Cement and Concrete Composites 125 (2022) 104316

Contents lists available at ScienceDirect

Cement and Concrete Composites

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

A comparative investigation on the effects of nanocellulose from bacteria

and plant-based sources for cementitious composites
Muhammad Intesarul Haque, Warda Ashraf *, Rakibul I. Khan, Surendra Shah
Department of Civil Engineering, Center for Advanced Construction Materials (CACM), University of Texas at Arlington, Nedderman Hall, Arlington, TX, 76010, USA

A R T I C L E I N F O A B S T R A C T

Keywords: Interest in cellulosic nanomaterials has recently gained momentum due to their high tensile strength and hy­
Cellulose nanofibrils groscopic properties. This study compared the effects of two different types of cellulose nanomaterials, including
Bacterial cellulose cellulose nanofibrils (CNF) produced from wood and bacterial cellulose (BC), on the macro, micro, and nano
Strength
scale performances of Ordinary Portland Cement (OPC) paste. Effects of CNF and BC on cement paste hydration,
Alkali silica reaction (ASR)
Mercury intrusion porosimeter (MIP)
microstructure, compressive strength, and flexural strength were monitored. Four dosages of nanocellulose (0%,
Nanoindentation 0.05%, 0.1% and 0.3%, by weight) were used to prepare cement paste samples. Both CNF and BC were found to
increase compressive strengths and flexural strengths by 10% and 55%, respectively, after 90 days of curing.
However, only CNF was able to suppress the expansion of mortar samples due to the alkali-silica reaction by
33%. At the microscale, CNF was found to accelerate the early age cement hydration, whereas BC delayed
cement hydration. Both nanocellulose types resulted in lower calcium hydroxide (CH) and higher CSH contents
compared to the control batch after long-term curing. Statistical nanoindentations showed that the additions of
nanocellulose increase the relative amounts of high-density CSH in the hydrated cement paste. The mercury
intrusion porosimeter (MIP) and dynamic vapor sorption (DVS) analyses indicated that both types of nano­
cellulose increase the nanoporosity and reduced the microporosity. However, such advantages were more
prominent in the case of CNF compared to the BC.

1. Introduction [11–13].
There are two alternative routes to synthesize different types of
Bio-based nanomaterials, including nanocellulose, have recently nanocellulose. The first one is a top-down process which is used to
attracted significant research interest because of their great potential for produce cellulose nanofibers (CNF) and cellulose nanocrystals (CNC)
producing a variety of high-value composites with low environmental from plants. This process is applied to lower the size of the fibers down to
impacts [1]. A fairly considerable amount of work involving cellulose in nano scale [14–17]. The second route is a bottom-up process by which
cement-based composites has already been published [2]. Cellulose is bacterial cellulose (BC) can be synthesized from cellulose-producing
the most widely available organic compound on Earth [3]. It can be bacteria (such as the Acetobacter xylinus and the Komagataeibacter xyli­
obtained from different sources like plants, animals, and bacteria. Cel­ nus species) in the fermentation process of low molecular weight sugar
lulose is a chain-shaped molecule which contains 14,000 units of [18].
D-glucose held by hydrogen bonding [4,5]. Conventionally, cellulose Applications of CNF in cementitious composites have been exten­
microfibers are used in cement-based composites as reinforcing in­ sively investigated in the past few years. High Young’s modulus
gredients [2,6]. Due to its high specific surface area and superior me­ (65–110 GPa) [19], large aspect ratio (4–20 nm width, 500–2000 nm
chanical properties [7] blended with the unique features of length) [20], and thermal stability [21] have enabled CNF to improve
nanomaterials [8], nanocellulose can also significantly enhance the mechanical properties such as elastic modulus, flexural and compressive
properties of concrete. Previous studies have shown that the addition of strengths of cementitious composites [22,23]. In addition to the me­
nanocellulose can control plastic shrinkage and increase the strength of chanical performance enhancement, CNF has shown great potential for
concrete [9,10]. Additionally, the use of nanocellulose fibers can pre­ improving the durability performances of cement-based composites [24,
vent the growth and propagation of cracks in cementitious composites 25]. Moreover, the addition of CNF in cement composites can increase

* Corresponding author.
E-mail address: [email protected] (W. Ashraf).

https://doi.org/10.1016/j.cemconcomp.2021.104316
Received 29 June 2021; Received in revised form 18 September 2021; Accepted 15 October 2021
Available online 19 October 2021
0958-9465/© 2021 Elsevier Ltd. All rights reserved.
M.I. Haque et al. Cement and Concrete Composites 125 (2022) 104316

Fig. 1. Scanning electron microscopic (SEM) images of the cellulose nanomaterials (a) Bacterial cellulose (BC), (b) Cellulose nano fibers (CNF). The scale bar
represents a distance of 2 μm.

the degree of hydration, reduce the setting time and densify the clearly emerged as a promising additive for improving the performance
microstructure [22,26–29]. of cement-based composites. However, the differences between the roles
Nanocellulose can also help reducing the formation of shrinkage of CNF and BC with respect to cement-based composites are not well
cracks in concrete. Deleterious autogenous shrinkage cracks occur at understood yet. Therefore, the primary objective of this article is to
very early ages before the cementitious composites gain sufficient highlight the differences in the effects of CNF and BC on the macro to
strength. Among various strategies, ‘internal curing’ can be a potential nano structural aspects of cementitious composites. At the macroscale,
solution to resist this problem by providing additional curing water the effects of nanocellulose on the strength and alkali-silica reaction of
through the inclusion of water-saturated porous materials in the hy­ mortar samples were monitored. The microscale investigation
drating cement paste [30,31]. It is widely accepted that adding cellulose comprised of monitoring the effects of nanocellulose on cement hydra­
fibers to cement-based systems helps control the properties of drying tion, hydration products, microstructure, and microporosity. To under­
shrinkage cracking and plastic shrinkage [32–36]. Additionally, since stand the effects of nanocellulose at the nanoscale of cementitious
cellulose fibers can be dispersed in hydrating cement paste and have the materials, the nanomechanical properties and the nanoporosity of the
capacity to absorb and release water, they can be considered as potential cement paste samples were evaluated.
internal curing agents. Previous studies [9,10,30,37] showed that, for
mortar, a 1% and 2% addition of cellulose fibers by mass of cement led 2. Materials and methods
to a 13% and 32% reduction respectively in autogenous deformation at 7
days. Then, the addition of 0.06% and 0.09% CNF into the cement paste 2.1. Raw materials
reduced the autogenous shrinkage up to 49% and 26% respectively.
Compared to CNF, the applications of BC in cementitious composites The effects of nanocellulose on cement hydration and microstructure
have not been well investigated yet. Nevertheless, the utilization of BC were monitored using paste samples. Ordinary portland cement (type I/
for environmental purposes is a quickly developing field of engineering II) and nanocellulose were used to prepare these samples. The ordinary
[38]. BC is an organic compound with the same chemical formula, portland cement (OPC) met the ASTM C150 [44] specification. Based on
(C6H10O5)n as CNF. Bacterial cellulose shows high levels of crystallinity the X-ray fluorescence test, OPC contained 21.2% SiO2, 65.3% CaO,
(60%) and a higher degree of polymerization (16,000–20,000) and pu­ 3.9% Al2O3, 3.1% Fe2O3. The bacterial cellulose (BC) and cellulose
rity compared to the plant cellulose [39,40]. It also has a higher water nanofibrils (CNF) were supplied by a commercial company, Cellulose
absorption capacity and high tensile strength (200–300 MPa), as well Lab, located in Canada. The origin of the CNF was bleached sulfate
[40,41]. In the past, BC was used for the surface treatment of fibers in hardwood pulp, and the BC was produced by Acetobacter xylinum bac­
the production of bagasse fiber–cement composites [42]. Furthermore, teria. The raw nanocellulose samples were in slurry form and the
researches showed that nanocellulose materials were able to improve composition was 1% weight solid in water. Fig. 1 represents the scan­
the healing capacity of cementitious composites [43]. ning electron microscopic (SEM) images of the raw BC and CNF. These
Based on the above-mentioned discussions, nanocellulose have fibers were appeared to form like thin films. The transmission electron

Fig. 2. Transmission electron microscopic (TEM) images of the cellulose nanomaterials (a) Bacterial cellulose (BC), (b) Cellulose nano fibers (CNF).

