Construction and Building Materials 275 (2021) 122154

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Construction and Building Materials

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Effect of a novel hybrid TiO2-graphene composite on enhancing

mechanical and durability characteristics of alkali-activated slag mortar
Su-Lei Zhang a, Xiao-Qiang Qi a, Si-Yao Guo a,c,⇑, Jie Ren b,c,⇑, Ji-Zhou Chen a, Bo Chi c, Xu-Chun Wang a
a
School of Civil Engineering, Qingdao University of Technology, Qingdao, China
b
Guangdong Provincial Key Laboratory of Durability for Marine Civil Engineering, College of Civil and Transportation Engineering, Shenzhen University, Shenzhen 518060, China
c
Huazhong University of Science and Technology, College of Materials Science and Engineering, Wuhan, China

h i g h l i g h t s

Irrespective of different dosages, TiO2-graphene composite improved the mechanical and durability properties of AAS mortars.

The optimal dosage of TiO2-graphene was 0.03% compared to a lower (0.01%) or higher one (0.05%).

TiO2-graphene is able to facilitate the hydration process of AAS and refine its porous microstructure.

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

Article history: A highly dispersed hybrid TiO2-graphene composite was synthesized in-situ and for the first time utilized
Received 10 August 2020 in alkali-activated slag (AAS) mortars. The effects of the TiO2-graphene composite in different dosages of
Received in revised form 12 November 2020 0.0, 0.1%, 0.3% and 0.5% on the mechanical and durability properties of AAS mortars were investigated.
Accepted 22 December 2020
The results showed that an optimal dosage of the TiO2-graphene composite exists which was 0.03 wt%
Available online 19 January 2021
in this study, leading to about 26.6%, 11.3% and 13.6% increase in compressive strength, flexural strength
and flexural-to-compressive strength ratio, respectively. In addition, the capillary sorptivity, chloride
Keywords:
penetration depth and diffusion coefficients were significantly reduced via TiO2-graphene additions.
TiO2-graphene composite
Alkali-activated slag
Similarly, 0.03 wt% dosage led to the best performance by decreasing these values by upto 32.0%,
Durability performance 66.5%, 68.7% respectively. All these experimental results were due to a densified microstructure of AAS
Mechanical properties incorporated TiO2-graphene composite, verified by lower porosity, especially at meso-capillary pore
Chloride diffusion levels and also probably due to wrinkled surface of TiO2-graphene nanosheets. It was also noticed that
an overdosage of the TiO2-graphene composite would compromise these beneficial effects due in large
part to agglomerations. The well-dispersed hybrid TiO2-graphene composite assisted by the in-situ inter-
calating method improves the AAS binder in terms of mechanical and durability performances, thus mak-
ing it more promising in partial replacement of ordinary Portland cement counterparts.
Ó 2020 Elsevier Ltd. All rights reserved.

1. Introduction
It is reported that ordinary Portland cement (OPC)-based con-
crete production accounts for a major part of the energy consump-
tion associated with the construction industry which is responsible
for 40% of the total energy consumption in the world [1–2]. Alkali-
activated slag (AAS) binder has been developed for decades due to
their lower CO2 emissions because of the use of slag which is an
industrial by-product and its calcination-free manufacturing pro-
cedure. Besides, cementless AAS binders often exhibit relatively
⇑ Corresponding authors at: Shenzhen University, Qingdao University of Tech-
nology and Huazhong University of Science and Technology, China.
E-mail addresses: siyaoguo@126.com (S.-Y. Guo), jier@szu.edu.cn (J. Ren).
higher durability [3], such as resistance against sulfate [4], acid
attacks [5–7] and freeze–thaw cycles [8]. These advantages are
mainly due to the absence of Portlandite and lower Ca/Si ratios
in C-S-H gel (one of main hydration products for AAS binding sys-
tems) compared to OPC-based binders as well as more compact
structures [4–5,8]. However, AAS binders display low fracture
toughness with a quasi-brittle mechanical behaviour when sub-
jected to various surrounding environments [9–10]. This would
result in the formation of many microcracks through which differ-
ent ion species may intrude into bulk specimens, posing a signifi-
cant threat for the durability of AAS binders. As a result, further
large-scale industrial applications of AAS binders are impeded.
Currently, a great deal of studies was carried out in terms of
mechanical and durability improvements of alkali activated

