Construction and Building Materials 199 (2019) 1–11

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Construction and Building Materials

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

Study on dispersion, mechanical and microstructure properties

of cement paste incorporating graphene sheets
Jintao Liu a, Jiali Fu a, Yang Yang a,b,⇑, Chunping Gu a
a
College of Architecture and Civil Engineering, Zhejiang University of Technology, Hangzhou 310014, China
b
Key Laboratory of Civil Engineering Structures & Disaster Prevention and Mitigation Technology of Zhejiang Province, Hangzhou 310014, China

h i g h l i g h t s

Dispersion of graphene in water is evaluated with different surfactants.

Graphene addition in cement paste increase strengths significantly.

Appropriate amount of graphene improves microstructure of composite.

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 influences of ultrasonic and surfactants on the dispersion of graphene sheets in water
Received 24 September 2018 were evaluated using UV–vis spectroscopy, and homogenous dispersions of graphene sheets in water
Received in revised form 27 November 2018 were obtained by using sodium dodecyl benzene sulfonate (SDBS). Then, the highly dispersed graphene
Accepted 2 December 2018
sheets were introduced to cement paste through high-speed mixing, and the mechanical and microstruc-
Available online 8 December 2018
tural properties of graphene-modified cement material was evaluated. Experiment results indicated that
the addition of 0.025 wt% graphene sheets increased the 7-day composite compressive strength by 14.9%,
Keywords:
the flexural strength by 23.6% and direct tensile strength by 15.2%. X-ray diffraction (XRD) analysis
Graphene
Mechanical properties
showed that the addition of graphene sheets lowered the orientation index of calcium hydroxide (CH)
Dispersion crystals significantly. Moreover, mercury intrusion porosimetry (MIP) and microscope imaging (SEM)
Microstructure indicated that a high degree of dispersion of graphene sheets was achieved, and the two-dimensional gra-
phene sheets promote hydration and suppress the extension process of cracks.
Ó 2018 Elsevier Ltd. All rights reserved.

1. Introduction allotropes, including graphite, CNTs and fullerenes [5,6]. The theo-
retical specific surface area (SSA) of graphene can reach 2630 m2/g,
As a main component of concrete, cement is the most widely which is much larger than that reported to date for CNTs [7]. In
used binder material in the world. However, one of cementitious addition, it has an intrinsic tensile strength of 130 GPa and a
materials’ biggest drawbacks is their quasi-brittle nature and poor Young’s modulus of 1 TPa [8]. Due to its remarkable mechanical
resistance to crack formation. Thus, many studies have been car- performance, great attention is paid to the graphene as the nano
ried out to combine nano-fiber with cementitious composites to reinforcing material in cement with greatest potential.
enhance their microstructure and mechanical properties, and Development of aqueous dispersions incorporating higher con-
results showed a small amount of carbon nanotubes (CNTs) can centrations of graphene sheets would facilitate scalable production
restrain the propagation of microcracks and improve the fracture of graphene sheets modified concrete [9]. Thorough dispersion of
toughness of the nanocomposites [1–3]. However, CNTs tend to graphene sheets in water is the key first step toward achieving uni-
agglomerate, hindering their dispersion in solvents because of form dispersions of graphene within cementitious composites [10].
their super high length-diameter ratio [4]. As a two-dimensional Different surface treatments have been investigated for improving
nanomaterial, graphene is the basic structural element of other the hydrophilic property of graphene. Current processing methods
involve acid treatment [2], oxidation via heating [11], ozone treat-
ment [12] and silane treatment [13]. Because of graphene’s innate
⇑ Corresponding author at: College of Architecture and Civil Engineering,
attribute of hydrophobicity, oxidation treatment has been sug-
Zhejiang University of Technology, Hangzhou 310014, China.
gested as an effective method to achieve consistent yet durable
E-mail address: [email protected] (Y. Yang).

