Construction and Building Materials 269 (2021) 121272

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Construction and Building Materials

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

Effect of graphene oxide dosage on the deterioration properties of

cement pastes exposed to an intense nitric acid environment
Murugan Muthu a,b,⇑, Neven Ukrainczyk a, Eddie Koenders a
a
Institute of Construction and Building Materials, Technische Universität Darmstadt, Darmstadt 64287, Germany
b
Larsen & Toubro Construction Research and Testing Center, Mount Poonamallee Road, Manapakkam, Chennai 600089, India

h i g h l i g h t s

Graphene oxide inclusion in cement matrix reduced the considered porosity to 48% by acting as crack-arrestor.

Addition of 0.03 wt% GO increased the quantity of portlandite in cement matrix to 4.9%.

Resistance and Young’s modulus of cement paste against nitric acid attack improved with an increasing GO dosage.

Mass loss in 0.03 wt% GO-modified cement specimen after HCl attack is 17% lesser than the control mix (i.e., without any GO).

GO inclusion did not influence the mineralogical composition of cement matrix altered by the nitric acid attack.

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

Article history: In this study, the effect of graphene oxide (GO) dosage on the performance of cement pastes against an
Received 3 August 2020 extreme nitric acid environment was investigated. A significant volume of cement matrix was affected
Received in revised form 3 October 2020 because of such attack. The loss in specimen mass and sectional area before and after acid attacks were
Accepted 6 October 2020
compared to validate the relative performance between the cement mixes. Compared to the 28-day cured
Available online 24 October 2020
reference mix, the mass and sectional area losses in the acid exposed cement specimen had reduced up to
17% and 25% when the matrix was modified using 0.03 wt% GO, respectively. With an increase in GO
Keywords:
dosage from 0 to 0.03 wt% at an interval of 0.01 wt%, it was found that the porosity of cement pastes sig-
Portland cement
Graphene oxide
nificantly declined due to crack-arresting effects, which also explained the improved resistance of cement
Acid attack composites against the acidic medium. The GO presence did not influence the mineralogy of the altered
Microstructure cement matrix. Still, it contributed to the material stiffness, which was determined after conducting mul-
Decalcification tiple characterisation studies. Thus, the GO-modified cement concrete was found to be a promising mate-
Crack-arresting rial to construct the storage structures operating under aggressive chemicals and crack inducing
conditions.
Ó 2020 Elsevier Ltd. All rights reserved.

1. Introduction GO is made up of a single layer of mixed sp2 and sp3 hybridized

Graphene, owing to its excellent properties, has been lauded as
the next fascinating nano-material additive for various applica-
tions such as anti-corrosion paints, sensors, electronics, flexible
displays, and drug delivery. Today, the manufacturing of graphene
at the bulk scale is mostly done through the initial oxidation of gra-
phite to produce graphene oxide (GO) [1,2]. The pristine graphene
material is hydrophobic and agglomerates in water, but GO has
high dispersion characteristics in polar solvents [1], which there-
fore expands its applications, especially in concrete manufacturing.
⇑ Corresponding author at: Larsen & Toubro Construction Research and Testing
Center, Mount Poonamallee Road, Manapakkam, Chennai 600089, India.
E-mail address: mnmuthu@lntecc.com (M. Muthu).
carbon atoms. The edges and basal plane of GO sheets are grafted
well with carboxyl, hydroxyl, and carbonyl functional groups
[3,4]. Hummer’s method is a widely used chemical process for syn-
thesis of GO on a massive scale. GO synthesized by this method is
of decent quality in terms of number of layers [5]. The single-layer
size in GO varies from 0.7 to 1 nm and 0.1–100 mm lateral size. The
surface area and in-plane Young’s modulus of GO are 1500–
1700 m2/g and 210–470 GPa, respectively [3].
The failure of concrete through physical and mechanical effects
is most likely, but chemical effects like acid-induced deterioration
do also affect the service life of concrete [6]. Concrete is porous
material and described by a substantial chemical reactivity, of
which its complexity is in practise often underrated. Concrete
undergoes mineralogical and chemical changes when exposed to

https://doi.org/10.1016/j.conbuildmat.2020.121272
0950-0618/Ó 2020 Elsevier Ltd. All rights reserved.
M. Muthu, N. Ukrainczyk and E. Koenders Construction and Building Materials 269 (2021) 121272

