Construction and Building Materials 50 (2014) 540–548

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Construction and Building Materials

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

Utilization of iron ore tailings as fine aggregate in ultra-high

performance concrete
Sujing Zhao ⇑, Junjiang Fan, Wei Sun
Jiangsu Key Laboratory of Construction Materials, School of Material Science and Engineering, Southeast University, Nanjing 211189, China

h i g h l i g h t s

 Iron ore tailings were used as aggregate at different replacement levels to make UHPC.
 The tailings were characterized by techniques like SEM, XRD and nanoindentation.
 The mechanical properties of UHPC mortars and UHPC were measured.
 The pore structure and microstructure of the UHPC matrix were studied.
 The UHPC with tailings content up to 40% showed comparable properties to the control.

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

Article history: Iron ore tailings are a common type of hazardous solid waste in China and have caused serious
Received 23 July 2013 environmental problems, and the high cost of producing ultra-high performance concrete (UHPC)
Received in revised form 2 October 2013 provides the motivation to look for low-priced raw materials. In this paper, the possibility of using iron
Accepted 4 October 2013
ore tailings to replace natural aggregate to prepare UHPC under two different curing regimes was inves-
Available online 26 October 2013
tigated. It was found that 100% replacement of natural aggregate by the tailings significantly decreased
the workability and compressive strength of the material. However, when the replacement level was
Keywords:
no more than 40%, for 90 days standard cured specimens, the mechanical behavior of the tailings mixes
Ultra-high performance concrete
Iron ore tailings
was comparable to that of the control mix, and for specimens that were steam cured for 2 days, the com-
Fine aggregate pressive strengths of the tailings mixes decreased by less than 11% while the flexural strengths increased
Strength by up to 8% compared to the control mix. In addition, pore structure analysis revealed a coarsening of
Pore structure micro-pore structure with an increase of the tailings content and a good correlation between the poros-
Microstructure ities and compressive strengths of the UHPC matrices, and microstructure image showed a possibly poor
interfacial transition zone around some tailings particles.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction of using some byproducts, such as slag which is used to produce

With the standard of living continually improving, the demand
for natural resources has also continued to increase and more and
more industrial wastes have been produced. In order to alleviate
environmental pressures and attain sustainability, one feasible
solution is to reuse waste materials as secondary resources. In this
regard, the concrete industry has already absorbed millions of tons
of industrial by-products that contain toxic elements [1].
The iron and steel industry is one of the major industries in
China. It has developed rapidly since China’s reform and
opening-up policy was implemented three decades ago. While it
has produced great economic benefits, it has also resulted in the
generation of a huge amount of industrial by-products. The value
⇑ Corresponding author. Tel.: +86 25 52090667.
E-mail address: zsj907@gmail.com (S. Zhao).
blended cements and concrete, has already been widely recog-
nized, but most hazardous materials like iron ore tailings have
been discarded as waste. This has led to a serious environmental
deterioration. Official statistics in 2008 showed that the annual
discharge of iron ore tailings in China was 0.6 billion tons and only
less than 7% had been recycled as resources [2]. These untreated
tailings not only occupy large amounts of land, pollute water re-
sources and the air but also pose threat to human beings’ safety.
A new class of construction material, ultra-high performance
concrete (UHPC), is a highly compact, dense material that exhibits
excellent properties. The material is usually self-consolidating and
highly moldable. The remarkable mechanical properties that can
be obtained include a compressive strength in the range of 150–
800 MPa, a flexural strength up to 50 MPa, a fracture energy
between 1200 and 40,000 J/m2, and an ultimate tensile strain on
the order of 1%. The material also has an extremely low porosity,
which gives it a low permeability and a high durability. The basic

