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Article M AT E R I A L S
Journal of Composite Materials
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of concrete canvas by anhydrite-modified DOI: 10.1177/0021998315597743
jcm.sagepub.com
calcium sulfoaluminate cement

Fangyu Han1, Huisu Chen1, Xiangyu Li2, Buchuan Bao1,

Tao Lv3, Wulong Zhang3 and Wen Hui Duan2

Abstract
A carefully designed formulation of dry cement powder for concrete canvas, which is expected to have both high
mechanical strengths and short setting times, is obtained by partially replacing calcium sulfoaluminate cement (CSA)
with anhydrite at four levels (0%, 10%, 20% and 30% by mass of CSA cement). The influence of anhydrite fineness on the
mechanical properties of concrete canvas and its mechanical anisotropy are both investigated. X-ray diffraction analysis
and isothermal calorimetry are used to investigate the underlying mechanism. Results reveal that increasing anhydrite
content or fineness improve the mechanical strengths of concrete canvas and shortened its setting times. However, a
slight decrease of mechanical strength occurs at the later age when the replacement level was 30 wt%. A large amount of
unhydrated particles is found in hardened specimens. The concrete canvas shows higher mechanical strengths in the
warp direction than in the weft direction, and it exhibits the lowest compressive strength in the through-the-thickness
direction.

Keywords
3D spacer fabric, concrete canvas, calcium sulfoaluminate cement, anhydrite, mechanical properties, mechanism

Crawford in 2005).9–11 Compared with conventional

Introduction
Three-dimensional (3D) spacer fabric can be defined as a
special type of textile with 3D yarn architecture and 3D
textile architecture.1,2 Due to the structure of an arma-
ture system of highly oriented yarns, 3D spacer fabric
has been shown to exhibit superior mechanical perform-
ance compared to traditional sandwich structures.3,4
Moreover, 3D spacer fabric can reinforce cementitious
composites along three aligned directions and provide
defined positioning via the two outer substrates.1
Meanwhile, 3D spacer fabric can be easily placed in a
mold and impregnated to its whole depth by cement-
based matrix in one step.5 Interest has recently increased
in the use of 3D spacer fabric as a novel reinforcement
for cement-based composite materials, such as prefabri-
cated wall panels, shell concrete members, retaining wall
and slope protection, and FRP reinforcement.6–8
In addition to its use in prefabricated elements, 3D
spacer fabric presents new opportunities to manufac-
ture more attractive cementitious composite concrete
canvas (CC, concept first proposed by Brewin and
3D spacer fabric reinforced cementitious composites,
CC has a completely different preparation process.
Before setting of the cement powder, CC is a flexible
3D spacer fabric impregnated with cement powder that
can be applied like a soft cloth. Then, one just needs to
spray or add water from the top surface of the CC for
construction. Once set, a thin composite layer, that is
durable, water-resistant and fire-resistant, forms and
covers the structure or element, whatever its shape.
1
Jiangsu Key Laboratory of Construction Materials, School of Materials
Science & Engineering, Southeast University, Nanjing, China
2
Department of Civil Engineering, Monash University, Clayton,
Melbourne, Australia
3
Architectural Engineering Institute of the General Logistic Department,
PLA, Xi’an, China
Corresponding author:
Huisu Chen, Jiangsu Key Laboratory of Construction Materials, School of
Materials Science & Engineering, Southeast University, Nanjing 211189,
China.
Email: chenhs@seu.edu.cn; xiangyu23@gmail.com; musult@126.com

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2 Journal of Composite Materials 0(0)