2
M.I. Haque et al. Cement and Concrete Composites 125 (2022) 104316

Table 1
Matrix of experiments with number of samples and sample type.
Tests Dosages Testing age Number of samples Sample type

Zeta potential measurement Control 0 days 1 Raw diluted samples

0.3% CNF 1
0.3% BC 1
Heat of hydration Control Up to 7 days 1 Cement paste (w/c = 0.35)
0.05% CNF 1
0.05% BC 1
0.1% CNF 1
0.1% BC 1
0.3% CNF 1
0.3% BC 1
Thermogravimetric Analysis (TGA) Control 7, 28, 56 & 90 days 4 Cement paste (w/c = 0.35)
0.05% CNF 4
0.05% BC 4
0.1% CNF 4
0.1% BC 4
0.3% CNF 4
0.3% BC 4
Scanning Electron Microscopy (SEM) Control 0 & 28 days 1 Cement paste (w/c = 0.35)
0.3% CNF 1
0.3% BC 1
Mercury Intrusion Porosimetry (MIP) Control 28 days 1 Cement paste (w/c = 0.35)
0.3% CNF 1
0.3% BC 1
Dynamic Vapor Sorption (DVS) Control 28 days 1 Cement paste (w/c = 0.35)
0.3% CNF 1
0.3% BC 1
Nanoindentation Control 28 days 1 Cement paste (w/c = 0.35)
0.3% CNF 1
0.3% BC 1
Compressive strength test Control 7, 28, 56 & 90 days 12 Cement paste (w/c = 0.35)
0.05% CNF 12
0.05% BC 12
0.1% CNF 12
0.1% BC 12
0.3% CNF 12
0.3% BC 12
Flexural strength test Control 7, 28, 56 & 90 days 12 Cement paste (w/c = 0.35)
0.05% CNF 12
0.05% BC 12
0.1% CNF 12
0.1% BC 12
0.3% CNF 12
0.3% BC 12
Alkali Silica Reaction (ASR) test Control Up to 16 days 4 Mortar (w/c = 0.50)
0.05% CNF 4
0.05% BC 4
0.1% CNF 4
0.1% BC 4
0.3% CNF 4
0.3% BC 4

microscopic (TEM) images (Fig. 2) also confirmed that the agglomera­ 2.2. Sample preparation
tions of the nanofibers were apparent at the nanoscale too. Accordingly,
it was difficult to measure the aspect ratio or fiber dimensions using SEM For the paste sample preparation, first, the nanocellulose material
or TEM images. Based on the information provided by the supplier, the was added to the water in the mixer and mixed at a slow speed (140 ± 5
width and length of the cellulose nanofibrils were 20–60 nm and several r/min) for 60 s. Then, cement was added to the mixer and the speed was
micrometers, respectively. On the other hand, the width of the bacterial changed to medium (285 ± 10 r/min) for 2 min.
cellulose was 50–100 nm, and the length was around 30 μm. For the mortar batches, first, the nanocellulose was mixed in the
Most of the studies on cementitious materials showed high im­ water at a slow speed (140 ± 5 r/min). Next, the cement was added to
provements with nanocellulose doses lower than 1 wt%, and some of the mixer and mixing was continued for 30 s. After that, the entire
them have proved that the effects of nanocellulose can be reverted if quantity of sodium borosilicate was added slowly over a 30 s period
they are overdosed [11,45–47]. Therefore, 0% (control), 0.05%, 0.1% while mixing at slow speed (140 ± 5 r/min). Next, the speed was
and 0.3% dosages were chosen. The water to cement ratio for the cement changed to medium (285 ± 10 r/min), and the mixing was continued for
paste was 0.35. 30 s. Then, the mixer was stopped for 90 s and the materials on the side
To monitor the effects of nanocellulose on alkali silica reactivity, the of the bowl were scrapped down into the mixing bowl. Lastly, the mixing
ASTM C1260 [48] test was performed. For this experiment, mortar was finished by continuing for another 60 s at medium speed (285 ± 10
samples were prepared with the sodium borosilicates as reactive ag­ r/min). Table 1 represents the matrix of experiments with total number
gregates maintaining w/c of 0.50 and cement to aggregate ratio of 2.25. of samples and sample type.
The details of this test method are given in section 2.3.10.