0950-0618/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.conbuildmat.2013.10.019
 S. Zhao et al. / Construction and Building Materials 50 (2014) 540–548
principles of developing UHPC have been established by Richard
and Cheyrezy in 1995 [3].
In the past few years, UHPC has been applied to coupling
beams in high-rise buildings, precast members, infrastructure re-
pairs and special facilities like nuclear waste storage containers.
It is regarded as a promising material for the future but its high
cost restricts its wider application. In order to lower costs, indus-
trial by-products such as fly ash and slag have been used to par-
tially replace cement without significantly impairing the
properties [4,5], and river sand has been employed successfully
as a substitute for the expensive quartz sand [6,7]. However,
the natural aggregate supply in many regions of China falls short
of market demand because of unprecedented large-scale con-
struction, and the price of natural aggregates goes up. Addition-
ally, the continuous extraction of natural aggregates has been
questioned due to a greater awareness of environmental protec-
tion. In light of this, finding a sustainable aggregate source has
recently become a popular research topic [8–10]. With respect
to UHPC, using recycled glass cullet as fine aggregate has been
studied and has been shown to lower the mechanical perfor-
mance by 15% [7].
Iron ore tailings have the potential to be used as fine aggregate
because they are relatively inert and the particle size of the tailings
is significantly larger than that of cement. This paper investigated
the use of iron ore tailings to replace natural sand as fine aggregate
and studied the impact that various replacement levels had on the
mechanical properties of UHPC. Additionally, the pore structure
and the microstructure were examined to interpret the macro-
performance of the material.
2. Raw materials
Ordinary Portland cement, with a strength class of 52.5 in accor-
dance with Chinese Standard GB 175-2007 [11] and two types of
supplementary cementitious materials, type F fly ash and silica
fume, were used as reactive powder. The physical and chemical
properties of the cementitious materials are given in Table 1.
The steel fiber was brass-coated with a tensile strength higher
than 2000 MPa. The length of the fiber was 13 mm and the aspect
ratio was 65. The mixing water was potable tap water. A polycar-
boxylate-based superplasticizer provided by Sika Ltd., was used.
Natural sand and iron ore tailings were used as aggregates. The
natural sand was originally excavated from the lower reaches of
Yangtze River and had an apparent density of 2.63 g/cm3. The tail-
ings were obtained from the local iron and steel industry and had
an apparent density of 2.62 g/cm3. The chemical composition of
the tailings is shown in Table 1. The particle size distribution of
the natural sand and the tailings was tested by a sieve analysis
and a Microtrac S3500 laser particle size analyzer respectively,
and the results are given in Fig. 1. The particle sizes of the natural
Table 1
Physical properties and chemical composition of cementitious materials and iron ore tailings.
Cement
Specific surface area, cm2/g 3620
Specific gravity 3.1
SiO2, % 21.35
Al2O3, % 4.67
Fe2O3, % 3.31
CaO, % 62.6
MgO, % 3.08
SO3, % 2.25
Na2O, % 0.54
K2O, % 0.21
TiO2, % – –
Mn2O3, % – –
LOI, % 1.45
541
sand mostly fell in the range of 0.15–5 mm. The tailings were much
finer with a range of 0.003–0.5 mm.
Fig. 2 shows scanning electron microscope (SEM) photos of the
two aggregates. Both of them had angular particle shapes. The tail-
ings had a highly rough and irregular surface while the natural
sand had a smoother surface.
The crystalline phases in the two aggregates were examined by
X-ray diffraction (XRD) using Cu Ka radiation (40 kV, 30 mA). The
aggregates were each ground to a powder and then were tested
at a step size of 0.02° and a scanning rate of 6°/min with the 2h
ranging from 5° to 70°. The XRD patterns given in Fig. 3 show that
the natural sand was mainly comprised of quartz, while the tailings
contained, in addition to quartz, other minerals such as albite,
diopside, clinochlore, calcite magnesium syn, meixnerite and mag-
nesium ferrous oxide.
Nanoindentation was performed to investigate the intrinsic
mechanical properties of the two aggregates. The test consists of
establishing contact between a sample and a diamond tip of known
geometry and then continuously measuring the applied load P and
the indentation depth h. Two mechanical properties, the indenta-
tion modulus M and the indentation hardness H, can be derived
by analyzing the P–h curve. Proper sample preparation is critical
for the test in order to achieve as flat a surface as possible [12].
In this study, the aggregate was initially vacuum impregnated by
a low-viscosity epoxy resin. After the resin solidified, the sample
was first ground by successively finer-grained silicon carbide paper
and then was polished by water-based diamond suspensions of
four successively finer particle sizes (9 lm, 3 lm, 1 lm and