https://doi.org/10.1016/j.conbuildmat.2020.122154
0950-0618/Ó 2020 Elsevier Ltd. All rights reserved.
Su-Lei Zhang, Xiao-Qiang Qi, Si-Yao Guo et al.
binders [11]. Yang et al. [12] investigated the effect of nano-TiO2
particles on the strength, shrinkage and microstructures of AAS
pastes. A lower shrinkage and enhanced mechanical strength were
achieved due to more hydration products and a denser structure. It
was reported that the porosity of mesopores (1.25–25 nm) was sig-
nificantly reduced because of the nano-TiO2 addition. Gao et al.
[13] found that nano-SiO2 particles (average size: 10 nm) were able
to accelerate geopolymerization process and improve flexural
strength of metakaolin-based geopolymer samples due to filler
effect of nano particles. Apart from these nano fillers, graphene
nanoplatelets have also been used recently to enhance mechanical
and durability characteristics of alkali activated binders concrete
due to their inherent strong mechanical properties [10,13–14].
According to the work conducted by Matalkah et al. [14], 0.2 vol%
of graphene nanoplatelets addition led to some increments in com-
pressive strength, a reduced sorptivity by 35% and an improved
abrasion resistance of an alkali activated binder. Saafi et al. [15]
confirmed that fly ash based geopolymers had a more densified
morphology and enhanced mechanical properties introduced by
a reduced graphene oxide (rGO) addition. Specifically, an optimal
dosage level of 0.35% (by mass) achieved the highest flexural
strength, flexural toughness and Young’s modulus, which was
increased by 134%, 56% and 376% respectively. They also pointed
out that an overdosage of rGO would cause restacking of graphene
sheets due to van-der-Waals forces, which results in the formation
of rigid laminates and brittle manner of structures. Moreover, Ran-
jbar et al. [10] found that 1% graphene nanoplatelets improved the
compressive strength and flexural strength by 1.44 and 2.16 times
respectively for fly ash-based geopolymer. All these studies show
that in order to improve mechanical and durability-related proper-
ties of alkali activated binders, there is an optimal dosage level of
graphene above which either more mixing water is needed or obvi-
ous overlapping and/or agglomeration of these nanoplatelets occur
despite of various preconditioning method such as sonication.
Hence, to obtain an optimal dosage level of graphene nanoplatelets
which could ensure a highly dispersion within the binding matrix
and effectively improve the microstructural, mechanical and dura-
bility properties of AAS binders is critical. It is worth noting that
most of the studies mentioned above are limited to alkali-
activated fly ash binders (also known as geopolymers) and related
literature focusing on the enhancement of AAS binders by integra-
tion of graphene-based nanoparticles is by far rather scarce.
This study, therefore, attempts to synthesis a highly dispersed
graphene nanosheets by using an in-situ TiO2 intercalating
method. Then the hybrid TiO2-graphene composite with three dif-
ferent dosages was added into AAS mortars with the purpose of
enhancing the mechanical and durability-related properties. The
effects of TiO2-graphene composite on the mechanical characteris-
tics including flexural, compressive strength and fractural tough-
ness indicated by flexural-to-compressive strength ratios were
examined. Besides, durability-related properties discussed herein
include capillary sorptivity, chloride migration coefficients and
porous structures. Transmission electron microscopy and X-ray
diffraction analysis were also employed to reveal the morphology
of the TiO2-graphene composite and hydration products of AAS
binders respectively.
2. Materials and methods
2.1. Materials
Natural flake graphite powders with an average particle size of
45 lm (carbon purity > 99.95%) were purchased from Qingdao
Tengshengda Carbon Machinery Co., Ltd. The density of this type
graphite is about 2.25 g/cm3. Concentrated sulfuric acid (H2SO4)
2
Construction and Building Materials 275 (2021) 122154
and hydrochloric acid (HCl) with a concentration at  98% and
10% (by mass) respectively were supplied by Qingdao Zhengye
Reagent Instrument Co., Ltd. Potassium permanganate (KMnO4),
hydrogen peroxide (H2O2, 30%) and sodium nitrate (NaNO3), all
of which are of analytical reagent (AR), were purchased from
Shanghai Wokai Biotechnology Co., Ltd. Sodium borohydride
(NaBH4  96%) as a reducing agent was provided by Shanghai
Shanpu Chemical Co., Ltd. Titania (TiO2) with a purity  99% (AR)
was purchased from Tianjin Zhiyuan Chemical Reagent Co., Ltd.
The slag used in this study is blast furnace slag and has a med-
ian particle size at 13.7 lm with fineness of 523 m2/kg. Its particle
size distribution determined by laser diffraction analysis is shown
in Fig. 1. The chemical compositions of the slag as determined by
X-ray florescence (XRF) analysis using PAN alytical Axios XRF spec-
trometer is tabulated in Table 1. Analytical grade sodium hydrox-
ide (NaOH) granular particles (purity  99.5%) were mixed with
sodium silicate solution (original composition: Na2O = 9.02%,
SiO2 = 26.96% and H2O = 64.02% by mass, modulus = 3.07) as well
as water as the alkaline activator. The NaOH and sodium silicate
solution were supplied by Shanghai Epi Chemical Reagent Co.,
Ltd. and Linyi Lusen Chemical Co., Ltd., respectively. The sand used
was standard ISO quartz sand from Xiamen ISO Standard Sand Co.,
Ltd with the maximum size of 5 mm.
2.2. Methods
2.2.1. Synthesis of TiO2-graphene composites
The study used a modified Hummers method to oxidize gra-
phite and an in-situ intercalating method to incorporate TiO2 into
the graphene system, as shown in Fig. 2: graphite powers were
firstly oxidized with a strong acid (concentrated H2SO4) pre-
mixed with NaNO3 power and a strong oxidant (KMnO4) for at
least 12 h under the ice-bath curing condition. Later, the mixture
suspension was diluted and washed using deionised water and
hydrochloric acid (HCl) as well as H2O2 to remove KMnO4 and
MnO2 during which process the suspension colour changed from
brown to bright yellow. Then centrifugation and washing process
continued until neutral followed by drying the product (graphene
oxide) in a vacuum with a low temperature for 48 h. Secondly,
the TiO2 nanoparticles were inserted into the graphene system
based on the following procedures: 1 g graphene oxide was soni-
cated in deionised water (400 ml) for two hours followed by add-
ing 10 g NaBH4 and 200 mg TiO2 particles into the system.
Subsequently, the mixture was allowed to react for one hour,
reacted in water bath (60 ℃) until no bubbles were observed. This
18
Differential distribution
Cumulative distribution 100
15
Differential distribution (%)
Cumulative distribution (%)
80
12
60
9
40
6
3 20
0 0
0.1 1 10 100 1000
Size diameter (μm)
Fig. 1. Particle size distribution of the slag used in the study.
Su-Lei Zhang, Xiao-Qiang Qi, Si-Yao Guo et al.
Table 1
Chemical composition of the slag determined by X-ray florescence (XRF) analysis.
Materials CaO SiO2 Al2O3
Slag 47.12 28.58 13.89
Hummers’
Flake graphite
Fig. 2. Schematic presentation of the in-situ synthesis of TiO2-graphene composites.
process usually takes about 12 h. At last, the composite was
obtained by vacuum filtering and drying for at least 24 h. For com-
parison purpose, graphene nanosheets without TiO2 particles were
also synthesised based on the above-mentioned method.
Graphene nanosheets with and without TiO2 nanoparticles
were both solved in distilled water, ultrasonicated for two hours
and the dispersion state of the two types of suspension was
observed after 12 h of holding time. A direct comparison between
the two types of the graphene in the mixing water is shown in
Fig. 3. It is apparent that without the TiO2 modification, graphene
nanosheets display obvious agglomerations which deposit on the
bottom of the aqueous solution, showing poor dispersibility and
uniformity. This phenomenon is very common for nanomaterials
because of their super high specific surface area [16–19]. In com-
parison, a uniform colour of the TiO2-graphene suspension indi-
cates a well-dispersed graphene nanosheets. In this study, the
improved dispersibility of graphene nanosheets is assumed to be
due to the negatively-charged TiO2 particles repelling each another
and thus enabling a greater distance between different layers of
graphene nanosheets [20,21]. As a result, the tendency of graphene
nanosheets to overlap or aggregate seems to decrease significantly.
Pure graphene TiO2-graphene composite
Fig. 3. The pure graphene nanoplatelets (left) and TiO2-graphene composite (right)
in water suspension.
Construction and Building Materials 275 (2021) 122154
Fe2O3 MgO SO3 K2O Others
0.35 5.53 2.60 0.32 1.61
TiO2
+
Hydrothermal
Graphene oxide TiO2-Graphene
In fact, the presence of graphene layers may also facilitate the dis-
persion of nano TiO2 particles [22] which in turn favour the disper-
sion of graphene in aqueous solutions.
2.2.2. Preparation of TiO2-graphene modified AAS mortars
For all AAS mortar groups, the alkaline activator used was a
combination of industrial grade sodium silicate solution (water
glass), sodium hydroxide (NaOH) pellets and additional water with
a constant molar ratio of SiO2/Na2O at 1.8. The alkali dosage was
7.0% by mass of the alkaline activator. The water-to-slag ratio
was about 0.37 by mass and the sand to slag mass ratio was
2.07. It is worth noting that the water in the water glass is also con-
sidered as part of the mixing water. Besides, part of the additional
water (except the water in the water glass) was used for making
graphene suspension and the rest of the additional water was used
for preparing alkaline activator solutions. The chemical index of
the water glass used and the specific mix proportions of AAS mor-
tars are formulated in Tables 2 & 3, respectively.
The detailed mixing process is shown in Fig. 4. Firstly, prepared
NaOH particles were dissolved in the sodium silicate solution grad-
ually and then the obtained alkaline activator was allowed to cool
down to room temperature for at least two hours. Meanwhile, the
TiO2-graphene composite in different dosages was dissolved in part
of the additional water and subjected to sonication for 1 h to obtain a
well-dispersed graphene suspension. Then the alkaline activator
accompanied with the rest of the additional water was poured in
the mixture of slag and sand which was premixed for 2 min in a
Hobart mixer. The obtained mixture was mixed at low speed for
three minutes followed by adding the TiO2-graphene suspension
into the mixer. The whole mixture was further mixed sufficiently
for about three minutes. Finally the newly mixed AAS mortars were
cast into different moulds, vibrated on a vibrating table for 30 s and
fully covered with a plastic film until demoulding after 24 h. After
demoulding, all samples were sealed in plastic bags and cured under
ambient conditions (23 ± 2 ℃) for 28 days prior to further tests. In
this study, the three different dosages of TiO2-graphene composites
by mass ratio of slag were 0.01%, 0.03% and 0.05%. The same AAS
mortar without the addition of TiO2-graphene composite was used
for comparison. The moulds used have different sizes including
prismatic moulds: 40 mm  40 mm  160 mm, cubic moulds:
70.7 mm  70.7 mm  70.7 mm and cylindrical moulds: U
100 mm  50 mm.
3
Su-Lei Zhang, Xiao-Qiang Qi, Si-Yao Guo et al. Construction and Building Materials 275 (2021) 122154

