 (2020) 120738

Fig. 19. Percentage strength Loss Due to immersion in MgSO4 for mix designs with Fig. 21. Percentage Strength Loss Due to immersion in H2SO4 for mix designs with
W/B 0.300. W/B 0.275.

Fig. 20. Percentage strength Loss Due to immersion in MgSO4 for mix designs with
Fig. 22. Percentage Strength Loss Due to immersion in H2SO4 for mix designs with
W/B 0.325.
W/B 0.300.

4.4. Sorptivity test

Hence, the sorptivity characteristics of the same mix were investi-
The initial rate of water absorption is the slope of the best fit gated by comparing its performance with the reference mix and a
line to the Absorption v/s Time1/2 plot, which was determined by mix design in which the UFFA was absent (NS 3).
linear regression analysis of this plot for all points ranging from The initial and secondary rate of absorption was determined
1 min to 6 h. The secondary rate of water absorption is the slope since the correlation coefficient was found to be more than 0.98
of the best fit line to the Absorption v/s Time1/2 plot, which was in each case. From Fig. 24, The average initial rate of absorption
determined by linear regression analysis of this plot for all points was found to be 4.83  104 mm/sec1/2, and the secondary rate
ranging from day 1 to day 8. For any of the absorption rates, if of absorption was found to be 1.40  104 mm/sec1/2 for the refer-
the correlation coefficient is less than 0.98 (it does not follow a lin- ence mix. For the mix with 15% UFFA and 3% nanosilica, the initial
ear relationship), the rate cannot be determined. rate of absorption was found to be 3.43  104 mm/sec1/2, and
From the test results in Sections 4.1–4.3, it was seen that the 1.17  104 mm/sec1/2 was its secondary rate of absorption. These
mix design with 15% UFFA, 3% nanosilica (UF NS 3) and 0.275 values are lower than both the reference mix and the same mix
W/B showed higher acid and chloride ion penetration resistance. without 15% UFFA. Lower water absorption and sorptivity resulted

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H.M. Sujay et al. Construction and Building Materials 262 (2020) 120738

resistance to an aggressive acidic environment as per the findings

of this study. The conclusions can be summarized as follows:

1. The RCPT conducted on CFRHPC mixes with partial replace-

ment of cement by UFFA exhibited better performance com-
pared to the reference mix. At 15% partial replacement of
cement by UFFA, the decrease in RCPT value is 47.01% at
28 days and 48.62% at 56 days relative to the reference mix.
2. The addition of nanosilica has reduced the chloride ion pen-
etration substantially in the system. The chloride ion pene-
tration decreases with increasing dosage of nanosilica. The
decrease in percentage of chloride ion penetration is high
up to 3% addition of nanosilica (61.67%), and at 4.5% addi-
tion, the decrease is marginal (60.71%).
3. The sorptivity test results revealed that both the initial and
secondary rate of absorption is lowest for the mix with
15% UFFA and 3% nanosilica.
4. The percentage weight loss due to acid attack increases with
an increase in W/B ratio for all the percentage replacements
of cement by UFFA, nanosilica. Also, the percentage weight
loss increases with an increase in the age of acid immersion.
This is true for all the three acids tried in this investigation.
Fig. 23. Percentage Strength Loss Due to immersion in H2SO4 for mix designs with 5. The best resistance to weight loss is observed by up to 15%
W/B 0.325.
partial replacement level of UFFA and 3% addition of nanosil-
ica. At 4.5% addition of nanosilica for the same replacement
level of UFFA, further decrease in percentage weight loss is
0% UF 0% NS marginal.
0.35 0% UF 3% NS
6. The UFFA and nanosilica based CFRHPC mixes resisted acid
15% UF 3% NS
attack in a better way as compared to the traditional con-
0.30 crete. It is also observed that the residual compressive
strengths of all CFRHPC mixes are considerably higher than
0.25 that of the reference mix. This holds true for all ages of acid
Absorption

exposure to HCl, MgSO4 and H2SO4.