3
M.I. Haque et al. Cement and Concrete Composites 125 (2022) 104316

2.3. Experimental methods generally researchers use γ = 0.485 N/m at 25 ◦ C [50]. The contact
angle between mercury and cement paste θ is more difficult to deter­
2.3.1. Zeta potential measurement mine, but after many investigations, researchers have agreed that θ =
The zeta potential of the BC and CNF samples were measured using 140◦ [51].The contact angle can vary due to several factors like the
Malvern Zetasizer 3000. One gram of nanocellulose suspension was chemical composition of the sample, the contamination of the surface,
mixed with 80 g of pH 7 solution and allowed to homogenize for 2 min etc. [52,53].
before measuring the zeta potential. For this research, the MIP test was performed on control batch and
cement paste samples containing 0.3% nanocellulose dosages after 28
2.3.2. Heat of hydration days of curing. The sample size was around 15 × 15 × 15 mm. The
Paste samples were prepared by mixing cement with water and surface tension γ of mercury is 0.485 N/m, and the average contact angle
nanocellulose as per the ratios mentioned in section 2.1. After mixing, θ between mercury and the pore wall is 130◦ . MIP tests were conducted
approximately 15 g of each paste sample was placed in a glass vial to on an AutoPore IV 9500 V2.03.01, from Micrometrics Instrument Cor­
monitor the heat of hydration. An isothermal calorimeter (TAM Air, TA poration, under a maximum pressure of 413 MPa to reach pores with a
instrument) was used to measure the heat release from the cement paste diameter of 3.02 nm.
over 100 h at an ambient temperature of 25 ◦ C. The effects of the
nanocellulose on the cement hydration products were determined by 2.3.7. Dynamic vapor sorption (DVS)
performing thermogravimetric analysis (TGA). Commercially available DVS equipment (Q 5000, TA instruments)
was used to obtain the sorption isotherms. The sample was first equili­
2.3.3. Thermogravimetric analysis (TGA) brated at 97.5% RH for 5760 s. After this point, the RH was gradually
BC and CNF paste samples were used for thermogravimetric analysis reduced (with 5–10% RH steps) to obtain the desorption isotherm. After
(TGA). Isopropanol was used to stop the hydration of the cement paste reaching 0%, the RH was gradually increased (with 5–10% RH steps) up
samples after 7, 28, 56 and 90 days of sealed curing following the solvent to 97.5% to obtain adsorption isotherms. A constant temperature was
exchange method. The cement paste samples were then dried in a maintained (23 ◦ C) during this experiment. The DVS measurements
desiccator for 24 h to avoid atmospheric carbonation. Finally, the dried were obtained from control batch and cement paste samples containing
paste samples were ground using mortar-and-pestle and the powder was 0.3% nanocellulose dosages after 28 days of curing. A thin slice of
used for TGA measurements. A commercially available instrument (TA around 1 mm thickness and 3–4 mm width was cut from the cement
instrument, TGA 550) was used for the TGA measurements. Approxi­ paste cubes using a water-cooled saw. The sliced samples were then
mately, 30–40 mg of powder sample was tested for each batch. The soaked in deionized water for around 24 h to ensure full saturation of the
powdered sample was loaded into a platinum pan and kept under pores before the measurements.
isothermal condition at room temperature for 5 min. The temperature of
the TGA furnace chamber was then raised up to 980 ◦ C at an increment 2.3.8. Nanoindentation test
rate of 15 ◦ C per min. Nitrogen was used as the purging gas during the To prepare the sample for nanoindentation, first, a half disc of the
experiment to maintain an inert environment. From this test, the paste sample, approximately 20 mm in diameter and 10 mm thick, was
quantitative amounts of chemically-bound water in C–S–H and Ca(OH)2 cut using a slow-cutting laboratory saw machine cooled with mineral oil.
in the hydrated cement paste were determined. Detailed sample preparations steps, test procedure and calculations
regarding this can be found elsewhere [54].
2.3.4. Scanning electron microscope (SEM) imaging For grid nanoindentation, cement paste samples containing 0.3% BC
The microstructures of the 28-day cured cement pastes containing and CNF were chosen with the control batch samples after 28 days of
CNF and BC were evaluated using the Hitachi 3000 N SEM. The in­ sealed curing. The load function had three segments: (i) loading from
strument was operated in high vacuum mode with a 30 kV accelerated zero to maximum load in the span of 5 s, (ii) holding at the maximum
voltage and a working distance of about 10 mm. The cement paste load for 5 s, (iii) unloading from maximum to zero load within 5 s. Se­
sample was coated with Platinum (Pt) before capturing the SEM images. lection of the appropriate load function is crucial for obtaining reliable
nanoindentation data. This is because, on the one hand, the indentation
2.3.5. Transmission electron microscope (TEM) imaging depth should be large enough with sufficient accuracy as these are based
TEM images of the bacterial cellulose (BC) and cellulose nanofibrils on contact micromechanics. On the other hand, the depth of the in­
(CNF) were obtained dispersing them into isopropanol solution. For well dentations should also be small enough to determine the mechanical
uniform dispersion, the solution was ultrasonicated for 10 min with properties of the individual microscopic phases (i.e. indentation depth
Cole-Parmer 8890. To collect the TEM images, firstly, the sample was ≪ characteristic size of each microscopic phases) [54]. Considering both
taken into lacey carbon 300 mesh, gold grid (Ted Pella Inc, USA) and criteria, the load function with a maximum load of 3000 μN was selected
then, Hitachi H-9500 was used at 300 kV. All the TEM images were for the SNI technique during this study. The average indentation depth
taken maintaining the same magnification level. for this load function was around 200–350 nm for a 30 μm × 30 μm area
containing all microscopic phases.
2.3.6. Mercury intrusion porosimetry (MIP) Nanoindentation tests were performed using a Hysitron Tri­
Mercury intrusion porosimetry (MIP) is one of the main methods for boindenter UB1 system (Hysitron Inc. Minneapolis, USA) fitted with a
investigating the mesoporous structure (pore radius between 2 and 50 Berkovich diamond indenter probe. The tip area function was calibrated
nm) and the macro-porous nature (apertures greater than 50 nm) of by performing several indents with various contact depths on a standard
cementitious materials. Its effectiveness is based on the principle that to fused quartz sample.
fill a non-wetting fluid into a pore of diameter d, a pressure P inversely Due to the heterogeneous nature of the microstructures containing
proportional to this diameter must be applied. This pressure is given by multiple phases, a large number (~225) of indentations needed to be
the Washburn equation below [49]. performed on each individual specimen. To aid in the interpretation of
the data, the resulting experimental values of the elastic modulus are
− 4*γ*cosθ
P= 1 presented in the form of frequency distribution plots. These plots are, in
d
turn, analyzed using the statistical deconvolution method [55,56] to
Where, P = Pore pressure, d = Pore diameter. estimate the intrinsic modulus of the individual phases. These include
The surface tension of the mercury (γ) is well established and the mean elastic modulus of each phase and their volume fractions, both
of which were estimated based on the best fit of the experimental data

4
M.I. Haque et al. Cement and Concrete Composites 125 (2022) 104316

Fig. 3. Compressive strength of different (a) bacterial cellulose dosages and (b) cellulose nanofibrils dosages.

Fig. 4. Flexural strength of containing different (a) bacterial cellulose dosages and (b) cellulose nanofibrils dosages.

with a limited number of Gaussian distribution functions. molds, they were kept in a moist cabinet for 24 h. Next, the specimens
were removed and placed in a storage container submerged under water
2.3.9. Compressive and flexural strength tests at 23 ◦ C for a period of 24 h. Then, upon drying the samples, zero
A total of 7 batches of cement pastes with w/c of 0.35, and with readings were taken, and after that the samples were put under a 1 N
different BC and CNF contents were prepared for a compressive strength NaOH solution at 80 ◦ C. The length changes were noted down every 24 h
test. A sealed curing condition was adopted by covering the fresh paste for 16 days.
samples with a plastic sheet and keeping them at 23 ◦ C for 24 ± 1 h.
After this period, the samples were demolded and stored in sealed plastic 3. Results and discussion
bags at 23 ◦ C temperature until the age of testing. Compressive strengths
were measured for the paste cube (50 mm sides) samples as per ASTM 3.1. Surface potentials of bacterial cellulose (BC) and cellulose
C109 [57] using a loading rate of 900–1800 N/s. Compressive strengths nanofibrils (CNF)
were determined after 7, 28, 56, and 90 days of sealed curing.
The flexural strength was determined by performing the three-points The absolute values of the zeta potential measurement of the BC and
bending test of beam samples with dimensions of 40 mm × 40 mm × CNF slurries were found to be 0.19 mV and 30 mV, respectively. The
160 mm. The paste samples were tested after 7, 28, 56 and 90 days of higher surface charge allowed higher dispersion stability of the CNF in
sealed curing. water suspension [46,59]. Moreover, the higher negative values of the
zeta potential indicated that the strong electrostatic repulsion between
2.3.10. Alkali silica reaction (ASR) test particles would prevent their aggregation and thereby stabilize the
A recycled, crushed type 33 alkali-borosilicate glass (NBS, Vitro nanoparticulate dispersion [60]. The CNF was negatively charged due to
Minerals) was used as a model reactive siliceous aggregate. The ASTM free hydroxyl groups (OH-) [61]. Based on this finding, it is apparent that
C1260 [48] standard test method was followed to conduct this experi­ BC will have a higher tendency of agglomeration compared to that of
ment. As per the specification, the dimension of the mortar beams were CNF.
25 mm × 25 mm × 285 mm, having a 250 mm gauge length as per the
standard ASTM C490 [58]. After the beam samples had been cast in the

5
M.I. Haque et al. Cement and Concrete Composites 125 (2022) 104316

Table 2 therefore, resulted in a higher compressive strength.