0.05 lm). After each polishing step, the sample was cleaned ultra-
sonically for 5 min to remove the debris left on the surface.
Approximately 20 indentations were carried out on each aggre-
gate. The spacing between neighboring indentations was set to
be at least 10 lm to avoid potential interferences. For an individual
test, load was linearly increased from the initial contact of the dia-
mond tip on the sample to 2 mN at a rate of 12 mN/min, and then
the load was held constant for 5 s to eliminate the creep effect be-
fore unloading the sample at the same constant rate. Typical P–h
curves for both aggregates are plotted in Fig. 4 and the statistical
mechanical properties of both aggregates are given in Table 2.
From the micromechanical perspective, phases with different
mechanical properties could be differentiated by nanoindentation.
The natural sand showed homogeneous mechanical behavior due
to the dominant quartz phase while the tailings had relatively var-
ied mechanical properties because of responses from the distinct
phases. These results are consistent with the XRD findings.
3. Mix proportions and specimen preparation
In this study, both UHPC mortars (the matrices of UHPC) and
UHPC were produced and tested. The purpose of studying the
Silica fume Fly ash Iron ore tailings
222000 4540 –
2.26 2.24 –
91.2 54.11 52.06
2.22 26.51 17.14
0.88 6.40 9.13
1.2 4.70 12.74
1.25 1.04 3.68
0.64 1.29 –
– 2.22 0.97
– 0.87 0.30
– 0.45
– 0.25
2.14 2.85 3.23
542 S. Zhao et al. / Construction and Building Materials 50 (2014) 540–548
Fig. 1. Particle size distribution of natural sand and iron ore tailings.
UHPC mortars was to investigate the influence of the tailings
content on the mechanical behavior of the UHPC matrix. The mix
design of the UHPC mortars is summarized in Table 3, in which
the contents of aggregates are given as oven-dry state. To prepare
the UHPC, 2% fiber by volume, which is considered an optimum
dosage with respect to performance and cost, was added to the
UHPC mortars. A naming convention for the mixes was used based
on the tailings content and the use of fiber. The UHPC mortars and
the UHPC were denoted by TX and FTX respectively, where X%
stands for the tailings proportion in the aggregate. As shown in
Table 3, the cementitious constituents were kept constant, i.e.
the cement was replaced by 35% fly ash and 15% silica fume in
all the mixes. T0 was the control mix that used 100% natural sand,
which was then replaced by the tailings in subsequent mixes at
five different replacement levels ranging from 20% to 100%. The
superplasticizer dosage was optimized by several trial mixes based
Fig. 2. SEM images of natural sand (a and b) and iron ore tailings (c and d).
on the principle of obtaining the lowest water to binder ratio (w/b).
The dosage was invariable for all the mixes because superplasticiz-
er has little effect on dispersing aggregate. Since superior workabil-
ity is a requirement for UHPC, flowability was tested according to
Chinese Standard GB/T 2419-2005 [13]. The w/b was adjusted for
each mix to achieve a flow diameter of no less than 180 mm for
the UHPC mortars. For T100, it was found that the target flowabil-
ity was hard to attain with a reasonable w/b. Considering that the
w/b for making UHPC is normally below 0.20, the w/b of T100 was
set at 0.2 as the mechanical properties could be significantly im-
paired with a higher w/b. From Table 3, we can see that the w/b in-
creased with an increase of the tailings content. This could be
explained by the following aspects. First, the tailings has a much
higher specific surface area compared to the natural sand, which
can absorb more water. Second, the fineness modulus of the
aggregate becomes lower with an increase of the tailings content,
which demands more water to keep the required workability.
Moreover, the more angular and irregular shape of the tailings
particles could increase the friction between the particles and thus
lower the flow of the material [14]. The flowability of the UHPC
mixes is also presented in Table 3. As was expected, the introduc-
tion of fibers reduced the flow of the mortars and thus slightly
decreased the flowability.
A JJ-5 mortar mixer was used to prepare the material. The mixer
had two revolving speeds (140 rpm and 285 rpm) and met the
requirements of Chinese Standard GB/T17671-1999 [15]. The
cementitious materials and aggregates were first mixed at the
low speed for 3 min, which helped to break apart the agglomerates
and disperse the cementitious materials. The water and superp-
lasticizer were then gradually added and the fresh material was
mixed at the high speed for another 5 min. When preparing the
UHPC, fiber was added subsequently and another 2 min mixing
was applied.
The fresh materials were then cast into steel molds and
compacted on a vibration table for 1 min. Prismatic specimens,
40  40  160 mm, were prepared for mechanical testing, and
30  30  30 mm cubes were prepared for microstructural
analysis. The specimens were cured in molds for 1 day at room
 S. Zhao et al. / Construction and Building Materials 50 (2014) 540–548 543