Thus CC can be quickly, efficiently and widely used as a and volume stability of products can be realized by
structural element to form a cover for prefabricated the addition of calcium sulfate in CSA. By increasing
shelters, paths for vehicles or for pedestrians, or a pro- the dosage of calcium sulfate, rapid hardening/high
tection layer for pipes and linings, etc.9 However, in strength or more expansive cement can be produced.19
order to guarantee that water penetrates through the In addition, the hydration of CSA cement and its prop-
whole depth of powder-impregnated 3D spacer fabric, erties depend on the reactivity of the applied calcium
over-dosage of water (higher than the minimum sulfate,14 such as the calcium sulfate fineness. If CSA is
requirement of water for complete hydration of the used as binder of CC, the optimal content and fineness
cement) is normal. Consequently, there is a greater like- of calcium sulfate would be two key parameters influ-
lihood of producing a hardened matrix with high por- encing setting times and mechanical properties.
osity due to loosening of the compacted powders and The contributions of calcium sulfate to the proper-
over-dosage of water. Moreover, the preparation of CC ties of CSA cement have been widely investigated and
can also lead to insufficient contact between cement well documented under the condition of normal cast-
powder and water, affecting the mechanical properties ing.19,20 However, as demonstrated in Figure 2,20 the
of hardened CC. optimized dosage of calcium sulfate in this traditional
Nevertheless, the mechanical properties of CC are system aiming to obtain highest strengths may not be
important in applications. Currently, the 10-day com- suitable for the CC system where the water is spraying
pressive and flexural strengths of the commercially instead of mixing. This is attributed to the fact that the
available CC product provided by Concrete Canvas bulk density of dry cement power-filled CC system is
Ltd. are 40 MPa and 3.4 MPa, respectively, according around 1250–1400 kg/m3, after spraying water, its bulk
to ASTM C473-07 and BS EN 12467:2004.12 However,
the compressive test is conducted on a 61-mm diameter
circular panel with a 6.4-mm diameter hole. If a cubic
sample with length equal to the thickness of CC is used
according to GB/T 50081-2002, its compressive
strength is only about 27 MPa after 60 days, which is
roughly 60% of the compressive strength value of the
panel with a hole based on our previous compressive
tests.13 In the current commercially available CC prod-
uct, calcium aluminate cement (CAC) powder is used as
the matrix,9 and can produce high mechanical perform-
ance in the early stage and better setting properties.
But, as Juenger et al.14 have demonstrated, the hydra-
tion product of CAC cement at ambient temperature is
CAH10. The metastable hydrates CAH10 (density
1720 kg/m3) and C2AH8 (density 1950 kg/m3) can tran- Figure 1. Schematic of conversion implies densification of
hydrates which leads to increased porosity and strength
sit to the stable C3AH6 (density 2520 kg/m3) with an
reduction.14
increase in temperature or during the curing process,
as shown in Figure 1. Consequently porosity of the
product increases and its mechanical strengths
decrease. Low mechanical strengths limit the applica-
tions of CC in civil engineering. Therefore, a suitable
binder with higher mechanical strengths must be
explored for CC.
Calcium sulfoaluminate cement (CSA) can be used
as binder for CC due to its low porosity, high early
strength, high frost resistance, low pH, high corrosion
resistance, dimensional stability and good setting prop-
erties.15–17 Furthermore, the production of CSA cement
generates lower CO2 emissions than that of CAC
cement because of its lower calcination temperature in
the kiln (around 1250–1350 C), lower CO2 release from
the raw materials (low calcium carbonate content), and Figure 2. Calculated phase diagram of the thermodynamic
lower electricity consumption for grinding.18 Typically, stable hydrate assemblages of the system ye’elimite-calcium
satisfactory setting properties, strength development sulfate-water.20