Statistical (t-test) analysis results (p-values) of compressive and flexural strength Fig. 4 shows the flexural strengths of the cement paste samples with
of BC batches. and without the nanocellulose additions. The beneficial effects of
BC Compressive strength Flexural strength nanocellulose on the flexural strengths of cement paste were signifi­
dosage
Curing age Curing age
cantly more pronounced compared to those observed in the case of
compressive strength. After 7 days of curing, the flexural strength of the
7 28 56 90 7 28 56 90
cement paste containing 0.3% CNF or 0.3% BC was increased by nearly
days days days days days days days days
100%. In the case of BC, a higher dosage resulted in higher flexural
0% – – – – – – – – strengths. On the other hand, for CNF, 0.1% was observed to be the
0.05% 0.01 0.33 0.28 0.09 0.00 0.02 0.04 0.02
0.1% 0.02 0.02 0.00 0.00 0.00 0.00 0.06 0.04
optimum dosage to improve the flexural strength. Addition of 0.3% BC
0.3% 0.38 0.08 0.00 0.00 0.00 0.03 0.05 0.00 increased the flexural strength by 57%, whereas 0.1% CNF dosages
increased the flexural strength by 63% compared to the control batch
*Note: Bold fonts (p-values>0.05) represent that the data are not statistically
after 90 days of curing. Therefore, in the case of flexural strength
significant.
enhancement, CNF performed slightly better than the BC. Such benefi­
cial effects of CNF and BC confirms that both of these nanomaterials can
Table 3 act as nano-reinforcement to bridge the microcracks in cement paste
Statistical (t-test) analysis results (p-values) of compressive and flexural strength [46].
of CNF batches. The statistical significance of the effects of nanocellulose on the
CNF Compressive strength Flexural strength compressive and flexural strengths of mortar samples were evaluated
dosage using the t-test. In this case, the level of statistical significance was
Curing age Curing age
expressed as the p-value. The compressive strength and flexural strength
7 28 56 90 7 28 56 90 results were compared with respect to the 0% nanocellulose dosage. The
days days days days days days days days
test was conducted at a confidence level of 95%. Statistical p-values less
0% – – – – – – – – than 0.05 indicated a statistically significant difference between the two
0.05% 0.02 0.39 0.33 0.34 0.01 0.01 0.07 0.13
0.1% 0.03 0.01 0.03 0.04 0.01 0.00 0.04 0.04
0.3% 0.21 0.01 0.01 0.04 0.00 0.02 0.01 0.01

*Note: Bold fonts (p-values>0.05) represent that the data are not statistically
significant.

3.2. Macroscale effects of CNF and BC

3.2.1. Effects of nanocellulose on compressive and flexural strengths

Fig. 3 shows the effects of nanocellulose on the compressive
strengths of the cement paste after different curing durations. Both types
of nanocellulose increased the compressive strength of the cement paste
by nearly 30% after 7 days of curing at 0.05% dosage. Such superior
strength at the early age due to the addition of CNF or BC was attributed
to the hydration acceleration effects of these nanomaterials (further
discussed in ‘heat of hydration’ section). It was observed that the
addition of 0.1% BC increased the compressive strength by around 10%
after 90 days of curing. On the other hand, addition of 0.3% CNF showed
the highest compressive strength, which was 10% higher than the con­
trol batch. Nanocellulose can act as an ‘internal curing’ agent in cement
paste samples [9]. Such internal curing might have resulted in a uni­
form– higher degree of hydration and denser microstructure in the Fig. 6. Comparison of percent expansion due to alkali silica reaction after
nanocellulose-containing batches compared to the control batch, and adding different dosages of nanocellulose (after 14 days).

Fig. 5. Percent expansion due to alkali silica reaction (a) BC batches, (b) CNF batches.

6
M.I. Haque et al. Cement and Concrete Composites 125 (2022) 104316

Fig. 7. (a) Heat flow per g of cement (BC); (b) Heat flow per g of cement (CNF); (c) Total heat per g of cement (BC); (d) Total heat per g of cement (CNF).

groups of samples and vice versa. dosages of CNF, 0.05% and 0.3% also reduced the ASR reaction by 5%
The results of the statistical analyses for the BC and CNF containing and 20%, respectively. The comparison of percent expansion due to
samples are given in Table 2 and Table 3, respectively. As observed from different nanocellulose dosages is shown in Fig. 6. Important to note,
these tables, at a low dosage (i.e., 0.05%), nanocellulose does not based on the zeta potential measurements, CNF had a higher negative
significantly improve the compressive strength of cement paste. surface charge (− 30 mV) compared to that of BC (+0.19 mV). Therefore,
Nevertheless, at higher dosages (that is 0.1% and 0.3%), both types of even though CNF and BC have same molecular structure, the number of
nanocellulose significantly enhanced the compressive strengths of the the negatively charged hydroxyl (OH− ) and carboxyl (COOH− ) surface
cement paste. On the other hand, nanocellulose can significantly groups in CNF is expected to be higher compared to that of BC. These
enhance the flexural strength even at a low dosage of 0.05%. negatively charged surface groups of CNF can bind alkali ions (K+ and
Na+). Due to the reduced availability of alkali ions, the extent of ASR gel
3.2.2. Nanocellulose for ASR suppression formation may have been reduced, and therefore, expansion was also
In addition to mechanical performance, application of nanocellulose lowered by the addition of CNF as observed from the length change
to improve durability performances has also gained tremendous interest measurements.
[24,25]. Because of nanocellulose’s affinity for alkali ions, we investi­
gated the potential role of these materials to mitigate the alkali-silica
reaction (ASR). The ASR occurs between the alkalis present in the 3.3. Microscale effects of CNF and BC
cement pore solution and the reactive aggregate. This reaction forms
expansive gels that results in cracking and, eventually, leads to the 3.3.1. Effects of nanocellulose materials on cement hydration
degradation of the mechanical properties of concrete [62–64]. By Fig. 7 (a) and (b) shows the rate of heat evolution of cement pastes
reducing the availability of alkali ions, nanocellulose could reduce the with different nanocellulose dosages up to first 40 h of hydration. The
detrimental effects of ASR. effects of BC and CNF were evaluated by comparing the primary
Fig. 5 shows the trend of percent expansion after addition of different exothermic heat flow peak and total heat release up to 150 h of hydra­
nanocellulose dosages. As expected, due to the usage of reactive boro­ tion (Fig. 7 (c) and (d)). Initially, it was observed that the heat flow was
silicate glass aggregates, the control mortar batch showed a high accelerated due to the addition of CNF, whereas BC delayed the early
expansion level. However, after the addition of BC, the expansion due to age hydration. The accelerating effect was attributed to the additional
ASR remained the same. There was even a slight increase in expansion surface area provided by the CNF. This additional surface area worked as
with the addition of 0.05% BC. Such increased expansion can be the nucleation sites for CSH which also increased the nucleation rate of
attributed to the hygroscopic properties of BC. On the other hand, the CSH [65–67]. The increased rate of CSH nucleation enhanced the
addition of CNF helped to reduce the expansion caused by ASR. It was cement hydration during the acceleration period [68,69]. Similar ac­
observed that the addition of 0.1% CNF was able to lower the expansion celeration of cement hydration due to the addition of CNF has been
of the mortar bar by 33% after 14 days of measurement. The other observed previously [46]. Contradictorily, the addition of BC was found
to delay the early-stage cement hydration reaction. Specifically, the