temperature at about 20 °C. Then they were de-molded and two

different succeeding curing regimes were applied. For standard
curing, the specimens were cured in a moisture room with a
controlled temperature and relative humidity (20 ± 2 °C and
relative humidity >95%) until prescribed ages. For heat curing,
the specimens were cured in an 80 °C steam tank for 2 days.

4. Experimental program

The mechanical properties were determined according to Chinese Standard GB/

T17671-1999 [15]. Three prisms for each mix were tested under three-point
bending to determine the flexural strength at a loading rate of 0.05 kN/s. The com-
pressive strength was then determined from the six broken pieces left from the
flexural test. The loaded area was 40  40 mm and the loading rate was 2.4 kN/s.
All microstructural analysis, including pore structure analysis and SEM
micrographs, were carried out on the standard cured UHPC mortars. After curing
to a designated age, the cubes were broken into pieces and then soaked in ethanol
for 7 days to terminate hydration. Afterwards, the specimens were oven dried at
50 °C for 2 days to remove the ethanol in the sample.
The pore structures of all the mortars were studied by mercury intrusion poros-
imetry (MIP) using an Autopore 9500 instrument. MIP is based on the principle that
a non-wetting liquid will only intrude into a porous medium under pressure. The
relationship between the applied pressure and the cylindrical pore diameter is
described by the Washburn equation [16]. In this study, the maximum and
minimum pressures generated were 310 MPa and 3.5 kPa, which corresponded to
a minimum pore size of 4.0 nm and a maximum pore size of 360 lm, respectively.
From the test, the total porosity and the pore size distribution could be obtained.
Due to the presence of ink-bottle type pores, MIP usually gives an underestimation
of large pores and an overestimation of small pores. However, the threshold pore
diameter above which very little intrusion occurs is still useful as a comparative in-
dex for the connectivity of different samples [17]. The threshold pore diameter is
closely related to the permeability and diffusivity of cementitious materials and
could be considered an indicator of material durability [18].
The microstructure was studied on selected 28-day standard cured mortars by a
FEI Quanta 3D FEG environmental SEM. The morphologies of the hydrated paste and
the interfacial transition zone (ITZ) for different samples were examined.

5. Results and discussion

Fig. 3. XRD patters of natural sand (a) and iron ore tailings (b). 5.1. Mechanical behavior

The compressive and flexural strengths were tested at 3, 7, 28

and 90 days for the standard cured specimens and at 3 days for
the steam cured specimens.