aggressive chemicals. Such deterioration processes mostly happen tates could be amorphous silica hydrogel that has a pH value the
at the interface between cement and water, and starts right away same as the acidic medium [23].
when the cement-based material comes in contact with the sur- The resistance of concrete against such chemical deterioration
roundings that provide the (aggressive) substances [7], which then can improve when the content is modified using pozzolanic mate-
diffuse into and react with the concrete’s microstructure. In recent rials, chemical admixtures, polymeric fibers, and sulfate-free
times, the mechanical strengths of cement-based systems modified aggregates [24]. The modification of concrete at the nanoscale level
with varying GO dosages have been extensively investigated by using silica nanoparticles also showed an excellent resistance
many researchers [4,8–11]. Still, to the author’s best knowledge, against acid attacks [25].
the behaviour of such composites under aggressive aqueous condi- In the present study, cement paste specimens modified with 0,
tions has not yet been fully understood. 0.01, 0.02, and 0.03 wt% GO dosages were exposed to an intense
The effect of good dispersion of GO sheets in concrete is attrib- HNO3 environment for 10 d. The HNO3 solution was replenished
uted to three main effects [12], i.e.: (i) GO regulates the microstruc- every 48 h to accelerate the damage in cement specimens, and this
ture morphology of concrete by assisting growth of the hydration action also assisted in achieving the results rapidly after exposure.
of clinker components, (ii) GO refines the pore-structure of con- The loss in specimen mass and sectional area at the end of the
crete by effectively filling the defective regions in the cement HNO3 attack was recorded to validate the relative performance in
matrix, and (iii) GO forms a strong bond between the cement between the different cement mixes. The HNO3 attack altered a
hydrates of concrete. Dimov et al. [13] compared the performance significant volume of the cement matrix, and such a part was care-
of ultra-high-performance concrete (UHPC) modified with water- fully removed out of the damaged specimen and assessed using
soluble exfoliated graphene flakes. Compared to a reference con- multiple characterisation techniques such as X-ray diffraction
crete, the compressive and flexural strengths increased to 146% (XRD), thermogravimetric analysis (TGA), energy dispersive spec-
and 80% because of the presence of well-dispersed GO sheets. An troscopy in conjunction with scanning electron microscopy
addition of 0.03 wt% GO could improve the compressive and tensile (SEM-EDS), and nanoindentation to study the chemical and
strengths in concrete by up to 41% and 13% [14], respectively. mechanical changes. The overall findings indicate the effect of
Besides, the diffusion of chloride ions into a concrete located in a GO dosages on the performance and microstructure of cement
coastal environment could also be monitored when GO was uni- composites damaged under aggressive chemicals.
formly dispersed in the cement matrix. Jin et al. [15] used electrical
impedance spectroscopy to quantify the amount of chloride ions
2. Experimental program
penetrated the GO-modified cementitious matrix. Apart from mon-
itoring, the presence of GO sheets could also curb the diffusion of
2.1. Materials
chloride ions from the aqueous medium [16]. Chen et al. [17]
examined the creep behaviour of a 0, 0.02, and 0.08 wt% GO-
In this study, the water-dispersible GO was self-synthesized
modified cementitious matrices through an experimental and
using the modified Hummers method. The GO synthesizing proce-
modelling approach. The creep coefficient of the 0.02 and 0.08 wt
dure suggested in Li et al. [5], and Ghazizadeh et al. [3] was fol-
% GO-modified cement composites was found to be 7% and 10% less
lowed in this study. High purity chemicals procured from Sigma
than the reference mix after testing for 60 d. A possible reason for
Aldrich was used in the GO synthesis. The GO sheets were primar-
this is that the presence of GO sheets restrained the formation of
ily extracted from 99% carbon pure graphite flakes that have an
micro-cracks by transferring the crack energy into the cement
average size of about 150 mm. A sample from the synthesized GO
matrices subjected to sustained loading [17]. Li et al. [14] have
was taken, dried overnight at 80 °C and assessed using a Horiba
reported that the workability of cement pastes decreased with an
HR 800 Raman spectrometer and Bruker D2 Phaser XRD machine.
increasing GO dosage. The GO surfaces and edges have the poten-
The Raman spectrum was collected up to a wavelength of
tial to entrap free water, and this effect could have been the reason
3650 cm1. The XRD scan ran for a scanning range 5-80° 2h at a
behind the reduced cement workability.
rate of 0.02° 2h per min. Fig. 1 and Fig. 2 show the Raman spectrum
Acid attack on concrete led in the beginning to a reactive trans-
and XRD pattern of the GO sample. The main XRD peaks at 13.1°
port process between the acidic medium and alkaline pore solution
of the cement matrix, which happened because of the ionic con-
centration gradient in between them [7]. Such ionically driven
movements create a chemical imbalance between the pore solu-
tion and the cement hydrates, which subsequently activates the
dissolution and crystallization reactions [7,18].
The concrete structures operating in chemical plants manufac-
turing artificial manure and/or fertilizer industries are often
exposed to aggressive chemicals containing large amounts of nitric
acid (HNO3) dissolved in them [19–21]. The HNO3 attack on
cement components of concrete results in the formation of a cal-
cium nitrate salt, which is soluble in water, and, therefore dissolves
into the aqueous solution [22,23]. A zone of altered products sur-
rounding the natural core material is generally seen across a con-
crete member damaged by chemical attack [18,20]. Pavlík [23]
has designated the formation of different zones across a cement
paste-based prismatic specimen subjected to the HNO3 attack. A
brown discoloured layer surrounding the innermost unaltered core
material, and outermost milky white precipitates encompasses
these two regions [23]. The brown discolouration in the damaged
cement specimen could be due to the formation of ferric oxyhy-
droxide (Fe(OH)3). In contrast, the porous and soft white precipi- Fig. 1. Raman spectrum of natural graphite and graphene oxide.

2
M. Muthu, N. Ukrainczyk and E. Koenders Construction and Building Materials 269 (2021) 121272

Table 2
Details of the different cement mixes prepared in this study.

Mix ID GO (%) Cement (%) PCE (%) w/c ratio

GO-0 0 100 0.05 0.3
GO-1 0.01
GO-2 0.02
GO-3 0.03

the cement matrix. A sample from the GO solution mixture was

Fig. 2. XRD pattern of raw cement and graphene oxide.
and 29.9° 2h confirmed the existence of a graphite-like structure,
whereas the Raman peak at wavelengths 1332 cm1 and
1566 cm1 corresponds to the graphene (G) and defect (D) bands,
respectively. The ratio of D to G band intensity (ID/IG) equals to
1.02, which indicates that the graphite planes are well-grafted with
the oxygen-containing functional groups. Also, the Raman spectra
confirm that there was a reduction in the average size of sp2 carbon
domains, which is due to the extensive oxidation of graphite.
Cement composites were prepared using distilled water, poly-
carboxylate ether (PCE)-based superplasticizer, graphene oxide,
and CEM I 52.5R Portland cement as per DIN standards [26]. The
chemical composition of raw cement was assessed using X-ray flu-
orescence, and results are shown in Table 1. The fineness of cement
was determined using the Blaine air permeability test [27], which
was calculated to be 4390 cm2/g. The XRD scan was also done for
raw cement to assess whether the material has undergone natural
carbonation. It was found that the XRD peaks confirmed the pres-
ence of clinker compounds such as tricalcium silicate (C3S), dical-
cium silicate (C2S), tricalcium aluminate (C3A) and tetracalcium
aluminoferrite (C4AF). No significant traces of calcite were noticed
in the cement sample.
taken, diluted 1000 folds, 30 mins sonicated, and finally analyzed
using Malvern Zetasizer Nano model dynamic light scattering
(DLS) instrument. This assessment gives the actual size distribu-
tion of graphene oxide sheets that exist in suspension. The PCE
and water was sonicated using the water bath in the case of GO-
0 mix. Fig. 3 shows the DLS results of the three solution mixtures
containing 0.01, 0.02, and 0.03 wt% GO. It was found that the size
of the GO sheets existing in these three solutions was found to fall
within 120 nm to 1.16 mm, respectively. Frankberg et al. [28]
reported about the same size range of well-dispersed GO, which
was synthesized by the Hummer’s method. With this comparison,
it can be said that the concentrated GO (0.01–0.03 wt%) used in
this study was effectively dispersed in water.
2.3. Isothermal calorimetry
The heat flow due to cement hydration in each mixture was
studied using an I-Cal 8000 high precision calorimeter conforming
to ASTM C1702-15a [29]. This experiment was done at 28 °C and
65% relative humidity (RH) conditions. The fresh cement pastes
after mixing were loaded into the calorimeter channels within the
next 10–15 s to record the heat of cement hydration for up to 48 h.
2.4. Acid attack
Laboratory reagent 67% concentrated nitric acid procured from
Sigma Aldrich was used in this study. After curing in water for 7 d

