Composites Part B 189 (2020) 107904

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Composites Part B
journal homepage: www.elsevier.com/locate/compositesb

Effects of brass coating and nano-SiO2 coating on steel fiber–matrix

interfacial properties of cement-based composite
Zhenyu Pi a, b, Huigang Xiao a, b, *, Rui Liu a, b, Min Liu a, b, Hui Li a, b
a
Key Lab of Structures Dynamic Behavior and Control of the Ministry of Education, Harbin Institute of Technology, Harbin, 150090, China
b
School of Civil Engineering, Harbin Institute of Technology, Harbin, 150090, China

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

Keywords: This study focused on the effects of steel fiber coatings on the interfacial properties of a fiber-reinforced cement-
Brass coating based composite. The impact of a brass coating on the interface between the steel fibers and cement matrix was
Nano-SiO2-coated fiber examined, and the improvement effects of a nano-SiO2 coating and nano-SiO2 powder on both the microstructure
Fiber–matrix ITZ
and interfacial bond properties were compared. A chemical simulation experiment was designed to analyze the
BSE-IA
Interfacial bond performance
brass coating state in a cement hydration environment. The backscattered electron image analysis (BSE-IA)
method was used to conduct quantitative analyses of the calcium hydroxide (CH), porosity, and unhydrated
cement (UHC) to investigate the microstructure of the fiber–matrix interfacial transition zone (ITZ). Pull-out tests
were conducted to determine the interfacial bond performance, and scanning electron microscopy (SEM) and
energy dispersive spectroscopy (EDS) were used for micro-observation and element analyses. The results indi­
cated that because of the destruction of the coating structure and the aggregation of CH caused by the dezin­
cification of the brass in a cement hydration environment, the brass coating did not improve (but weakened) the
interfacial microstructure and bond performance. Adding the nano-SiO2 powder directly was a useful method for
achieving microstructure densification and defect reduction in both the ITZ and bulk paste, while the nano-SiO2
coating provided a more targeted improvement in the fiber–matrix ITZ, particularly near the fibers, leading to a
more effective enhancement of the bond performance.

1. Introduction
Plain concrete is a brittle material that exhibits good compressive
performance but poor tensile performance. The addition of fibers en­
hances the ductility of a cement-based composite and considerably ex­
pands the application range of concrete [1–5]. Because of their high
modulus, strength, and ductility, as well as the ability to easily indus­
trialize their production, steel fibers are widely used as reinforcing
materials in cement-based composites. The fiber reinforced
cement-based composite must have good interfacial properties in order
for the fibers to provide efficient reinforcement and to obtain synergy
between the two materials [6–11]. The surface coating on the steel fibers
is in direct contact with the matrix and is an important factor in deter­
mining the interfacial properties. However, there is still insufficient
research on such surface coatings and their impact on the interfacial
properties.
The most commonly used type of coating for steel fibers is brass,
which effectively prevents corrosion during transportation and storage.
Regarding its influence on the interfacial properties, Li et al. found that
brass-coated fiber changed from a bright gold to a dull dark color and
proposed that the dissolution of the brass coating leads to a weak ad­
hesive strength at the interface [2]. Yeomans obtained a similar result,
reporting that the mean bond stress of a galvanized steel bar was less
than that of a black steel bar in concrete [12]. However, Corinaldesi
et al. found that a brass coating made a positive contribution to the bond
behavior between the steel fibers and the surrounding cement paste
when a CaO-based expansive agent was used in a fiber-reinforced
cement-based composite [13]. However, there has been little research
on this issue, and these opposite conclusions indicate that the effect of a
brass coating on the interfacial properties is still unclear. In addition to a
brass coating, several other coatings have been proposed for fibers with
the goal of improving the interfacial properties or preventing corrosion.
He et al. presented an approach for growing a nanoscale Fe2O3 coating
on steel fibers using the electrodeposition method, which increased the
pull-out force between the steel fibers and the concrete matrix [14].
Morks deposited a layer of magnesium phosphate on steel fibers, which

* Corresponding author. Key Lab of Structures Dynamic Behavior and Control of the Ministry of Education, Harbin Institute of Technology, Harbin, 150090, China.
E-mail address: xiaohg@hit.edu.cn (H. Xiao).

https://doi.org/10.1016/j.compositesb.2020.107904
Received 15 December 2019; Received in revised form 21 February 2020; Accepted 22 February 2020
Available online 27 February 2020
1359-8368/© 2020 Published by Elsevier Ltd.
Z. Pi et al. Composites Part B 189 (2020) 107904