Table 2
Chemical index of the water glass used in this study.

Chemical index w(SiO2) w(Na2O) Baume degree Molar Modulus Transparency

Content 26.96% 9.02% 40.2° 3.07 82

Table 3
Mixture proportions of the samples in this study.

Sample TiO2-graphene Alkali-activator composition Water/Slag Sand/Slag

AAS0 0 Na2O:SiO2:H2O = 7.0%:12.2%:80.8% 0.37 2.07
AAS1 0.01% Na2O:SiO2:H2O = 7.0%:12.2%:80.8% 0.37 2.07
AAS3 0.03% Na2O:SiO2:H2O = 7.0%:12.2%:80.8% 0.37 2.07
AAS5 0.05% Na2O:SiO2:H2O = 7.0%:12.2%:80.8% 0.37 2.07

TiO2-graphene
suspension
Water
TiO2-Graphene Newly-mixed AAS mortar
Sonication added with TiO2-graphene
suspension
1hour

Mix for
+ 3 min

Mix for

3 min

Alkali-activator solution Slag/sand mixture Pure AAS mortar

Fig. 4. Specific presentation of the TiO2-graphene modified AAS mortar manufacturing process.

2.2.3. Testing procedure

Morphology of TiO2-graphene and mineralogy of AAS hydra-
tion products
Transmission electron microscope (TEM) was applied to unfold
the morphology of the newly-fabricated TiO2-graphene composite.
X-ray diffraction (XRD) analysis was conducted by using an auto-
matic X-ray diffractometer (D8 ADVANCE, Germany) with copper
radiation. The scanning rate was 2 deg/min with a scanning range
between 10 and 70 deg (two-theta).

Assessment of mechanical properties
The three-point flexural bending strength was tested on pris-
matic samples (40 mm  40 mm  160 mm) with a fully auto-
matic testing machine (DY208-M20) at a speed of 50 N/s.
Triplicates were used for each mortar mix and the averaged results
were expressed as the final flexural strength. After the flexural
strength test, the residual split samples (six for each mixture) were
used for compressive strength test with a constant loading rate
(2.4 kN/s). The final results were obtained as the average reading
of the six specimens.
of different mortar mixes. Samples were first dried in an laboratory
oven at 50 ℃ until a constant mass was obtained and allowed to
cool down in the ambient environment (23 ± 2 ℃) according to
ASTM C1585-04 [24]. After cooling down, four side surfaces of
the samples were sealed with aluminum foil tape to ensure a
one-dimensional ingress of water from the bottom to the top of
samples. Before placing on sponges soaked with water, the initial
masses of samples were recorded. After that, samples were placed
on sponges as the support and the water surface level was kept
about 3 mm higher than the bottom of the samples, as shown in
Fig. 5. Sample masses were measured after 0.5, 1, 2, 4, 8, 12 and
24 h as well as 2, 3, 4, 5, 6 and 7 days by using a digital scale (a pre-
cision of 0.01 g). At each time interval for mass measurements,
samples were taken out from the container and the surface water
was removed using a lint-free dampened cloth. The measuring

Assessment of durability-related properties

Capillary sorptivity test was performed on samples sizing

70.7 mm  70.7 mm  70.7 mm after 28 days of curing to reflect
the tendency of mortar samples to absorb water via capillary forces
[23]. As water is the primary vehicle for ion transportation, capil-
lary sorptivity is thus able to yield information about the durability Fig. 5. Experimental setup of the capillary sorptivity test.