5.1.1. Compressive strength

The compressive strengths of the UHPC mortars that underwent
the different curing regimes are presented in Fig. 5. For the stan-
dard cured specimens, the compressive strength increased with
age. Note that extended curing from 28 to 90 days gave a signifi-
cant strength gain, which indicates the pozzolanic reaction of the
mineral admixtures at later ages. The heat-treated specimens
showed higher compressive strengths than their 28-day standard
cured counterparts did. This could be explained by the acceleration
of the hydration process under high temperature curing which
leads to a significant increase of the early age strength. However,
the rapid formation of hydration products around unhydrated ce-
ment grains retards further hydration and causes increased poros-
ity that negatively affects the strength development [19].
Fig. 4. Typical indentation load–depth curves of natural sand and iron ore tailings.
Therefore, the compressive strengths of the heat-treated speci-
mens did not match that of the 90-day standard cured specimens,
Table 2 with the exception of the control mix.
Indentation modulus (M) and indentation hardness (H) results of natural sand and Fig. 5 also shows that the compressive strengths of the UHPC
iron ore tailings (statistics from 20 indentations for each aggregate). mortars generally decreased with an increase of the tailings con-
Max. Min. Avg. Sd. tent. Two factors could contribute to the strength decrease. First,
Natural sand M, GPa 146.5 101.3 113.6 12.3
the increase of the tailings content increased the w/b, which would
H, GPa 23.23 14.54 17.72 2.41 result in the strength loss. Second, as indicated by the nanoinden-
Iron ore tailings M, GPa 234.4 8.5 90.3 51.1
tation test results, the stiffness and hardness of the tailings were on
H, GPa 20.79 0.92 9.14 5.37 average lower than those of the natural sand, which could also con-
tribute to the strength decrease. On the other hand, however, the
544 S. Zhao et al. / Construction and Building Materials 50 (2014) 540–548
Table 3
Mix proportions and flowability of UHPC mortars and UHPC.
Cementitious components (%) Aggregate to binder ratioa
Cement Fly ash Silica fume Natural sand Iron ore tailings
T0 50 35 15 1.2 – 0.16
T20 50 35 15 0.96 0.24
T30 50 35 15 0.84 0.36
T40 50 35 15 0.72 0.48
T50 50 35 15 0.6 0.6
T100 50 35 15 – 1.2
a
Contents of aggregates are given in oven-dry state.
b
Water in superplasticizer is included.
surface texture of an aggregate has a significant influence on the
compressive strength [20]. The rough surface of the tailings could
improve the grip between the aggregates and the paste, which is
beneficial to strength development. Therefore, this could help mit-
igate the strength loss to some extent. Based on the experimental
results shown in Fig. 5, we can see that, generally, the strength-
impairing effect outweighs the strength-beneficial effect. With
standard curing, the compressive strength of T0 was 93.1 MPa at
28 days, and the tailings mixes showed a strength loss of less than
10% when the tailings content was no more than 50%. At 90 days,
the compressive strengths of T20, T30 and T40 were even higher
than that of the control mix. T20 showed the highest strength of
118.2 MPa, which was almost 10% higher than the strength of T0.
This indicates that a higher rate of strength increase is achieved
from 28 to 90 days for these three mortars than that of the control
mix. The compressive strength of T100 is about 14% lower than T0
at both 28 and 90 days. With steam curing, the strength loss with
an increase of the tailings content was more significant compared
to standard curing. The control mix showed a compressive strength
of 116.8 MPa, and every 10% increase in the tailings content caused
a 4% compressive strength drop when the tailings content in-
creased from 0% to 40%. T50 showed similar compressive strength
to T30, and T100 had a strength loss of 26%.
The compressive strengths of UHPC mixes are given in Fig. 6. The
introduction of 2% steel fiber remarkably increased the compressive
strength. The basic trend of the influence of the curing and tailings
content on the compressive strength was similar to the trend shown
in Fig. 5. The major difference was that, with steel fibers, the com-
pressive strengths of the steam cured mixes were higher than that
of their 90-day standard cured counterparts. This indicates that
the strength enhancing effect of steel fiber might be more signifi-
cant when heat treatment is applied. For the steam cured UHPC,
the control mix showed the highest strength of 174.6 MPa, and