improved both the corrosion resistance and adhesion properties [15].
Zhang et al. grafted SiO2 nanoparticles on polyvinyl alcohol fibers to
enhance the interfacial bonding strength with cement [16]. Recently,
Xiao et al. proposed an interesting method for coating steel fibers with a
nano-SiO2 multilayer film, achieving enhanced interfacial properties
and a dense microstructure near the fiber [17]. Adding the nano-SiO2
powder directly to the matrix is another method for improving the
performance of a steel fiber cement-based material and has been proven
to be useful for enhancing the interfacial bond performance [18].
However, the difference between the direct addition of nano-SiO2 and
the use of nano-SiO2-coated fibers and the effects of these methods on
the steel fiber–cement interfacial properties are unclear.
A clear understanding of the effects of the coating on the interfacial
microstructure and bond properties is important to improve the rein­
forcing efficiency of steel fibers. Because a brass coating is commonly
used at present, and nano-SiO2 is an attractive coating that reacts with
cement, these two coatings were the focus of this study. One of the
objectives of this study was determining the influence of a brass coating
on the interfacial properties and the evidence of this influence in both
the interfacial bond performance and microstructure. The other objec­
tive was clarifying the effects on the interfacial properties and the dif­
ferences between the use of nano-SiO2-coated steel fiber and the direct
addition of nano-SiO2 powder. A chemical simulation experiment was
designed to analyze the brass coating state in a cement hydration
environment, and pull-out tests were conducted to provide information
on the interfacial bond behavior. In addition, polished interfacial cross-
section samples with fibers were observed using backscattered electron
(BSE) microscopy and then their phases were analyzed quantitatively
using image analysis (IA) technology. With the exception of the simu­
lation experiment, the same methods were used to investigate the effects
the microstructure of a sample and can provide clear 3D depth-of-field
images based on the reflected electrons. Energy dispersive spectros­
copy (EDS) is a semi-quantitative micro-area composition analysis
method. In this study, SEM was used to observe the surface morphology
of the fibers, and EDS was used to determine the element type and
content. An ultra-high-resolution field emission scanning electron mi­
croscope (MERLIN Compact) manufactured by Carl Zeiss was used for
the SEM, and the image resolution was 1024 � 768. Gold was used to
coat the samples before observing them to increase their conductivity
and facilitate the imaging.
2.2. BSE-IA used for quantitative analysis of interfacial characteristics
2.2.1. BSE images
BSE images were used to distinguish the different phases in the
interfacial transition zone (ITZ) and bulk paste. In a BSE image, the
factor that determines the contrast of the various phases is the relative
difference between the signals, which are dependent on the backscat­
tering coefficients (η) for these phases. Furthermore, the backscattering
coefficient is a function of the atomic number (Z), and for a pure
element, η may be calculated using equation (1) [14].
η¼ 0:0254 þ 0:016Z 1:86 � 10 4 Z 2 þ 8:3 � 10 7 Z 3 ; (1)
For a homogeneous mixture such as a mixture of various phases in a
cement-based material, the backscattering coefficient of a phase (ηmix) is
calculated based on the weight fractions of the elemental components
[19]:
X
ηmix ¼ Ci ηi (2)
i

on the interfacial properties and the differences between the use of nano-
SiO2-coated steel fiber and the direct addition of nano-SiO2 powder. where Ci and ηi are the weight fraction and backscattering coefficient of
Scanning electron microscopy (SEM) and energy dispersive spectros­ element i, respectively.
copy (EDS) were also used for micro-observation and micro-area The average atomic number (Z) of a phase is calculated as follows
composition analyses. [20]:
X
Z¼ Ci Zi (3)
2. Materials and experimental methods i

Fig. 1 gives the calculated results for the average atomic numbers
2.1. Brass coating in simulated hydration environment
and corresponding backscattering coefficients of the main phases in the
The color of the brass-coated steel fiber was bright gold. After the
pull-out test, the surface color of the pulled-out fiber changed to dark
silver, and apparent longitudinal grooves appeared on the fiber surface.
To determine the reason for the disappearance of the brass coating and
its potential effect on the interfacial bond properties, the behavior of the
brass coating in a simulated cement hydration environment was
investigated.

2.1.1. Simulated cement hydration environment and experimental program

Many detailed features of the fiber surface were disturbed when the
fiber was pulled out of the matrix. However, the in-situ observation of
fibers in a cement matrix is difficult, particularly for coated fibers with a
small diameter. Therefore, a slightly saturated calcium hydroxide solu­
tion without obvious precipitation at room temperature was used to
create an alkaline environment similar to that produced by cement hy­
dration. This simulated environment may not have been exactly the
same as an actual cement hydration environment, but it highlighted the
main factors and reduced the interference from secondary factors. In
addition, it was particularly suitable for the in-situ observation of the
fiber coating state. Brass-coated steel fibers were placed in the simulated
hydration solution at 20 � 2 � C for three days, after which the fibers
were removed from the solution and rinsed with ethyl alcohol. At the Fig. 1. Average atomic numbers and the corresponding backscattering co­
end of each step, some fibers were retained and analyzed. efficients of the main phases in cement-based material: CH-calcium hydroxide;
OHP-Other hydration product, including calcium silicate hydrate (CSH1.5,
2.1.2. SEM-EDS for fiber surface observation and element analysis C1.5SH2), ettringite (C3 AS3 H32 ) and calcium aluminate monosulphate
Scanning electron microscopy (SEM) is a useful method for observing (C3 ASH12 ); UHC-Unhydrated cement, including C3S, C2S, C3A and C4AF.