4
Su-Lei Zhang, Xiao-Qiang Qi, Si-Yao Guo et al. Construction and Building Materials 275 (2021) 122154

process was completed within 30 s so as to avoid water loss due to

evaporation [22]. Finally the masses of different mortar mixes at
each time interval in sequence were recorded and the cumulative
amount of water (g) as a function of time (hour) was also recorded.
The rapid chloride ion migration coefficient was determined
according to Rapid Chloride Migration (RCM) NT BUILD 492 test
to quantify the chloride penetration resistant of different AAS bin- TiO2 particles
ders [25–28]. Cylinder samples (100 mm in diameter and 50 mm in
height) were used for the test and the experimental setup is shown
in Fig. 6. As shown, the upper side of the cylinder samples was
exposed to NaOH solution (0.3 mol/L) and the lower side was
placed in a tank containing aqueous NaCl solution (10% by mass).
During the 24 h of testing, the current, voltage and temperature
were recorded. After 24 h, the diffusion coefficient (DRCM) is calcu- Graphene surface
lated by means of the colorimetric method. Specimens were split
from the middle and 0.1 M AgNO3 solution was sprayed onto both
halves of the split specimens. As a result, a visible white deposit of 100 nm
AgCl2 indicates the penetration depth of chloride ions. For each half
of the specimen, 6–9 places were randomly selected for measure-
Fig. 7. A TEM image of the prepared TiO2-graphene composite.
ments with an interval greater than 10 mm and the final results
were the averaged value of 12–18 values.

Characterization of porous structures C C:Calcite

CS:C-A-S-H
The pore structure of AAS mortar specimens was characterised CS Hy:Hydrotalcite
by conducting mercury intrusion porosimetry (MIP) test with a
specific porosimeter (Autopore IV 9510) after 28 days of curing.

3. Results and discussion CS C

Hy/CS C
Hy CS C C AAS3
3.1. TEm

The morphology of the TiO2-graphene nano-composite is

shown in Fig. 7 based on TEM analysis. It can be seen that the
obtained TiO2-graphene composite has a textured or wrinkled sur-
face, indicating a crumpled morphology. This wrinkled surface is
likely to result from the in-situ reduction process of graphene AAS0
oxide into graphene particles [29]. A closer examination verified
the presence of TiO2 particles with darker colour randomly dis-
tributed on the surface of the graphene nanosheets, which are 10 20 30 40 50 60 70
highlighted in yellow circles. It can be seen that these particles 2θ (°)
have a size ranging between 20 and 30 nm, corresponding well
with the data reported from other studies [11,30]. Fig. 8. XRD patterns of the AAS mortars with 0.03% dosage of TiO2-graphene (AAS3)
and with no graphene addition (AAS0).

3.2. XRD analysis

to the unavoidable natural carbonation during the sample prepara-
Based on the XRD patterns of AAS3 and AAS0 samples shown in
tion or later curing processes [31,32]. Besides, it is noticed that all
Fig. 8, it is apparent that the main diffraction peaks in the AAS mor-
the corresponding peaks seem to be slightly stronger for AAS3
tar samples are similar regardless of TiO2-graphene addition or not,
sample compared to the ones for AAS0, indicating that the addition
which can be assigned to the presence of calcite, hydrotalcite and
of TiO2-graphene composites (0.03% dosage level) promotes the
C-A-S-H gels. This implies that TiO2-graphene did not lead to the
formation of C-(A)-S-H phases and hydrotalcite as well as calcite.
formation of new phases. The existence of calcite is probably due
This finding is in line with another literature [13] which reported
that nanoplatelets surfaces could serve as nucleation sites for
hydration products to build up, thus promoting distributed forma-
tions of these products. It is worth pointing out that there are no
obvious diffraction peaks assigned to the TiO2-graphene composite
possibly due to its relatively low dosages.

3.3. Flexural and compressive strength

The flexural and compressive strength of all AAS mortars after

7 days and 28 days of curing with different TiO2-graphene con-
tents are presented in Fig. 9(a) and (b) respectively. It is obvious
that the corresponding values of both flexural and compressive
Fig. 6. Experimental setup of the rapid chloride migration test. strength for a certain type of AAS mortars obtained an increase
5
Su-Lei Zhang, Xiao-Qiang Qi, Si-Yao Guo et al. Construction and Building Materials 275 (2021) 122154

Similar to the flexural strength, compressive strength presented

8.5 (a) 7d in Fig. 9(b) also increased first from 0% to 0.03% followed by a slight
28 d decrease when the dosage increased up to 0.05%. The highest com-
8.0
pressive strength for AAS3 after 7-day and 28-day curing was 44.7
Flexural strength (MPa)

and 60.5 MPa respectively, increasing by 28.6% and 11.3% respec-

tively in comparison to the AAS0 as the control. This was also con-
7.5 firmed by the research conducted by Lu et al. [35] in which
graphene oxide was used to enhance mechanical behaviours of
7.0 strain hardening cementitious composites. This result can be con-
tributed to the inherent stronger mechanical properties of the gra-
phene honeycomb carbon nanostructures and pore-filling effect of
6.5 the TiO2-graphene composite which make the AAS binding matrix
denser [14,36]. The increments in the compressive strength might
6.0 also result from the interlocking between TiO2-graphene
nanosheets and AAS binding matrix because of a wrinkled mor-
phology of the TiO2-graphene composite, corresponding well with
5.5
the TEM analysis, as shown in Fig. 7 [14,37]. The slightly lower
0.00 0.01 0.02 0.03 0.04 0.05
compressive strength for the dosage of 0.05% (AAS5) than that of
TiO2-graphene content (wt.%) AAS3, similar to flexural strength, can be attributed to the aggrega-
tions/agglomerations of TiO2-graphene nanosheets because of
their super high specific surface area, corresponding well with
(b) the findings from other literature data [34,36].
60
The flexural-to-compressive strength ratio is often used to
Compressive strength (MPa)