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Han et al.
density reached to 1800–1950 kg/m3, which is lower
than the average value of ordinary mortar (around
2200–2400 kg/m3). So incorporation of extra amount
of calcium sulfate may increase the mechanical strength
of the CC product without introducing over-expansion
cracks, whereas this is not true for the CSA cement with
traditional mixing-casting procedure as shown in
Figure 3. Moreover, the mechanical properties of CC
can be improved by increasing the fineness of calcium
sulfate used, because the higher specific surface area of
powders may increase the contact area between powder
and water, and consequently accelerate chemical reac-
tion progress and improves the early-age strength of
CC. Therefore, for CSA-based CC, in order to make
Figure 3. Over-expansion cracks induced by extra amount of
calcium sulfate in CSA cement with mixing.
Figure 4. Structures of 3D spacer fabric designed for CC application: (a) Global view; (b) Local view.
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3
denser microstructure, the optimal content and fineness
of calcium sulfate has to be investigated carefully.
This study aims to optimize the mix proportion of
CSA cement-based binder for CC in terms of setting
times as well as mechanical tests. Moreover, the influ-
ence of anhydrite fineness on the performance of CC is
addressed. X-ray diffraction (XRD) and isothermal cal-
orimetry are used to analyze the mechanism. The mech-
anical anisotropy of CC samples due to the anisotropic
structure of 3D spacer fabric is also discussed.
Experimental methodology
Raw materials
As depicted in Figure 4(a), a special 3D spacer fabric
15 mm in thickness, designed for CC, is produced on a
double-needle bar Rachel machine. One of the two
outer textile substrates is knitted into mesh fabric
(MF) and the other one is knitted into solid fabric
(SF), as illustrated in the leftmost and rightmost of
Figure 4(b). Three characteristic directions are
warp, weft and through-the-thickness directions.21
The warp direction is along the machine direction.
The warp yarns in the warp direction are inserted into
the stitches and assembled together with the weft yarns
in the weft direction, and then a grid net is produced
and the meshes in the net were knitted in rectangle
shapes. Additionally, oriented spacer yarns are inserted
into the structure to the amount of 70 yarns/cm2. All
warp/weft yarns of the 3D spacer fabrics are in twisted
4 Journal of Composite Materials 0(0)

Table 1. Properties of various yarns of 3D spacer fabrics.

Diameter Fineness Ultimate Tensile Young’s

Components (-) Materials (-) (mm) (dtex) elongation (%) strength (MPa) modulus (GPa)

Warp/ weft yarn-MF PET multifilaments – 339 9.2  0.6 443  8 4.85  0.19
Warp/ weft yarn-SF PET multifilaments – 396 6.1  0.5 731  24 11.39  0.46
Spacer yarn PET monofilament 0.18 495 9.8  0.8 705  26 7.23  0.65

Table 2. Mineralogical and chemical compositions of calcium sulfoaluminate cement (CSA), anhydrite and hemihydrate.

Mineralogical compositions CSA (wt%) Anhydrite (wt%) Chemical compositions CSA (wt%) Anhydrite (wt%)

C4A3S 65.51 – SiO2 8.5 0.68

CT 6.48 – Al2O3 32.6 0.40
C2S- 16.52 – Fe2O3 2.7 –
C4AF 2.12 – CaO 41.7 39.0
C12A7 4.27 – MgO 3.5 1.95
CS 0.45 92.64 SO3 9 49.5
 2
CSH – 6.80 TiO2 1.5 –
 0.5
CSH – 0.56 L.O.I 0.5 5.46
CaO 1.52 –
CaMg (CO)2 3.14 –

form. The properties of the various yarns of the 3D

spacer fabric, as determined by a yarn tensile tester
with 30N capacity (XL-2), are summarized in Table 1.
With this beneficial structure, dry mixed cement
powder could be easily impregnated into the 3D
spacer fabric from the MF and fill the internal free
space between the spacer yarns. Once the MF is
coated with PVC adhesive the cement powder was
kept from leaking out of the 3D spacer fabric.
The chemical and mineralogical compositions of the
commercial CSA cement and the anhydrite are deter-
mined by X-ray fluorescence (XRF) (ThermoFisher
Scientific ARL QUANTX) and XRD (Bruker-AXS
Discover 8), respectively. The results are given in
Table 2. XRD patterns are carried out using a Cu Ka
radiation source with a Lynx Eye detector operated at
40 kV and 30 mA. Step scanning is performed with a
dwell time of 0.50 s at each step using a 2y scan step of
Figure 5. Particle size distribution of anhydrites at different
0.020 between 5 and 90 . The CSA cement contains grinding times.
65.5% ye’elimite and its Blaine specific surface (Blaine
SSA) is 442 m2/kg. The original anhydrite, labeled as
AI, has a Blaine SSA of 387 m2/kg. To determine the
influence of anhydrite fineness, the original anhydrite
Specimens preparation and characterization
powder is milled in a planetary ball mill using an agate The specimen preparations are conducted at tempera-
jar and four agate balls at 150 r/min for 15, 30 and ture of 25 C and relative humidity of 75%. The prep-
45 min and labeled AII, AIII and AIV, respectively. aration process is given in Figure 6. First, powder
Their Blaine SSA and particle size distributions deter- mixture with the designed proportion is poured into a
mined by laser diffraction (Microtrac S3500) are given Thunderbird ARM-02 mixer and stirred for 10 min at
in Figure 5. 94 r/min. The mixed powder is then gradually placed