7
M.I. Haque et al. Cement and Concrete Composites 125 (2022) 104316

Fig. 8. Typical TGA-DTG plot of BC and CNF after 7 and 90 days of sealed curing.

addition of 0.3% BC delayed the acceleration period by around 7 h. Such the degree of hydration after a long curing duration. Such enhanced
a substantial delay can be attributed to the agglomeration of BC, as hydration due to the addition of nanocellulose was previously reported
indicated by the zeta potential measurements. Nevertheless, the total by Cao et al. [72]. The presence of carboxyl and hydroxyl groups on the
heat release after 150 h of hydration was same for cement samples with surface of cellulose made it active in hydrated cement paste, and pore
and without BC and CNF. Therefore, even though the additions of CNF water was likely to be trapped on the surface, promoting hydration [25].
and BC affected the early-stage hydration, the degree of hydration was However, during our previous studies [46], such an increased degree of
the same after 7 days of curing. hydration was not observed. Therefore, we conclude that the role of
nanocellulose on the degree of hydration after long-term curing depends
3.3.2. Effects of nanocellulose materials on cement hydration products on the source of the nanocellulose. All of the dosages of BC and CNF
The composition of the hydrated cement paste was evaluated by TGA resulted in a lower amount of CH compared to the control batch. This
and derivative of thermogravimetric (DTG) graphs. Fig. 8 represents the observation is similar as before [73], and can be attributed to the Ca2+
typical TGA and DTG curve after 7 and 90 days of sealed curing. The binding by the carboxyl surface sites of nanocellulose.
DTG can be used to locate the temperature ranges corresponding to
thermal decompositions of different hydrated phases present in cement 3.3.3. Microstructure of cement paste with and without BC and CNF
paste [70,71]. The TGA data was further analyzed to quantify the Fig. 10 (a) shows the microstructure of the control batch without the
amounts of Ca(OH)2 and chemically bound water present in CSH. The inclusion of cellulose. Fig. 10 (b) and (c) show the SEM images of cement
amounts of Ca(OH)2 were determined by integrating the DTG peak in paste containing BC and CNF, respectively. Cellulose fibers are marked
the temperature range of 400–500 ◦ C [71]. The chemically bound water with yellow dotted lines in the images. Microstructure analysis was
content of CSH was determined by subtracting the weight loss corre­ performed on the batches with 0.3% dosages of cellulose since cellulose
sponding to Ca(OH)2 decomposition from total weight loss in the tem­ was easily visible in this case. The formations of ettringite and CSH gel
perature range of 150 ◦ C and 600 ◦ C. are clearly visible in the control batch (Fig. 10 (a)). As observed from
Fig. 9 presents the CH and CSH bound water contents in cement paste Fig. 10 (b) and (c), the fibers protruded from the fractured cement paste
with different dosages of BC and CNF. As observed from Fig. 9 (a) and surface. Such pull-out failure type indicates that these fibers were
(b), after 7, 28, 56 and 90 days both BC and CNF resulted in lower CH bridging the cracks of the cement paste. The visible fiber diameter in the
contents compared to those of the control batch. On the other hand, the cement paste batches containing BC was around 60 nm, while the visible
chemically bound water present in CSH was actually increased due to fiber diameter in CNF was around 30 nm. The distribution of fibers
the addition of cellulose nano materials. The increase in chemically appeared to be uniform throughout the matrix.
bound water content indicated that the addition of BC or CNF enhanced

8
M.I. Haque et al. Cement and Concrete Composites 125 (2022) 104316

Fig. 9. (a) CH contents due to different dosages of BC, (b) CH contents due to different dosages of CNF, (c) Chemically bound water for CSH gel due to different
dosages of BC, (d) Chemically bound water for CSH gel due to different dosages of CNF.

Fig. 10. SEM images showing the microstructure of 28 days cured cement paste containing (a) 0% CNF/BC, (b) 0.3% Bacterial cellulose (BC), (c) 0.3% Cellulose
nanofibrils (CNF). The scale bar represents 2 μm.

3.3.4. Pore size comparison by mercury intrusion porosimetry (MIP) results. It was expected that both CNF and BC increased the amounts of
Fig. 11 shows MIP results conducted on control and 0.3% nano­ CSH present in the hydrated matrix.
cellulose batches after 28 days of curing. Fig. 11 (a) indicates that the
samples containing BC had lower porosity compared to the control and 3.4. Nanoscale effects of BC and CNF
CNF containing batches. However, the addition of CNF was found to
increase the total porosity compared to that of the control batch. The 3.4.1. Nano-structural properties
incremental intrusion curves shown in Fig. 11 (b) provide extended in­ Vapor sorption analysis is generally considered as the preferred
formation on pore structure. As observed from this figure, the additions technique for characterizing the CSH present in the cementitious matrix
of both BC and CNF reduced the amounts of larger porosity and compared to MIP or nitrogen sorption, because: (i) water has the
increased the amounts of smaller pores in the hydrated cement paste. smallest molecular size compared to nitrogen or mercury, and thus, can
Thus, both types of nanocellulose caused pore refinement of the hy­ access smaller pores; and (ii) as reported by Odler [74], differences in
drated cement paste matrix. CNF noticeably reduced the critical pore the employed temperature for water and nitrogen adsorption, causes
diameter of the cement paste compared to those observed in the case of water to pass over the energy barrier required for diffusion about 50
the control batch. Such pore refinement effect due to the addition of times more rapidly than nitrogen (nitrogen would take several years to
nanocellulose was attributed to the higher degree of hydration (i.e., equilibrate). Thus, the nitrogen sorption technique in general un­
higher amounts of chemically bound water) as observed from the TGA derestimates the surface area of cementitious matrixes in comparison to

9
M.I. Haque et al. Cement and Concrete Composites 125 (2022) 104316

Fig. 11. (a) Cumulative intrusion vs pore size due to 0.3% nanocellulose dosage, (b) Incremental intrusion vs pore size due to 0.3% nanocellulose dosage.

Fig. 12. (a) Pore size distribution, (b) specific surface area, and (c) volume of different pore categories for paste samples with and without cellulose nanofibers.

that of water sorption. Fig. 12 shows the pore size distributions in the nanocellulose [Fig. 12 (b)]. Following the convention similar to that
cement paste samples with and without nanocellulose. From these used when describing the hydrated cement system [75], the distribution
graphs, two major peaks in pore sizes were observed for all of the cement of different categories of pores in cement paste samples with and
paste matrixes at around 11.4 Å and 5 Å radius. The peak at 11.4 Å without nanocellulose are given in Fig. 12 (c). It can be observed that the
represents the interlayer porosity of CSH. As observed from Fig. 12 (a), additions of either BC or CNF significantly increased (more than 66%)
there is no change in peak location; the intensity of this peak increased both interlayer and gel porosity present in the cement paste. Therefore,
due to the addition of nanocellulose. This observation indicates that the the addition of nanocellulose essentially modified the nanostructure of
addition of nanocellulose did not alter the structure/polymerization of the cement paste by forming additional CSH, and therefore densifying
CSH, but instead a higher amount of CSH was formed. This was also the matrixes. The addition of CNF resulted in a slightly higher amounts
evidenced by the increase in specific surface area due to the addition of of interlayer and gel porosities compared to those of the BC containing

