Construction and Building Materials 179 (2018) 186–197

Contents lists available at ScienceDirect

Construction and Building Materials

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

Nano boron nitride modified reactive powder concrete

Wei Zhang a, Baoguo Han a,⇑, Xun Yu b,c, Yanfeng Ruan a, Jinping Ou a
a
School of Civil Engineering, Dalian University of Technology, Dalian 116024, China
b
Department of Mechanical Engineering, New York Institute of Technology, New York, NY 11568, USA
c
School of Mechanical Engineering, Wuhan University of Science and Technology, Wuhan 430081, China

h i g h l i g h t s

 Nano boron nitride (nano-BN) is used to reinforce reactive powder concrete (RPC).
 Effects of nano-BN size and content on strength and durability of RPC are studied.
 Properties of nano-BN reinforced RPC with water and heat curing are compared.
 Low dosage nano-BN can obviously improve strength, toughness and durability.
 Nano-BN reinforcing effects are due to its properties and RPC structure improvement.

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

Article history: This paper aims to investigate the effects of particle size and content of nano boron nitride (nano-BN) as
Received 24 March 2018 well as curing method on the strength and durability of reactive powder concrete (RPC). The enhancing
Received in revised form 6 May 2018 mechanisms are analyzed through performance, X-ray diffraction, nuclear magnetic resonance, thermo-
Accepted 27 May 2018
gravimetry and scanning electron microscope tests. The flexural strength and compressive strength of
RPC containing 0.5 wt% of 120 nm nano-BN achieve an increase of 2.65 MPa/15.7% and 11.61
MPa/12.96% at standard curing age of 28 d, respectively. Furthermore, heat curing for 2 d causes the
Keywords:
increasing compressive strength of 120 nm nano-BN filled RPC, compared to standard curing for 28 d.
Reactive powder concrete
Nano boron nitride
For the durability performance, the introduction of 0.5 wt% of 120 nm nano-BN enhances the resistance
Strength of RPC with standard curing and heat curing maximally by 55.56% and 34.96%, respectively. The chloride
Durability penetration resistance of RPC containing appropriate amount of 120 nm nano-BN is improved by 100%.
Mechanisms Experimental results show that the strengthening mechanisms of nano-BN on RPC performances are mul-
tifaceted, and can be attributed to small size, nucleation, filling, bridging, lubrication and layered blocking
effects.
Ó 2018 Elsevier Ltd. All rights reserved.

1. Introduction to traditional concrete. Therefore, RPC was selected as the matrix

Reactive powder concrete (RPC) is a high performance cementi-
tious material with high strength and outstanding durability. The
high properties of RPC are mainly attributed to its optimized par-
ticle size, lower porosity and improved microstructure [1,2]. The
combination of RPC and nano boron nitride (nano-BN) with excel-
lent properties is of great interests for developing a new type of
concrete with (ultra)high strength and durability. Moreover,
nano-sized boron nitride particles can fill the pores of RPC at
nanoscale, making the microstructure more compact. It is expected
that RPC has a better composition effect with nano-BN compared
⇑ Corresponding author.
E-mail address: hanbaoguo@dlut.edu.cn (B. Han).
of nano-BN reinforced cementitious composites.
As an emerging nanomaterial, nano-BN has been widely studied
and applied in recent years. Similar to the structure of graphene
[3], nano-BN is a two-dimensional crystal material with a layered
structure. Due to its high mechanical strength [4–6,8–11], high
thermal conductivity [4,7], high resistivity [12], excellent heat
resistance [13], lubricity [5], corrosion resistance [14], low friction
coefficient and low expansion coefficient [13,15], nano-BN has
greater potential in the fields of machining, electronics, aerospace
as well as reinforced composites. However, the reinforcing effect of
nano-BN on cementitious composites has less been researched. In
2013, Rafiee et al. studied the cementitious composites incorporat-
ing nano-BN and nano graphite oxide (nano-GO). Experimental
results indicated that concrete containing 1 wt% nano-BN reached
an enhancement of 64% in compressive strength and 200% in