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Z. Pi et al.
cement-based material. It can be seen that for these phases, the values of
the backscattering coefficients are consistent with those of the average
atomic numbers (the determination coefficient of the fitting curve R2 >
0.99). Therefore, the grey level of the BSE image, which is dependent on
the backscattering coefficients, can reflect the difference in the average
atomic numbers of the various phases [20]. Hence, in this study, image
analysis technology was applied to BSE images to conduct quantitative
analyses of the interfacial microstructures and compositions of different
fibers in various cement matrixes.
In this study, BSE images of polished sections of the samples were
obtained using a tungsten filament scanning electron microscope (VEGA
3) with a backscattering detector, manufactured by TESCAN. The BSE
images had a resolution of 1024�768 pixels, with a magnification of
500 � . Fig. 2 shows part of a typical BSE image analyzed in this study.
The BSE image of a hardened cement matrix showed four main phases:
unhydrated cement (UHC, including C3S, C2S, C3A, and C4AF), CH, other
hydration products (OHP; mainly C–S–H), and pores [21].
2.2.2. Materials and sample preparation
Ordinary Portland cement (P.O.42.5) produced by the Yatai Group
Harbin Cement Co., Ltd. was used in this study. Table 1 gives the
chemical composition of the cement. Standard sand produced by Xia­
men Aisio Standard Sand Co., Ltd. and conforming to ISO 679 was
applied. The nano-SiO2 powder used had a specific surface area of 640
� 60 m2/g, particle size range of 20–50 nm, purity of 99.5%, and bulk
density of �100 g/L. A polycarboxylate superplasticizer with a solid
content of approximately 40% was used.
The steel fibers used in this study included a brass-coated fiber, fiber
without a brass coating, and nano-SiO2-coated fiber. All of these fibers
had the same diameter of 0.22 mm and a length of 13 mm. The brass-
coated fiber was an industrial product, as shown in Fig. 3 (a). A
retreat plating agent was used to remove the brass coating of the brass-
coated fiber and prepare the fiber without a brass coating, as shown in
Fig. 3 (b). A sol–gel method involving the hydrolysis of ethyl orthosili­
cate (TEOS) in an alkaline environment was adopted to coat the steel
fiber with a nano-SiO2 multilayer film to prepare the nano-SiO2-coated
steel fiber, as shown in Fig. 3 (c). More details about the steps used to
coat the steel fiber with nano-SiO2 can be seen in our previous work
[17].
Cubic 16 � 16 � 16 mm BSE samples with at least 16 fibers each
were cast, with four samples for each mix. Table 2 gives the mix pro­
portions, but no sand was used in the BSE samples (sand was used in the
pull-out dog-bone-shaped specimen). The plain cement matrix and
nano-SiO2 cement matrix were denoted as PC and NC, respectively,
while the brass-coated steel fibers, steel fibers without brass coating, and
nano-SiO2-coated steel fibers were denoted as BSF, SF, and NSF,
respectively. The freshly cast samples were covered with plastic film.
They were demolded after 24 h and cured in lime-saturated water at 20
Fig. 2. A part of the typical BSE image analyzed in this study.
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Composites Part B 189 (2020) 107904
� 2 � C. These samples were soaked in ethyl alcohol to stop hydration,
and then dried at 60 � C for 24 h.
Fig. 4 (a) shows the self-made vacuum impregnation apparatus,
which could maintain a vacuum pressure of more than 0.095 MPa for at
least 15 min. A high-fluidity epoxy resin (EPO-TEK 301) was used to
impregnate the dried samples in the vacuum impregnation apparatus.
After impregnation, these samples were kept at room temperature for
24 h and then demolded.
A Tegramin-20 automatic polishing machine, as shown in Fig. 4 (b),
was used to grind and polish the impregnated samples. The impregnated
samples were ground to remove the extra resin and expose the surface to
be observed. They were then polished with a lapping film until an
extremely smooth mirror-like surface was achieved. Table 3 gives the
applied grinding and polishing program, and Fig. 5 shows the polished
samples before and after coating with gold.
2.2.3. Image processing and phase segmentation
The quantitative analysis of a BSE image requires some processing.
The processing of the phase segmentation for the BSE image is shown in
Fig. 6. First, the brightness and contrast should be adjusted so that all the
phases can be clearly distinguished, and this step is usually done at the
time of the imaging, as given in Fig. 6 (a). Second, it can be seen in Fig. 6
(b) that a Gaussian filter, a median filter, and several other filters are
used to enhance the image. Third, an appropriate threshold is selected
for segmenting each phase using certain measures, as shown in Fig. 6 (c),
and detailed explanations are given below. Finally, the image is binar­
ized and segmented. Some typical segmented binary images of the CH,
pores, and UHC are shown in Fig. 6 (d), (e), and (f), respectively. After
the phase segmentation, the segmented image is divided into several
concentric ring strips at intervals of 10 μm, as shown in Fig. 7 (b). Next,
the pixels in every ring strip are counted. The typical results are given in
Fig. 7 (c). MATLAB and Image-Pro Plus 6.0 were used to process and
analyze the BSE image.
Each step is important for BSE-IA, but the key is the image seg­
mentation. The CH, pores, and UHC were the three main phases
considered in this study, and they were segmented based on a grey level
histogram of the BSE image.
A separate peak for one phase in the grey level histogram indicated
the easy segmentation of the phase. However, the CH phase peak could
coincide with the OHP phase peak in the grey level histogram. The
Gaussian filter is a useful tool for improving the signal/noise ratio and
reducing the noise [21,22]. A separate peak for the CH phase could also
be revealed in the grey level histogram using the Gaussian filter, as
shown in Fig. 6 (c). The binary images of CH are shown as Fig. 6 (d).
The lower threshold for the pores could be considered to be zero, and
the upper threshold could be estimated using several strategies. If the
pore phase of the grey level histogram has a separate peak (i.e., the
porosity is high), the upper threshold can be determined to be the
minimum point between the pore peak and the OHP peak, which results
in the smallest error [23]. If a separate peak does not exist, there are
usually three ways to estimate the upper threshold: using a manual
threshold, the tangent-slope method, or an overflow criterion. A manual
threshold may contain the most details, but the deviation is too large.
Even the same operator may obtain different results at different times.
Both the tangent-slope method and overflow criterion are programmatic
approaches with a smaller deviation based on the grey level distribution.
The tangent-slope method proposed by Scrivener et al. selects the grey
value of the point at which the first tangent of the grey level histogram
and the tangent of the first half of the OHP peak intersect as the upper
threshold [24]. The overflow criterion proposed by Wong et al. regards
the critical point where the segmented area suddenly starts to increase as
the upper threshold point, and it is estimated by the intersection be­
tween two linear segments of the cumulative curve of the grey level
histogram [25]. The tangent-slope method is an empirical method, and
the results of the overflow criterion are slightly overestimated (multi­
plying by a factor of less than 1.0 when used). The tangent-slope method
Z. Pi et al. Composites Part B 189 (2020) 107904