10
M.I. Haque et al. Cement and Concrete Composites 125 (2022) 104316

modulus frequency increase at around 35 GPa can be attributed to the

increased amount of HD CSH. On the other hand, the frequency around
25 GPa, which represents LD CSH, was decreased due to the addition of
nanocellulose. Such effect was more pronounced in the case of BC
compared to that of the CNF.
To obtain a quantitative comparison, the cumulative frequency dis­
tributions functions (CDF) of the elastic modulus (E) were then statis­
tically deconvoluted assuming normal frequency distribution function of
elastic modulus values for all the individual microscopic phases. Details
of the CDF deconvolution methods and the necessary explanations for
this statistical process for determining the intrinsic elastic modulus of
individual microstructural phases can be found elsewhere [55,56]. The
deconvolution process yields the probability distribution function (PDF)
of the elastic modulus (i.e., the mean and the corresponding standard
deviation) for all of the microstructural phases. However, in this work,
the deconvolution process was performed for the elastic modulus range
of 0–60 GPa only to primarily focus on the cement hydration products.
Table 4 represents the mean modulus, standard deviation, and volume
fractions of LD CSH, HD CSH, and CH present in the cement paste with
and without nanocellulose. The statistical deconvolution results confirm
that the relative fraction of the LD CSH was decreased for the cement
paste samples containing nanocellulose. Specifically, the relative vol­
ume fractions of LD CSH in the control, 0.3% BC, and 0.3% CNF con­
taining batches were found to be 38.5%, 28.3%, and 34.4%. The relative
amounts of the HD CSH were higher in the cellulose containing batches
compared to that of the control batch. Cement paste containing 0.3%
CNF was found to have the highest amount of HD CSH. This finding
corroborated the observation from the MIP and vapor sorption pore
analysis results, which showed that the CNF containing batch had higher
amounts of smaller pores. Therefore, the addition of either type of
nanocellulose made the cement paste matrix denser.

4. Conclusions

This article presented a comprehensive investigation on the effects of

Fig. 13. Percent frequency vs elastic modulus of (a) control, (b) 0.3% BC and CNF and BC on the nano to macroscale properties of cement-based
(c) 0.3% CNF after 28 days of sealed curing. materials. The followings are the concluding remarks from this study:

1. Nanocellulose significantly improved the compressive and flexural

Table 4
strengths of cement paste in the early stage (e.g., after 7 days of
Relative proportions of cement hydration products as obtained from statistical
curing). At this curing duration, the compressive and flexural
nanoindentations.
strengths due to the addition of nanocellulose were increased by
Phase Properties Control 0.3% BC 0.3% CNF
nearly 30% and 100%, respectively.
LD CSH Modulus (GPa) 27.4 25.9 28.3 2. After 90 days of curing, both types of nanocellulose increased the
Standard deviation (GPa) 3.2 2.9 2.2 compressive and flexural strength of the mortar samples up to 10%
Relative volume fraction 38.5 28.3 34.4
and 60%, respectively. The suitable dosage of nanocellulose was
HD CSH Modulus (GPa) 33.9 31.9 33.4
Standard deviation (GPa) 3.7 2.8 5.02 found at 0.1% by weight of cement. A higher dosage (i.e., 0.3%)
Relative volume fraction 24.2 42.4 50.9 showed a decrease in compressive strength for BC and decrease in
CH Modulus (GPa) 39.4 40.3 42.9 flexural strength for CNF.
Standard deviation (GPa) 7.7 5.7 5.6
3. The addition of 0.1% CNF was able to reduce the mortar bar
Relative volume fraction 37.3 29.3 14.7
expansion due to the ASR by 33%. Usage of BC did not show any
significant effect on the ASR of the mortar bars.
samples. 4. BC was found to delay the early stage (less than 40 h) cement hy­
dration, whereas CNF slightly accelerated the cement hydration.
3.4.2. Nanomechanical properties 5. After long-term curing (up to 90 days), cement paste samples con­
Each sample was subjected to grid indentations over two different 60 taining either BC or CNF were found to contain lesser amounts of
μm × 60 μm areas, resulting in a total of 225 indentations. For all of portlandite and higher amounts of CSH compared to that of the
these indentations, the values of the elastic modulus (E) and the hard­ control batch. Accordingly, it was postulated that the addition of
ness (H) values were calculated using equations given elsewhere [54]. these nanomaterials improved the degree of cement hydration and
The frequency distribution of the elastic modulus of the control, 0.3% entrapped calcium ions.
BC, and 0.3% CNF batches are given in Fig. 13. Based on the literature 6. Based on the MIP results, the addition of BC reduced the total
data [76–78], approximate ranges for Low-density (LD) CSH, porosity of the cement paste. On the other hand, the addition of CNF
High-density (HD) CSH, and portlandite (CH) were marked in this reduced the size of critical porosity. Such effects on the porosity of
figure. As observed from this figure, due to the addition of nano­ the cement paste were attributed to the increased cement hydration
cellulose, the frequency was increased at around 35 GPa modulus. The after the addition of the nanocellulose.