https://doi.org/10.1016/j.conbuildmat.2018.12.006
0950-0618/Ó 2018 Elsevier Ltd. All rights reserved.
2 J. Liu et al. / Construction and Building Materials 199 (2019) 1–11

aqueous dispersion [14], and these oxygen-containing functional 2. Materials and methods
groups attached to the graphene sheet improve its dispersion in
2.1. Materials
water and cement matrix. Meanwhile, the bonding strength
between graphene sheets and cement hydration products was also Ordinary Portland Cement P O 42.5 was used in this study and its chemical
improved. Thus, many researchers have investigated the effects of composition was given in Table 1. Graphene was purchased from Chengdu Organic
graphene oxide (GO) on the mechanical properties of cement- Chemicals (China) Co. Ltd. and its properties were listed in Table 2. The morphology
and particle diameter distribution of graphene sheets were shown in Fig. 1 and
based materials [15–18]. Lu et al. [19] demonstrated that the addi-
Fig. 2(a). The tributyl phosphate (TBP) provided by Aladdin Co. Ltd (Shanghai,
tion of GO shorted the setting time and decreased the workability China) was used to eliminate bubbles.
of the magnesium potassium phosphate cement paste, but the Different kinds of superficial active agents (SAAs) were used for graphene dis-
mechanical properties of the composites were improved by GO. persion, including anionic surfactant sodium dodecyl benzene sulfonate (C12H25C6-
According to Chen [20], the compressive strengths of cement paste H4SO3Na, AR), anionic surfactant sodium dodecyl sulfate (CH3(CH2)11SO3Na, AR),
cationic surfactant CTAB (C16H33(CH3)3NBr, AR), and non-ionic surfactant Triton
with 0.04 and 1 wt% GO are increased by 24.95% and 46.90%,
X-100 (C8H17C6H4(OCH2CH2)10OH, AR). These SAAs were all purchased from Alad-
respectively. Meng and Khayat [21] also indicated that the tensile din reagent (Shanghai, China) Co., Ltd. As a contrast, commercially available poly-
strength of ultra-high-performance concrete was increased by 40% carboxylate superplasticizer (SP) from BASF was also used as an SAA to improve
with the addition of 0.3% graphite nanoplatelets. Yang et al. [22] the workability.
found that the hydrated degree of cement paste was increased
2.2. Dispersion of graphene
with GO, but the C–S–H structure of the composite was not
observed to have undergone any change. Li et al. [23] dispersed Graphene tends to form aggregates due to strong intermolecular van der Waals
GO in a pore solution and cement paste, and GO dispersion in interactions. Thus, the key to increasing the interfacial interaction between gra-
the cement paste was highly improved with the silica fume addi- phene and the cement matrix is improving the graphene dispersity. Recently, a vari-
tion and 0.02 wt% GO was the appropriate amount. Lv et al. [24] ety of SAAs have been applied to solve the sedimentation problem of nanomaterials
in aqueous solutions, such as sodium dodecyl sulfate (SDS), sodium dodecyl ben-
reported that the introduction of 0.04% by weight of GO into
zene sulfonate (SDBS), Triton X-100 (TX10), polycarboxylate superplasticizer, etc.
cement paste produced a 37.5% improvement in the compressive In this study, the processes of ultrasonic dispersion and chemical functionalization
strength at 28 days. Another study showed the same weight dose were experimentally utilized to disperse graphene in aqueous solution. Thus, SDBS,
increased compressive strength by 14% [25]. In addition, an SDS, TX10, CTAB and SP were initially chosen based on the literature. A probe type
enhancement of about 41% has been achieved in tensile strength ultrasonic instrument of Scientz-750F model (20 kHz, 150–750 W, Ningbo, China)
was used to disperse graphene sheets. The ultrasonic treatment equipment was
by incorporating 0.03 wt% GO sheets, and the hydration rate of designed for dispersing nanomaterials and it had the advantages of strong power
cement can be accelerated by the nucleation effect of GO [26]. output and good dispersion effect. The mechanical energy delivered by sonication
However, the process of oxidation lowering the mechanical was related to the sonication power. Thus, the study initially deals with the sonica-