FT20, FT30, FT40, FT50 and FT100 showed a strength loss of 3.3%,
6.1%, 10.8%, 19.1% and 24.4%, respectively. For the 28-day standard
cured UHPC, the compressive strength of FT20 was close to that of
FT0, but with the tailings content further increased from 20% to
100%, the compressive strength decreased linearly from 139.2 to
97.2 MPa. The strength loss of FT50 and FT100 was 12.6% and
29.3% compared to FT0, respectively. For the 90-day standard cured
UHPC, however, the compressive strengths of the tailings mixes
were comparable to that of the control mix when the tailings con-
tent ranged from 20% to 50%. FT0, FT20, FT30, FT40 and FT50
showed compressive strengths of 147.0, 144.0, 149.0, 148.9 and
140.5 MPa, respectively. The strength loss of FT100 was 19.5%. This
again indicates that a higher rate of strength gain is obtained for the
tailings mixes in the later curing period.
5.1.2. Flexural strength
Both compressive strength and flexural strength are a function
of the porosity of a material, but flexural strength is more sensitive
Water to binder ratiob Superplasticizer Flow diameter (mm)
(% solid by weight of binder)
Mortars UHPC
0.98 190 175
0.165 0.98 180 165
0.17 0.98 180 160
0.175 0.98 195 180
0.18 0.98 195 180
0.20 0.98 160 150
to features/defects in the microstructure, like micro-cracks in the
material, than compressive strength [21,22]. Therefore, as shown
in Figs. 7 and 8, the flexural strength results showed higher scatter
due to the complex microstructure of concrete materials.
The flexural strengths of the UHPC mortars that underwent dif-
ferent curing regimes are presented in Fig. 7. With standard curing,
the incorporation of the tailings into the mix showed no impair-
ment on the flexural strength at early ages. T20, T30 and T100 even
had higher flexural strengths than T0 at 3 and 7 days. At 28 days,
however, the control mix had a flexural strength of 18.6 MPa,
and all the tailings mortars showed a strength loss of 1017%. At
90 days, the flexural strength of T0 increased to 22.5 MPa, and
the strength gap between T0 and the tailings mortars became even
more significant. The flexural strength decreased by about 20%
when the tailings content ranged from 20% to 50% and decreased
by 29% for T100. For steam curing, the control mix had a similar
flexural strength compared to its 28-day standard cured counter-
part; however, all the tailings mortars exhibited higher strengths
than their 28-day standard cured counterparts and had strengths
comparable to the control mix.
The introduction of fibers into cementitious materials is more
effective at enhancing the flexural strength than the compressive
strength of the materials when the fiber content is higher than a
critical value [23]. For example, comparing Figs. 5–8, the increase
in the flexural strengths when fibers were added was about 70%
while the increase in the compressive strengths was only about
50% for the 90-day standard cured mixes. In Fig. 8, for the standard
cured UHPC at early ages, there was no obvious trend of the flex-
ural strength development versus the tailings content. At 28 days,
the flexural strength of the control mix was 29.65 MPa, and the
flexural strength decreased with an increase of the tailings content.
FT20 only showed a strength loss of 2.0% while FT100 showed the
lowest strength of 24.29 MPa (18% drop). At 90 days, the flexural
strength fluctuated with the tailings content and the variation
range was below 8% compared to the control. Note that FT100
showed the highest flexural strength of 32.85 MPa at 90 days. For
the steam cured UHPC, some of them showed higher flexural
strengths than their 90-day standard cured counterparts, and it is
interesting that all of the tailing mixes showed higher flexural
strengths than the control mix. The flexural strength increased
from 30.17 to 33.18 MPa with an increase in the tailings content
from 0% to 50%, and then the strength decreased to 31.42 MPa
for 100% tailings content. For UHPC, fibers bridge the cracks in
the matrix and continue to carry load after the matrix reaches its
peak load. Therefore, the ultimate flexural strength of UHPC is
dominated by the dispersion of the fibers and the interaction be-
tween the fibers and matrix. This interaction is further related to
the microstructure of the fiber–matrix interfacial zone and the
homogeneity of the matrix, which affect the fiber debonding
behavior. The tailings, with a smaller average particle size than
the natural sand, could give a better dispersion of the fibers [24]
 S. Zhao et al. / Construction and Building Materials 50 (2014) 540–548 545