11
M.I. Haque et al. Cement and Concrete Composites 125 (2022) 104316

7. Additions of nanocellulose were found to increase the amounts of HD [14] H.P.S. Abdul Khalil, Y. Davoudpour, Md. Nazrul Islam, Asniza Mustapha,
K. Sudesh, Rudi Dungani, M. Jawaid, Production and modification of
CSH in the cement paste compared to the control batch. The amount
nanofibrillated cellulose using various mechanical processes: a review, Carbohydr.
of HD CSH was higher in the CNF containing batch compared to that Polym. 99 (2014) 649–665.
of the BC containing samples. [15] C.J. Chirayil, L. Mathew, S. Thomas, Review of recent research in nano cellulose
preparation from different lignocellulosic fibers, Rev. Adv. Mater. Sci. 37 (1–2)
(2014).
Since addition of lower dosages of nanocellulose improved the [16] P. Phanthong, P. Reubroycharoen, X. Hao, G. Xu, A. Abudula, G. Guan,
flexural strength by up to 60%, it would help to reduce crack formation Nanocellulose: extraction and application, Carbon Resour. Convers. 1 (1) (2018).
in real world structures like bridge deck, pavements, etc. Accordingly, [17] O. Nechyporchuk, M.N. Belgacem, J. Bras, Production of cellulose nanofibrils: a
review of recent advances, Ind. Crop. Prod. 93 (2016).
by providing high flexural strength along with reduced autogenous [18] C. Campano, A. Balea, A. Blanco, C. Negro, Enhancement of the fermentation
shrinkage and expansion due to alkali silica reaction, nanocellulose can process and properties of bacterial cellulose: a review, Cellulose 23 (1) (2016).
help concrete structures become more durable. [19] L. Zhai, H.C. Kim, J.W. Kim, J. Kang, J. Kim, Elastic moduli of cellulose nanofibers
isolated from various cellulose resources by using aqueous counter collision,
Based on the presented comparative investigation for the selected Cellulose 25 (7) (2018).
dosages of nanocellulose, CNF offers superior enhancement in ASR [20] R.J. Moon, A. Martini, J. Nairn, J. Simonsen, J. Youngblood, Cellulose
resistance, cement hydration rate, pore structure, and HD CSH forma­ nanomaterials review: structure, properties and nanocomposites, Chem. Soc. Rev.
40 (7) (2011).
tion in the cementitious system compared to BC. [21] Q. Tarrés, S. Boufi, P. Mutjé, M. Delgado-Aguilar, Enzymatically hydrolyzed and
TEMPO-oxidized cellulose nanofibers for the production of nanopapers:
Credit author statement morphological, optical, thermal and mechanical properties, Cellulose 24 (9)
(2017).
[22] L. Jiao, M. Su, L. Chen, Y. Wang, H. Zhu, H. Dai, Natural cellulose nanofibers as
Muhammad Intesarul Haque: Data curation, Formal analysis, sustainable enhancers in construction cement, PLoS One 11 (12) (2016).
Investigation, Writing – original draft. Warda Ashraf: Conceptualization, [23] S. Parveen, S. Rana, R. Fangueiro, M.C. Paiva, A novel approach of developing
micro crystalline cellulose reinforced cementitious composites with enhanced
Formal analysis, Investigation, Funding acquisition, Supervision, microstructure and mechanical performance, Cement Concr. Compos. 78 (2017).
Writing - review & editing. Rakibul I. Khan: Data curation, Investigation. [24] J. Goncalves, Y. Boluk, V. Bindiganavile, Cellulose nanofibres mitigate chloride ion
Surendra Shah: Supervision, Writing - review & editing. ingress in cement-based systems, Cement Concr. Compos. 114 (2020), 103780.
August.
[25] J. Goncalves, M. El-Bakkari, Y. Boluk, V. Bindiganavile, Cellulose nanofibres (CNF)
for sulphate resistance in cement based systems, Cement Concr. Compos. 99 (2019)
Declaration of competing interest 100–111. March.
[26] X. Sun, Q. Wu, S. Lee, Y. Qing, Y. Wu, Cellulose nanofibers as a modifier for
rheology, curing and mechanical performance of oil well cement, Sci. Rep. 6
The authors declare that no conflict of interest is involved in this (2016).
paper and the authors are responsible for the content and writing. [27] Z. Tang, et al., Influence of cellulose nanoparticles on rheological behavior of
oilwell cement-water slurries, Materials 12 (2) (2019).
[28] S. Chakraborty, S.P. Kundu, A. Roy, B. Adhikari, S.B. Majumder, Effect of jute as
Acknowledgement fiber reinforcement controlling the hydration characteristics of cement matrix, Ind.
Eng. Chem. Res. 52 (3) (2013).
[29] X. Sun, Q. Wu, S. Ren, T. Lei, Comparison of highly transparent all-cellulose
This work was conducted with partial funding support from the US
nanopaper prepared using sulfuric acid and TEMPO-mediated oxidation methods,
National Science Foundation (NSF # ECI - 2028462) and the P3Nano - U. Cellulose 22 (2) (2015).
S. Endowment for Forestry and Communities (#21-00184) for Dr. [30] S. Kawashima, S.P. Shah, Early-age autogenous and drying shrinkage behavior of
Warda Ashraf at the University of Texas at Arlington. All opinions, cellulose fiber-reinforced cementitious materials, Cement Concr. Compos. 33 (2)
(2011).
findings, and conclusions or recommendations expressed in this material [31] L.R. Betterman, C. Ouyang, S.P. Shah, Fiber-matrix interaction in microfiber-
are those of the authors and do not necessarily reflect the views of the reinforced mortar, Adv. Cement Base Mater. 2 (2) (1995).
sponsoring agencies. [32] M. Sarigaphuti, S.P. Shah, K.D. Vinson, Shrinkage cracking and durability
characteristics of cellulose fiber reinforced concrete, ACI Mater. J. 90 (4) (1993).
[33] P. Soroushian, S. Ravanbakhsh, Control of plastic shrinkage cracking with specialty
References cellulose fibers, ACI Mater. J. 95 (4) (1998).
[34] N. Buch, O.M. Rehman, J.E. Hiller, Impact of processed cellulose fibers on portland
cement concrete properties, Transport. Res. Rec. 1668 (1999).
[1] R.J. Moon, G.T. Schueneman, J. Simonsen, Overview of cellulose nanomaterials,
[35] J.R. Rapoport, S.P. Shah, Cast-in-place cellulose fiber-reinforced cement paste,
their capabilities and applications, J. Occup. Med. 68 (2016) 9.
mortar, and concrete, ACI Mater. J. 102 (5) (2005).
[2] O. Onuaguluchi, N. Banthia, Plant-based natural fibre reinforced cement
[36] B. Mohr, L. Premenko, K. Kurtis, Examination of Wood-Derived Powders and Fibers
composites: a review, Cement Concr. Compos. 68 (2016).
for Internal Curing of Cement-Based Materials, 2005.
[3] M.R. Hossen, N. Dadoo, D.G. Holomakoff, A. Co, W.M. Gramlich, M.D. Mason, Wet
[37] H.J. Lee, S.K. Kim, H.S. Lee, W. Kim, A study on the drying shrinkage and
stable and mechanically robust cellulose nanofibrils (CNF) based hydrogel,
mechanical properties of fiber reinforced cement composites using cellulose
Polymer 151 (2018).
nanocrystals, Int. J. Concr. Struct. Mater. 13 (1) (2019).
[4] C. Son, S. Chung, J. Lee, S. Kim, Isolation and cultivation characteristics of
[38] H. Kalhori, R. Bagherpour, Application of carbonate precipitating bacteria for
Acetobacter xylinum KJ-1 producing bacterial cellulose in shaking cultures,
improving properties and repairing cracks of shotcrete, Construct. Build. Mater.
J. Microbiol. Biotechnol. 12 (5) (2002).
148 (2017).
[5] D. Mazlan, M.F. Md Din, C. Tokoro, I.S. Ibrahim, Cellulose nanocrystals addition
[39] M. Shoda, Y. Sugano, Recent advances in bacterial cellulose production,
effects on cement mortar matrix properties, Int. J. Adv. Mech. Civ. Eng. 3 (1)
Biotechnol. Bioproc. Eng. 10 (1) (2005).
(2016).
[40] N. Reddy, Y. Yang, “Bacterial Cellulose Fibers,” in Innovative Biofibers from
[6] S.J. Peters, T.S. Rushing, E.N. Landis, T.K. Cummins, Nanocellulose and
Renewable Resources, 2015.
microcellulose fibers for concrete, Transport. Res. Rec. (2142) (2010) 25–28.
[41] P.R. Chawla, I.B. Bajaj, S.A. Survase, R.S. Singhal, Microbial cellulose: fermentative
[7] A. Balea, E. Fuente, A. Blanco, C. Negro, Nanocelluloses: natural-based materials
production and applications, Food Technol. Biotechnol. 47 (2) (2009).
for fiber- reinforced cement composites. A critical review, Polymers 11 (3) (2019).
[42] F. Mohammadkazemi, K. Doosthoseini, E. Ganjian, M. Azin, Manufacturing of
[8] D. Klemm, et al., Nanocellulose as a natural source for groundbreaking applications
bacterial nano-cellulose reinforced fiber-cement composites, Construct. Build.
in materials science: today’s state, Mater. Today 21 (7) (2018).
Mater. 101 (2015) 958–964.
[9] H.H. Kolour, M. Ahmed, E. Alyaseen, E.N. Landis, An investigation on the effects of
[43] E. Cuenca, A. Mezzena, L. Ferrara, Synergy between crystalline admixtures and
cellulose nanofibrils on the performance of cement paste and concrete, Adv. Civ.
nano-constituents in enhancing autogenous healing capacity of cementitious
Eng. Mater. 7 (1) (2018).
composites under cracking and healing cycles in aggressive waters, Construct.
[10] H.H. Kolour, W. Ashraf, E.N. Landis, Hydration and early age properties of cement
Build. Mater. 266 (2021).
pastes modified with cellulose nanofibrils, Transport. Res. Rec. 2675 (9) (2020)
[44] ASTM C150/150M-18, Standard Specification for Portland Cement, Annu. B. ASTM
38–46.
Stand, 2018.
[11] O.A. Hisseine, A.F. Omran, A. Tagnit-Hamou, Influence of cellulose filaments on
[45] M.A. Akhlaghi, R. Bagherpour, H. Kalhori, Application of bacterial nanocellulose
cement paste and concrete, J. Mater. Civ. Eng. 30 (6) (2018) 1–14.
fibers as reinforcement in cement composites, Construct. Build. Mater. 241 (2020),
[12] O. Onuaguluchi, D.K. Panesar, M. Sain, Properties of nanofibre reinforced cement
118061.
composites, Construct. Build. Mater. 63 (2014) 119–124.
[13] W. Sekkal, A. Zaoui, Enhancing the interfacial bond strength of cement
nanocomposite with carbonate nanostructure, Compos. B Eng. 124 (2017).