properties of graphene sheets, and it exhibit a lower elastic mod- tion power impacting on dispersion of graphene sheets, and the proper output
power was selected and used for further study.
ulus and tensile strength than graphene [27]. In the case of
Furthermore, the TD 80-1 model centrifugal machine (Shanghai, China) with a
cementitious composites, there is still a need to develop a disper- maximum speed of 4000 rpm was employed to observe the stability of the gra-
sion method for graphene sheets in water, and it should be low- phene dispersion. The great surface area of graphene sheets means a high surface
cost and suitable for large-scale applications. Alkhateb et al. [28] energy and agglomeration tendency, which needs an effective dispersion method.
compared the effects of pristine and acid-functionalized graphene In this experiment, the mass ratios of graphene to SAAs were 1:2, 1:4, 1:6, and
1:8, and the entire dispersion procedure had the following steps:
on the microstructure and elastic modulus of cement paste, and
results showed that the attachment of carboxyl (–COOH) and (1) Firstly, the SAA was dissolved in water and stirred evenly. Then, graphene
hydroxyl (–OH) groups increase the interfacial bond strength sheets were placed in this solution and stirred until the graphene were
between graphene and C–S–H approximately 10 fold. Peyvandi completely wetted, and this step took about 2 min.
(2) An ultrasonic disrupter (20 kHz, 450 W) was employed to disperse the gra-
et al. [10] investigated the flexural strength of cement with the
phene sheets in the solution. The sonication process was performed for 1–6
addition of 0.13 wt% of graphite nanoplatelets, and various gains times, with a duration of each stage of 5 min. It was found that sonication
ranging from 27% to 73% were achieved. Sun et al. [29] observed caused both heating and foaming of the dispersion fluid. Therefore, the
that the compressive strength and elastic modulus of cement dispersion fluid was placed in ice water to de-foam after each sonication
stage.
paste filled with multi-layer graphene increased by 54% and
50%, respectively. However, graphene would modestly weaken
2.3. Preparation of specimens and testing procedure
the compressive strength of cement by 20% under high addition
due to the weak interfacial bonding strength between graphene The optimal ultrasonic dispersion time and graphene-to-surfactant mass ratios
and the cement matrix [30]. The main problem with using gra- were determined by ultraviolet–visible (UV–vis) spectroscopy. According to the
phene is its negligible dispersibility in water, and avoiding entan- Beer–Lambert Law, the degree of dispersion of graphene sheets in water was eval-
uated using UV–vis spectroscopy, and the absorbance A can be measured as follow:
glement and agglomeration of graphene is a perplexing challenge
[14,31].
A ¼ logðI=I0 Þ ¼ e  c  d ð1Þ
To achieve sufficient dispersion of graphene in cementitious
materials, raw graphene sheets must be with enough dispersiv-
ity initially. In this work, with the supersonic and centrifuge as
supplementary tools, the effects of surfactants on the disper-
sion of graphene in water were evaluated by ultraviolet–visible Table 1
Chemical properties of cement (wt%).
(UV–vis) absorption spectra and sedimentation test. Moreover,
different amounts of added graphene sheets were considered Fe2O3 Al2O3 CaO MgO SiO2 SO3 Loss
(relative to the cement quantity): 0.01 wt%, 0.025 wt% and 2.91 4.58 61.08 3.19 19.50 2.50 3.60
0.05 wt%, and the influences of the graphene on the mechanical
properties of the cement paste were investigated at different
ages. Furthermore, scanning electron microscope (SEM), Table 2
X-ray diffraction (XRD) and mercury intrusion porosimetry Properties of graphene sheets.
(MIP) were employed to investigate the degree of hydration
Purity Thickness Diameter Specific surface area Density PH
and pore size distribution of graphene-cement composite,
99.5% 4–20 nm 2–16 lm 40 m2/g 0.6 g/cm3 7.3
respectively.
 J. Liu et al. / Construction and Building Materials 199 (2019) 1–11 3