2.2. Specimens preparation

A prismatic specimen of size 10  10  50 mm3 was used to

conduct the HNO3 attack experiment. Four different cement mix-
tures admixed with 0, 0.01, 0.02, and 0.03 wt% GO were prepared
with the same water-to-cement (w/c) ratio and PCE content of
0.3 and 0.05 wt%, respectively (see Table 2).
Cement pastes were cast into silicone rubber moulds. These
four mixtures were named as GO-0, GO-1, GO-2, and GO-3, respec-
tively. The vibration table was used to consolidate the fresh cement
paste. The cement specimens were demolded after 24 h and then
cured in distilled water for up to 7 d and 28 d at room conditions
(25 °C and 65% RH). Before preparation of each cement paste, a
solution mixture containing GO, PCE, and water was sonicated at
50 W for 30 mins using an ultrasonic water bath. This process Fig. 3. DLS results showing the size distribution of GO sheets in the three different
was mainly done to improve the dispersibility of GO sheets in GO concentrated aqueous solutions.

Table 1
Chemical composition of raw cement.

Oxide compounds CaO SiO2 Al2O3 Fe2O3 SO3 MgO Na2O K2O Ignition loss
wt% 64.6 21.4 3.7 4.6 1.5 0.8 0.3 0.4 2.7

3
M. Muthu, N. Ukrainczyk and E. Koenders
and 28 d, the saturated surface dry cement paste specimens were
directly immersed in a 100 mL glass beaker containing an HNO3
solution of 1 M concentration for the next 10 d. Three specimens
from each cement mix were individually submerged in the HNO3
solution. To accelerate the cement deterioration and to achieve test
data promptly, the HNO3 solution was replenished every 2 d during
the exposure time. The pH of the HNO3 solution was frequently
monitored using a Hanna 211 model pH meter that was three-
point calibrated as per the NIST standards. This calibration was
done before analysing the acid samples. The average of three repli-
cates was calculated.
2.5. Recording specimen mass and sectional area
The specimen mass before and after acid exposures were
recorded using a 0.001 g precise weigh balance. The loss in speci-
men mass due to the HNO3 attack was calculated according to
Eq. (1).
Mass loss in % ¼ ððM1  M2 Þ=M1 Þ  100
Fig. 4. Sound zone remaining in the acid exposed cement specimen.
Fig. 5. (a) Typical load–displacement curve of the nanoindentation test and (b) laser micrograph clearly showing the indent mark in the GO-3 sample.
Construction and Building Materials 269 (2021) 121272
where M1 is the mass of the cured specimen, and M2 is the mass of
the acid exposed specimen. Other than the mass change, the pris-
matic sample exposed to acidic medium had undergone severe
alteration across its length, which is described as loss in the sec-
tional area in this study. The acid attack on the cement matrix is
generally characterized by the formation of an altered zone sur-
rounding the sound zone. The weak and soft altered region in the
cement specimen was scratched using a fingernail protected by
latex glove, and the remaining solid material was imaged under
Keyence VHX-600 optical microscope to find the loss in the sec-
tional area. Before imaging, the acid exposed cement specimen
was sectioned into five pieces along its length using a Buehler
Isomet-1000 model precision diamond-tipped saw. Then, the
dimension of such solid pieces was assessed using the image pro-
cessing software that is equipped with the microscope (Fig. 4).
The image analysis procedure includes (i) first adjusting the
image brightness, (ii) calibrating the image size, and (iii) finally
measuring the dimensions using software tools. The sectional area
loss was calculated using Eq. (2).
ð1Þ
Sectional area loss in % ¼ ððA1  A2 Þ=A1 Þ  100 ð2Þ
where A1 is the cross-sectional area of the original specimen, and A2
is the area of unaltered cement matrix post-acid exposure. The
average of the three samples was calculated.
2.6. Microstructure assessment
2.6.1. Mercury intrusion porosimetry
The dosage effect of graphene oxide on the pore-structure of 28-
d cured cement pastes were assessed using a Thermo Scientific
Pascal 140/440 series Mercury (Hg) intrusion porosimetry (MIP)
instrument. The cement specimens were sectioned into multiple
pieces using a precision saw. The inner middle parts were further
sectioned to a size lesser than 8  8  8 mm3, vacuum dried at
30 °C for 48 h, and finally involved in MIP investigations. After test-
ing, the samples were carefully discarded as per the University
norms and regional authority regulations. The altered cement
matrix in the acid exposed specimen was very soft and weak,
and it got collapsed when sectioned under the saw. Therefore, this
study limited the MIP assessment to the cement specimens unex-
posed to an acidic solution.
4
M. Muthu, N. Ukrainczyk and E. Koenders
2.6.2. XRD and TGA
The cement specimens before and after acid exposures were
vacuum dried at 30 °C for 24 h and then powdered to a size less
than 54 mm using a mortar and pestle, and standard sieve. Such
powdered samples were analyzed using XRD and TGA studies. In
the case of acid exposed specimens, the altered and unaltered
regions were separated and individually characterized. Care was
taken to avoid the intermixing between the altered and unaltered
zones of the acid exposed specimen. The XRD scans were con-
ducted for a scanning range 5–80° 2h at a rate of 0.02° 2h per
min whereas the TGA study was performed by heating the cement
powders from 35 to 1000 °C at a rate of 10 °C/min under nitrogen
purged condition.
2.6.3. SEM-EDS, nanoindentation and laser microscopy
The cut-section of the cement specimens before and after acid
exposures was vacuum dried and epoxy impregnated using a
Struers Citovac model impregnation device. The sample after
impregnation was left undisturbed for the next 14 h. The hardened
epoxy polymer was polished using a Struers LaboPol-100 grinding
cum polishing machine as per the procedure suggested in Ukrainc-
zyk et al. [30]. The altered zone in the cement specimen was soft
Fig. 6. Isothermal calorimetry results of the fresh cement pastes.
Fig. 7. (a) Cumulative porosity and (b) differential mercury intrusion curve of the different cement samples (offset was given to the differential curves for better readability).
5
Construction and Building Materials 269 (2021) 121272
and weak, and therefore, the cut-section having both unaltered
and altered zones bonded together was difficult to extract using
a precision saw. So, the unaffected zone in the acid exposed spec-
imen was polished with care and finally used in the microstructure
assessment. Both the polished section of cement specimens before
and after acid exposures were assessed using a Zeiss EVO LS25
SEM-EDS machine and Agilent Nanoindenter G200 testing system.
The SEM imaging was done at low voltage and medium vacuum
under the backscattered electrons mode. Therefore, no special
coating was done over the polished surface to eliminate the elec-
trons charging effect.
The load-controlled method was used in the Berkovich indenta-
tion testing. About 50 indents were conducted on each sample by
maintaining a targeted strain rate of 0.05 s1. A range of loads up to
45 mN was used in this experiment. The maximum load was held
for 10 s, followed by 10 s of unloading period. Such loading condi-
tions led to a penetration depth range of 500–1000 nm in the acid
exposed sample based on the hardness of the indented cement
components. The spacing between the indents was fixed at
50 lm on center in both the X and Y directions. Such spacing
was found enough to eliminate any adjacent indents from affecting
the next indentation result. Each indentation curve was validated
after testing the sample (Fig. 5a).
Indentations were meticulously selected using microscopy
images and analyzing the results to choose the indents that repre-
sent only the binder matrix and thus avoid cement particles. The
abnormal curves due to improper contact in between the Berko-
vich tip and cement sample or cracking of the immediate sur-
rounding sample area during testing were removed. The elastic
modulus of each valid indent was then calculated using the widely
employed model recommended by Oliver and Pharr [31]. The Pois-
son’s ratio was assumed to be 0.3 for all calculations [32]. The
indented mark in the polished surface was imaged using an Olym-
pus LEXT OLS4000 3D laser measuring microscope. Berkovich
nanoindenter tip is a three-sided pyramid, which is geometrically
self-similar. Under the laser confocal microscope, the pyramid
shape of this tip indented on the clinker was clearly visible, and
thus not considered in the statistical analysis of the results, i.e. only
the binder matrix was selected. Moreover, indent trials were car-
ried out also on the clinker particles, present in the polished
cement sample (Fig. 5b). The GO sheet in the polished sample is
very difficult to locate under SEM because its grey scale value
and shape is almost like the cement components. However, the
M. Muthu, N. Ukrainczyk and E. Koenders Construction and Building Materials 269 (2021) 121272