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Han et al. 5

Figure 6. Flow chart of preparation process of CC: (a) Placing powder into the 3D spacer fabric, (b) the 3D spacer fabric compactly
impregnated with powder by vibration, (c) water spraying.

and vibrated into the mold containing 3D spacer fabric

of 160 mm  130 mm  15 mm until the 3D spacer
fabric is compactly impregnated with powder. Finally,
tap water at the temperature of 24.3 C is uniformly
sprayed onto the surface of the CC sample via spray
bottle (as shown in Figure 6c). The spray is stopped
immediately if the water slightly penetrated through
the bottom of 3D spacer fabric. The water spray pro-
cess takes roughly 10 s. The water-to-binder (W/B)
ratio is recalculated based on the mass of the sample
before and after spray. After final setting, the samples
are demolded and cured at the temperature of 25  2 C
and relative humidity of 60  5%.
In an attempt to optimize the binder system, the ori-
ginal anhydrite AI is partially replaced in the CSA
cement at four replacement levels (0, 10, 20 and 30%
by mass of CSA cement). The upper limit of replace-
ment levels is determined based on the maximum attain-
able ettringite produced in the CSA-CaSO4 mixtures, as
shown in Figure 2.20 These formulations with different
dosages of anhydrite were labeled CTRL, AI10, AI20 and
AI30. The optimized formulation is then used to inves-
tigate the influence of anhydrite fineness on the mech-
anical performance of CC and its mechanical
anisotropy. Four anhydrite finenesses as shown in
Figure 4 are considered and three loading directions
(warp, weft, and through-the-thickness, as shown in
Figure 4) are investigated. In flexural tests, only the
warp and weft loading directions are considered due
to the small thickness of the 3D spacer fabric.
For the setting times test, the powder mixture with
specified proportion is placed and vibrated into the set-
ting time mold without fabric, then water with given
dosage which is calibrated based on the W/B ratio used
in the corresponding CC sample is sprayed onto the
surface of the powder. The setting times of the mixtures
are determined by Vicat penetrometer according to GB/
T 1346-2011,22 except that the water is sprayed other
than mixed. At different curing ages (1 d, 5 d, 10 d, 30 d,
60 d) the mechanical strengths of the CCs are measured
using a uniaxial mechanical test machine (CMT 5105)
equipped with a 100 kN load cell at a stroke-control
Figure 7. Schematic diagram of set-up for compressive and
three-point flexural testing of samples: (a) cross section of har-
dened sample; (b) compression; (c) three-point bending.
rate of 1 mm/min. As shown in Figure 7, CCs are cut
into samples of sizes 15 mm  15 mm  15 mm and
160 mm  40 mm  15 mm for compressive and
three-point bending tests, respectively. At least three
parallel samples are tested for each group and both
the average values and standard deviation are
calculated.
The phase composition of the CCs is assessed by
XRD with Rietveld refinement. An isothermal calorim-
eter (TAM Air) is used to determine the rate of hydra-
tion heat liberation of pastes during the first 70 h. The
powders are first dry mixed. The powders are then
mixed with a certain amount of water using a small
stirrer for 60 s and immediately placed in the calorim-
eter for heat collection. The hydration process is moni-
tored for 72 h at 20 C. Due to the external mixing, the
very early thermal response of the samples could not be
recorded in the calorimetric curves. The total heat
release is determined by integration of the heat flow
curve.
Results and discussion
Formulation of the binder
The apparent densities of fresh CC and the hardened
samples are tested. The corresponding W/B ratio of