reflect the toughness of cementitious binders [38,39] and the

55 specific values for all mortar mixes after 28-day curing is shown
in Fig. 10. It is apparent that all mortar mixes reinforced by the
50
TiO2-graphene composite obtain a higher flexural-to-compressive
strength ratio than that of the control specimen, indicating a higher
fractural toughness [40,41]. Moreover, the highest value is also
45 seen in AAS3 which is 0.134, representing an increase by approxi-
mately 13.6% as a comparison to the control mortar (0.118), which
is in consistent with the results from the compressive and flexural
40
strength. Either a slightly higher (AAS5) or lower content (AAS3) of
TiO2-graphene composite resulted in a decreased flexural-to-
7d
35 compressive strength ratio (0.128 and 0.126 respectively) as com-
28 d
pared to the AAS3. These results imply that an optimal dosage of
0.00 0.01 0.02 0.03 0.04 0.05 TiO2-graphene composites exists for the AAS mortar specimens
to obtain the greatest toughness, which is 0.03%. The values from
TiO2-graphene content (wt.%) different mechanical property tests are consistent with each other,
implying that 0.03% dosage level is the optimised selection within
Fig. 9. Flexural and compressive strength of the AAS mortars with different TiO2-
graphene contents, (a) flexural strength and (b) compressive strength.
the range considered.

from 7 days to 28 days due to the continuous hydration process.

0.20
For flexural strength shown in Fig. 9(a), it can be seen that the
AAS mortars with TiO2-graphene additions obtained higher flex-
Flexural-to-compressive strength ratio

ural strength compared to the control AAS peer. Moreover, the

highest flexural strength which was 7.3 MPa (7-day) and
8.1 MPa (28-day) was seen in the AAS3 specimen with 0.03%
dosage of the TiO2-graphene composite, indicating an increase 0.15
by 22.7% and 26.6% compared to the control accordingly. In com- 0.134
0.126 0.128
parison, the values for AAS1 and AAS5 were similar which were
0.118
6.65 and 6.7 MPa after 7 days, 7.1 and 7.3 MPa after 28-day
respectively. The continuous increase in flexural strength from
0% to 0.03% dosage level can be due to the toughening actions 0.10
induced by the TiO2-graphene composite, corresponding well
with the results from another literature [10]. In contrast, how-
ever, the reduced flexural strength for AAS5 as compared to
AAS3 can be explained by considering that an excessive dosage
of the TiO2-graphene composite might lead to some aggregations 0.05
and the poor dispersion of the composite, to some extent, com- 0.00 0.01 0.02 0.03 0.04 0.05
promising the toughening effect. This result suggests that 0.03% TiO2-graphene content (wt.%)
dosage of TiO2-graphene is the threshold for AAS mortars in this
case, and this mechanical percolation threshold phenomenon is Fig. 10. Flexural-to-compressive strength ratios of all AAS mortar samples after
in accordance with other reports [33,34,14]. 28 days of curing.

6
Su-Lei Zhang, Xiao-Qiang Qi, Si-Yao Guo et al. Construction and Building Materials 275 (2021) 122154

3.4. Capillary sorptivity 12

Water ingress by capillary sorptivity (mm)

AAS0
AAS1 K4=0.615
The cumulative amount of water (g) over 168 h (7-day) of water
10 AAS3
absorption for different mortar mixes is presented in Fig. 11. It is
apparent that the increasing rate of cumulative amount of water AAS5 K1=0.635
gradually decreased as the immersion time processed, implying 8
Fitted line (AAS0)
that the total amount of water absorbed would gradually stabilise Fitted line (AAS1)
K2=0.610
after 7 days. According to other research works [22,40,7], the cap- Fitted line (AAS3)
illary sorptivity coefficient is defined as the slope of the initial lin- 6 Fitted line (AAS5)
ear part in the curve describing the water ingress (mm) as a
function of square root of time (min0.5). The water ingress can be K3=0.432
4
calculated by Eq. (1).

mt 2
I¼ ð1Þ
Sq

0
where I is the water ingress (mm); mt is the change in mass at the 0 2 4 6 8 10 12 14 16
time interval (t); S is the exposed surface area of the specimen; and Time (min0.5)
q is the density of water (g/mm3).
A closer observation shows that the initial linear part of water Fig. 12. Water ingress via capillary forces (mm) over the first four hours of water
ingress increase versus square root of time occurs within 4 h, as absorption.

shown in Fig. 12. Hence, the slope of the corresponding linear part,
known as capillary sorptivity coefficient, is obtained by linear fit-
Table 4
ting method with the results shown in Table 4 and Fig. 12. The total Total water ingress and capillary sorptivity of the four AAS mortar mixes.
amount of water absorbed after 7 days for each mortar mix is also
Sample Total cumulative Total ingress of water Capillary
shown in Table 4. It is obvious that all mortar mixes enhanced by
amount of water after 4 h (linear ingress of sorptivity
TiO2-graphene composite obtained lower cumulative amount of after 7 days (g) water period) in mm coefficient
water and capillary sorptivity coefficient compared to the control (mm/min0.5)
AAS0 specimen. This result indicates that TiO2-graphene composite AAS0 6.62 10.03 0.635
could make AAS binding matrix more tortuous, improving the AAS1 4.53 9.40 0.610
resistance towards water intrusion via capillary forces [42]. This AAS3 3.09 6.60 0.432
benefit would then translate into improved durability performance AAS5 5.60 9.60 0.615