Fig. 1. Scanning electron microscope (a), atomic force microscope (b) and transmission electron microscope (c) images of graphene sheets.

Table 3
Mix proportion of composite cement paste.

Type Cement/g SDBS/g Graphene/g TBP/g Water/g

R1 100 0.06 0 0.2 40
G1 100 0.06 0.01 0.2 40
R2 100 0.15 0 0.2 40
G2 100 0.15 0.025 0.2 40
R3 100 0.3 0 0.2 40
G3 100 0.3 0.05 0.2 40

and stirred for 60 s. Then, cement particles were placed into the pot and stirred
for 180 s, and the cement paste appeared to be homogeneous. Finally, the paste
was stirred at high-speed for another 120 s in order to effectively further disperse
the graphene.
In accordance with Chinese standard GB/T 8077-2000 (Methods for testing uni-
formity of concrete admixture), the mixtures were poured into a truncated cone
mold to perform the fluidity test immediately after mixing. The dimensions of
the cone model were bottom diameter 60 mm, top diameter 36 mm, and height
60 mm. The cement paste was tipped into the mold and smoothed with a spatula.
The mold was removed vertically, and the horizontal diameters of the paste were
measured. After fluidity test, the cement paste was then poured into molds and
vibrated for compaction.
According to Chinese standard GB/T1764-1999, cube specimens with dimen-
sions of 40  40  40 mm3 were used for compression tests and samples with
dimensions of 160  40  40 mm3 were prepared for flexural tests. Cubic compres-
sion and flexural strength were tested at the age of 3, 7 and 28 days, and the loading
rate was set to 2.4 kN/s and 50 N/s, respectively. According to standard test ASTM
C307-03, the tensile strength of cement paste containing different percentages of
graphene sheets were investigated. The specimens were loaded in a tensile testing
machine at a speed of 5 mm/min. The mechanical test was shown in Fig. 3. All sam-
ples were removed from their molds after 24 h and transferred to standard curing
room (20 ± 2 °C, RH > 95%) for 28 days.
Furthermore, microstructure investigations were carried out with scanning
electron microscope (SEM, FEI Quanta 650 FEG) and mercury intrusion porosimetry
(MIP, AutoPore IV9500). Moreover, X-ray powder diffraction (XRD) data were test
on a Bruker D8 Advance diffractometer.

3. Results and discussion

Fig. 2. The particle size distribution (a) and UV–vis spectrum (b) of graphene
sheets.
3.1. Effect of SAAs on the graphene dispersion

Due to the high specific surface area, graphene exists as large

where c and d are the concentration and the path length through the absorbing sam- aggregates in water before ultrasonic treatment. During sonication,
ples, respectively. For each species and wavelength, e is a constant known as the vibration produced by ultrasonic waves can overcome the van der
molar absorptivity or extinction coefficient. The UV absorbance of graphene was
Waals interactions between the graphene sheets and lead to their
shown in Fig. 2(b), and the absorbance maximum was around 265 nm.
Three different amounts of added graphene were considered (relative to the dispersion. The performances of surfactants CTAB, SDBS, SDS,
cement weight), in addition to a blank: 0.01 wt%, 0.025 wt% and 0.05 wt%. The TX100, and SP at various concentrations for graphene dispersion
mix proportion of all mixtures is shown in Table 3. The ratio of water to cement were tested. The absorption peak of graphene dispersion was mea-
was 0.4 for all preparations, and it should be noted that the amount of water in
sured at the wavelength of 265 nm for all spectra. The most suit-
the dispersion was also included. JJ-5 type cement mixer (Wuxi Jiangong Test Facil-
ity Co. Ltd., China) with the rotation rate 285 r/min was used for the mixing of
able graphene/SAA weight ratio was estimated by comparing the
cement paste, and the volume of the bowl was 5 L. The mixing process was as fol- absorbance of graphene dispersions containing the same amount
lows: firstly, graphene dispersion liquid and water were placed in the mixing pot of graphene and different amounts of surfactant. Furthermore,
4 J. Liu et al. / Construction and Building Materials 199 (2019) 1–11

Fig. 3. Pictures of compressive (a), flexural (b) and tensile test (c) for specimens.

the UV–vis absorbency result of graphene solution without SAA the absorption peak remained stable after 15 min of sonication
was added as a reference sample. (corresponding to a total sonication energy of 270 kJ). It was found
Changing ultrasonic energy has a great effect on the dispersion that the aqueous solution with high amount of SDBS exhibited
degree of graphene, and more notably, the ultrasonic energy is higher dispersing capacity. A high level of SDBS produced an effi-
related to the sonication power and time. Therefore, the influence cient coating on the surface of the graphene to prevent re-
of ultrasonic time and power on the absorbance of 0.05 wt% gra- aggregation, however, an excessive dose of SDBS introduced a lot
phene dispersion was firstly analyzed. As shown in Fig. 4, the of bubbles. In this research, the optimum weight ratio of graphene
absorbance of graphene dispersion had higher values when output to SDBS was identified as 1:6 by weight.
power was 450 W. In addition, the dispersion degree was opti-
mized with 15 min of ultrasonic time.
For further study, the output power of 450 W was selected for
ultrasonic dispersion process. Fig. 5(a) compares the evolution of
the absorbance of 0.05 wt% graphene in aqueous solution for dif-
ferent optimum SAAs. It is advisable to plot the absorbance versus
the total energy supplied to the dispersion instead of sonication
time [32]. The general trends of the UV absorbance versus sonica-
tion time obtained for graphene–SDS and SDBS solutions were sim-
ilar. The value of absorbance increases with sonication time and
then reaches a saturation value, which corresponds to the maxi-
mum achievable degree of dispersion of the graphene in water.
However, ultrasonic wave usually the rise of solution temperature,
which cause the random molecular motion and decrease disper-
sion stability. Thus, prolonged sonication was negative to the dis-
persion degree of graphene.
Fig. 5(b) illustrates UV–vis spectra of graphene–SDBS solutions,
obtained after different SDBS concentrations and sonication times.
The addition of SDBS also accelerated the dispersion process, and