7. The residual compressive strength of CFRHPC mixes sub-
0.20
jected to acid attack decreases with an increase in water-
to-binder ratio. A similar trend is observed for all the
0.15 replacement levels of nanosilica and the type of acids tried
in the investigation.
0.10 8. The percentage loss of residual compressive strength is least
at 15% partial replacement of cement by UFFA and 3% addi-
0.05
tion of nanosilica. The loss of compressive strength is 11.38%
0 200 400 600 800 for the same mix after 56 days of immersion in H2SO4, while
Sqrt of time similar exposure for the reference mix resulted in a loss of
14.81%. This confirms the superior resistance of CFRHPC to
Fig. 24. Graph of Absorption v/s Time1/2 showing Sorptivity characteristics of an aggressive acidic environment.
CFRHPC. 9. The addition of composite fibers to the CFRHPC matrix mar-
ginally improved the durability characteristics.
10. Based on this experimental study, a combination of 15%
is due to a decrease in the number of capillary pores with an replacement of cement by UFFA, 3% addition of nanosilica,
increase in the formation of calcium hydrated jelly from higher and 1.25% composite fibers (steel and polypropylene) found
reactivity of nanosilica. Additionally, nanosilica fills the voids to be an optimal recommendation in the present context.
between cement particles because of its nano-scale particle size
improving the packing and reducing the porosity in the concrete This investigation proves that the use of nanosilica for enhanc-
matrix. Hence, it can be concluded that the presence of 15% UFFA ing the durability properties of high-performance concrete has a
and 3% nanosilica in the concrete has drastically lowered the water huge potential in the industry. It has been observed that different
absorption characteristics of CFRHPC and can be considered as an studies made by researchers do not generalize the optimum dosage
optimum replacement level. of nanosilica, and this needs to be further investigated. The biggest
challenge is to achieve a homogeneous dispersal of nanosilica in
the concrete matrix. Many researchers have put forward alterna-
5. Conclusions tive procedures such as sonication process to obtain a homoge-
neous distribution of nanosilica. However, very few pieces of
The structures that were constructed in the past three decades literature are available on the use of nanosilica in combination
did not meet their designed service life, particularly offshore struc- with other mineral admixtures and fibers. Optimization and math-
tures. The High-Performance concrete developed with partial ematical correlations in the durability properties of concretes
replacement of cement by UFFA and nanosilica exhibits superior incorporating nanosilica can be researched in the future.

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H.M. Sujay et al. Construction and Building Materials 262 (2020) 120738

CRediT authorship contribution statement [15] M.H. Beigi, J. Berenjian, O. Lotfi Omran, A. Sadeghi Nik, I.M. Nikbin, An
experimental survey on combined effects of fibers and nanosilica on the
mechanical, rheological, and durability properties of self-compacting concrete,
Sujay H.M. Methodology, Validation, Investigation, Data cura- Mater. Des. 50 (2013) 1019–1029, https://doi.org/10.1016/
tion, Writing - original draft. Nishant A. Nair: Writing - review & j.matdes.2013.03.046.
[16] H. Du, S. Du, X. Liu, Durability performances of concrete with nano-silica,
editing, Resources. H. Sudarsana Rao: Conceptualization, Method-
Constr. Build. Mater. 73 (2014) 705–712, https://doi.org/10.1016/
ology, Supervision. V. Sairam: Conceptualization, Methodology, j.conbuildmat.2014.10.014.
Supervision. [17] X. He, X. Shi, Chloride Permeability and Microstructure of Portland Cement
Mortars Incorporating Nanomaterials, Transp. Res. Rec. J. Transp. Res. Board.
2070 (2008) 13–21, https://doi.org/10.3141/2070-03.
Declaration of Competing Interest [18] P. Chindaprasirt, S. Homwuttiwong, V. Sirivivatnanon, Influence of fly ash
fineness on strength, drying shrinkage and sulfate resistance of blended
cement mortar, Cem. Concr. Res. 34 (2004) 1087–1092, https://doi.org/
The authors declare that they have no known competing finan- 10.1016/j.cemconres.2003.11.021.
cial interests or personal relationships that could have appeared [19] P. Chindaprasirt, C. Jaturapitakkul, T. Sinsiri, Effect of fly ash fineness on
compressive strength and pore size of blended cement paste, Cem. Concr.
to influence the work reported in this paper.
Compos. 27 (2005) 425–428, https://doi.org/10.1016/j.
cemconcomp.2004.07.003.
[20] R. Malathy, Role of super fine fly ash on high performance concrete, in: Role
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