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6 Journal of Composite Materials 0(0)

each sample are calculated. As shown in Table 3, the Table 4, both initial and final setting times decrease
apparent densities of both fresh and hardened CCs with increasing anhydrite dosage. A large decrement
samples are almost identical at around 1300 kg/m3 in setting times is observed for pastes when the replace-
and 1700 kg/m3, respectively, regardless of the dosage ment is higher than 10 wt%. The setting times of CSA
of anhydrite. As a result, the recalculated W/B ratios of cements depend on their ye’elimite content, the dosage
various CC samples are similar and around 0.45. and the reactivity of anhydrite,14 because the early
The influence of anhydrite dosage on setting times (tI hydration of ye’elimite is accelerated due to the add-
and tF) of all pastes is depicted in Table 4. As shown in ition of anhydrite. This is consistent with the results
from isothermal calorimetry, as shown in Figure 8(a).
Increasing anhydrite dosage generally accelerates the
initial rate of heat evolution and cumulative heat
Table 3. Apparent densities of dry-fresh and hardened samples release within the first 0.6 h, a finding that was also
and the corresponding water-to-binder (W/B) ratios. reported by Winnefeld and Barlag.20 The initial heat
Bulk density of samples (kg/m3) evolution peak can be attributed to the formation of
ettringite and monosulfate at very early stages.18
CCs Dry-fresh Hardened W/B ratio (-) Furthermore, the setting of the CSA cements is
CC_CTRL 1260 1660 0.43 mainly influenced by the morphology and the interlock-
ing of early hydrates,16 which can be examined by the
CC_ AI10 1300 1700 0.44
heat release per milliliter of initial water by assuming
CC_AI20 1280 1780 0.45
that heat release is potentially related to the space-fill-
CC_AI30 1260 1700 0.45 ing capabilities of the ongoing reactions (e.g. setting
and compressive properties).23 The cumulative heat
release values up to the stages of initial and final setting
are also presented in Table 4. The cumulative heat
Table 4. Measured setting times and concurrent heat releases release does not include the contributions of the initial
for pastes with different anhydrite dosage. mixing and dissolution of powders, as data acquisition
began 60 s after the mixing. For a similar W/B ratio,
Property CTRL AI10 A I20 A I30
the cumulative heat release for initial and final settings
tI (min) 140 130 85 70 decreases with the increasing anhydrite dosage, espe-
tF (min) 300 250 165 140 cially when the replacement is higher than 10 wt%. It
Cumulative heat release 35.39 30.30 27.04 22.48 indicates that the amount of hydration products
at tI (J/mL water) required to reach setting reduced with a higher replace-
Cumulative heat release 80.33 76.56 56.56 49.21 ment of anhydrite.
at tI (J/mL water) Figure 9 shows the effect of the anhydrite dosage on
mechanical strengths of all CC samples at different

Figure 8. Influence of anhydrite dosage on heat evolution of pastes: (a) Before 0.6 h; (b) over 70 h.