Fig. 5. UV–Vis spectrum of the graphene dispersion with different SAAs (a) and
Fig. 4. Absorbance of graphene in aqueous solution with different sonication. SDBS (b).
 J. Liu et al. / Construction and Building Materials 199 (2019) 1–11 5

In this study, graphene sheets were used as raw materials and

uniformly dispersion was obtained by using ultrasonication and
surfactant treatment. However, there were still small amount of
unexfoliated graphene sheets in the dispersion, and these gra-
phene sheets would be hold together as clumps over time. Conse-
quently, the poor dispersion of agglomerates in the matrix affect
the strength of composites partly. Thus, most of previous studies
used static settlement method to evaluate the long-term stability
of dispersion. In this research, an acceleration sedimentation
experiment was carried out using a centrifugal machine, which
was usually employed for separating dense particles from solution.
The agglomerates of graphene sheets were subjected to centrifugal
force and sedimented at the bottom of the tube in a short time. The
graphene solutions were put in a high-speed centrifuge for 20 min
with a relative centrifugal force (RCF) of 1435g, which was equiv-
alent to 20 days of natural precipitation. Firstly, graphene was dis-
persed with each type of surfactant with their optimal addition.
Then, the mixture was centrifuged (2000 rpm, 20 min) to acceler-
ate the stabilization stage. As previously mentioned, graphene
was practically insoluble in water without physical or chemical
modification. Graphene dispersion was treated by ultrasonic wave
for 30 min without SAA, and sediment was observed at the bottom
of the tube, as shown in Fig. 6. The graphene could maintain its
well-dispersed state when SDBS was used as surfactants. The
SDBS–graphene solutions remained totally opaque and homoge-
neous. Although the stability of solution with much longer time Fig. 6. Digital images of graphene dispersions after centrifugation.
was not tested, the graphene sheets solution could maintain its
well-dispersed state for a long time. Furthermore, we can improve
cement particles, which increased the interaction between the
the long-term stability of dispersion by reducing the concentration
cement particles and caused the degradation of cement paste
of graphene sheets and adding the centrifugal time.
liquidity.
The direct dispersion of hydrophobic graphene in water without
At the same time, the impact of SDBS on the workability of
the assistance of SAA has generally been considered to be a chal-
cement paste was evaluated since the dosage of SDBS was 6 times
lenge. Fig. 5(b) showed the influence of different SDBS concentra-
of graphene. Fig. 7 indicated that the increased content of SDBS had
tion on the absorbance of graphene in aqueous solution. The
an adverse effect on the fluidity of cement paste, especially when
dispersion degree increased at the beginning of the sonication pro-
the amount of SDBS was high. SDBS used in this research was a
cess. However, after 15 min of sonication (corresponding to a total
type of anionic surfactants with amphiphilic structures, and its
sonication energy of 270 kJ), the value of absorbance reaches a pla-
steric hindrance and electrostatic repulsion were the main stabiliz-
teau value, which corresponds to the maximum achievable degree
ing dispersion mechanism. Considering the dosage of SDBS was 6
of dispersion of the graphene in water. SDBS is a kind of anionic
times of that of graphene sheets, SDBS could have an impact on
surfactants, which consist a hydrophilic sulfonate head-group
the workability of cement paste. Test results in Fig. 7 also sug-
and a hydrophobic alkylbenzene tail-group. The steric hindrance
gested that the influence of additives on workability was stronger
and electrostatic repulsion of SDBS were the main stabilizing dis-
for SDBS than for graphene sheets, and the increased content of
persion mechanism. However, excessive SDBS concentration
SDBS had an adverse effect on the fluidity of cement paste.
increased the number of like charges, which destroyed the balance
Compared with P1 and R1 group, the low adding amount of SDBS
force between graphene sheets and caused graphene particle to
slightly improved the workability of cement paste, which is
aggregate again [33,34]. Thus, over dosage surfactant had little
promotion effect on the dispersion degree of graphene. Based on
the graphene dispersion results determined by UV–vis spec-
140
troscopy, a graphene to-SDBS ratio of 1:6, and a sonication time
of 15 min was used to prepare all dispersions used with cement
paste. 120
Slump diameter (mm)