https://doi.org/10.1016/j.conbuildmat.2018.05.244
0950-0618/Ó 2018 Elsevier Ltd. All rights reserved.
 W. Zhang et al. / Construction and Building Materials 179 (2018) 186–197
toughness. Also, the compressive strength and toughness of nano-
BN filled cement were increased by 89% and 85% compared to pure
cement, respectively [16]. In 2015, He reported that the introduc-
tion of 1 wt% of 5 mm nano-BN and 1 wt% of 0.5 mm nano-BN
improved the compressive strength of concrete by 4.27 MPa/8.6%
and 6.59 MPa/13.26%, respectively. Moreover, concrete with 1 wt
% of 5 mm nano-BN obtained a higher compressive strength when
soaked in a 20 wt% of NaCl solution, compared to concrete without
nano-BN [17]. In 2018, Wang et al. studied the exfoliation and dis-
persion of nano-BN and its enhancing effect on strength of cement
paste. They reported that cement paste with 0.003 wt% nano-BN
gained a rise of 13% and 8% in compressive and tensile strength
at 7 d, respectively [18]. To sum up, fewer researches about the
application of nano-BN in civil engineering were conducted, and
the research of nano-BN filled cementitious composite principally
focused on the strength. A comprehensive study on the mechanical
properties, durability and reinforcing mechanisms of nano-BN
cementitious composite is necessary.
This paper aims to fabricate a new type of concrete with (ultra)
high strength and durability by combining nano-BN and RPC. The
influences of 1 wt%, 3 wt% and 5 wt% nano-BN on the flexural
strength and compressive strength of RPC were researched.
Nano-BN with particle sizes of 120 nm, 500 nm and 1 lm were
used. Then 120 nm nano-BN with better modifying effect was
selected as a filler to further study its effect on mechanical
strength, abrasion resistance and chloride permeability of RPC.
Moreover, the effects of standard curing and heat curing methods
on RPC composites were compared. Finally, the enhancing mecha-
nisms of nano-BN on RPC were analyzed by thermogravimetry
(TG), X-ray diffraction (XRD), 29Si nuclear magnetic resonance
(NMR) and scanning electron microscope (SEM) tests.
2. Materials and experimental method
2.1. Materials
The nano-BN with a thickness of 5–10 nm is produced by
Shanghai Xiang Tian Nano Materials Co., Ltd. in China. The proper-
ties of nano-BN are shown in Table 1, and their morphologies
under transmission electron microscope (TEM) are shown in
Fig. 1. It should be noted that TEM observation only gives the
image in a local area. Actually, the average particle sizes are 120
nm, 500 nm and 1 lm for three types of nano-BN, respectively.
As listed in Table 1, the contact angles between nano-BN parti-
cles and water are all less than 90°, indicating that nano-BN is
hydrophilic [19]. This ensures the solubility of nano-BN in water.
Moreover, the wettability of nano-BN is enhanced with the
increase of its particle size. The zeta potential, also known as elec-
tric potential, is an important indicator of the stability of colloidal
dispersion. The smaller the dispersed particles, the higher the zeta
potential (positive or negative), i.e., the more stable the dispersion
system. Conversely, the lower the zeta potential (positive or nega-
tive), the easier to condense or agglomerate for nano-BN [20]. It is
confirmed that when zeta potential is between 0 and ±5mV, the
colloid in solvent is unstable and tends to coagulate and agglomer-
ate. Obviously, the zeta potentials of nano-BN particles listed in
Table 1
Properties of nano-BN.
Average particle Specific surface area Bulk density Density
size (m2/g) (g/cm3) (m3)
120 nm 19 0.30 2.30
500 nm 9.16 0.45 2.30
1 lm 9 1.6 2.30
187
Table 1 manifest that nano-BN can easily agglomerate in water.
The water adsorption and desorption isotherms of nano-BN along
with pressure under room temperature are diagramed in Fig. 2.
With the increase of particle size, the surface area of nano-BN
reduces, resulting in the decline of adsorption capacity per gram
of nano-BN. This means that the workability of nano-BN filled
RPC does not reduce with the rise of nano particle size.
The Portland cement (P∙O 42.5R) provided by Dalian Onoda
Cement Co. Ltd. in China was used as a binder. The mineral admix-
tures include fly ash produced by Dalian Daokete Building Materi-
als Co. Ltd. in China, and silica fume produced by Elkem Materials
Ltd. in Shanghai, China. The properties of silica fume and fly ash are
listed in Tables 2 and 3. The particle size of quartz sand is 0.12–
0.83 mm and its SiO2 content is >99%. RHEOPLUS411 (BASF411),
a polycarboxylate superplasticizer (SP), was used to adjust the
workability of concrete. Its solid concentration was 45%.
2.2. Preparation
Nano-BN with average particle sizes of 120 nm, 500 nm and 1
lm were used. The dosages of nano-BN for each size are designed
as 1 wt%, 3 wt% and 5 wt% of cement weight. The water to cement
ratio of RPC was fixed at 0.38 for all mixtures. The dosage of SP was
adjusted according to the workability of concrete and represented
as a percentage of cement weight. The mix proportion of RPC con-
taining nano-BN with different particle sizes is listed in Table 3.
Besides, the mix ratio of raw materials for RPC used in this exper-
iment was referenced to that proposed by Richard [21]. Specimens
were numbered according to the rule of ‘Nano particle size -
Dosage’. For example, ‘120-1’ represents RPC blending 1 wt% of
120 nm nano-BN.
The above experimental results indicated the addition of 120
nm nano-BN at lower content had better reinforcing effects on
the strength of RPC. Therefore, 120 nm nano-BN was adopted in
the following experiments. The ratios of 120 nm nano-BN were
adjusted to 0.5 wt%, 1 wt% and 1.5 wt% of cement weight, and
the dosage of SP is fixed at 0.8% of cement weight. Besides, the pro-
portion of other materials was the same with Table 4. Samples
were numbered following the method of ‘BN + dosage’. For
instance, ‘BN05’ represents RPC with 5 wt% of 120 nm nano-BN.
The specimen sizes for strength test is 40 mm  40 mm160
mm, for abrasion resistance test is 150 mm  150 mm150 mm
and for rapid chloride migration (RCM) test is U100mmh50mm.
The process of fabricating nano-BN filled RPC is as follows: (1)
Water, nano-BN and water reducer were mixed in a mixing pot
and stirred for 20 s at low speed. (2) Then silica fume was added
and stirred for 60 s at low speed. (3) Cement and fly ash were
put into the mixing pot and stirred at low speed for 2 min firstly
and then at high speed for 2 min. (4) Finally, quartz sand was
added and stirred at low speed for 1 min and then at high speed
for 4 min. Nano-BN with sheet-like structure exhibits lubricated
effect during mechanical stirring. As a result, the inclusion of
nano-BN has no obvious effect on the workability unlike other
nano fillers (e.g., carbon nanotubes, nano-SiO2, nano-TiO2 or
nano-ZrO2) [22–27]. The mixture was poured into the oiled mold
in two layers and each layer was compacted. Then the mold was
vibrated in the table vibrator for 60 s to eliminate bubbles. All
Pure Crystal Contact angle Zeta potential Adsorption capacity
(%) form (°) (mV) (mg/g)
99.9 Hexagon 40.7 4.89 58.1
99.9 Hexagon 37.9 4.58 47.3
99.9 Hexagon 30.3 6.3 43.3
188 W. Zhang et al. / Construction and Building Materials 179 (2018) 186–197

200 nm 0.5 µm
(a) (b)

1 µm
(c)
Fig. 1. TEM image of nano-BN: (a) 120 nm; (b) 500 nm; (c) 1 lm.

60 compressive strength were tested by universal electronic testing

machine (WDW-200E, Jinan Times Shi Jin Test Machine Co., Ltd)
50 according to GB/T17671-1999 of China. The loading rate for flexu-
Adsorption capacity (mg/g)

ral test was 0.05 mm/min and 1.2 mm/min for compressive test.
40 The abrasion resistance was tested according to JTG E30-2005
highway engineering cement and concrete test procedures of
30 120nm adsorption China. RCM test at the absolute voltage of 60 V was adopted to
120nm desorption measure chloride permeability. After curing for 3 d and 28 d, the
20 500nm adsorption cement pastes were dried, crushed and milled below 80 lm for
500nm desorption XRD, NMR and TG tests. Moreover, the milled powder at curing
10 1 m adsorption age of 3 d was soaked in alcohol to stop hydration. The scanning
1 m desorption angle for XRD test was 5–80°. For NMR test, the rotational speed
0 was 8000r/s, the relaxation delay was 4 s and the resonance fre-
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
quency of 29Si was 79 MHz. The condition of TG analysis was under
Balanced partical pressure (P/P0) nitrogen atmosphere at a heating rate of 10 °C/min up to 1000 °C.
SEM analysis was performed after flexural and compressive
Fig. 2. Water adsorption and desorption isotherms of nano-BN along with pressure
strength test at curing age of 28 d.
under room temperature.

concretes were cured in standard curing box with relative humid-
ity of 95% for 24 h. Then the specimens were demolded and cured
in standard curing room for 2 d and 27 d, while the heat curing
specimens were cured in water at 90 °C for 48 h. The preparations
of cement paste and control RPC were the same as above.
2.3. Measurement
The measured properties of samples include flexural strength,
compressive strength, abrasion resistance, chloride penetration
resistance, and microstructure analyses. The flexural strength and
3. Results and discussion
3.1. Strength of RPC with nano-BN
3.1.1. Effect of nano-BN particle size on strength
3.1.1.1. Flexural strength. The flexural strength of RPC containing
nano-BN with particle sizes of 120 nm, 500 nm and 1 lm at 3 d
and 28 d of curing ages is shown in Fig. 3. The RPC with 1 wt% of
1 lm nano-BN reaches the highest flexural strength at 3 d of curing
age, which is 2.45 MPa/31.09% over that of control RPC. Besides,
the enhancing effect of 120 nm nano-BN on flexural strength of
RPC is weaker than that of 500 nm and 1 lm at 3 d of curing age.

Table 2
Properties of silica fume.

Average particle size (nm) Specific surface area (m2/g) Bulk density (kg/m3) Density (g/cm3) Color
150 8.78 46.62 8.99 Gray
 W. Zhang et al. / Construction and Building Materials 179 (2018) 186–197 189

Table 3
Properties of fly ash.

Fineness (0.045 mm square hole sieve residue, %) water demand ratio (%) Ignition loss (%) Water content (%) Sulfur dioxide (%)
20 105 8 1 3

Table 4
Mix proportion of RPC containing nano-BN with different particle sizes.