Table 1
Chemical composition of cement.
Composition SiO2 Al2O3 Fe2O3 CaO MgO Na2O K2O SO3 Loss on ignition

Content (%) 24.66 7.09 2.71 55.46 2.15 0.685 0.648 1.40 2.00

Fig. 3. SEM image of steel fibers.

was used to fix the fibers in the opening in the sheet and ensure the
Table 2
correct fiber orientation and embedment length. To avoid adhesion
Mix proportion of BSE samples and dog-bone-shaped specimens (weight ratio).
between the sheet and matrix, the sheet was covered with a plastic film.
No. W/B Cement Nano-SiO2 Sand Type of steel Fiber Four fibers were installed in each specimen to reduce the contingency
BSF-PC 0.35 1 0 1 Brass-coated fiber and make the pull-out test less cumbersome. The embedded length of the
SF-PC 0.35 1 0 1 Fiber without brass coating fibers in the pull-out part was 5 mm, and the ends of the fibers in the
BSF-NC 0.35 0.99 0.01 1 Brass-coated fiber
fixed part were bent to ensure that the fibers were all pulled out from the
NSF-PC 0.35 1 0 1 Nano-SiO2-coated fiber
pull-out part and useful data could be obtained.
There were four different cases for the pull-out tests, as given in
was used for the pore phase segmentation in this study, as shown in Table 2. Four groups of dog-bone-shaped specimens were cast, and each
Fig. 6 (c), and a binary segmented image of the pores is given in Fig. 6 group had at least five specimens for each curing age. The preparation
(e). process and curing conditions of the dog-bone-shaped specimens were
The UHC phase segmentation is much easier because compared with the same as those of the BSE samples, and the curing ages were 3, 7, and
the other phases, the UHC contrast is distinct, and in most cases, the 28 days. After the pull-out tests, SEM and EDS were used to observe and
UHC phase of the grey level histogram has a separate peak [24–26]. In analyze the fibers.
addition, a median filter can remove any isolated bright pixels caused by
local charging or contamination, making the UHC peak more visible [21,
Table 3
26], as given in Fig. 6 (c). Fig. 6 (f) shows a binary image of the UHC. Grinding and polishing program.
When applying filters, care must be taken not to over-process to avoid
Step Lapping Particle Time (s) Force Fixing Turntable
losing useful information. To preserve the original information, this
film type size (μm) (N) device speed
study did not use any morphological filters such as an open filter, an speed (rpm)
erosion filter, or a close filter [27]. (rpm)

1 D 45 Remove 25 200 100

extra
2.3. Pull-out test epoxy
2 SiC 30 Remove 25 200 100
A fiber double-sided pull-out test was designed to measure the extra
epoxy
interfacial bond properties between the steel fiber and the cement ma­ 3 SiC 9 120 15 160 80
trix, and the test device is shown in Fig. 8 (a). Fig. 8 (b) shows a dog- 4 D 3 150 15 140 70
bone-shaped specimen that was divided into two parts by a stainless- 5 D 1 180 15 120 60
steel sheet, which were called the pull-out part and fixed part. Paraffin

Fig. 4. (a) Self-made vacuum impregnation apparatus and (b) automatic polishing machine.

4
Z. Pi et al. Composites Part B 189 (2020) 107904

Fig. 5. The polished samples for BSEM (a) before and (b) after coating gold. (For interpretation of the references to color in this figure legend, the reader is referred
to the Web version of this article.)

Fig. 6. The processing of phase segmentation for BSE image.

Based on some previous studies [28–30], a loading rate of 1.0 pull-out test, df (mm) is the diameter of the steel fiber, le (mm) is the fiber
mm/min was used in this research. The test was performed using a embedment length in the pull-out part (5 mm in this research), and n is
universal testing machine with a displacement sensor to record the the number of fibers fixed in a specimen (four in this research).
relative displacement between the pull-out part and fixed part. In addition, Δτmax is used to characterize the difference between the
The bond strength is an important index for measuring the interfacial bond strengths for four cases: the BSF-PC, SF-PC, BSF-NC, and NSF-PC.
bond performance of a fiber-matrix interface. According to some related The corresponding expressions are shown below:
studies [17,18,28–31], it is calculated as follows:
τmax ðSF PCÞ τmax ðBSF PCÞ
ΔτmaxjSF BSF ¼ (4-1)
P τmax ðBSF PCÞ
τmax ¼ max ; (4)
nπdf le
τmax ðBSF NCÞ τmax ðBSF PCÞ
ΔτmaxjNC ¼ (4-2)
where τmax (MPa) is the bond strength, Pmax (N) is the peak load during a PC
τmax ðBSF PCÞ

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Z. Pi et al. Composites Part B 189 (2020) 107904

Fig. 7. The processing of quantitative counting for BSE image.

Fig. 8. Illustration of (a) pull-out test device and (b) dog-bone shaped specimen and layout of fibers.