as water is the major vehicle for most ion species. In addition,

among all mortar mixes containing the TiO2-graphene composite,
AAS3 had the lowest amount of water absorbed both after 7 days
or water ingress after 4 h as well as the lowest capillary sorptivity
coefficient, which was 3.09 g, 6.60 mm and 0.432 mm/min0.5
respectively. These are also in line with the results of flexural
and compressive strengths. In fact, the lowest amount of water
absorbed after stabilising reveals the lowest water porosity of
AAS3 specimen, which then leads to the highest mechanical
strengths as they are closely associated with porous structures.
Compared to AAS0 with the capillary sorptivity coefficient at
AAS0
7
6.62
AAS1
Cumulative amount of water (g)
0.635 mm/min0.5, the reduction in the capillary sorptivity coeffi-
cient of AAS3 was 32.0% which was 0.432 mm/min0.5.
3.5. Chloride penetration
The chloride penetration depth for AAS0, AAS1, AAS3 and AAS5
was 9.41, 4.78, 3.15, 5.33 mm respectively, as shown in Fig. 13.
Therefore, the optimal dosage of TiO2-graphene composite was
0.03% (AAS3) again as evidenced by the least chloride penetration
depth. Compared to the pure AAS mortar (AAS0), the chloride pen-
etration depth experienced a reduction by 66.5%, 49.2% and 43.3%
respectively for AAS3, AAS1 and AAS5 mortar types. Considering
the low dosage of TiO2-graphene composite in the AAS binding
matrix, this improved resistance towards chloride penetration is

AAS3 remarkable.
6
AAS5 5.60 Besides, based on the final penetration depth and other param-
eters during the RCM test, the different diffusion coefficients of
5 chloride ions for AAS mortars expressed as DRCM was calculated
4.53 according to the following equation:
4 rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi


0:0239  ð273 þ TÞL ð273 þ TÞLX d
3.09 DRCM ¼ X d  0:0238
3 ðU  2Þt U2

2
where U is the absolute value of the applied voltage; T is the aver-
age temperature of the anode solution; L is the thickness of the
specimen; Xd is the average value of the penetration depth of chlo-
1
ride ions; t is the duration of the test. The results are displayed in
Fig. 14. Again the least DRCM was obtained by AAS3 (0.640  1012
0
0 20 40 60 80 100 120 140 160 180 m2/s) followed by AAS1 (1.048  1012 m2/s) and AAS5
(1.136  1012 m2/s), which are all much less compared to that of
Time (hour)
AAS0 control specimen (2.046  1012 m2/s). Thus, the maximum
Fig. 11. Cumulative amount of water (g) gained over 7 days of capillary sorptivity reduction was upto 68.7% for AAS3 as compared to AAS0 (control
test. specimen).
7
Su-Lei Zhang, Xiao-Qiang Qi, Si-Yao Guo et al. Construction and Building Materials 275 (2021) 122154

(a)
DD=9.41 mm AAS0
0.016
AAS3

Cumulative pore volume (mL/g)

AAS0
downward
0.012

DD=4.78 mm 5500-6000 nm
0.008

AAS1

0.004

DD=3.15 mm
0.000

AAS3
100 1000 10000 100000
Pore Diameter (nm)

DD=5.33 mm
(b)
AAS5 AAS0
0.0016
AAS3

Fig. 13. The split specimens showing the chloride penetration depths after RCM
Pore volume (mL/g)

test. 0.0012

0.0008
Chloride diffusion coefficient (10-12 m2/s)

2.046
2.0

0.0004

1.5
0.0000
1.136
1.048
1.0 100 1000 10000 100000
Pore Diameter (nm)
0.640
Fig. 15. Cumulative pore volumes (a) and pore size distributions (b) for AAS0 and
0.5 AAS3 specimens after 28 days of curing.