Sample code Mix proportion

Cement Fly ash Silica fume Sand Water SP Nano-BN
(wt%) (wt%)
Control 1 0.25 0.31 1.38 0.38 1.1 0
120-1 1 0.25 0.31 1.38 0.38 2.5 1
120-3 1 0.25 0.31 1.38 0.38 2.7 3
120-5 1 0.25 0.31 1.38 0.38 2.8 5
500-1 1 0.25 0.31 1.38 0.38 2.6 1
500-3 1 0.25 0.31 1.38 0.38 2.7 3
500-5 1 0.25 0.31 1.38 0.38 2.8 5
1000-1 1 0.25 0.31 1.38 0.38 2.5 1
1000-3 1 0.25 0.31 1.38 0.38 2.6 3
1000-5 1 0.25 0.31 1.38 0.38 2.6 5

18 3.1.1.2. Compressive strength. Fig. 4 shows the compressive

3d
14.09 strength of RPC containing nano-BN with particle sizes of 120
15 13.41 12.59 12.95 28d
Flexural strength (MPa)

12.9 11.78 13.13 nm, 500 nm and 1 lm at curing ages of 3 d and 28 d. As it shows,
10.98 10.73
12 9.59 9.48 10.33 10.13 the addition of nano-BN reduces the compressive strength of RPC
9.02 8.59 8.75 9.26
7.88 8.07
7.95 by 14.54%  35.62% at 3 d of curing age. With the increase of
9
nano-BN content, the compressive strength of RPC composite
6 decreases gradually. After 28 d of curing age, only the compressive
strength of RPC with 1 wt% of 120 nm nano-BN is higher than that
3
of control RPC.
0 In summary, the addition of nano-BN improves the flexural
Control 120-1 120-3 120-5 500-1 500-3 500-5 1000-11000-31000-5 strength of RPC but decreases its compressive strength at 3 d of
Sample code
curing age. This is because the nano-BN can improve the toughness
Fig. 3. Flexural strength of RPC containing nano-BN with different particle sizes at 3 of the RPC significantly (as shown in Fig. 19). However, the flexural
d and 28 d of curing ages. strength and compressive strength are significantly enhanced at 28
d of curing age. This may be due to that excess nano-BN inhibits
the internal hydration reaction of cement. Therefore, the content
After 28 d of curing, the strengthening effect of nano-BN with dif-
of nano-BN should be modified to a lower value in subsequent
ferent particle sizes decreases in the order of 120 nm > 500 nm > 1
experiments. The results also show that the enhancing effect of
lm. Whereas, only the incorporation of 1 wt% of 120 nm nano-BN
120 nm nano-BN on compressive strength of RPC is stronger than
leads to the increase in the flexural strength of RPC at 28 d of cur-
other two types of nano-BN.
ing age, which is 0.68 MPa/5.07% higher than that of control RPC.
The incorporation of nano-BN with three particle sizes all
improve the flexural strength of RPC at 3 d of curing age, but 3.1.2. Effect of 120 nm nano-BN content on strength
reduce the flexural strength at 28 d of curing age. The greater the 3.1.2.1. Flexural strength. Based on the above experimental results,
particle size of nano-BN, the lower the flexural strength at 28 d 120 nm nano-BN has better modifying effect. To find the optimal
of curing age. Therefore, 120 nm nano-BN is a more effective filler doping level, content level of 0.5 wt%, 1 wt% and 1.5 wt% are
for modifying RPC. In addition, high nano-BN contents of 3% and 5% further tested. The flexural strength of RPC with 120 nm nano-BN
are not conducive to flexural strength growth of RPC composites. is illustrated in Fig. 5. It manifests that the flexural strength of

3d
19.5
120 20 28d 18.06
3d 17.53
Compressive strength (MPa)

Flexural strength (MPa)

16.85
100 89.43 28d
79.33 16
69.73 75.29 65.67 69.6 74.02 71.74
80 64.4 67.43 12
8.21
60 54.18 43.32 46.3 7.68 7.76 6.84
38.03 37.49 41.54 44.19 44.01 45.3 8
34.88
40
4
20

0 ControlBN05 BN10 BN15ControlBN05 BN10 BN15

Control 120-1 120-3 120-5 500-1 500-3 500-5 1000-11000-31000-5
Sample code Sample code