Fig. 5. Compressive strength results of UHPC mortars under different curing Fig. 6. Compressive strength results of UHPC mixes under different curing regimes.
regimes.

and a more homogeneous matrix, which are beneficial to the flex-
ural strength.
From the strength results shown above, we can see that the
addition of the tailings into the UHPC generally decreased the
mechanical properties of the UHPC matrix. However, with the
introduction of fibers, the UHPC tailings mixes exhibited compara-
ble mechanical properties to the control mix when the tailings con-
tent ranged from 20% to 40%. Specifically, for the 90-day standard
cured UHPC tailings mixes, the mechanical properties were close to
those of the control mix, and for the steam cured mixes, the com-
pressive strengths decreased by less than 11% while the flexural
strengths increased by up to 8% as compared with the control
mix. Therefore, based on the mechanical behavior, it can be con-
cluded that iron ore tailings can be used to partially replace natural
sand to produce UHPC.
5.2. Micro-analysis
T40, T50 and T100 had porosities of 3.8%, 4.7%, 5.3%, 5.7%, 6.4%
and 7.3%, respectively. This could be explained by the increased
w/b with an increase of the tailings content. In Fig. 10b, it is ob-
served that all the mixes showed almost the same threshold pore
diameter (20 nm), which implies that the addition of tailings does
not significantly affect the transport property and durability of the
material. But with an increase of the tailings content, the pore size
distribution curve shifted toward larger pore size. So we can con-
clude that under standard curing, the addition of the tailings into
the UHPC had little impact on the threshold pore size, but tended
to increase the total porosity and slightly coarsen the micro-pore
structure of the material.
In general, compressive strength is closely related to the total
porosity of cementitious materials. Fig. 11 shows the compressive
strength of the 28-day standard cured specimens versus the total
porosity. The coefficient of determination (R2) of the linear fit is
0.90, which indicates a good correlation between the experimental
compressive strength and the total porosity.

5.2.1. Pore structure 5.2.2. Microstructure

The development of pore structure with curing age was investi- Fig. 12a–c show the morphologies of T0, T50 and T100 at a
gated on sample T30. Cumulative porosity and differential pore relatively large scale. It was difficult to identify the aggregate from
size distribution of T30 at different curing ages are presented in the images because the grey levels of the aggregate and the paste
Fig. 9. It can be observed that the measured pores were mainly were similar in the SEM images. The boundary of the river sand
composed of macro-pores with pore sizes of several tens to hun- could be observed in Fig. 12a and b, but the tailings were
dreds of micrometers, and micro-pores with pore sizes below
100 nm. The macro-pores mainly come from entrapped air bub-
bles, and the micro-pores can be attributed to the capillary and
gel pores formed during hydration. In Fig. 9a, it is shown that there
was only a very slight decrease in porosity from 3 to 7 days, but
prolonged curing to 28 days significantly reduced the total porosity
from 10% to 5.3%. Fig. 9b shows the similar trend for the pore size
distribution. The threshold pore size decreased remarkably from
100 nm at early age to 20 nm at 28 days. This indicates that aging
promotes the refinement of pores through filling the pores with
hydration products.
The effect of the tailings content on the pore structure of the 28-
day standard cured samples is illustrated in Fig. 10. From Fig. 10a,
We can see that the entrapped air content varied with different
mixes. This could be related to the flowability and viscosity of
the fresh mixes because the air bubbles formed during mixing is
more likely to be entrapped in a low flowable and high viscous
mix. T100 had the lowest flowability and thereby had the highest
entrapped air content. Fig. 10a also shows that the total porosity
increased with an increase of the tailings content. T0, T20, T30, Fig. 7. Flexural strength results of UHPC mortars under different curing regimes.
546 S. Zhao et al. / Construction and Building Materials 50 (2014) 540–548
Fig. 8. Flexural strength results of UHPC mixes under different curing regimes.
Fig. 9. Pore size distribution of T30 (the mortar using 30% iron ore tailings as fine
aggregate) at ages of 3, 7 and 28 days.
completely indistinguishable in Fig. 12b and c probably due to
their smaller particle size. Entrapped air voids could be observed
in the photos. Their content increased with an increase of the tail-
ings content, which is consistent with the MIP results. Fig. 12d and
e presents the microstructure of the paste in T0 and T100. As all the
mixes had almost the same paste constituents, the two mixes
showed essentially the same micro-features. The spherical fly ash
particles of different sizes were scattered throughout the dense
Fig. 10. Pore size distribution of UHPC mortars at 28 days.
Fig. 11. Correlation between compressive strength and porosity of UHPC mortars at
28 days.
paste and embedded in hydrated calcium silicate hydrate gel and
calcium aluminum silicate hydrate gel. At 28 days, most fly ash
particles were still unreacted or only partially reacted due to their
low pozzolanic reactivity. In addition, the spherical holes shown in
the image were created by removed fly ash particles that had re-
mained on the other fracture surface.
In ordinary concrete, the ITZ is considered the weakest part of
the material due to the high porosity in this zone [25]. In
Fig. 12f, the morphology of the ITZ around a natural sand particle
 S. Zhao et al. / Construction and Building Materials 50 (2014) 540–548 547