beneficial in reducing total volume of pores, which is especially

0.0
AAS0 AAS1 AAS3 AAS5 evident for meso-capillary pores (500–15000 nm) [44]. This can
be contributed to the fact that some of these pores were partially
Different AAS mortar samples
filled by the TiO2-graphene composite, leading to reduced pore vol-
Fig. 14. Chloride diffusion coefficient (DRCM) of different AAS mortar samples. umes. This phenomenon reveals that TiO2-graphene composite is
beneficial in densifying the AAS binding matrix, presumably lead-
ing to higher durability in harmful environments ladened with var-
3.6. MIP analysis ious aggressive agents. The reduced porosity and densified
microstructure induced by graphene-based nanoparticles were
The results of MIP analyses for pore structure characterisation also verified by other researchers [14,41,45].
of two AAS mortar samples, namely AAS0 and AAS3 are presented
in Fig. 15(a) and (b). Porous structures provide important informa-
4. Concluding remarks
tion with regards to the durability performances as they are closely
associated with ion transportation properties in cementitious bin-
In this study, 0.01, 0.03%, 0.05% (by mass) of the TiO2-graphene
ders [7,43]. According to Fig. 15(a), the cumulative pore volume
composite which was synthesized by using a novel intercalating
displayed a significant reduction evidenced by the downward
method was exploited in alkali activated slag mortar specimens.
moving of curves for AAS3 compared to AAS0, especially for the
The inserted TiO2 nanoparticles ensured a high dispersion and uni-
pores with sizes smaller than 5500–6000 nm. In addition, the pore
formity of graphene nanosheets in aqueous solutions. Mechanical
size distributions in Fig. 15(b) also show that the total pore volume
properties, durability-related performances as well as porous
of the pores ranging approximately between 800 and 2000 nm
microstructures of AAS mortar groups were investigated and com-
became much less for the AAS3 containing 0.03% TiO2-graphene
pared to the control AAS mortar without any TiO2-graphene addi-
composite. The result suggests that TiO2-graphene composite is
tion. Some conclusions can be drawn which are listed below:
8
Su-Lei Zhang, Xiao-Qiang Qi, Si-Yao Guo et al.
(1) The addition of TiO2-graphene composite led to increases in
the compressive, flexural strength and flexural-to-
compressive strength ratio of AAS mortars irrespective of
different dosages.
(2) Durability-related performance including capillary sorptiv-
ity and chloride penetration were all enhanced due to the
TiO2-graphene composite additions as evidenced by lower
capillary sorptivity coefficients, chloride penetration depth
and migration coefficients.
(3) TiO2-graphene composite facilitated the hydration process
of AAS mortar specimens and refined the microstructure of
AAS binding matrix verified by XRD and MIP analysis
respectively.
(4) An optimal dosage of TiO2-graphene composite exists for the
AAS mortars, which is 0.03% compared to the other two
dosages, namely 0.01% and 0.05%. A lower dosage might
not be enough whereas a higher dosage tends to limit dis-
persion of graphene nanoplatelet clusters.
(5) The AAS binder enhanced by the relatively simple in-situ
made and cheap TiO2-graphene nanoplatelets is considered
as an ideal candidate for structural materials because of
the improved mechanical and durability behaviours.
CRediT authorship contribution statement
Su-Lei Zhang: Conceptualization, Investigation, Funding acqui-
sition, Data curation, Writing - review & editing. Xiao-Qiang Qi:
Methodology, Formal analysis. Si-Yao Guo: Funding acquisition,
Supervision Writing - review & editing. Jie Ren: Experimental
investigation, Writing - original draft, Supervision. Ji-Chou Chen:
Writing - review & editing, Resources, Validation. Bo Chi: Writing
- review & editing, Resources, Validation. Xu-Chun Wang: Writing
- review & editing, Resources, Validation.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgements
This work was supported by the National Natural Science Foun-
dation of China (51978354), major program of Shandong province
(2019GGX102079). The China Ministry of Science and Technology
under Grant 2015CB655100, open fund of Key Laboratory of Large
Structure Health Monitoring and Control (KLLSHMC1906) and
Major International Joint Research Project under Grant
51420105015 are also gratefully acknowledged. Prof. Si-yao Guo
would like to acknowledge the fellowship support received from
the Tai Shan Scholar Programme.
References
[1] M. Abdulkareem, J. Havukainen, M. Horttanainen, How environmentally
sustainable are fibre reinforced alkali-activated concretes?, J Cleaner Prod.
236 (2019).
[2] Z. Jokar, A. Mokhtar, Policy making in the cement industry for CO2 mitigation
on the pathway of sustainable development- A system dynamics approach, J.
Cleaner Prod. 201 (2018) 142–155.
[3] S. Al-Otaibi, Durability of concrete incorporating GGBS activated by water-
glass, Constr. Build. Mater. 22 (10) (2008) 2059–2067.
[4] T. Bakharev, J.G. Sanjayan, Y.B. Cheng, Sulfate attack on alkali-activated slag
concrete, Cem. Concr. Res. 32 (2) (2002) 211–216.
[5] T. Bakharev, J.G. Sanjayan, Y.B. Cheng, Resistance of alkali-activated slag
concrete to acid attack, Cem. Concr. Res. 33 (10) (2003) 1607–1611.
[6] J. Ren, L. Zhang, R. San Nicolas, Degradation process of alkali-activated slag/fly
ash and Portland cement-based pastes exposed to phosphoric acid, Constr.
Build. Mater. 232 (2020) 117209.
9
Construction and Building Materials 275 (2021) 122154
[7] J. Ren, S. Guo, J. Su, T. Zhao, J. Chen, S. Zhang, A novel TiO2/Epoxy resin
composited geopolymer with great durability in wetting-drying and
phosphoric acid solution, J. Cleaner Prod. 227 (2019) 849–860.
[8] Y.W. Fu, L.C. Cai, Y.G. Wu, Freeze-thaw cycle test and damage mechanics
models of alkali-activated slag concrete, Constr. Build. Mater. 25 (7) (2011)
3144–3148.
[9] C. Ferone, G. Roviello, F. Colangelo, R. Cioffi, O. Tarallo, Novel hybrid organic-
geopolymer materials, Appl. Clay Sci. 73 (2013) 42–50.
[10] N. Ranjbar, M. Mehrali, M. Mehrali, U.J. Alengaram, M.Z. Jumaat, Graphene
nanoplatelet-fly ash based geopolymer composites, Cem. Concr. Res. 76 (2015)
222–231.
[11] S. Guo, X. Zhang, J. Ren, J. Chen, T. Zhao, T. Li, L. Zhang, Preparation of TiO2/
epoxy resin composite and its effect on mechanical and bonding properties of
OPC mortars, Constr. Build. Mater. 272 (2021) 121960.