Fig. 4. Compressive strength of RPC containing nano-BN with different particle Fig. 5. Flexural strength of RPC containing 120 nm nano-BN with different filler
sizes at 3 d and 28 d of curing ages. contents.
190
120 nm nano-BN filled RPC first increases and then decreases at 3 d
of curing age. RPC with 0.5 wt% of 120 nm nano-BN obtains the
maximum of 8.21 MPa, which is 0.53 MPa/6.9% higher than that
of control RPC. The flexural strength of RPC with 1 wt% and
1.5 wt% of 120 nm nano-BN are enhanced by 1.04% and reduced
by 10.9% at curing age of 3 d, respectively. When cured to 28 d,
RPC with nano-BN all showed a higher flexural strength than that
without nano-BN. With the increase of nano-BN content, the
flexural strength declines. The flexural strength of RPC containing
0.5 wt%, 1 wt% and 1.5 wt% of 120 nm nano-BN are improved by
2.65 MPa/15.73%, 1.21 MPa/7.18% and 0.68 MPa/4.04% at curing
age of 28 d, respectively. Compared with the previous experimen-
tal results, the reinforcing effect of nano-BN on strength of RPC
significantly improves after adjusting the content of nano-BN and
SP. This verifies the preceding conjecture that large amount of
nano-BN and SP lead to poor strength improvement.
3.1.2.2. Compressive strength. The compressive strength of 120 nm
nano-BN filled RPC at curing ages of 3 d and 28 d is shown in
Fig. 6. The compressive strength of RPC with 0.5 wt%, 1 wt% 1.5
wt% of 120 nm nano-BN at 3 d of curing age are 1.02%, 3.99% and
4.66% lower than that without nano-BN, respectively. This illus-
trates that the addition of nano-BN has little impact on the early
strength. The compressive strength of 120 nm nano-BN modified
RPC at curing age of 28 d first increases and then decreases. The
enhancements of compressive strength are 11.61 MPa/12.96%
and 1.88 MPa/2.1% when 0.5 wt%, 1 wt% and 1.5 wt% of 120 nm
nano-BN are introduced into RPC, respectively. While, the com-
pressive strength of RPC containing 1.5 wt% of 120 nm nano-BN
is decreased by 5.83 MPa/6.51% compared to that of control RPC.
Flexural and compressive strength tests both indicate that the opti-
mum content of 120 nm nano-BN is 0.5 wt%.
In this study, the maximum absolute increase of compressive
strength of RPC with 120 nm nano-BN reaches 11.61 MPa, which
far exceeds the absolute increase in researches of references
[16,17] although the maximum relative growth of 12.96% is not
the highest. Moreover, the maximum relative enhancement of
compressive strength of nano-BN filled RPC in this experiment is
higher than the relative increase of 8% reported by Wang et al. [18].
3.1.3. Effect of curing method on strength
3.1.3.1. Flexural strength. Fig. 7 shows the increase of flexural
strength of 120 nm nano-BN modified RPC with heat curing for
48 h relative to the flexural strength of 120 nm nano-BN filled
RPC with standard curing for 28 d. The effect of heat curing in
water at 90 °C for 48 h is similar to the effect of standard curing
for 28 d. For control RPC and RPC with 0.5 wt% of 120 nm nano-
BN, the standard curing method endows them with a slightly
higher flexural strength compared to heat curing method, but the
120
3d
28d 89.55
100
Compressive strength (MPa)
80
65.64 64.97 63.02 62.58
60
40
20
0 0
ControlBN05 BN10 BN15ControlBN05 BN10 BN15
Sample code
Fig. 6. Compressive strength of RPC containing 120 nm nano-BN with different
filler contents.
W. Zhang et al. / Construction and Building Materials 179 (2018) 186–197
Increase of flexural strength (%)
12 10.09
8 5.52
4
-1.16
0 -1.97
Control BN05 BN10 BN15
Sample code
Fig. 7. Increase of the flexural strength of RPC containing 120 nm nano-BN with
heat curing, compared to normal curing.
increase of flexural strength is not over than 2%. When nano-BN
content exceeds 1 wt%, the flexural strength of heat curing speci-
mens is higher than that of the standard curing specimens. The
increase reaches the maximum value of 10.9% when the 120 nm
nano-BN ratio raises to 1.5 wt%. In addition, the improving effect
of 120 nm nano-BN on the flexural strength of heat curing RPC sur-
passes that on the flexural strength of standard curing RPC.
To sum up, both curing methods lead to an enhancement in
flexural strength of RPC with nano-BN relative to that without
nano-BN. When the dosage of 120 nm nano-BN exceeds 1 wt%,
the flexural strength of heat curing RPC composites continue to
increase, being higher than that of the standard cured RPC
composites.
3.1.3.2. Compressive strength. The increase of compressive strength
of heat curing RPC with 120 nm nano-BN relative to the compres-
sive strength of standard curing nano-BN filled RPC at curing age of
28 d is diagramed in Fig. 8. The compressive strength of all samples
under heat curing condition is significantly higher than that under
standard curing conditions. The increase of compressive strength
ranges between 8.34  22.69%, and is maximally 22.69% as 1.5 wt
% of 120 nm nano-BN is added into RPC. Moreover, the strengthen-
ing impact of 120 nm nano-BN on compressive strength of stan-
dard curing RPC is stronger than that of heat curing RPC only
when 0.5 wt% of 120 nm nano-BN is incorporated into RPC.
Because of the high content of reactive powder in RPC, volcanic
ash reaction in heat curing RPC is promoted to form a denser struc-
ture. This helps to achieve a higher compressive strength of the
specimen in a short period of time and allows more nano-BN to
Increase of compressive strength (%)
24 22.69
101.16
91.43
83.72 18 13.91
12.23
12 8.34
6
Control BN05 BN10 BN15
Sample code
Fig. 8. Increase of compressive strength of RPC containing 120 nm nano-BN with
heat curing, compared to normal curing.
 W. Zhang et al. / Construction and Building Materials 179 (2018) 186–197
play the role of improving flexural strength. However, because the
effect of high-temperature curing offset the filling effect of part of
nano-BN, the enhancement effect of 0.5 wt% nano-BN on the com-
pressive strength of heat curing RPC is weaker than that of stan-
dard curing RPC.
3.2. Durability of RPC with 120 nm nano-BN under different curing
methods
3.2.1. Abrasion resistance
The abrasion loss per unit area of RPC with 120 nm nano-BN at
standard curing age of 28 d and at heat curing age of 2 d is shown
in Fig. 9. The abrasion resistance of standard curing RPC first
increases and then declines with the increase of nano-BN content.
RPC with 0.5 wt% of 120 nm nano-BN obtains the minimum abra-
sion loss of 0.28 kg/m2, which is 0.35 kg/m2/55.56% lower than that
of control RPC. As the content of nano-BN increases to 1.5 wt%, the
abrasion loss of RPC composite gradually enhances to 0.43 kg/m2,
but is still 0.20 kg/m2/32.32% lower than that of control sample.
For 120 nm nano-BN modified RPC with heat curing for 2 d, the
abrasion resistance shows the same trend as nano-BN ratio
increases. The incorporation of 0.5 wt% nano-BN leads to a decline
of 0.17 kg/m2/34.96% in abrasion loss per unit area, resulting in the
lowest value of 0.32 kg/m2. In addition, the abrasion loss of RPC
with 1 wt% of 120 nm nano-BN is decreased by 14.63%, and that
of RPC containing 1.5 wt% of 120 nm nano-BN is increased by
5.69%. As shown in Fig. 9, higher nano-BN dosage leads to a greater
error bar. On one hand, the workability of RPC composite reduces
with the increase of nano-BN dosage gradually because of the fixed
amount of SP. On the other hand, nano-BN easily reunites, forming
defects inside composites. Therefore, the abrasion resistance
shows a gradual deterioration trend with the rise of nano-BN
content.
In summary, the abrasion resistance of RPC with 120 nm nano-
BN under standard curing condition surpasses that under heat cur-
ing condition. The optimum content of 120 nm nano-BN is 0.5 wt%
for RPC composites with both curing methods. When the dosage of
120 nm nano-BN increases to 1.5%, the difference in abrasion loss
of RPC composite with two curing methods reaches the largest
value of 0.09 kg/m2.
3.2.2. Chloride penetration resistance
The chloride transport coefficients of RPC with 120 nm nano-BN
at standard curing age of 28 d and at heat curing age of 2 d are
summarized in Fig. 10. With the increase of nano-BN content, the
chloride transport coefficient of 120 nm nano-BN filled RPC under
standard curing condition is reduced, which means that the chlo-
ride penetration resistance is enhanced. The chloride transport
0.8
0.63
Abrasion loss (kg/m2)
0.6 0.49
0.4
0.4 0.32
0.28
0.2
0.0
Control BN05 BN10
Sample code
Fig. 9. Abrasion loss per unit area of RPC with 120 nm nano-BN with different
curing methods.
191
Chloride transport coefficient (×10-14m2/s)
28d
2.0 1.9
H
1.5
1.5
1.2
1.0 0.8 0.8 0.8
0.5
0.02 0.02
0.0
0.0 0.5 1.0 1.5
BN contents (%)
Fig. 10. Chloride transport coefficient of RPC with 120 nm nano-BN with different
curing methods.
coefficients of RPC with 0.5 wt%, 1 wt% and 1.5 wt% of 120 nm
nano-BN are 1.2  10 14 m2/s, 0.8  10 14 m2/s and 0.02  10 14
m2/s, respectively. The reduction of chloride transport coefficient,
i.e., the improvement of chloride penetration resistance is 20%,
46.67% and 100% accordingly.
The chloride penetration resistance of heat curing RPC with 120
nm nano-BN first increases and then decreases with the rise of
nano-BN content, but is still superior to that of control RPC. When
0.5 wt% of 120 nm nano-BN is incorporated, the chloride transport
coefficient of RPC is reduced by (0.8  10 14 m2/s)/57.89%. The
same decline of the chloride transport coefficient is obtained in
RPC with 1.5 wt% of 120 nm nano-BN. The optimal chloride pene-
tration resistance is obtained in RPC with 1 wt% of 120 nm nano-
BN, which is increased by 100%.
Compared to 120 nm nano-BN filled RPC with standard curing
age of 28 d, RPC incorporating 0.5 wt% and 1 wt% of 120 nm
nano-BN with heat curing age of 2 d attains a higher chloride pen-
etration resistance. When 1.5 wt% of 120 nm nano-BN is intro-
duced into RPC, the chloride penetration resistance of heat curing
RPC composite is reduced, while that of standard curing RPC is
enhanced by 100%. This is because high amount of nano-BN can
reunite and form defects, which decreases the crack resistance.
Consequently, micro cracks connect defects in series, leading to
the decline of chloride penetration resistance. On the contrary,
only relatively isolated defects exist in nano-BN modified RPC with
standard curing, which have little effect on chloride penetration
resistance.
3.3. Modifying mechanisms of nano-BN to RPC
3.3.1. Microscopic analysis
28d
3.3.1.1. XRD analysis. Figs. 11 and 12 show the XRD pattern of 120
H
nm nano-BN filled RPC and control RPC at standard curing ages of 3
0.52 d and 28 d, respectively. It can be seen from diffraction peaks that
0.42 0.43
hydration products contain ettringite, Ca(OH)2 (i.e. CH), CaCO3,
SiO2 and tricalcium silicate (C3S) crystals. Compared to control
RPC, no new diffraction peaks are observed, indicating that no
new hydration products form [28]. This shows that nano-BN does
not participate in the cement hydration reaction, neither acceler-
ates the cement hydration through chemical reaction.
Fig. 11 shows that the CH peaks of specimens at 3 d of curing
age are much low. In addition, the CH peaks of RPC with 0.5 wt%
BN15
and 1 wt% nano-BN are slightly lower than that of control sample
and RPC with 1.5 wt% nano-BN. This indicates that the volcanic
ash reaction which is caused by the reactive admixture in
RPC matrix and CH crystals consumes CH produced by cement
192 W. Zhang et al. / Construction and Building Materials 179 (2018) 186–197