presence of such GO sheet can be easily located under laser confo-
cal microscope because of its flaky structure, size and higher
brightness level in comparison to cement hydrates.
3. Results and discussion
3.1. Heat of hydration
Fig. 6 shows the calorimetry results of the different GO-
modified cement pastes. The heat flow curve of the four cement
mixtures resembles that of a typical Portland cement paste, which
encompasses the initial reaction, and induction, acceleration,
deceleration, and decline periods. It was noticed from the heat flow
curve that the GO-3 mix exhibited higher heat of hydration than
the GO-0 mix, especially during the acceleration period. The pres-
ence of GO sheets enhanced the cement matrix through the accel-
eration of the hydration process by supplying many nucleation
sites and high surface area to volume ratios. By promoting the
cement hydration, the inclusion of GO increases the generation of
cement hydrates by surface related promotion of the boundary
nucleation and growth kinetic mechanism, which subsequently
improves the matrix strength by filling the pores/voids.
3.2. Pore-structure
The MIP technique is often used to study the pore-structure
characteristics of cement-based materials. It gives the considered
porosity, which refers to the fraction of open pores that are mea-
surable using MIP [33,34]. Fig. 7a shows the cumulative porosity
of 28-d cured cement samples that were found using MIP. The dis-
tribution of pore sizes in these cement samples was illustrated
using a logarithm curve of differential mercury intrusion volume
(Fig. 7b).
The cumulative porosity in GO-0, GO-1, GO-2, and GO-3 sam-
ples was determined to be 14.02%, 10.32%, 9.25%, and 7.25% by vol-
ume. It shows that the porosity in the cement matrix decreased
with an increase in GO dosage. Notably, the presence of 0.03 wt%
GO reduced the formation of permeable pores in the cement
matrix by almost half. This finding explains that the presence of
well-dispersed GO sheets could effectively refine the pore-
structure of the cement matrix. The size of GO sheets varied from
120 nm to 1.16 mm, which is evident from the DLS results. The
inclusion of these small sheets reduced the inter pore-
connectivity inside the binder matrix by significantly refining the
capillary pores ranging from 10 nm to 10 mm, respectively. Besides,
the presence of GO sheets influenced the formation of micro-cracks
occurring at the drying time of the MIP sample. Although the incor-
poration of GO sheets can increase the hydration rate at early ages,
such presence can effectively arrest the micro-cracks developing in
the cement matrix [17,35,36]. The removal of water from the inter-
layer spaces of cement hydrates contributes to irreversible volume
changes. This effect is particularly more on the severe drying of the
sample where the water previously removed cannot re-enter the
interlayer spaces up on resaturation [37]. GO sheets can also fill
in the micro-cracks that prevent free water from moving to an
external dry environment [8]. The diameter of that pore beyond
which there is a sudden surge in the mercury intrusion curve is
described as the threshold pore diameter [38]. The shift in such
value provides information about the effect of fillers on the
microstructure of the cement matrix. Aligizaki [38] has classified
the ranges of the diameter (d) of gel and capillary pores in the
cement matrix as d < 10 nm and 10–10000 nm, respectively. The
volume of these pores available in the cement matrix was inter-
preted using the logarithm differential intrusion curve (see
Table 3).
It was noticed that the volume of capillary pores (10 nm to
10 mm) reduced with the rise in GO dosage available in the cement
matrix. The size range of GO sheets determined using the DLS tech-
nique falls within 120 nm to 1.16 mm, suggesting that the presence
of GO sheets could have adequately filled the defects formed dur-
ing the preparation of the cement matrix by the capillary action of
water. The pores existing within the structure of cement hydrates
are classified as gel pores [9,39]. The volume of cement hydrates is
proportional to the number of gel pores [40].

Table 3
Characteristics of pore-structure in the 28-d cured cement samples.