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Han et al.
Figure 9. Mechanical strengths development of CCs with different formulations: (a) Compressive strength in through-the-thickness
direction; (b) three-point flexural strength in warp direction.
curing ages. A large standard deviation of mechanical
strengths is observed. As discussed above, the mechan-
ical strengths of each specimen are calculated by at least
three parallel samples cut from the same harden plate.
Unlike the traditional mixing process, although we try
our best to uniformly spay water, a local fluctuation of
W/B ratio cannot be completely avoided in the overall
sample. Thus, large standard deviation of mechanical
strengths may occur. However such deviation does not
affect the general tendency of time-dependent strength
development of samples as shown in Figure 9. After 1
day curing, the mechanical strengths of the CC samples
increase with the increasing anhydrite dosage. In the
following days this trend is maintained except for
CC_AI30, where a slight decrease of mechanical
strengths is observed. The main strength development
of CC samples occurs within 10 days and some almost
reach their maximum value after 10 days. This is con-
sistent with the results obtained by Winnefeld and
Barlag.24 The CC_A I20 shows the best mechanical per-
formance. After 1 day, the compressive and flexural
strengths of CC_AI20 are close to 25 MPa and
4.5 MPa, respectively, in contrast to CC_CTRL,
which achieves only around 10 MPa and 3 MPa. After
10 days, compressive and flexural strengths reach
40 MPa and 6.5 MPa, whereas the strengths of
CC_CTRL are only around 17 MPa and 4 MPa.
These results are much superior to those of the CC
product provided by Concrete Canvas Ltd.12 The
improvements in compressive and flexural strengths
are about 48% and 76%, respectively, after 10 days.
Furthermore, its final setting time only 2.75 h is
needed for final setting, a significantly shorter time
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7
than that required by the CC samples provided by
Concrete Canvas Ltd. (4 h). The results show that
the mechanical properties of CC can be improved by
partially replacing CAC cement with the combination
of CSA and a certain amount of anhydrite.
The strength development of CSA cement is closely
related to the formation of hydrates. The effect of
anhydrite dosage on the early-age strength develop-
ment is further investigated via the isothermal heat
release and mineral composition of hardened sample.
The results are given in Figures 8(b) and Figure 10,
respectively. Figure 8(b) reveals that the addition of
anhydrite accelerates the hydration of CSA cement.
Dormant periods after the initial peak decrease from
around 9 h to about 2 h. In the pastes with anhydrite,
the increase of heat flow occurs simultaneously with the
end of the dormant period. However, the two peaks
after the dormant period occur and the time to the
last hydration exothermic peak decreases with the
increasing dosage of anhydrite. The occurrence of the
first heat release peak can be explained by the forma-
tion of massive hydrates, whereas the second peak indi-
cates the consumption of anhydrite, and the formation
of monosulfate instead of ettringite.16 This phenom-
enon was also observed by Winnefeld and Barlag.24 It
occurs because anhydrite on the one hand affects the
first peak of the heat flow curve after about 3 h, but it
does not influence the position of first peak in the heat
flow; on the other hand, it influences the subsequent
peak and its position in the further heat flow after 3 h
of hydration. Greater consumption of anhydrite exhi-
bits enough reacted anhydrite, and Ca2+, and SO42
ions from the dissolution of the anhydrite is rapidly
8 Journal of Composite Materials 0(0)

Figure 10. XRD quantitative Rietveld analysis of CCs with different formulations after 10 days of curing: (a) CC_CTRL; (b) CC_AI10;
(c) CC_AI20; (d) CC_AI30.

consumed by the formation of ettringite.14,16 The con-
sumption of anhydrite increases considerably from
around 10 h for AI10 to around 5 h for AI20 and AI30.
The increased cumulative heat release indicates that
more hydration products are generated and early-age
mechanical strengths are improved.
The hydration process is similar for all samples, but
the main differences are the quantity of hydrates
produced and reactants consumed, as shown in
Figure 10 for 10 day cured CC samples. The differences
in produced/consumed quantities of phases in Figure
10 are summarized in Figure 11. It is clear that the
total quantity of the main hydrates (e.g. ettringite and
monosulfate) increases with the increasing dosage of
anhydrite except for CC_AI30. Based on its rapid
hydration rate as shown Figure 8, the reduction in