3.2. Effect of graphene on fluidity of cement paste 100

The effects of graphene on fluidity of the cement paste were 80

investigated using slump test, and the results are given in Fig. 7.
Most of previous studies showed that the addition of graphene 60
reduce workability of cementitious composites because of the high
specific surface energy of graphene sheet. In this study, the influ- 40
ence of undispersed graphene on the fluidity of cement past was
also tested. Three different amounts of added graphene were con-
20
sidered: 0.01 wt% (mix P1), 0.025 wt% (mix P2) and 0.05 wt% (mix
P3), and SAA wasn’t used and the ratio of water to cement was 0.4
0
for all preparations. Results showed that the fluidity of cement P1 R1 G1 P2 R2 G2 P3 R3 G3
paste decreased with increasing addition of undispersed graphene
sheets. Graphene was nearly 1000 times the specific surface area of Fig. 7. Slump test results of mixtures.
6 J. Liu et al. / Construction and Building Materials 199 (2019) 1–11

consistent to reported literature. When SDBS concentrations reach

the critical micellar level in aqueous solution, the surface tension
of the solution was increased, and the stability of dispersion was
reduced [35]. It explained why the workability of R3 was reduced
significantly when the amount of SDBS was high, as shown in
Fig. 7.
It was found that the workability of the G2 and G3 group was
higher than their control groups (R2 and R3). There existed a strong
bonding interaction between the benzene ring of the SDBS and gra-
phene due to the p-p stacking interactions [36]. During the disper-
sion process, the co-action of electrostatic repulsion and steric
hindrance of SDBS decreased graphene surface energy, which
improved the dispersing performance of solution [37]. In this case,
excess SDBS adsorb on the surface of graphene sheets when gra-
phene sheets was added into the solution. Therefore, the addition
of graphene mitigated the impact of high dosage SDBS on the
workability of paste, and the fluidity of G2 and G3 mixture were
improved.