Mix ID GO-0 GO-1 GO-2 GO-3

Total pore volume (mm3/g) 82.98 55.24 54.44 37.6
Capillary pore (10 nm to 10 mm) (mL/g) 11.49 8.98 7.48 4.46
Gel pore (<10 nm) (mL/g) 2.09 1.19 1.71 2.64
Threshold pore diameter (nm) 8.4 5.9 6.2 3.2

Table 4
Change in the pH of distilled water at the end of curing time.

Mix ID GO-0 GO-1 GO-2 GO-3

At the end of 7 d 11.82 11.54 11.58 12.14
At the end of 28 d 11.64 11.38 11.01 11.51

Table 5
Change in the pH of HNO3 solution due to cement leaching from the specimens.

Acid change time Specimen cured for 7 d Specimen cured for 28 d

GO-0 GO-1 GO-2 GO-3 GO-0 GO-1 GO-2 GO-3
2d 3.17 3.19 3.43 3.26 2.92 2.99 3.22 3.11
4d 2.83 2.86 2.52 2.76 2.78 2.47 2.42 2.68
6d 2.12 2.12 2.39 2.25 2.21 2.03 1.94 2.13
8d 2.29 2.08 2.27 2.07 2.15 2.13 2.23 1.98
10 d 2.34 2.34 2.36 2.28 2.35 2.27 2.25 2.27

pH of 1 M HNO3 solution = 0.12.

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M. Muthu, N. Ukrainczyk and E. Koenders Construction and Building Materials 269 (2021) 121272

When compared to the GO-0 mix, the formation of gel pores in Table 5 shows the change in pH of the HNO3 solution at the end
the GO-3 mix increased to 26%, explaining that the presence of GO of every replenishment stage. It was found that the pH change
sheets promoted the hydration of cement hydrates in the matrix by showed a decreasing trend during the first 6 d, but the direction
acting as nucleation seeds. This observation correlates well with suddenly surged with the remaining storage time. This change in
the calorimetry data. The shift in threshold pore diameter from pattern suggests that the leaching was rapid at the start, and it
8.4 nm (GO-0) to 3.2 nm (GO-3) indicates that the addition of decreased with the increase in the volume of the cement matrix
0.03 wt% GO sheets significantly densified the microstructure in altered in the damaged specimen. Still, the frequent replenishment
the cement matrix. of the HNO3 solution disturbed the altered cement matrix zone,
which generally curbs the further onset of damage to the sound
zone by acting as a protective barrier.
3.3. pH observation
The pH of the sonicated solution mixture (containing GO, PCE,
and water) that was used in the preparation of cement pastes var-
In this study, the cement specimens were cured with the dis-
ied from 6.71 to 7.27. It was seen from the pH results that the
tilled water, having a pH value of about 6.52. Table 4 shows the
leaching of GO sheets along with the cement components from
change in the pH of distilled water at the end of the curing periods.
the specimen had not greatly influenced the characteristics of the
Leaching of the cement matrix under real water involves two sub-
HNO3 solution.
sequent stages. First, the concentration gradient existing between
the pore solution and water led to the diffusion of calcium and
hydroxyl ions into the pores of the cement matrix. Next, the disso-
lution of cement components by a hydrolysis reaction, which sup-
plies the calcium ions to maintain the equilibrium [20]. The
leaching of alkalis, free lime, and portlandite from the cement
specimen had increased the pH of distilled water at the end of
the curing periods. It was further noticed that the presence of GO
did not influence the leaching kinetics of the cement matrix sub-
merged in distilled water. The pH rise was found to be marginally
higher from the 7-d cured specimens than the other case.
The pH of 1 M HNO3 solution was found to be 0.12. The strength
of the acid in contact with the cement matrix reduced with time.
The HNO3 attack on the cement matrix results in the formation
of highly soluble calcium nitrate (Ca(NO3)2) salt, see Eqs. (3)–(7)
[41,42].

CaO ðfreelimeÞ + 2HNO3 ! Ca(NO3 )2 + H2 O ð3Þ

Ca(OH)2ðportlanditeÞ + 2HNO3 ! Ca(NO3 )2 + 2H2 O ð4Þ

CaCO3ðcalciteÞ + 2HNO3 ! Ca(NO3 )2 + CO2 + H2 O ð5Þ

(CaO)1:5 (SiO2 )(H2 O)3ðCSHÞ + 2HNO3 ! 1.5Ca(NO3 )2

ð6Þ
þð1=mÞ  ðSiO2 Þm  ðH2 OÞn þ ð4:5—n=mÞ  H2 O

(CaO)3 (Al2 O3 )(CaSO4 )3 (H2 O)3ðettringiteÞ + 6HNO3 ! 3Ca(NO3 )2 Fig. 8. Heavy crazing on the surfaces of 28-d cured cement specimen after acid
þ 2AlðOHÞ3 þ 3CaSO4 þ 32H2 O exposure.

ð7Þ
Dissolution reactions for the acid attack of cement components
are not readily available in the literature, mainly due to the vari-
able stoichiometry of C-S-H reactants as well as of silica- or
alumina-based hydrogel products. Therefore, the chemical equa-
tions for the dissolution of C-S-H and ettringite under the HNO3
attack were derived in this work (see Eqs. (6) and (7)). This was
done by using a classical stoichiometry and mass balancing
approach for chemical equations, where the number of atoms of
each element in the reactants must be equal to the number of
atoms of those same elements in the products. This resulted in a
system of linear equations (for each atom), which was relatively
simple in this case and was thus solved manually. The products
of these reactions result in a relatively soluble nitrate and sulfate
salts and silica- or alumina-based gel as relatively insoluble solids
(Eqs. (6) and (7)). The water content of silica gel is variable, and
thus not explicitly written by introducing unknown stoichiometric
coefficients n and m. For alumina gel, the water content may also
be variable, but according to our XRD analyses, it could be repre-
sented as gibbsite, which is shown later in the sub-Section 3.6.2. Fig. 9. The loss in specimen mass and sectional area due to HNO3 attack.