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Han et al.
Figure 11. Quantity of phases consumption and formation of
CCs with different formulations after 10 days of curing.
the total main hydrates of CC_A I30 may be attributed
to that the early-produced hydrates act as a diffusion
barrier which obstructs further hydration. This result
reveals that the optimal anhydrite dosage, correspond-
ing to the maximal dosage of hydrates discussed by
Winnefeld and Barlag,20 is not suitable for the CSA
system when spraying water is used for hardening.
Further analysis involved the relationship between the
main hydrates and the mechanical strengths of the CC
samples. As shown in Figure 12, these experimental
data basically follow a straight line for compressive
strength and flexural strength. It is also confirmed
that a larger anhydrite dosage leads to improved mech-
anical strengths due to the increased amount of the
formed hydrates.
It is also noted that CC_A I30 is favorable for form-
ing ettringite instead of monosulfate, as shown in
Figure 11. The quantity of monosulfate reduces by
59% compared with that of CC_AI20. The reason is
that the larger contact area between anhydrite and
water at higher dosage of calcium sulfate supplies
enough calcium and sulfate ions which are favorable
for the formation of ettringite. This phenomenon is
also confirmed by the larger quantity of anhydrite con-
sumed in CC_A I30, which is consistent with the results
obtained by isothermal heat release curves as shown in
Figure 8(b). In addition, it should be noted from Figure
11 that a considerable amount of unreacted ye’elimite
and anhydrite are also found in samples after 10 days,
although unreacted anhydrite can be identified even in
the mixture with an undersupply of anhydrite and a
great surplus of water.20 The CC_AI20 consumes the
largest quantity of ye’elimite, which is only about
36% of the initial content of ye’elimite. This suggests
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9
Figure 12. Relationship between main generated hydrates and
mechanical strengths for CCs with different formulations after 10
days of curing.
that the special preparation process leads to remarkedly
insufficient contact between unhydrated particles and
water, thereby impeding the hydration process of unhy-
drous particles.
Because of its superior mechanical strengths and sat-
isfactory setting properties, the binder system contain-
ing CSA and 20 wt% anhydrite is selected as the
optimized formulation of CC for the following studies.
Influence of anhydrite fineness
As mentioned above, another key parameter affecting
the fresh and hardened performance of CSA-based CC
products is the chemical reactivity of anhydrite. In this
section, with the anhydrite dosage is fixed at 20 wt% of
CSA cement, four different finenesses of anhydrite are
adopted as shown in Figure 4 to study the influence of
anhydrite reactivity.
The effect of anhydrite fineness on the setting times
(tI and tF) of pastes is given in Table 5. It can be seen
from Table 5 that both the initial and final setting times
continue to decrease as the anhydrite fineness increases.
It indicates that early hydration is accelerated by the
finer anhydrite due to its higher specific surface area.
This result is consistent with the isothermal calorimetric
results. As shown in Figure 13(a), a higher initial rate of
heat evolution and cumulative heat release of the
samples, related to early hydration, can be observed
for finer anhydrite, which promotes the hydration pro-
cess. As shown in Table 5, the cumulative heat release
per milliliter of initial water up to the initial and final
settings also explains the decrease in setting times,
10 Journal of Composite Materials 0(0)

Table 5. Measured setting times and concurrent heat release where a shorter hydration process is required for the
for pastes with different anhydrite fineness. setting of paste with finer anhydrite.
As shown in Figure 13(b), the length of the dormant
Property A I20 AII20 AIII20 AIV20
period after the initial peak is almost identical for each
tI (min) 85 70 60 55 sample, it indicates that the onset of hydration is not
tF (min) 165 135 120 120 influenced by the anhydrite fineness. After the dormant
Cumulative heat release 27.04 24.08 21.15 19.86 period, the first maximum in the calorimetric curves
at tI (J/mL water) decreases slightly with the increasing fineness of anhy-
Cumulative heat release 56.56 37.94 30.51 30.74 drite, but the consumption of anhydrite is advanced
at tI (J/mL water) greatly by more than 10 h compared with the time of
AI20 and the second peak is significantly increased. As a

Figure 13. Influence of anhydrite fineness on heat evolution of pastes: (a) Before 0.6 h; (b) Over 70 h.

Figure 14. Influence of anhydrite fineness on the development of mechanical strengths of CCs: (a) Compressive strength in through-
the-thickness direction; (b) three-point flexural strength in warp direction.

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Han et al. 11

Figure 15. XRD quantitative Rietveld analysis of CCs with different anhydrite fineness after 10 days of curing: (a) CC_AI20; (b)
CC_AII20; (c) CC_AIII20; (d) CC_AIV20.

result, the cumulative heat release and the amount of
hydration products both increase. The mechanical
strength development of the CC samples with varied
anhydrite fineness conforms to the results from the iso-
thermal calorimetric measurements. As shown in
Figure 14, the mechanical strengths of the CCs are
improved with the increasing fineness of anhydrite,
especially in the early stage, for instance after 1 day.
To further illustrate how anhydrite fineness affects
the mechanical strengths of CC, the phase composition
of 10-day hardened samples is analyzed and presented
in Figure 15. And the variation of phases’ dosage is
summarized in Figure 16. It can be easily seen that an
increase in the total quantity of hydrates is accompa-
nied by an increase of anhydrite fineness, which is con-
sistent with the isothermal calorimetric results.