12
M.I. Haque et al. Cement and Concrete Composites 125 (2022) 104316

[46] K.S. Kamasamudram, W. Ashraf, E.N. Landis, Cellulose nanofibrils with and [62] Significance of tests and properties of concrete and concrete-making materials,”
without nanosilica for the performance enhancement of portland cement system, ASTM (Am. Soc. Test. Mater.) Spec. Tech. Publ., vol. 169 D-STP. 2006.
Construct. Build. Mater. 285 (2021), 121547. [63] F. Rajabipour, E. Giannini, C. Dunant, J.H. Ideker, M.D.A. Thomas, Alkali-silica
[47] T.F.R. Claramunt J, M. Ardanuy, R. Arevalo, F. Pares, Mechanical performance of reaction: current understanding of the reaction mechanisms and the knowledge
ductile cement mortar composites reinforced with nanofibrillated cellulose, Strain gaps, Cem. Concr. Res. 76 (2015).
hardening Cem. Compos., no. December (2011) 131–138. [64] A. Poole, Introduction to alkali-aggregate reaction in concrete, in: The Alkali-Silica
[48] ASTM Committee C09, 26, “ASTM C1260-14 standard test method for potential Reaction in Concrete, 1998.
alkali reactivity of aggregates ( mortar-bar method), Annu. B. ASTM Stand. 4.2 [65] E.H. Kadri, R. Duval, Effect of Ultrafine Particles on Heat of Hydration of Cement
(2014) 1–5. Mortars, ACI Mater. J., 2002.
[49] E.W. Washburn, The dynamics of capillary flow, Phys. Rev. 17 (3) (1921). [66] W.A. Gutteridge, J.A. Dalziel, Filler cement: the effect of the secondary component
[50] David R. Lide, CRC Handbook of Chemistry and Physics, 84th Edition, 2003-2004, on the hydration of Portland cement. Part I. A fine non-hydraulic filler, Cem.
Handb. Chem. Phys., 2003. Concr. Res. 20 (5) (1990) 778–782.
[51] R.A. Cook, K.C. Hover, Experiments on the contact angle between mercury and [67] B. Lothenbach, K. Scrivener, R.D. Hooton, Supplementary cementitious materials,
hardened cement paste, Cem. Concr. Res. 21 (6) (1991). Cement Concr. Res. 41 (12) (2011).
[52] S.P. Rigby, New methodologies in mercury porosimetry, in: Studies in Surface [68] J.W. Bullard, et al., Mechanisms of cement hydration, Cement Concr. Res. 41 (12)
Science and Catalysis, vol. 144, 2002. (2011).
[53] J. Kaufmann, R. Loser, A. Leemann, Analysis of cement-bonded materials by multi- [69] K.L. Scrivener, A. Nonat, Hydration of cementitious materials, present and future,
cycle mercury intrusion and nitrogen sorption, J. Colloid Interface Sci. 336 (2) Cement Concr. Res. 41 (7) (2011).
(2009). [70] I. Pane, W. Hansen, Investigation of blended cement hydration by isothermal
[54] W. Ashraf, J. Olek, N. Tian, Multiscale characterization of carbonated wollastonite calorimetry and thermal analysis, Cem. Concr. Res. 35 (6) (2005).
paste and application of homogenization schemes to predict its effective elastic [71] K. Scrivener, R. Snellings, B. Lothenbach, A Practical Guide to Microstructural
modulus, Cement Concr. Compos. 72 (2016) 284–298. Analysis of Cementitious Materials 62 (10) (1962).
[55] F. Ulm, M. Vandamme, C. Bobko, J.A. Ortega, Statistical indentation techniques for [72] Y. Cao, et al., The influence of cellulose nanocrystals on the microstructure of
hydrated nanocomposites: concrete, Bone, and Shale 2692 (2007). cement paste, Cement Concr. Compos. 74 (2016) 164–173.
[56] G. Constantinides, K.S. Ravi Chandran, F.J. Ulm, K.J. Van Vliet, Grid indentation [73] W. Ashraf, K. Kamasamudram, K. Kamasamudram, W. Ashraf, and E. Landis,
analysis of composite microstructure and mechanics: principles and validation, “Construction and Building Materials Cellulose Nanofibrils with and without
Mater. Sci. Eng. A 430 (1–2) (2006) 189–202. Nanosilica for the Performance Enhancement of.”.
[57] ASTM International, ASTM C109/C109M - 20b. Standard test method for [74] I. Odler, The BET-specific surface area of hydrated Portland cement and related
compressive strength of hydraulic cement mortars (using 2-in. Or [50 mm] cube materials, Cem. Concr. Res. 33 (12) (2003) 2049–2056.
specimens), Annu. B. ASTM Stand. 4 (9) (2020). [75] H.M. Jennings, A. Kumar, G. Sant, Quantitative discrimination of the nano-pore-
[58] American Society for Testing and Materials, Standard Practice for Use of Apparatus structure of cement paste during drying : new insights from water sorption
for the Determination of Length Change of Hardened Cement Paste , Mortar , and isotherms, Cem. Concr. Res. 76 (2015) 27–36.
Concrete, ASTM Int., 2011, pp. 1–5. [76] M.J. Dejong, F. Ulm, The Nanogranular Behavior of C-S-H at Elevated
[59] M.S. Sajab, et al., Telescopic synthesis of cellulose nanofibrils with a stable Temperatures ( up to 700 ◦ C ), vol. 37, 2007, pp. 1–12. February 2006.
dispersion of Fe(0) nanoparticles for synergistic removal of 5-fluorouracil, Sci. Rep. [77] G. Constantinides, F.J. Ulm, The effect of two types of C-S-H on the elasticity of
9 (1) (2019). cement-based materials: results from nanoindentation and micromechanical
[60] J. Luan, et al., Impregnation of silver sulfadiazine into bacterial cellulose for modeling, Cem. Concr. Res. 34 (1) (2004) 67–80.
antimicrobial and biocompatible wound dressing, Biomed. Mater. 7 (6) (2012). [78] G. Constantinides, F. Ulm, K. Van Vliet, On the Use of Nanoindentation for
[61] S. Sepahvand, M. Jonoobi, A. Ashori, F. Gauvin, H.J.H. Brouwers, Q. Yu, Surface Cementitious Materials, vol. 36, 2003, pp. 191–196. April.
modification of cellulose nanofiber aerogels using phthalimide, Polym. Compos. 41
(1) (2020).

13