A - AFt B - CH C - CaCO3 D - SiO2 E - C3S All of these contribute to the improvement of the microstructure
C/E and strength of hardened cement paste.
D
A E
BD B CE B C BN15 3.3.1.2. 29Si NMR spectral analysis. NMR spectroscopy is an impor-
tant method of material structure analysis. The structural informa-
BN10 tion of materials can be acquired by analyzing the characteristic
parameters of NMR spectroscopy such as chemical shift, relaxation
time. The chemical shifts of 29Si in the NMR spectrum generally
BN05 correspond to the different environments in which 29Si is located.
The chemical environment of 29Si is represented by Qn, where n
is the amount of bridging oxygen atoms that connect other Si
Control atoms with every siloxane tetrahedron [29,30].
The 29Si NMR spectra of control sample and RPC with 0.5 wt% of
120 nm nano-BN is shown in Fig. 13.
8 16 24 32 40 48 56 Through peak fitting and the calculation of cumulative intensity
E1 of peaks, the data of Q0  Q4, nc, MCL and b can be obtained, which
respectively represents chemical environment of 29Si, the polymer-
Fig. 11. XRD patterns of control sample and RPC containing 120 nm nano-BN at 3 d ization degree of [SiO4]4 in C-S-H gels, the average molecular
of curing age. chain length of C-S-H gels and the degree of cement hydration
are listed in Table 6. The results indicate that the polymerization
degree of [SiO4]4 in C-S-H gels and the average molecular chain
A - AFt B - CH C - CaCO3 D - SiO2 E - C3S length of C-S-H gel slightly increase in RPC with 0.5 wt% of 120
0
C/E nm nano-BN, but the cement hydration degree reduces by 3% com-
D
A EB BN15 pared with that of control RPC at curing age of 28 d. According to
AB D CE BC the regularity of NMR spectrum data, the polymerization degree
of [SiO4]4 in C-S-H gels and the molecular chain length of C-S-H
0

(001) (101) BN10 gel are positively correlated. The improved polymerization degree
of [SiO4]4 in C-S-H gels is mainly on account of active admixtures
0

in RPC matrix such as silica fume and fly ash. The results of cement
BN05 hydration degree in Table 6 reflect that the amount of C-S-H gel in
RPC containing 0.5 wt% of 120 nm nano-BN does not increase. In
0

conclusion, the results of 29Si NMR spectral analysis manifest no

Control significant changes in the structure and amount of C-S-H gel.
0

3.3.1.3. TG analysis. Figs. 14 and 15 is the TG and DTG diagrams of

8 16 24 32 40 48 56
2θ (°)
Fig. 12. XRD patterns of control sample and RPC containing 120 nm nano-BN at 28
d of curing age.
hydration. Moreover, the lower CH peak means the lower CH
crystallinity, manifesting that the CH crystal is refined.
The influence of nano-BN on CH orientation in specimens can be
confirmed by the CH diffraction peaks in different crystallographic
directions in the XRD pattern, as shown in Fig. 12. The orientations
of the CH crystal include (0 0 1), (1 0 0) and (1 0 1). The CH orien-
tation index can be obtained by comparing peak intensities of CH
crystal planes in different crystal orientations. The calculated val-
ues of CH crystal orientation of RPC with 120 nm nano-BN at cur-
ing age of 28 d are listed in Table 5. It shows the intensity of (1 0 1)
peak of nano-BN engineered RPC is lower than that of plain RPC.
RPC incorporating 120 nm nano-BN at standard curing ages of 3 d
and 28 d, respectively. The TG and DTG diagram represent the
weight loss and loss rate for sample powder heated from 50 °C to
1000 °C, respectively. It can be seen from Fig. 14 (a) that large
weight loss rates of samples occur at 105 °C, 430 °C, 640 °C, 720
°C and 850 °C. It can be concluded from weight loss peaks in
Fig. 14 (b) that the first peak at 105 °C results from the evaporation
of free water, the second peak at 430 °C results from the decompo-
sition and dehydration of calcium hydroxide, and the peak after
720 °C is caused by the decomposition of calcium carbonate.
The weight loss rates of specimens in range of 50–350 °C at
standard curing ages of 3 d and 28 d are summarized in Table 7.
The weight loss rates of RPC introducing 0.5 wt% and 1 wt% of
120 nm nano-BN are relatively 1.29% and 1.48% higher than that
of control RPC at 3 d of curing age, respectively. This shows that
150000

Also, the CH crystal orientation of RPC with 0.5 wt% of 120 nm Control
nano-BN is below that of control RPC. These manifest that the BN05
2
incorporation of 0.5 wt% nano-BN effectively restrains the growth
100000

Q
of CH crystal, refines CH crystal and reduces CH crystal orientation. Q
1
0
50000
Q
4
Q
3
Q
Table 5
Diffraction intensity and orientation of CH at 28 d of curing age. 0

Sample code (0 0 1) CH (1 0 1) CH CH orientation

Control 226 245 1.245 -40 -60 -80 -100 -120 -140
BN05 223 243 1.238
PPM
BN10 233 240 1.311
BN15 232 241 1.299 29
Fig. 13. Si NMR spectra of control sample and BN05 at 28 d of curing age.
 W. Zhang et al. / Construction and Building Materials 179 (2018) 186–197 193

Table 6
29
Si NMR analysis of control sample and BN05 at 28 d of curing age.