[12] L. Yang, Z. Jia, Y. Zhang, J. Dai, Effects of nano-TiO2 on strength, shrinkage and
microstructure of alkali activated slag pastes, Cem. Concr. Compos. 57 (2015)
1–7.
[13] K. Gao, K.-L. Lin, D. Wang, C.-L. Hwang, B.L. Anh Tuan, H.-S. Shiu, T.-W. Cheng,
Effect of nano-SiO2 on the alkali-activated characteristics of metakaolin-based
geopolymers, Constr. Build. Mater. 48 (2013) 441–447.
[14] F. Matalkah, P. Soroushian, Graphene nanoplatelet for enhancement the
mechanical properties and durability characteristics of alkali activated binder,
Constr. Build. Mater. 249 (2020) 118773.
[15] M. Saafi, L. Tang, J. Fung, M. Rahman, J. Liggat, Enhanced properties of
graphene/fly ash geopolymeric composite cement, Cem. Concr. Res. 67 (2015)
292–299.
[16] S. Chuah, W. Li, S.J. Chen, J.G. Sanjayan, W.H. Duan, Investigation on dispersion
of graphene oxide in cement composite using different surfactant treatments,
Constr. Build. Mater. 161 (2018) 519–527.
[17] W. Li, X. Li, S.J. Chen, Y.M. Liu, W.H. Duan, S.P. Shah, Effects of graphene oxide
on early-age hydration and electrical resistivity of Portland cement paste,
Constr. Build. Mater. 136 (2017) 506–514.
[18] Z. Luo, W. Li, V.W.Y. Tam, J. Xiao, S.P. Shah, Current progress on
nanotechnology application in recycled aggregate concrete, Journal of
Sustainable Cement Based Materials (2018) 1–18.
[19] Yan Liu, Li Ming, Long Wengui, Duan Guangcheng, Hui Wen, Effects of
Nanoalumina and Graphene Oxide on Early-Age Hydration and Mechanical
Properties of Cement Paste, J. Mater. Civ. Eng. (2017).
[20] J.W. Jang, S. Cho, G.H. Moon, K. Ihm, J.Y. Kim, D.H. Youn, S. Lee, Y.H. Lee, W.
Choi, K.H. Lee, Photocatalytic Synthesis of Pure and Water-Dispersible
Graphene Monosheets, Chemistry–A European Journal 18 (10) (2012) 2762–
2767.
[21] Z. Yu, H. Di, M. Yu, H. Yi, L. Zhi, Preparation of graphene oxide modified by
titanium dioxide to enhance the anti-corrosion performance of epoxy coatings,
Surf. Coat. Technol. 276 (2015) 471–478.
[22] H. Liu, Y. Yu, H. Liu, J. Jin, S. Liu, Hybrid effects of nano-silica and graphene
oxide on mechanical properties and hydration products of oil well cement,
Constr. Build. Mater. 191 (2018) 311–319.
[23] M. Albitar, M.M. Ali, P. Visintin, M. Drechsler, Durability evaluation of
geopolymer and conventional concretes, Constr. Build. Mater. 136 (2017)
374–385.
[24] C. ASTM, 1585-04. Standard test method for measurement of rate of
absorption of water by hydraulic-cement concretes, ASTM International
(2004).
[25] R.W. Shiu, C.C. Yang, Evaluation of migration characteristics of OPC and slag
concrete from the rapid chloride migration test, Journal of Marine Science and
Technology-Taiwan 28 (2) (2020) 69–79.
[26] P.H. Gao, J.X. Wei, T.S. Zhang, J. Hu, Q.J. Yu, Modification of chloride diffusion
coefficient of concrete based on the electrical conductivity of pore solution,
Constr. Build. Mater. 145 (2017) 361–366.
[27] A. Noushini, A. Castel, J. Aldred, A. Rawal, Chloride diffusion resistance and
chloride binding capacity of fly ash-based geopolymer concrete, Cem. Concr.
Compos. 105 (2020).
[28] W.U. Li-Jun, D.H. Deng, Z. Zeng, T.P. Yuan, RCM testing the penetration and
diffusion of chloride ion in concrete, Concrete (2006).
[29] S. Bai, X. Shen, G. Zhu, A. Yuan, J. Zhang, Z. Ji, D. Qiu, The influence of wrinkling
in reduced graphene oxide on their adsorption and catalytic properties, Carbon
(2013).
[30] C. Pei, J.-H. Zhu, F. Xing, Photocatalytic property of cement mortars coated with
graphene/TiO2 nanocomposites synthesized via sol–gel assisted electrospray
method, J. Cleaner Prod. 279 (2021).
[31] S.A. Bernal, J.L. Provis, B. Walkley, R. San Nicolas, J.D. Gehman, D.G. Brice, A.R.
Kilcullen, P. Duxson, J.S.J. van Deventer, Gel nanostructure in alkali-activated
binders based on slag and fly ash, and effects of accelerated carbonation, Cem.
Concr. Res. 53 (2013) 127–144.
[32] S.A. Bernal, R. San Nicolas, J.L. Provis, R. Mejía de Gutiérrez, J.S.J. van Deventer,
Natural carbonation of aged alkali-activated slag concretes, Mater. Struct. 47
(4) (2014) 693–707.
[33] M.A. Rafiee, J. Rafiee, Z. Wang, H. Song, Z.Z. Yu, N. Koratkar, Enhanced
Mechanical Properties of Nanocomposites at Low Graphene Content, Acs Nano
3 (12) (2009) 3884.
[34] M.A. Rafiee, J. Rafiee, I. Srivastava, Z. Wang, H. Song, Z.Z. Yu, N. Koratkar, Fracture
and Fatigue in Graphene Nanocomposites, Small 6 (2) (2010) 179–183.
[35] C. Lu, Z. Lu, Z. Li, C.K.Y. Leung, Effect of graphene oxide on the mechanical
behavior of strain hardening cementitious composites, Constr. Build. Mater.
120 (2016) 457–464.
Su-Lei Zhang, Xiao-Qiang Qi, Si-Yao Guo et al.
[36] C. Lee, X. Wei, J.W. Kysar, J. Hone, Measurement of the elastic properties
and intrinsic strength of monolayer graphene, Science 321 (5887) (2008)
385–388.
[37] R.R. Bellum, K. Muniraj, C.S. Reddy Indukuri, S.R. Chand Madduri, Investigation
on Performance Enhancement of Fly ash-GGBFS Based Graphene Geopolymer
Concrete, Journal of Building Engineering (2020).
[38] C. Duran Atisß, C. Bilim, Ö. Çelik, O. Karahan, Influence of activator on the
strength and drying shrinkage of alkali-activated slag mortar, Constr. Build.
Mater. 23 (1) (2009) 548–555.
[39] S. Kahraman, R. Altindag, A brittleness index to estimate fracture toughness,
Int. J. Rock Mech. Min. Sci. 2 (41) (2004) 343–348.
[40] K.T. Gunsallus, F. Kulhawy, A comparative evaluation of rock strength
measures, International Journal of Rock Mechanics and Mining Sciences &
Geomechanics Abstracts, Elsevier (1984) 233–248.
10
Construction and Building Materials 275 (2021) 122154
[41] J. Ren, S. Guo, T. Zhao, J. Chen, R. San Nicolas, L. Zhang, Constructing a novel
nano-TiO2/Epoxy resin composite and its application in alkali-activated slag/
fly ash pastes, Constr. Build. Mater. 232 (2020) 117218.
[42] H. Du, H.J. Gao, S.D. Pang, Improvement in concrete resistance against water
and chloride ingress by adding graphene nanoplatelet, Cem. Concr. Res. 83
(2016) 114–123.
[43] J.L. Provis, R.J. Myers, C.E. White, V. Rose, J.S. van Deventer, X-ray
microtomography shows pore structure and tortuosity in alkali-activated
binders, Cem. Concr. Res. 42 (6) (2012) 855–864.
[44] H.-W. Reinhardt, M. Stegmaier, Cem. Concr. Res. 36 (5) (2006) 879–885.
[45] J. Tao, X. Wang, Z. Wang, Q. Zeng, Graphene nanoplatelets as an effective
additive to tune the microstructures and piezoresistive properties of cement-
based composites, Constr. Build. Mater. 209 (2019) 665–678.