τmax ðNSF PCÞ τmax ðBSF PCÞ

ΔτmaxjNSF BSF ¼ (4-3) ΔWpjSF ¼
Wp ðSF PCÞ Wp ðBSF PCÞ
(5-1)
τmax ðBSF PCÞ BSF
Wp ðBSF PCÞ
The pull-out energy, which is defined as a portion of or the entire
Wp ðBSF NCÞ Wp ðBSF PCÞ
area under the load–displacement curve, characterizes the mechanical ΔWpjNC PC ¼ (5-2)
energy consumed when the fiber is pulled out of the matrix and can be Wp ðBSF PCÞ
calculated as follows:
Wp ðNSF PCÞ Wp ðBSF PCÞ
Z le ΔWpjNSF BSF ¼ (5-3)
Wp ðBSF PCÞ
Wp ¼ pðsÞds (5)
0

3. Results and discussion

where Wp is the pull-out energy, and P(s) is the pull-out load at
displacement s.
3.1. Chemical analysis of brass coating in cement paste
Here, ΔWp is used to characterize the difference in the pull-out en­
ergy values for the four cases mentioned above. The corresponding ex­
3.1.1. Surface characteristics of brass-coated steel fiber before and after
pressions are as follows:
being pulled out
Fig. 9 (a) shows the surface morphology of a brass-coated steel fiber
before the pull-out test. The surface longitudinal grooves are not very

6
Z. Pi et al.
clear. The EDS results proved that the brass coating consisted of Cu and
Zn. After being pulled out from the cement matrix, the color of the fiber
changed from bright gold to dark silver, which also occurred in the study
by Li [2], and the fiber surface longitudinal grooves became visible, as
shown in Fig. 9 (b). In addition, there were almost no other elements on
the fiber surface, with the exception of Fe, as shown in the EDS results.
These changes revealed that the brass coating was debonded from the
fiber surface during the pull-out test, and the fiber surface grooves may
not have been due to friction between the fiber and the matrix. To
determine the reason for the debonding of the brass coating from the
fiber surface, the previously mentioned simulation experiment was
carried out.
3.1.2. Dezincification and brass coating destruction
After being immersed in a simulated hydration solution for three
days, the color of the brass-coated steel fibers had changed to dark silver.
These fibers were removed from the solution and observed using SEM
without cleaning. It can be seen in Fig. 10 (a) that some quadrilateral
crystals had crystallized on the fiber surface, and many small particles
had filled in the surface grooves. The main elements of these quadri­
lateral crystals were Zn, Ca, and O, with no Cu, whereas the main ele­
ments of the small particles that filled in the surface grooves were Cu,
Ca, and O, with no Zn. Based on the related literatures [12,32–34], these
quadrilateral crystals composed of Zn, Ca, and O were determined to be
Ca(Zn(OH)3)2⋅2H2O. Dezincification can explain this phenomenon: in
an aqueous solution, particularly an alkaline solution such as cement
paste, one constituent of the brass coating (Zn) will be selectively
removed, leaving the other (Cu) [12,35]. The Zn removed from the brass
coating becomes Zn(OH)2 and reacts with CH to form Ca(Zn
(OH)3)2⋅2H2O. In addition, because of the dezincification, the remaining
Cu and deposited CH fill the surface grooves, which is consistent with
the EDS results. After cleaning with ethyl alcohol, the fibers were
observed again using SEM, as shown in Fig. 10 (b). Neither the Ca(Zn
(OH)3)2⋅2H2O crystals nor the remaining Cu and deposited CH particles
were found because they had all been washed away with the ethyl
alcohol, and the surface longitudinal grooves of the cleaned fibers
Fig. 9. Surface morphology and elementary composition of (a) brass-coated steel fiber and (b) fiber after pull-out test.
7
Composites Part B 189 (2020) 107904
became obvious, just like the pulled-out fibers. Both the surface
morphology and elemental composition of the cleaned fibers were
almost the same as those of the pulled-out fibers.
The chemical simulation experiment on the coating state of a brass-
coated steel fiber in the cement hydration environment showed that the
disappearance of the brass coating on the surface was due to the
dezincification of the brass in the calcium hydroxide solution, which
caused the structure of the brass coating to be destroyed and easily
washed away by the ethyl alcohol. As a result, the bond between the
brass coating and fiber surface no longer existed. The surface longitu­
dinal grooves of the pulled-out fibers could be fiber bundles of the fiber
itself rather than friction traces. In most cases, these fiber bundles are
covered by the brass coating, which prevents them from being observed
very clearly.
3.2. BSE-IA for ITZ
To understand and explain the interfacial properties, BSE-IA was
used to quantitatively analyze the fiber–matrix ITZ, which had a
composition and properties that were different from those of the bulk
paste, such as a higher porosity and less dense microstructure. The CH,
UHC, and pores, as the three main components, were analyzed, with a
focus on the absolute values and the values relative to the control group
(BSF-PC).
3.2.1. CH
The CH content is an important parameter for characterizing the ITZ
microstructure, and BSE-IA is a useful method for a quantitative analysis
of the CH that has been used in other studies [24,36,37]. At present, only
BSE-IA can quantitatively measure the distribution of CH in different
micro-zones in cement-based materials. The CH fractions for four cases
(BSF-PC, SF-PC, BSF-NC, and NSF-PC) were determined, and both the
absolute and relative values in relation to BSF-PC were analyzed.
The absolute CH distribution around the fiber was measured, as
shown in Fig. 11 (a). The CH content of BSF-PC was high within the first
50 μm, and slightly fluctuated in the bulk paste. An interesting
Z. Pi et al. Composites Part B 189 (2020) 107904

Fig. 10. Surface morphology of brass-coated steel fiber immersed in simulated hydration solution.

Fig. 11. Change of fraction of CH with different distances from fiber edge.