Sample code Qn Percentage of integral intensity (%) nc MCL b

0 1 2 3 4
Q Q Q Q Q
Control 12.09 24.22 41.54 7.23 14.92 1.72 5.43 0.84
BN05 14.13 21.35 38.07 0 26.44 1.78 5.57 0.81

100 100
Control 3d Conctrol 28d
BN05 3d BN05 28d
H2O

Weight loss (%)

95 BN10 3d BN10 28d
95
Weight loss (%)

BN15 3d
BN15 28d
Ca(OH)2
90 90
CaCO3
85
85

0 200 400 600 800 1000

0 200 400 600 800 1000
Temperature (°C)
Temperature (°C)
(a) TG diagram
(a) TG diagram
0.0000
0.0000
Weight loss rate (%)

105°C

Weight loss rate (%)

-0.0004 -0.0004 105°C
430°C 430°C
-0.0008
-0.0008
Control 3d
-0.0012
Control 28d
-0.0012 BN05 3d BN05 28d
-0.0016
BN10 3d BN10 28d
BN15 3d -0.0020 BN15 28d
-0.0016
0 200 400 600 800 1000
0 200 400 600 800 1000
Temperature (°C)
Temperatutre (°C)
(b) DTG diagram
(b) DTG diagram
Fig. 14. TG diagram (a) and DTG diagram (b) for control sample, BN05, BN10 and
BN15 at 3 d of curing age. Fig. 15. TG diagram (a) and DTG diagram (b) for control sample, BN05, BN10 and
BN15 at 28 d of curing age.

appropriate content of nano-BN can significantly accelerate the It is noteworthy that the values of cement hydration degree at
early hydration progress of RPC, and the acceleration effect is most curing age of 28 d calculated by TG analysis are not consistent with
evident when 1 wt% of 120 nm nano-BN is incorporated. Whereas, the values obtained by NMR analysis. This is due to their different
the weight loss rate of RPC containing 1.5 wt% of 120 nm nano-BN calculation methods. In TG analysis, the overall hydration degree of
is relatively 0.95% lower than that of control RPC at curing age of 3 cement, silica fume and fly ash is calculated, but the hydration of
d, meaning the cement hydration of RPC is inhibited. In addition, active admixture is not considered in the calculation of NMR spec-
the weight loss rate at curing age of 28 d manifests that the trum. However, the two methods basically reach the same conclu-
amount of C-S-H produced in RPC with nano-BN is greater than sion that cement hydration degree does not be enhanced at 28 d of
that without nano-BN. curing age.
According to the mixing ratio of samples as shown in Fig. 14
and ignition loss as shown in Fig. 15, the degree of cement 3.3.1.4. SEM analysis. Fig. 16 shows the distribution of nano-BN
hydration can be calculated. It can be seen from Table 8 that particles in RPC with 0.5 wt% of 120 nm nano-BN measured by
RPC with 1 wt% of 120 nm nano-BN reaches the highest hydration EDS. The white dots in the figure represent N elements. Because
degree at 3 d of curing age, which is relatively 7.3% above the of its small size effect, nano-BN is dispersed widely and uniformly
hydration degree of control RPC. However, the addition of without any agglomeration. This enables the bridging and filling
1.5 wt% of 120 nm nano-BN reduces the hydration degree of RPC effects of nano-BN to be fully utilized.
at curing age of 3 d. This illustrates that appropriate amount of The SEM micrographs of control sample and nano-BN filled RPC
nano-BN can accelerate the early hydration of RPC to a certain at curing age of 28 d are shown in Fig. 17. In the SEM images of
extent. After 28 d of curing age, the hydration degree of samples BN15, some of nano-BN particles reunite into blocks. This illus-
is 9.4%  21.2% over than the hydration degree at 3 d of curing trates that the nano-BN ratio of 1.5 wt% is not conducive to its dis-
age. However, the hydration degree of nano-BN filled RPC is not persion in RPC matrix, thus affecting the development of strength.
significantly enhanced compared RPC without nano-BN at curing However, the micrograph of BN05 shows no nano material agglom-
age of 28 d, since nano-BN does not participate in the cement eration. The agglomeration of nano-BN is an important reason
hydration reaction. affecting the strength of specimens. This is because nano-BN has
194 W. Zhang et al. / Construction and Building Materials 179 (2018) 186–197

Table 7
Weight loss rate in range of 50–350 °C.

Age Weight loss rate (%)

Control BN05 BN10 BN15
3d 8.47 9.76 9.95 7.52
28 d 9.32 10.16 9.88 10.09

Table 8
Cement hydration degree at 3 d and 28 d of curing age.

Curing age Hydration degree (%)

Control BN05 BN10 BN15
3d 50.0 55.6 57.3 45.1
28 d 65.7 66.4 66.7 66.3

size crystals are observed in the SEM image of RPC containing

0.5 wt% of 120 nm nano-BN (Fig. 17(b)), and the structure is denser
than control RPC. Fig. 18 (b) is a local high magnification SEM
image of BN05, showing that the C-S-H gels in matrix is much
denser.
Fig. 19 gives the SEM image of RPC with 0.5 wt% of 120 nm
nano-BN. The crack marked in the picture is deflected under the
barrier of nano-BN. Due to the two-dimensional stacked sheet
structure and high strength of nano-BN, it can play a bridging role
in RPC and hinder the development of cracks. This more clearly
reflects in the flexural strength of RPC composites. As summarized
in Fig. 3, the incorporation of nano-BN with larger particle size, the
more significant enhancement of the flexural strength at curing
age of 3 d.

3.3.2. Enhancing mechanisms of strength

Fig. 16. The surface scanning of nitrogen element in BN05.
a two-dimensional flaky structure. Plane slip easily occurs in the
agglomeration zone and causes crystal slip in RPC. Therefore, the
strength of sample is influenced. As shown in Fig. 17, there are
some large pores in control RPC, while fewer tinier pores exist in
RPC with 0.5 wt% of 120 nm nano-BN and the matrix is denser.
RPC incorporating 1.5 wt% nano-BN also has fewer pores, and some
micro cracks appear.
Fig. 18 demonstrates the morphology and distribution of CH
crystals in SEM image of 120 nm nano-BN modified RPC. Fig. 18
(a) illustrates that the CH crystals in control RPC have a large size
of about 10 lm and grew in clusters. However, almost no large-
Through the strength and microscopic analyses of RPC compos-
ites, it can be seen that the enhancing mechanism of nano-BN on
strength of RPC is multiple. For RPC without nano-BN, C-S-H gels
grow from the surface of cement particles resulting in limited
internal products, thus most C-S-H gels disperse in water as exter-
nal products. The external products have a low density and easily
formed pores when hindered by CH crystals and ettringite, result-
ing in low strength of control RPC. For RPC with nano-BN, nano-BN
is widely distributed in the water surrounding cement clinker in
fresh cement slurries attributed to its small size effect. Because
the Ca2+ ions in the cement particles are positively charged and
the zeta potential of nano-BN particles are negative, they adsorb
each other due to static electricity and form many ‘nuclei’ that
adsorb C-S-H gels and allow them to grow on its surface. This
was the nucleation effect of nano-BN which can promote the early
hydration of cement [31]. Because of the large surface area of
nanoparticles, more C-S-H gels grow on them, leading to a denser