3.3. Compressive and flexural strengths

The influence of different amount of graphene on the mechan-

ical properties of cement paste was investigated, and the test
results are presented in Fig. 8. For the compressive and bending
tests, the standard deviation of the six specimens was lower than
10%, which indicated that the dispersion process was effective for
dispersing graphene in a cementitious matrix. Fig. 8(a) shows the
compressive strength of specimens at 3, 7 and 28 days. With the
addition of 0.01 wt% and 0.025 wt% graphene sheets, the compres-
sive strength of cement paste was enhanced (relative to their con-
trol group). Compared with the R2 group, the compressive
strengths of the G2 group were increased by 23.7%, 14.9% and
10.0% at 3, 7 and 28 days, respectively. Similarly, the compressive
strengths of the G1 group were increased by 15%, 5.1% and 13.5%
at 3, 7 and 28 days, respectively. However, a high amount of gra- Fig. 8. Compressive and flexural strengths of samples at 3, 7 and 28 days.
phene sheets (0.05 wt%) led to a decrease in the compressive
strength of the cement paste; this was for the following reasons:
firstly, the use of SDBS caused the formation of foam and increased graphene sheets increased 18.6% and 16.7%, respectively. At 7 days,
the porosity of the matrix; secondly, increasing the graphene the tensile strength of G1 and G2 increased by 14.1% and 15.2%
sheets concentration may result in an increased number of gra- respectively, compared with R1 and R2. However, continued
phene agglomerates, which reduced the interfacial bond between increase of graphene sheets could not improve the strength of
graphene sheets and cement hydration. the cement paste; the tensile strength of specimens containing
The incorporation of well-dispersed graphene also increased 0.05 wt% graphene sheets was almost same as the control group
the flexural strength of cement paste beams, as shown in Fig. 8 at different curing ages. This may be attributed to the agglomera-
(b). The addition of 0.01 wt% graphene produced a slight increase tion of the graphene sheets in the cement matrix. It was difficult
in the flexural strength at different ages. Compare to the R2 sam- to achieve uniform distribution of graphene sheets throughout
ple, the flexural strengths of specimens containing 0.025 wt% gra- the matrix, and graphene sheets can more easily aggregate with
phene were improved by 12.5%, 23.6%, and 16% at 3, 7 and 28 days, the increase of volume fraction. Agglomeration of graphene sheets
respectively. The flexural strength of cement paste was primarily hindered their potential to improve the mechanical properties of
affected by the presence of macro-defects that were inevitably cement-based materials.
introduced during the mixing process. As an ideal two-
dimensional nano-material, graphene may improve the cement 3.5. Morphology and microstructure
matrix resistance to cracking by offsetting the coalescence of smal-
ler cracks into larger micro-cracks. However, the flexural strength The microstructural characteristics of cement paste affect its
of the G3 group was significantly decreased with the addition of mechanical properties. The cement hydration products were com-
0.05 wt% graphene sheets, which was similar to the situation of pacted at 28 days, and graphene sheets could barely be distin-
compressive strength. guished. Thus, the distribution and condition of graphene sheets
in the cement paste were observed at 7 days. Fig. 10(a) shows
3.4. Tensile strength the microstructure images of cement paste without graphene
sheets. The structure of products is loose and there are many
The results of tensile strength tests of each group at 3, 7, and defects in them. Considering that the micrographs of hexagonal
28 days are shown in Fig. 9. The tensile strength of the specimens platy crystals of calcium hydroxide (CH) are similar to that of gra-
increased with increasing curing age. The addition of graphene phene, the EDS analysis result was employed to determine the
sheets had obvious influence on the tensile strength of samples existence of graphene sheets. The areas with box markings in
at an early age. Compared with their control groups, the 3-day Fig. 10 are the selected areas for EDS detection, and the results
tensile strength of samples containing 0.01 wt% and 0.025 wt% are shown in Table 4. It can be found that area II, III and Ⅳ contain
 J. Liu et al. / Construction and Building Materials 199 (2019) 1–11 7

The typical microstructure of graphene-reinforced cement paste

at 0.05 wt% concentration was illustrated in Fig. 10(f), and agglom-
erates were found more frequently on the fracture surfaces of sam-
ples. Obvious voids can be seen in the interfacial zone between
graphene sheets and the cement hydration products. High levels
of graphene weakened the strength of cement, which can be attrib-
uted to defects resulting from a less effective compaction. In addi-
tion, the poor dispersion of graphene in the matrix and the low
fluidity of the paste also decreased the strength of composites
and the natural morphology of graphene with a wrinkled structure
could be identified. However, wrinkles in graphene may improve
the interlocking mechanism, which has a positive effect on the
mechanical properties of the matrix [38].

3.6. XRD analysis

The XRD patterns of the cement paste modified with different

Fig. 9. Tensile strength of samples at 3, 7 and 28 days.
graphene sheets additions are shown in Fig. 11. Portlandite (CH),
ettringite (AFt), tricalcium silicate (C3S) and dicalcium silicate
a lot of calcium, silicon and oxygen elements, it may be due to the (C2S) were found to be major phases for samples. Moreover, the
active functional groups on the surface of graphene sheets promote amount of these hydration products increases with increasing
the formation of hydrated products. hydration time. The XRD results showed the amount of calcium sil-
For the G1 and G2 groups at 7 days (Fig. 10(b) and (c)), graphene icate hydrates (C–S–H) gels in G1 and G2 samples was higher than
sheets were mostly found as individual sheet with a particle size of in the normal cement paste (R1 and R2), which was caused by the
below 5 lm indicating that an effective dispersion was achieved. nucleation of C–S–H by the graphene sheets.
Moreover, graphene sheets had a seeding effect in the cement The orientation index reflect the growth of CH crystal during
hydration, which advanced the growth of hydration products. As cement hydration, and the influence of graphene sheets on CH ori-
indicated in Fig. 10(c), graphene was mostly found as individual entation can be determined by XRD pattern [39]. In general, the
graphene sheet, thus showing that a good dispersion was achieved lower orientation index, the more compact of hardening cement
by means of SDBS and sonication. In addition, graphene was coated paste [40,41]. The orientation index in part reflect the mechanical
by cement hydrates in the majority of the areas inspected. As strength enhancement of graphene. According to Grandet and Olli-
shown in Fig. 10(d), a crack-bridging mechanism of well-bonded vier [42], the (1 0 1) crystal plane of CH could be used as a refer-
graphene sheets in cement matrix at 0.025 wt% inhibited crack ence plane, and the orientation index R of (0 0 1) crystal plane
development. Graphene sheets formed a net-like arrangement can be calculated by R = 1.35  I(0 0 1)/I(1 0 1), where I(0 0 1) and
showing good incorporation into the cement matrix, as Fig. 10(e) I(1 0 1) are (0 0 1) and (1 0 1) crystal face peak intensity of CH crys-
shows. tal, respectively. As shown in Fig. 11(d), orientation indexes of the