7
M. Muthu, N. Ukrainczyk and E. Koenders
3.4. Visual appearance
Fig. 8 shows the cement specimen that got damaged because of an
intense chemical attack for 10 d. Through visual inspection, it was
found that a significant volume of cement matrix got altered because
of the HNO3 attack. Heavy crazing was seen on the surface of the
damaged specimen. The formation of surface cracks might be due
to the shrinkage led by the leaching of calcium ions from the cement
components under the HNO3 solution. The decalcification induced
shrinkage caused by the chemical attack would create differential
stresses, putting the surfaces of the cement matrix under tension.
Shallow cracks at the micro-scale level may form at the surface of
the cement matrix when the tensile stress is enough to induce frac-
ture [43]. The altered cement matrix in the damaged specimen was
found to be white-coloured, soft, and weak. It was quickly removed
out of the damaged sample using a fingernail. The remaining cement
matrix seemed to be still grey and unaltered by the acidic medium.
3.5. Loss in specimen mass and sectional area
The loss in specimen mass and sectional area at the end of HNO3
attack was recorded (Fig. 9). It seems the acid exposure for 10 d had
reduced the mass and sectional area of the 28-d cured cement spec-
imen by up to 32.5% and 28%. However, these specimen losses could
decrease when the cement matrix was reinforced with GO sheets of
dosage varying from 0.01 to 0.03 wt%, which was evident in this
study. The formation degree of gel pores in GO-1 mix was compar-
atively lesser than the other three mixes. This explains that the
inter-connectivity of capillary pores and gel pores in the GO-1 sam-
ple was poor, which might be the reason behind the largest differ-
ence in its mass loss and sectional area loss rather than GO-3 mix.
It was further noticed that the degree of damage by the acid in
7-d and 28-d cured cement specimens had reduced with an
increase in GO dosage added in such specimens. The amount of
damage in the 7-d cured specimen was much higher than the
28-d cured specimen, which is because the prolonged curing time
improved the stability of the composite by enhancing the hydra-
tion degree of raw cement. The GO sheets adequately filled the
defective regions in the cement matrix and thereby resisted the
free movement of acid species from the external solution by acting
as a protective or diffusion barrier.
3.6. Microstructural assessment
3.6.1. SEM-EDS and nanoindentation
Fig. 10 show the SEM image cum EDS line scan result of the
sound zone remaining in the acid damaged sample. The sample
Fig. 10. EDS line scan analyses of the sound zone remaining in the acid damaged cement sample not reinforced with GO sheets: (a) 7-d and (b) 28-d cured specimens.
8
Construction and Building Materials 269 (2021) 121272
collected after HNO3 attack for 10 d was conditioned, polished,
and assessed under SEM using the backscattered electrons mode.
The SEM image clearly showed the presence of long cracks that
were running from the exterior surface of the sound zone. These
cracks might have formed due to the shrinkage resulting from
the decalcification of cement components.
Further, a lot of enclosed micro-pores near the exterior surface
of its sound zone could be seen, which explains that the damaged
front due to the HNO3 attack was moving inward from the outer
surface of the sample. Across this damaged front, the EDS line scan
was done to assess the profile of significant elements that form the
cement hydrates. In this study, the EDS line scan was limited to
calcium, silica, alumina, and sulfur elements. Among these four
elements, the profile of calcium was found useful in precisely
locating the damage front in the acid exposed sample. The calcium
profile dips beyond the damage front, suggesting that the cement
components in the sound zone had undergone a marginal degree
of decalcification because of acid exposure. In other words, the
damage front (or leaching front) in the binder matrix is the point
beyond which the cement components could have undergone a
minimum decalcification because of the acid exposure. The silica,
alumina, and sulfur patterns had no significant change, explaining
that these elements may remain and involve in the precipitation of
reaction products in such a zone.
The extent of damage in the 7-d cured sample was 50% more
than the deterioration that occurred in the 28-d cured sample,
which was roughly estimated with the line scan result. The depth
of damage front located in the sound zone of the 7-d and 28-d
cured samples was 0.8 mm and 0.4 mm (Fig. 10a-b). In the sound
zone closer to its exterior surface, multiple EDS area scans were
taken to evaluate the atomic percentage of calcium (Ca), silica
(Si), alumina (Al), and sulfur (S) elements remaining in such a por-
ous zone. In this study, the EDS area scan analyses were limited to
GO-0 and GO-3 mixtures. The ratios, including Si/Ca, and Al/Ca,
were calculated and presented as a scatter plot (Fig. 11).
Both Si/Ca and Al/Ca ratios were found to be 2.2% and 6.2% less
in the GO-3 sample, in comparison to GO-0. This SEM-EDS observa-
tion suggests that the presence of GO sheets might have improved
the generation of cement hydrates, especially C-S-H and port-
landite (higher degrees of hydration, in agreement with kinetics
from calorimetry) in comparison to the reference mix. It was fur-
ther noticed that these two ratios Si/Ca, and Al/Ca had increased
to 8.8%, 9%, and 11.6%, 12.7% in the case of GO-0 and GO-3 samples
after acid exposure. These changes explain that the cement compo-
nents until the damage front in the sound zone of the two samples
had undergone decalcification, but rather insignificant. The
removal of Ca2+ ions from the GO-3 sample was marginally higher
M. Muthu, N. Ukrainczyk and E. Koenders
Fig. 11. EDS area scan analyses of the 28-d cured cement sample before and after
acid exposures.
than in the case of the GO-0. This may be due to the higher pres-
ence of Ca-bearing compounds that got generated in the assistance
of GO sheets. Fig. 12 compares the appearance of micro-cracks in
the sound zone of GO-0 and GO-3 samples. When compared to
the GO-0, the formation degree of micro-cracks in the GO-3 mix
was found to be relatively less. This change suggests that the pres-
ence of GO sheets might have hindered the formation of micro-
cracks occurring because of the decalcification induced shrinkage.
Multiple indents across this area were created using the
nanoindentation technique to evaluate the change in Young’s mod-
ulus (E) of the composite (Fig. 13). The cement hydrates seen under
the optical microscope were indented (Fig. 13a). Still, the clinker
Fig. 12. SEM image of the sound zones remaining in the (a) GO-0 and (b) GO-3 samples.
9
Construction and Building Materials 269 (2021) 121272
components and voids that appeared extremely bright and dark
in the polished surface were mostly omitted during the assess-
ment. The average value of the elastic modulus with a standard
deviation of the typical cement components such as low stiffness
C-S-H, high stiffness C-S-H, portlandite, calcite, C4AF, C2S, C3S,
and C3A is 21.7 ± 2.2 GPa, 29.4 ± 2.4 GPa, 38 ± 5 GPa, 80 ± 8 GPa,
125 ± 25 GPa, 130 ± 20 GPa, 135 ± 7 GPa, and 145 ± 10 GPa, respec-
tively [44,45]. The E modulus of the ettringite and monosulfate is
almost the same as C-S-H [46].
It was noticed from the indentation data that the incorporation
of 0.03 wt% GO sheets improved the average E modulus of the
cement composite in comparison to the reference mix (Fig. 13b).
This observation indicates that the presence of GO sheets might
have created a strong bond with the surrounding cement hydrates,
which thus increased the E modulus of the composite. However,
the E modulus of cement hydrates available in the sound zone of
the acid damaged specimen got reduced, which is because the area
had undergone decalcification and became porous. This finding
indicates that the sound zone may not possess the same strength
as the cement matrix unexposed to an acidic solution. The carboxyl
groups attached to the GO edges can protonate under acidic condi-
tions [47]. The migration of acid species might have affected the
bond between the GO and cement hydrates in this study.
3.6.2. XRD
Fig. 14 shows the XRD pattern of the cement samples that were
cured for 7 d and 28 d.
The major XRD peaks at 9.21°, 12.23°, 15.83°, 18.03°, 22.9°,
29.42°, 32.19°, 34.07°, 39.36°, 41.45°, 47.02°, 54.37°, and 62.46°
2h attributes to the presence of ettringite (Ca6Al2(SO4)3(OH)12-
26H2O, portlandite (Ca(OH)2), calcite (CaCO3), and Portland clinker
M. Muthu, N. Ukrainczyk and E. Koenders
Fig. 13. (a) Laser micrograph showing the indent created in C-S-H, and (b) E modulus of the cement hydrates present in the 28-d cured cement specimens before and after
acid exposures.
Fig. 14. XRD pattern of the cement matrix before acid exposure (a) 7-d and (b) 28-d cured cement samples.
compounds such as alite (3CaOSiO2) and belite (2CaOSiO2) in the
sample. All these crystalline products were seen in the cement
samples modified with and without GO sheets. It was found that
the intensity of the XRD peaks corresponding to the clinker compo-
nents decreased with an increase in curing time. This observation
explains that the hydration of clinker compounds could improve
when the curing time was prolonged. The amorphous hump (fall-
ing in between 26° to 37° 2h) seen in the XRD patterns of GO-0
and GO-3 correspond to C-S-H gel, which is the major binding
component of the cement matrix. The height of this hump from
the baseline in these two cement mixes (GO-0 and GO-3) was
observed to be almost the same, which indicates that the inclusion
of GO had no major influence on the generation of C-S-H gel. Fig. 15
presents the XRD pattern of the altered and sound zones remaining
in the sample that was exposed to the HNO3 solution.
The sound zone in the cement sample was still occupied with
the cement hydrates such as ettringite, and portlandite. Whereas,
the region which got wholly altered due to acid attack was found
to have no traces of ettringite, portlandite, calcite, and clinker com-
pounds remaining in them. This observation indicates that the
intense HNO3 attack had destabilized the cement matrix and
10
Construction and Building Materials 269 (2021) 121272
turned it into a highly porous, weak, and soft material. An amor-
phous hump at 24.42° 2h corresponding to quartz (SiO2) and gibb-
site (Al(OH)3) was found in the XRD pattern of the altered cement
matrix. This finding shows that the modified zone was utterly
occupied with amorphous alumina-silica hydrogel. The presence
of GO sheets did not influence the mineralogical composition of
the altered area, which was evident in this study.
3.6.3. TGA
The TGA results of the 7-d and 28-d cured cement samples are
presented in Fig. 16. The weight loss in the temperature range from
35 to 272 °C was due to the evaporation of free water, C-S-H gel,
and dehydroxylation of ettringite [48,49]. The weight loss due to
the decomposition of portlandite and calcite was found in the tem-
perature ranges 378–484 °C and 587–768 °C, respectively. Scrive-
ner et al. [34] recommended the procedure to quantify the
bound water (BW), portlandite, calcite, and other cement hydrates
from the TGA data, which was likewise followed in this study.
Table 6 shows the TGA quantification of the cement samples before
the acid attack.
M. Muthu, N. Ukrainczyk and E. Koenders Construction and Building Materials 269 (2021) 121272