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Z. Pi et al.
phenomenon was that the highest value of CH occurred in the range of
10–20 μm from the fiber edge, rather than in the range of 0–10 μm. The
CH distribution of SF-PC followed a distribution rule similar to that of
BSF-PC except in the first 10 μm. BSF-NC had a relatively constant dis­
tribution of CH in both the ITZ and bulk paste. The amount of CH in NSF-
PC was very small near the fiber, and it increased until the distance from
the fiber edge reached approximately 50 μm, after which it fluctuated.
Fig. 11 (b) shows the CH fractions relative to BSF-PC. In the first 10 μm,
SF-PC showed an approximately 10.5% decrease in CH compared with
that of BSF-PC. The CH content of BSF-NC was approximately 18.0%
lower than that of BSF-PC in the ITZ, and this decrease effect was
approximately 6.8% in the bulk paste. As for NSF-PC, a CH decrease of
nearly 35% was achieved in the first 10 μm, but the decrease effect
gradually weakened and disappeared beyond 50 μm.
The packing of the matrix particles was looser near the brass-coated
fiber because of the wall effect and bleeding effect, and more spacious
nucleation sites were provided for CH crystals. Thus, the CH value was
higher near the fiber than in the bulk paste, which has been proposed in
other studies [38–40]. Furthermore, the dezincification of the brass
coating promoted an increase in Zn content near the fiber and caused
more CH aggregates to form Ca(Zn(OH)3)2⋅2H2O. A similar phenome­
non has occurred with galvanized concrete reinforcement [12,41]. As a
result, there were more CH crystals near the brass-coated fiber than near
the fiber without the brass coating in the first 10 μm. The growth and
precipitation of CH required a large free space, whereas the fiber edge
could hinder crystallization. Thus, the highest CH value occurred in the
range of 10–20 μm from the fiber, rather than in the range of 0–10 μm.
Adding the nano-SiO2 powder could achieve a decrease in CH in both the
ITZ and bulk paste not only because of the reaction between CH and the
nano-SiO2 but also because of the preventive effect of the CH crystal
growth [42,43]. This CH decrease effect of the nano-SiO2 was been
verified by Liu using thermogravimetric analysis (TGA) [44]. In addi­
tion, the decrease effect of CH was obvious in the first 30 μm because the
nano-SiO2 powder had a small size and was more easily distributed near
the fiber edge. Between the nano-SiO2-coated fiber and the matrix, the
nano-SiO2 multilayer film reacted with CH to form an adequate amount
of CaO⋅SiO2⋅nH2O near the fiber and bonded the fiber and matrix.
Therefore, the CH decrease effect for NSF-PC was more effective within
10 μm of the fiber edge compared with BSF-NC. However, because of the
limited influence range of the nano-SiO2 coating, the decrease effect of
CH was not as significant for BSF-NC beyond 10 μm from the fiber edge,
and the effect even disappeared beyond 50 μm. Fig. 12 shows the for­
mation of CaO⋅SiO2⋅nH2O from the reaction of the nano-SiO2 multilayer
film and CH, which not only consumes the CH content but also has the
potential to decrease the porosity, which is beneficial to the ITZ
microstructure.
3.2.2. Pores
The porosity characterized the number of defects in cement stone to
some degree. The pore distribution around the fiber was determined for
each of the four cases mentioned above. The absolute porosity values are
given in Fig. 13 (a), and the porosity values for the four cases relative to
BSF-PC are given in Fig. 13 (b).
For BSF-PC, it can be seen in Fig. 13 (a) that within 50 μm of the fiber
edge, and particularly in the first 30 μm, the porosity near the fiber is
high and decreases sharply as the distance from the fiber edge increases.
Outside the ITZ, the porosity is basically unchanged. A similar porosity
change law near the fiber is also found in SF-PC and BSF-NC. Conversely,
the porosity of NSF-PC is quite a bit lower, and the change in porosity
with distance is slight. More detailed information about the porosity
differences between BSF-PC and the other three cases is given in Fig. 13
(b). It is obvious that the porosities of BSF-PC and SF-PC are almost the
same, indicating that the brass coating did not influence the porosity
around the fiber. Comparing BSF-NC and BSF-PC, the direct addition of
the nano-SiO2 powder decreased the porosity in both the ITZ and bulk
paste, and the 20–30% decrease in the bulk paste was more remarkable
9
Composites Part B 189 (2020) 107904
Fig. 12. Reaction of nano-SiO2 multilayer film and CH to form
CaO⋅SiO2⋅nH2O [16].
than that of 7–17% in the ITZ. A decrease in the porosity of a cement-
based material containing nano-SiO2 has also been observed using the
mercury intrusion porosimetry (MIP) method [18,44]; however, the MIP
method cannot distinguish the ITZ and bulk paste. The porosity of
NSF-PC was quite a bit lower than that of BSF-PC in the ITZ, with a
decrease of nearly 70% in the first 10 μm. In addition, within the first 30
μm, the decrease effect of NSF-PC was obviously better than that of
BSF-NC. However, in the bulk paste, the decrease effect of NSF-PC was
less remarkable than that of BSF-NC and even invalid.
For the steel fiber in the matrix, because of the wall effect and
bleeding effect, more water and smaller sized cement particles existed
near the fiber, resulting in more pores, more CH, and more defects. The
nano-SiO2 could react with CH to form CaO⋅SiO2⋅nH2O and fill the pores.
Therefore, adding nano-SiO2 powder could reduce the porosity and
densify the microstructure in both the ITZ and bulk paste. However,
because the pores near the fiber were usually large, the CaO⋅SiO2⋅nH2O
formed by the reaction between the nano-SiO2 and CH might not have
effectively filled these defects. Thus, the porosity decrease effect in the
ITZ was not as good as that in the bulk paste, which was also mentioned
in the study by Xiao [45]. As for the ITZ of NSF-PC, a more targeted
nano-SiO2 aggregated near the fiber. Thus, an effective decrease in
porosity near the fiber was achieved as a result of the pozzolanic reac­
tivity of the nano-SiO2, as explained in 3.2.1.
3.2.3. UHC