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12
Figure 16. Quantity of phases consumption and formation of
CCs with different anhydrite fineness after 10 days of curing.
Figure 17. Relationship between main generated hydrates and
mechanical strengths for CCs with different anhydrite fineness
after 10 days of curing.
Meanwhile, the consumption of both ye’elimite and
anhydrite increases and results in the significantly
reduce in the amount of unhydrated particles, it reveals
that the degree of hydration of CSA-based CC is effect-
ively increased via increasing the anhydrite fineness.
Furthermore, good correlation between main hydrates
and mechanical strengths is observed from Figure 17.
Thus, our studies show that the setting properties
and mechanical performance of CSA-based CC can
be improved by increasing the fineness of the anhydrite.
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Journal of Composite Materials 0(0)
An alternative method would be to use calcium sulfate
with higher reactivity, such as hemihydrate25 or a com-
bination of calcium sulfate and calcium hydroxide.14
However, the much higher exothermic rate would be
a potential problem for these systems.13
Anisotropy of mechanical performances
As shown in Figure 4, the 3D spacer fabric presents an
anisotropic geometric pattern, which clearly leads to
anisotropy in the mechanical strengths of CC.
Therefore, the anisotropic mechanical strength of CC
with curing time is investigated and the results are pre-
sented in Figure 18. It can be seen from Figure 18(a)
that the highest compressive strength of CC is along the
warp direction, followed by weft, and the through-the-
thickness directions. As shown in Figure 18(b), the flex-
ural strength of CC in the warp direction is higher than
that in the weft direction.
After 10 days, the compressive strengths of CC in the
warp and weft directions are improved by about 23%
and 18%, respectively, compared with that in the
through-the-thickness direction. These improvements
can be attributed mainly to the confining effect induced
by the outer textile substrates of the 3D spacer fabric.
The outer textile substrates anchored in the paste of the
CC are tightly connected by spacer yarns and can be
considered as two additional strengthening layers. Due
to the confining effect, a multi-axial stress state occurs
in the CC and confinement is realized, improving the
compressive strength of the CC.26 Another factor is the
fiber reinforcing effect, which is dependent on the com-
ponent properties and geometric pattern of the 3D
spacer fabric. The effective orientation angle of spacer
yarns in the warp direction is less than that in the weft
direction due to the layout pattern.10 This leads to
higher compressive and flexural strengths of CC in
the warp direction.
Therefore, according to the load situation to which
CC is subjected, its laying direction should be logically
chosen to effectively withstand unfavorable external
stress and improve service life.
Conclusions
In this study, combination of CSA and anhydrite is
investigated to replace CAC cement as binder system
of CC. The results showed that mechanical strengths of
CC can be dramatically improved and its setting times
can be greatly shortened by increasing the dosage or
fineness of anhydrite. However, the mechanical
strengths of CC decrease when the replacement level
exceeds 20 wt%. Moreover, the special preparation pro-
cess of CC leads to markedly insufficient and heteroge-
neous contact between unhydrated particles and water,
Han et al.
Figure 18. Mechanical strengths development of CCs in different loading directions: (a) Compressive strength; (b) three-point
flexural strength.
as a result of which a considerable amount of unhy-
drated particles is found. Additionally, due to its mech-
anical anisotropy, CC has higher mechanical strengths
in the warp direction than that in the weft direction and
it exhibits the lowest compressive strength in the
through-the-thickness direction. Apart from the
cement composition of CC, the component properties
and geometric pattern of 3D spacer fabric critically
influence its mechanical strengths. Future study is
needed to explore the optimal geometric pattern and
identify a component material with superior properties.
Declaration of Conflicting Interests
The author(s) declared no potential conflicts of interest with
respect to the research, authorship, and/or publication of this
article.
Funding
The authors gratefully acknowledge financial support from
the Architectural Engineering Institute of the General
Logistic Department of P.L.A., China.
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