Fig. 10. SEM micrographs of the R1 (a), G1 (b), G2 (c, d, e) and G3 (f) samples at 7 days.
8 J. Liu et al. / Construction and Building Materials 199 (2019) 1–11

Table 4 age pore diameter of the G2 group were also reduced. These indi-
EDS test results. cated that the addition of graphene sheets increased the
Area Element (wt%) compactness of the matrix. Consequently, the strength of the
Ca O Si Al Mg C cement paste was increased by the addition of graphene sheets
due to the improved pore characterization. Although the total
Ⅰ 72.9 18.3 5.3 1.5 1.6 0.4
Ⅱ 50.2 33.0 9.6 1.8 0.8 4.6
porosity of the G3 sample was higher than that of R3, the average
III 48.9 33.2 11.5 1.3 0.4 4.7 pore diameter of the cement was reduced from 41.2 nm to 34.1 nm
Ⅳ 41.1 38.0 10.2 3.0 1.5 6.2 with the addition of 0.05 wt% of graphene sheets. The relationship
between the log differential intrusion and pore size diameter is
shown in Fig. 12. It demonstrated that the addition of 0.025 wt%
R2 sample were 2.6, 1.88 and 1.63 at ages of 3d, 7d and 28d, and 0.01 wt% of graphene sheets refined the microstructure of
respectively, and the indexes of the G2 sample were 1.87, 1.71 cement paste by reducing the number of macroscopic pores
and 1.43. The addition of 0.025 wt% graphene sheets lowered the (>50 nm).
orientation index of CH crystals significantly, which enhances the
interface properties of cement-based materials.
4. Discussion

3.7. Porosity and pore size distribution The main challenges associated with the incorporation of gra-
phene are attaining uniform dispersion and interfacial bonding
By using MIP analysis, the pore information of cement paste within the cement matrix. The dispersion process is shown in
with different amounts of graphene sheets at 7 days is summarized Fig. 13; the ultrasonication formed a cavitation field and produced
in Table 5. The experimental results indicated that a high concen- millions of microbubbles during the dispersion, which accelerated
tration of SDBS leads to foam formation and high porosity of the the exfoliation of graphene agglomerates. However, excessive son-
cement paste. However, the results also verified that the pores in ication may result in breakage of graphene sheets, reducing their
cement paste were refined through the addition of graphene aspect ratio. The proper choice of a suitable surfactant and sonica-
sheets. Compared with the R2 group, the total porosity of samples tion time require consideration of its structure and its optimum
decreases from 29.580% to 28.739% by incorporating 0.025 wt% of ratio to graphene. Previous studies have shown that anionic surfac-
graphene sheets. Meanwhile, the median pore diameter and aver- tants have higher dispersion capability than cationic surfactants or

Fig. 11. XRD analysis of composites at 3 (a), 7 (b) and 28 (c) days, and orientation index of CH crystals (d).
 J. Liu et al. / Construction and Building Materials 199 (2019) 1–11 9

Fig. 12. Pore size distribution of samples at 7 days.

Fig. 13. Schematic representations of the mechanisms by SDBS help disperse graphene.

Table 5
MIP analysis of specimens at 7 days.

No. Total intrusion volume (mL/g) Porosity (%) Median pore diameter (nm) Average pore diameter (nm)
R1 0.1695 27.151 63.8 37.9
G1 0.1591 26.472 58.2 36.2
R2 0.1861 29.580 51.3 32.5
G2 0.1818 28.739 43.7 29.0
R3 0.1953 30.279 48.5 41.2
G3 0.1997 31.137 48.1 34.7
10 J. Liu et al. / Construction and Building Materials 199 (2019) 1–11

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