The amount of UHC can be used to determine the degree of hydration
of cement clinker. It has been quantitatively analyzed using BSE-IA in
numerous studies [24,44,46–48], and this approach has been proven to
yield accurate results similar to other methods [44,46,47]. The UHC
fractions for the same four cases previously discussed were determined,
and both the absolute values and the values relative to BSF-PC were
analyzed.
Fig. 14 (a) shows the relationship between the absolute value of the
UHC fraction and the distance from the fiber edge. For BSF-PC, SF-PC,
and BSF-NC, the UHC values were lower near the fiber. They increased
with the distance away from the fiber, and then remained unchanged
beyond 30 μm. For NSF-PC, the range where UHC was less than that in
the bulk paste was approximately 60 μm. The UHC fractions for the
other three cases relative to BSF-PC are given in Fig. 14 (b). The UHC
fractions for BSF-PC and SF-PC were substantially equal in both the ITZ
and bulk paste, whereas that of BSF-NC decreased by nearly 20% near
the fiber. The decrease effect for NSF-PC relative to BSF-PC was 30%–
50% in the range of 60 μm from the fiber edge.
Because of the wall effect and bleeding effect, more water and
Z. Pi et al.
Fig. 13. Change of porosity with different distances from fiber edge.
Fig. 14. Change of fraction of UHC with different distances from fiber edge.
smaller sized particles existed near the fiber edge, providing sufficient
hydration conditions and a larger specific surface area for the cement
particles to come into contact with the water, which was beneficial for
the complete hydration of the cement [49]. As a result, the hydration
degree was higher, and the UHC fraction was lower near the fiber edge
than that in the bulk paste. The UHC results for BSF-PC and SF-PC
indicated that the brass coating did not influence the hydration. The
nano-SiO2 accelerated the hydration to consume C3S and form C–S–H
during the initial stages of hydration (4–12 h) [50], with more nano-­
SiO2 powder in the vicinity of the fiber but less in the bulk paste.
Therefore, the UHC decrease effect for BSF-NC was remarkable near the
fiber but not obvious in other zones. In contrast, the nano-SiO2 coated on
the fiber surface was adequate for accelerating the dissolution and hy­
dration of the C3S phase and forming more CaO⋅SiO2⋅nH2O near the
fiber, resulting in a more significant UHC decrease for NSF-PC relative to
BSF-NC.
3.3. Interfacial bond properties
3.3.1. Pull-out curves
Fig. 15 shows the typical pull-out load–displacement curves for the
four cases: BSF-PC, SF-PC, BSF-NC, and NSF-PC. In the initial stage, the
slopes of the four curves are almost the same because the load is too
small to reach the bond strength, and the curve in this stage mainly
10
Composites Part B 189 (2020) 107904
reflects the fiber property itself. As the load increases, the curves grad­
ually rise and reach the peak values. The peak load of BSF-PC is lower
than that of SF-PC, indicating that the interfacial bond properties are
weakened by the brass coating. In the following pull-out stage, there is
no difference between the two curves. In other words, the brass coating
does not change the fiber pull-out process.
The curve for BSF-NC completely encloses the first two curves,
indicating that the interfacial bond behavior was considerably improved
by adding the nano-SiO2 powder. The highest peak load and unstable
debonding occur in the curve for NSF-PC, which is usually considered to
be the performance of the chemical bond between the fiber and the
matrix, as mentioned in 3.2.1 and confirmed in other studies [51,52].
BSF-NC and NSF-PC show the same trend in the fiber pull-out stage
because after the bond breaks, the main factor affecting the curve is the
friction.
3.3.2. Effect of brass coating on interfacial bond properties
The bond strength and pull-out energy results for BSF-PC and SF-PC
are given in Fig. 16(a) and (b), respectively. SF-PC has 36.6%, 14.1%,
and 10.6% higher bond strengths and 26.0%, 17.2%, and 5.1% higher
pull-out energy values than BSF-PC at 3, 7, and 28 days. It can be seen
that for the same cement matrix (PC), the interfacial bond properties of
BSF are not as good as those of SF for both the bond strength and pull-out
energy values. Further, the gap between BSF-PC and SF-PC is not large
Z. Pi et al.
Fig. 15. Typical pull-out load-displacement curves of pull-out tests.
and gradually decreases with an increase in the curing age. These results
indicate that the brass coating does not enhance but instead weakens the
bond properties. However, the effect of the brass coating on the inter­
facial properties is slight. Li [2] mentioned the color change in the
brass-coated steel fiber and proposed “the dissolution of the brass
coating leading to a weak adhesive strength at the interface for this
system.” Yeomans [12] obtained a similar result from a reinforcement
pull-out test, reporting that the mean bond stress of a galvanized steel
reinforcement was less than that of a black steel reinforcement in con­
crete specimens. However, the opposite view that the brass coating can
enhance the fiber–matrix interface has also been reported. Corinaldesi
[13] performed a bending test of fiber-reinforced cement-based com­
posites with brass-coated steel fibers and a CaO-based expansive agent
and obtained an improved flexural strength. It was believed that the
formation of calcium hydroxide zincate crystals enhanced the quality of
the fiber–matrix interface. Regardless of which point of view is correct,
the occurrence of dezincification and formation of Ca(Zn(OH)3)2⋅2H2O
have been recognized. Based on the results of the pull-out test, simula­
tion experiments, and BSE-IA for the ITZ, this study seemed to support
the view that the alkaline environment of cement hydration causes
dezincification of the brass coating, damaging the coating structure and
Fig. 16. Interfacial bond properties of BSF-PC and SF-PC: (a) bond strength and (b) pull-out energy.
11
Composites Part B 189 (2020) 107904
promoting the aggregation of CH, which weakens the fiber–matrix
interface. Because the coating is very thin, the impact is not significant.
As the curing age increases, the ITZ microstructure is improved by the