(a) (b) (c)

tiny
pores cracks
pores

pores
agglomeratioQ

Fig. 17. SEM micrographs of RPC at curing age of 28 d: (a) control sample; (b) BN05; (c) BN15.
 W. Zhang et al. / Construction and Building Materials 179 (2018) 186–197
(a)
CH
Fig. 18. CH crystal of cement paste at curing age of 28 d in SEM micrographs: (a) control sample  5000; (b) BN05  60000.
bridging effect
Fig. 19. Cracks in SEM micrograph of BN05.
internal product structure. Therefore, the strength of samples is
increased. In addition, the nano-BN dispersed in the RPC fills the
pores of the matrix to form a dense network structure. This filling
effect can not only increase the density of structure, but also
restrict the growth of the CH crystals to refine CH crystals. Thus,
the decrease of strength due to large CH crystals is avoided. Mean-
while, because of the hindrance of nano-BN, CH crystals do not
grow in clusters and the orientation of CH crystal also decline.
Besides, the insertion of nano-BN into RPC matrix plays a bridging
effect, hindering the development of cracks. Moreover, the high
thermal conductivity of nano-BN helps to release heat generated
by cementitious composite hydration, especially in the early stage
hydration process [32–35]. As a result, the primary cracks inside
RPC composite are reduced and its strength is improved eventu-
ally. Additionally, the improvement of strength may be due to
the increase in the path of the crack around the small dispersed
nano boron particles.
Table 9
Density of RPC with nano-BN at 28 d of curing age.
Curing age Density (g/cm3)
Control
28 d 2.169
195
(b)
C-S-H gel
It should be noted that as exhibited in Table 9, when 120 nm
nano-BN content raises from 0% to 1.5 wt%, the density of RPC
changes slightly. As a result, there is no difference between the
porosity of RPC with and without nano-BN. Therefore, the addition
of nano-BN does not lead to the change of porosity.
3.3.3. Enhancing mechanisms of abrasion resistance
As shown in Figs. 6 and 9, the variation trend of abrasion is con-
sistent with that of compressive strength basically. This is because
the higher compressive strength of nano-BN modified RPC, the
stronger bond between agglomerate and cement mortar, which
leads to the increase of abrasion resistance. Moreover, because
the effect of heat curing offsets the filling effect of part of nano-
BN, a lower enhancement of abrasion resistance occurs in heat cur-
ing RPC containing nano-BN.
The improvement of abrasion resistance is also due to the excel-
lent thermal conductivity, high heat resistance and chemical sta-
bility of nano-BN. These properties can not only ensure the rapid
transfer of heat during friction and reduce the temperature cracks
caused by local temperature difference, but also maintain the
chemical stability of nano-BN at the frictional high temperature,
thereby increase the abrasion resistance of nano-BN filled RPC. In
addition, nano-BN has excellent lubricity and low friction coeffi-
cient [5,13]. All of these contribute to reducing abrasion loss of
RPC composite.
3.3.4. Enhancing mechanisms of chloride penetration resistance
The enhancement of chloride penetration resistance is attribu-
ted to the following reasons. Firstly, the blend of nano-BN results
in a more compact microstructure of RPC, which prevents chloride
ions penetration. Secondly, nano-BN plays a layered blocking effect
due to its lamellar structure. Part of erosion solution is adsorbed in
the voids between the layers of nano-BN, hindering the longitudi-
nal intrusion of chloride ions. Moreover, nano-BN with high resis-
tivity hinders the passage of electrical current of an ionic nature,
further slowing down all corrosion reactions. Owing to its low
expansion coefficient, hexagonal sheet-shaped nano-BN can
effectively prevent micro cracks in the matrix that caused by the
BN05 BN10 BN15
2.166 2.159 2.159
196 W. Zhang et al. / Construction and Building Materials 179 (2018) 186–197
expansion of air and water at high temperature. Therefore, the
chloride penetration resistance of nano-BN modified RPC with heat
curing is generally higher than that with standard curing.
4. Conclusion
The flexural strength, compressive strength, abrasion resistance
and chloride penetration resistance of nano-BN filled RPC were
investigated in this paper. Three factors including the particle size
of nano-BN, the nano-BN content and curing method were studied.
The modification mechanisms of nano-BN were explored through
performance tests and microscopic analyses. The main conclusions
are as follows.
(1) Nano-BN with particle size of 120 nm has the best reinforc-
ing effect on mechanical strength of RPC among nano-BN
with particle sizes of 120 nm, 500 nm and 1 lm.
(2) With the increase of 120 nm nano-BN content, the flexural
strength, compressive strength and abrasion resistance of
RPC composite first enhance and then reduce, while the
chloride penetration resistance continues to increase. The
introduction of 0.5 wt% of 120 nm nano-BN improves the
flexural strength and compressive strength of RPC maxi-
mally by 2.65 MPa/15.7% and 11.61 MPa/12.96%, respec-
tively, and reduces the abrasion loss per unit area of RPC
maximally by 0.35 kg/m2/55.56%. The chloride penetration
resistance of RPC with 1.5 wt% of 120 nm nano-BN even is
improved by 100%.
(3) The incorporation of 120 nm nano-BN enhances the com-
pressive strength, flexural strength and durability of RPC
with different curing methods. Moreover, the compressive
strength of standard curing RPC with 0.5 wt% nano-BN are
higher than that of heat curing RPC with 0.5 wt% nano-BN.
What’s more, the abrasion resistance of standard curing
RPC composites containing nano-BN is higher than that of
heat curing RPC composites.
(4) The enhancing mechanisms of nano-BN on performances of
RPC can be mainly summarized into six aspects including
small size effect, nucleation effect, filling effect, bridging
effect, lubrication effect and layered blocking effect. Nano-
BN can not only accelerate the early cement hydration and
promote more C-S-H formation through nucleation effect,
but also widely distribute in cement matrix to fill pores
and prevent the growth of CH crystals, thus resulting in a
denser microstructure. Additionally, the superior mechani-
cal and thermal properties of nano-BN endow RPC with high
strength, toughness and durability.
Conflict of interest
The author declares that there is no conflict of interest regard-
ing the publication of this paper.
Ethical statement
The author confirms that the manuscript is not under review or
published elsewhere.
The author states that the research was conducted according to
ethical standards.
There is no ethical concern.
Acknowledgments
The authors thank the funding supported from the National
Science Foundation of China (51578110 and 51428801), and the
Fundamental Research Funds for the Central Universities in China