Fig. 15. XRD pattern of the cement matrix after acid exposure (a) unaltered and (b) altered zones of 7-d cured specimen, and (c) unaltered and (d) altered zones of 28-d cured
specimen.

Fig. 16. TGA results of the cement matrix before the HNO3 attack (a) 7-d and (b) 28-d cured cement specimens.

Table 6
TGA quantification of cement samples before acid exposure (% mass loss corresponds to the loss in water).

Curing time Mix ID BW* (%) EW* (%) + ettringite (%) CH* (%) Calcite (%)
7d GO-0 13.49 7.92 10.85 7.19
GO-1 13.51 7.44 11.35 7.31
GO-2 13.76 7.66 11.51 7.38
GO-3 15.06 8.78 12.35 6.15
28 d GO-0 15.58 9.92 12.92 6.00
GO-1 15.82 9.92 12.49 7.64
GO-2 16.39 10.27 13.16 6.53
GO-3 15.52 9.49 13.56 5.96
*
The acronyms BW, EW, and CH, indicates chemically bound water, evaporable water, and portlandite.

11
M. Muthu, N. Ukrainczyk and E. Koenders Construction and Building Materials 269 (2021) 121272

Fig. 17. TGA results of the cement matrix after the HNO3 attack (a) unaltered and (b) altered zones of 7-d cured specimen, and (c) unaltered and (d) altered zones of 28-d
cured specimen.