cement hydration. Thus, the gap between BSF-PC and SF-PC gradually
decreased.
3.3.3. Effects of addition of nano-SiO2 powder and nano-SiO2-coated fiber
on interfacial bond properties
The effects of the addition of the nano-SiO2 powder and the nano-
SiO2-coated fiber on the interfacial bond properties are given in Fig. 17.
Compared with BSF-PC, the bond strength of BSF-NC increases by
57.1%, 44.8%, and 57.4%, and the pull-out energy increases by 65.9%,
62.0%, and 81.3% at curing ages of 3, 7, and 28 days, respectively. It is
obvious that the direct addition of the nano-SiO2 powder enhanced the
interfacial bond properties, and this enhancement may have had a
greater effect on the energy consumption, which has been proposed in
another study with a similar conclusion [18]. For NSF-PC in comparison
to BSF-PC, 204.2%, 186.3%, and 137.0% improvements in the bond
strength and 100.2%, 95.1%, and 104.0% improvements in the pull-out
energy were achieved at 3, 7, and 28 days, respectively. These results
revealed that nano-SiO2-coated fibers can also enhance the interfacial
bond properties, and the enhancement effect on the bond strength may
be more significant at an early curing age. Fig. 17 also shows the dif­
ference in the enhancement effects of the above two methods on the
interfacial properties. The enhancement effects for NSF-PC are 147.1,
141.5, and 79.6% points higher for the bond strength and 34.3, 33.1,
and 22.7% points higher for the pull-out energy compared to those of
BSF-NC at 3, 7, and 28 days, respectively. The NSF (modifying the fibers
with nano-SiO2) has a more pronounced effect on the interfacial bond
properties than NC (modifying the cement matrix with nano-SiO2),
particularly for the bond strength at an early curing age.
3.4. Relationship between interfacial microstructure and bond behavior
As previously analyzed, for BSF-PC, there were many more pores and
more CH in the ITZ, particularly in the first 30 μm near the fiber,
resulting in a loose and defective microstructure. Furthermore, the
corresponding pull-out behavior was poor. The dezincification of the
brass coating led to the destruction of the coating structure and the
aggregation of CH. Thus, there were more defects near the fiber in BSF-
PC compared to SF-PC. Therefore, the pull-out behavior of SF-PC was not
weakened but instead was slightly enhanced. However, the brass coating
was so thin that its weakening impact on the interfacial properties was
limited. Directly adding the nano-SiO2 powder was a useful method for
Z. Pi et al.
Fig. 17. Interfacial bond properties of BSF-PC, BSF-NC and SF-PC.
densifying the microstructure and decreasing the defects of the cement
matrix [53] and offered effective decreases in the pores and CH for both
the ITZ and bulk paste, leading to the improved bond strength and
pull-out energy. However, the improvement effect of the nano-SiO2
powder in the fiber–matrix ITZ was not better than that in the bulk paste,
whereas modifying the fiber with nano-SiO2 was a more targeted
approach for the interface. This method promoted cement hydration and
significantly decreased the porosity and CH, particularly in the first 10
μm from the fiber edges. Moreover, the reaction between the nano-SiO2
film and Ca(OH)2 increased the amount of CaO⋅SiO2⋅nH2O, which was
the adhesive material in cement stone. As a result, the ITZ microstruc­
ture near the nano-SiO2-coated fiber was considerably enhanced, and
was even better than that in the bulk paste in some respects. Corre­
spondingly, the best pull-out behavior was achieved among these four
cases.
4. Conclusions
This study focused on the influences of a brass coating and nano-SiO2
coating on the fiber–matrix ITZ microstructure and interfacial bond
properties of a cement-based composite. A chemical simulation experi­
ment was designed to analyze the brass coating state in a cement hy­
dration environment. SEM-EDS was used for micro-observations and
micro-area composition analyses, and BSE-IA was used for phase
quantitative analyses. Pull-out tests were conducted to provide infor­
mation about the interfacial bond behavior. Based on the results of this
study, the following conclusions can be drawn:
(1) The dezincification of the brass coating on the fiber surface will
occur in the cement hydration environment, resulting in the
destruction of the coating structure and the aggregation of CH.
Therefore, a brass coating does not improve interfacial bond
properties but has a slight weakening effect.
(2) Adding nano-SiO2 powder to the cement material decreases the
microstructure defects in both the fiber–matrix ITZ and bulk
paste because of the pozzolanic activity and preventive effect of
nano-SiO2. Correspondingly, the interfacial bond properties,
including the bond strength and pull-out energy, are both effec­
tively enhanced.
(3) Coating steel fibers with a nano-SiO2 multilayer film is another
method for using nano-SiO2 to enhance the fiber–matrix inter­
facial properties. Compared with the direct addition of nano-SiO2
powder, using nano-SiO2-coated fiber has a more targeted effect
on the improvement of the fiber–matrix ITZ microstructure. A
12
Composites Part B 189 (2020) 107904
more effective enhancement of the interfacial bond properties is
then achieved.
Declaration of competing interest
The authors declare that they have no conflict of interest.
CRediT authorship contribution statement
Zhenyu Pi: Conceptualization, Methodology, Investigation, Formal
analysis, Writing - original draft, Writing - review & editing. Huigang
Xiao: Conceptualization, Supervision, Funding acquisition, Writing -
original draft, Writing - review & editing, Resources, Project adminis­
tration. Rui Liu: Methodology, Formal analysis, Investigation, Valida­
tion. Min Liu: Supervision, Funding acquisition, Resources, Project
administration. Hui Li: Supervision, Funding acquisition, Resources,
Project administration.
Acknowledgements
This work was supported by the NSFC [grant numbers 51978212,
51678206]; Natural Science Foundation of Heilongjiang
[JQ2019E001]; National Key R&D Program of China [grant number
2018YFC0705404].
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