(DUT18GJ203).
References
[1] Y. Wang, Z.A. Ming, Z.R. Yu, S. Han, W.Y. Ji, Durability of reactive powder
concrete under chloride-salt freeze–thaw cycling, Mater. Struct. 50 (1) (2017)
1–9.
[2] S.F. Dong, B.G. Han, J.P. Ou, Z. Li, L.Y. Han, X. Yu, Electrically conductive
behaviors and mechanisms of short-cut super-fine stainless wire reinforced
reactive powder concrete, Cem. Concr. Compos. 72 (2016) 48–65.
[3] M.M. Mokhtara, S.A. Abo-El-Eneinb, M.Y. Hassaanc, M.S. Morsya, M.H. Khalila,
Mechanical performance, pore structure and micro-structural characteristics
of graphene oxide nano platelets reinforced cement, Constr. Build. Mater. 138
(2017) 333–339.
[4] S.H. Kim, G.H. Shin, B.K. Kim, K.T. Kim, D.Y. Yang, C. Aranas Jr., J.P. Choi, J.H. Yu,
Thermo-mechanical improvement of Inconel 718 using ex situ boron nitride-
reinforced composites processed by laser powder bed fusion, Sci. Rep. 7 (2017)
1–13.
[5] R. Palanivel, I. Dinaharan, R.F. Laubscher, J.P. Davimb, Influence of boron nitride
nanoparticles on microstructure and wear behavior of AA6082/TiB2 hybrid
aluminum composites synthesized by friction stir processing, Mater. Des. 106
(2016) 195–204.
[6] Z.W. Li, S.C. Di, The microstructure and wear resistance of microarc oxidation
composite coatings containing nano-hexagonal boron nitride (HBN) particles,
J. Mater. Eng. Perform. 26 (4) (2017) 1551–1561.
[7] T. Wang, M.J. Wang, L. Fu, Z.H. Duan, Y.P. Chen, X. Hou, Y.M. Wu, S.Y. Li, L.C.
Guo, R.Y. Kang, N. Jiang, J.H. Yu, Enhanced thermal conductivity of polyimide
composites with boron nitride nanosheets, Sci. Rep. 8 (2018) 1–8.
[8] F. Liu, X.H. Mo, H.B. Gan, T.Y. Guo, H.B. Wang, B. Chen, J. Chen, S.Z. Deng, N.S.
Xu, T. Sekiguchi, D. Golberg, Y. Bando, Cheap, gram-scale fabrication of BN
nanosheets via substitution reaction of graphite powders and their use for
mechanical reinforcement of polymers, Sci. Rep. 4 (2014) 4211.
[9] R. Jan, P. May, A.P. Bell, A. Habib, U. Khan, J.N. Coleman, Enhancing the
mechanical properties of BN nanosheet-polymer composites by uniaxial
drawing, Nanoscale. 6 (9) (2014) 4889–4895.
[10] D.J. Lee, S.H. Song, J. Hwang, S.H. Jin, K.H. Park, B.H. Kim, S.H. Hong, S. Jeon,
Enhanced mechanical properties of epoxy nanocomposites by mixing
noncovalently functionalized boron nitride nanoflakes, Small 9 (15) (2013)
2602–2610.
[11] R. Saggar, H. Porwal, P. Tatarko, I. Dlouhý, M.J. Reece, Boron nitride nanosheets
reinforced glass matrix composites, Adv. Appl. Ceram. 114 (S1) (2015) S26–
S33.
[12] Y.S. Li, J. Yin, H.B. Wu, H. Deng, J. Chen, Y.J. Yan, X.J. Liu, Z.R. Huang, D.L. Jiang,
Enhanced electrical resistivity in SiC-BN composites with highly-active BN
nanoparticles synthesized via chemical route, J. Eur. Ceram. Soc. 35 (5) (2015)
1647–1652.
[13] A. Pakdel, Y. Bando, D. Golberg, Nano boron nitride flatland, Chem. Soc. Rev. 43
(3) (2014) 934–959.
[14] M. Yi, Z.G. Shen, X.H. Zhao, S.S. Liang, L. Liu, Boron nitride nanosheets as
oxygen-atom corrosion protective coatings, Appl. Phys. Lett. 104 (2014)
143101.
[15] Z. Trojanova, Z. Drozd, P. Minarik, P. Lukac, A. Kasakewitsch, Influence of
texture on the thermal expansion coefficient of Mg/BN nanocomposite,
Thermochimica Acta. 644 (2016) 69–75.
[16] M.A. Rafiee, T.N. Narayanan, D.P. Hashim, N. Sakhavand, R. Shahsavari, R.
Vajtai, P.M. Ajayan, Hexagonal boron nitride and graphite oxide reinforced
multifunctional porous cement composites, Adv. Functional Mater. 23 (45)
(2013) 5624–5630.
[17] Q. He, The Study of Comprehensive Reinforcement Mechanism of Hexagonal
Boron Nitride on Concrete (Dissertation for the Degree of Master of Science),
University of North Texas, USA, 2015.
[18] W. Wang, S.J. Chen, F.B. Souza, B. Wu, W.H. Duan, Exfoliation and dispersion of
boron nitride nanosheets to enhance ordinary Portland cement paste,
Nanoscale 10 (3) (2018) 1004–1014.
[19] A.W. Adamson, A.P. Gast, Physical Chemistry of Surfaces, Wiley-Interscience,
New York, 1997.
[20] H. Sis, M. Birinci, Effect of nonionic and ionic surfactants on zeta potential and
dispersion properties of carbon black powders, Colloids Surf., A 341 (1–3)
(2009) 60–67.
[21] P. Richard, M. Cheyrezy, Composition of reactive powder concretes, Cem.
Concr. Res. 25 (7) (1995) 1501–1511.
[22] B.G. Han, Y.Y. Wang, S.F. Dong, L.Q. Zhang, S.Q. Ding, X. Yu, J.P. Ou, Smart
concrete and structures: a review, J. Intel. Mat. Syst. Str. 26 (2015) 1303–1345.
[23] B.G. Han, S.Q. Ding, X. Yu, Intrinsic self-sensing concrete and structures: A
review, Measurement 59 (2015) 110–128.
[24] E. García-Macías, A. D’Alessandro, R. Castro-Triguero, D. Pérez-Mira, F.
Ubertini, Micromechanics modeling of the uniaxial strain-sensing property
of carbon nanotube cement-matrix composites for SHM applications, Compos.
Struct. 163 (2017) 195–215.
[25] B.G. Han, Z. Li, L.Q. Zhang, S.Z. Zeng, X. Yu, B. Han, J.P. Ou, Reactive powder
concrete reinforced with nano SiO2-coated TiO2, Constr. Build. Mater. 148
(2017) 104–112.
[26] R.B. Ardalan, N. Jamshidi, H. Arabameri, A. Joshaghani, M. Mehrinejad, P.
Sharafi, Enhancing the permeability and abrasion resistance of concrete using
 W. Zhang et al. / Construction and Building Materials 179 (2018) 186–197
colloidal nano-SiO2 oxide and spraying nanosilicon practices, Constr. Build.
Mater. 146 (2017) 128–135.
[27] B.G. Han, Z. Wang, S.Z. Zeng, D.C. Zhou, X. Yu, X. Cui, J.P. Ou, Properties and
modification mechanisms of nano-zirconia filled reactive powder concrete,
Constr. Build. Mater. 141 (2017) 426–434.
[28] L.Q. Zhang, N. Ma, Y.Y. Wang, B.G. Han, X. Cui, X. Yu, J.P. Ou, Study on the
reinforcing mechanisms of nano silica to cement-based materials with
theoretical calculation and experimental evidence, J. Compos. Mater. 50 (29)
(2016) 4135–4146.
[29] W. Kurdowski, Cement and Concrete Chemistry, Springer, 2014.
[30] P.C. Hewlett, Lea’s Chemistry of Cement and Concrete, Elsevier, 2011.
[31] Q.F. Zheng, B.G. Han, X. Cui, X. Yu, J.P. Ou, Graphene-engineered cementitious
composites: small makes a big impact, Nanomater. Nanotechnol. 7 (2017) 1–
18.
197
[32] B.M. Tyson, S.M. Asce, R.K. Abu Al-Rub, M. Asce, A. Yazdanbakhsh, Z. Grasley,
Carbon nanotubes and carbon nanofibers for enhancing the mechanical
properties of nanocomposite cementitious materials, J. Mater. Civ. Eng. 23
(7) (2011) 1028–1035.
[33] Y.F. Ruan, B.G. Han, X. Yu, Z. Li, J.L. Wang, S.F. Dong, J.P. Ou, Mechanical
behaviors of nano-zirconia filled reactive powder concrete under compression
and flexture, Constr. Build. Mater. 162 (2018) 663–673.
[34] C. Gogtas, H.F. Lopez, K. Sobolev, Effect of nano-YSZ and nano-ZrO2 additions
on the strength and toughness behavior of self-flowing alumina castables,
Ceram. Int. 42 (1) (2016) 1847–1855.
[35] B.G. Han, L.Q. Zhang, S.Z. Zeng, S.F. Dong, X. Yu, R.W. Yang, J.P. Ou, Nano-core
effect in nano-engineered cementitous composites, Compos. Part A: Appl. Sci.
Manuf. 95 (2017) 100–109.