It was clear from the TGA results that the inclusion of GO sheets
improved the generation of C-S-H gel, ettringite, and portlandite in
the cement matrix. The bound water remaining in the cement
matrix increased from 13.49% to 15.58% when the curing time
was prolonged from 7 d to 28 d. Compared to the reference mix,
the quantity of portlandite increased up to 13.8% and 4.9% when
the 7-d and 28-d cured cement samples were modified using
0.03 wt% GO sheets. The formation of calcite in the cement matrix
is due to the reaction of free lime and portlandite crystals with car-
bon dioxide (CO2) gas from the room environment [50]. The car-
bonation of these products mainly depends on the permeability
of the cement matrix [51]. The availability of calcite in the GO-3
mix was lesser than the GO-0 mix, which suggests that the GO
sheets might have inhibited the ingress of CO2 gas into the cement
matrix. The TGA, XRD and SEM results confirm that the regular
cement hydrates like C-S-H, ettringite, and portlandite were seen
in the cement pastes modified with and without any GO. The for-
mation of new compounds was not seen in the GO-modified
cement pastes. This indicates that the GO inclusion did not cause
any mineralogical changes in the cementitious matrix. Fig. 17
shows the TGA result of the altered and sound zones remaining
in the cement samples that were deteriorated because of the
HNO3 attack.
From the TGA and XRD results, it was evident that the cement
components in the specimen had wholly decalcified because of
acid exposure. Whereas, the sound zone remaining in the acid
exposed sample was still occupied with C-S-H, portlandite,
ettringite, and clinker compounds. Table 7 shows the TGA quantifi-
cation of the acid exposed cement samples. The XRD pattern con-
firmed the precipitation of amorphous silica-based gel in the
altered zone.
Additionally, such an area was also found to have aluminium
hydroxide and silicon dioxide in them, which was noticeable in
the TGA data. The weight loss due to the evaporation of decompo-
sition of aluminium hydroxide (alumina gel) and silicon dioxide
(silica gel) was found in the temperature range of 35 °C to

Table 7
TGA quantification of cement samples after acid exposure (% mass loss attributes to the loss in water).

Curing time Mix ID Sound zone Altered zone

BW* (%) EW* (%) + Ettringite (%) CH*(%) Calcite (%) TWL* (%) Alumina-silica gel (%) CH* (%) Calcite(%)
7d GO0 14.72 8.76 10.5 9.89 20.65 17.72 – –
GO-1 14.4 8.52 9.44 10.82 19.37 16.33 – –
GO-2 14.02 8.29 9.2 11.27 20.44 17.21 – –
GO-3 14.6 8.57 10.31 9.59 21.05 17.93 – –
28 d GO-0 15.99 9.08 11.01 9.21 21.46 18.47 – –
GO-1 15.47 9.04 10.64 10.65 21.26 18.21 – –
GO-2 15.48 9.39 10.14 10.12 21.87 18.68 – –
GO-3 15.75 9.44 11.43 9.57 22.18 19.09 – –
*
The acronyms BW, EW, CH, and TWL, represents the bound water, evaporable water, portlandite, and total weight loss.

12
M. Muthu, N. Ukrainczyk and E. Koenders
413 °C. The traces of carbonates were not seen in the altered zone
of the acid exposed sample, suggesting that the CO2 ingress from
the environment had not influenced the mineralogy of the
precipitated alumina-silica hydrogels. The total weight loss in the
altered zone was much higher than the sound zone. The loss of
weight due to the evaporation of free water was substantial in
the altered area.
The quantity of alumina-silica hydrogel precipitated in the GO-
3 mix was relatively higher than the remaining combinations. This
observation suggests that the addition of 0.03 wt% GO sheets might
have enhanced the generation of ettringite and monosulfate, which
turned into an alumina gel post-acid attack. From the TGA and XRD
results, it was found that the precipitation of alumina-silica hydro-
gel was commonly noticed in the altered area of the acid exposed
cement specimens with and without any GO. This confirms that
the presence of GO (a carbon-based material) in the altered area
had no influence on the crystallization and precipitation of com-
plex salts in the binder matrix exposed to HNO3 attack. When com-
pared to cement samples before the HNO3 attack, the quantity of
portlandite remaining in the sound zone had decreased, suggesting
that this zone was vulnerable to carbonation.
4. Conclusions
In this study, the effect of GO dosage on the microstructure and
performance of the cement matrix exposed to an intense HNO3
environment for a duration of 10 days was examined. The change
in specimen mass and sectional area at the end of the acid attack
were recorded to validate the relative performance between the
cement mixes. The HNO3 attack had influenced the chemical, min-
eralogical and nanomechanical properties of the binder matrix. The
change in these properties was assessed by performing the SEM-
EDS, TGA, XRD, and nanoindentation analysis. The key findings
are listed below.

The calorimetry results showed that the presence of GO sheets
improved the heat of cement hydration by acting as nucleation
sites.

The GO sheets resulted in densified microstructure and acted as
pore filler to adequately resist shrinkage induced cracks of size
ranging from 10 nm to 10 mm in the cement matrix.

When compared to the 28-d cured reference mix, the inclusion
of GO sheets had improved Young’s modulus of the cement
composite up to 16.4% by effectively reinforcing the microstruc-
ture. Although the sound zone in the acid exposed sample was
chemically unchanged, the nanomechanical properties in such a
region got marginally reduced because of the shrinkage induced
by the HNO3 attack. With an increase in GO dosage, the loss in
specimen mass and sectional area due to acid exposure had
reduced. This finding confirmed that the incorporation of GO
sheets could resist the movement of acid species from the
external solution into the cement matrix by acting as a protec-
tive barrier.

The damaged front in the acid exposed sample could be easily
located with the use of SEM-EDS investigation. When compared
to the 28-d cured reference mix, the loss in specimen mass (and
sectional area) at the end of the HNO3 attack was 6%, 9%, and
17% (and 18%, 21%, and 25%) less in the case of GO-1, GO-2,
and GO-3 mixtures, respectively. The degree of damage in the
7-d cured cement specimen due to acid attack was 50% higher
than the 28-d cured specimen.

The XRD and TGA results confirmed that the altered zone in the
acid exposed samples was occupied with the alumina-silica
hydrogels. In contrast, the presence of different cement
hydrates and clinker compounds was noticed in the unaltered
13
Construction and Building Materials 269 (2021) 121272
region of the cement specimens damaged under the acidic envi-
ronment. The unaffected zone was vulnerable to carbonation,
which was evident in the TGA data.
CRediT authorship contribution statement
Murugan Muthu: Methodology, Investigation, Writing - origi-
nal draft, Data curation. Neven Ukrainczyk: Resources, Methodol-
ogy, Writing - review & editing, Supervision. Eddie Koenders:
Resources, Methodology, Writing - review & editing, Supervision,
Project administration.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgements
The authors would like to thank the two Postdoc Career Schol-
arship Programs: 2017 ‘Future Talents’ Postdoc Career Days and
Career Bridging Grants funded by the Ingenium Organization of
the TU Darmstadt for supporting Murugan Muthu and the research
program, which is sincerely acknowledged.
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