Fig. 12. Microstructure of T0 (a, d and f), T50 (b) and T100 (c, e, g and h) which use 0%, 50% and 100% iron ore tailings as fine aggregate, respectively. (a–c) Show the profiles at
low magnification; (d and e) show the morphologies of the paste; (f–h) shows the microstructure of the aggregate–paste interfacial zone.

in T0 is given and it appeared very dense. There were no large vis-
ible pores in this zone and the bond between the sand and the
paste seemed to be very strong. Previous nanoindentation work
confirmed that the micro-mechanical properties were similar be-
tween the interfacial zone and the bulk paste of the UHPC [26].
This is mainly attributed to the use of silica fume, which densifies
the packing in the ITZ [27]. Moreover, the dense ITZ is related to
the high water-retention ability and high homogeneity of the fresh
UHPC, without which the bleeding water could gather around the
aggregate and result in a porous and weak ITZ. Fig. 12g shows a
tailings particle in T100. Though the surface of the particle was
angled to the plane surface, a dense ITZ surrounding the particle
could still be observed. However, a different case in T100 is pre-
sented in Fig. 12h. Oriented crystalline calcium hydroxide (CH)
was observed in the ITZ, which is harmful to strength because
CH is prone to fracture and thereby can initiate cracks under load.
As described above, some tailings particles with a porous surface
could absorb extra water during mixing, which provides adequate
room for the growth of CH during hydration and hence form the
porous ITZ.
548 S. Zhao et al. / Construction and Building Materials 50 (2014) 540–548
6. Conclusions
In this study, the feasibility of using iron ore tailings as fine
aggregate in UHPC was studied. Based on the experimental results,
several conclusions can be drawn:
1. The tailings included several inert phases and its average
particle size was much larger than that of cement, which
indicates that it could be used as fine aggregate to produce
UHPC. The stiffness and hardness of the tailings were on
average lower than those of the natural sand.
2. Incorporation of the tailings into the mix increased the
water demand and lowered the flowability of the fresh
material due to the high specific surface area and rough
surface of the tailings.
3. The mechanical behavior of the UHPC matrix generally
decreased with an increase of the tailings content. How-
ever, the presence of fiber changed the material behavior.
When the tailings content was no more than 40%, the UHPC
tailings mixes showed comparable mechanical properties
to the control mix. Therefore, from the perspective of
mechanical behavior, it is feasible to use iron ore tailings
to partially replace natural sand to make UHPC.
4. The porosity and the threshold pore diameter of the UHPC
matrix significantly decreased from 7 to 28 days under
standard curing. The increase of the tailings content did
not affect the threshold pore size, but tended to slightly
increase the porosity and coarsen the micro-pore structure
of the UHPC matrix. Moreover, there was a good correlation
between the compressive strength and porosity of the
UHPC matrix.
5. The microstructure of the paste appeared to be very dense.
With regards to the ITZ, there was generally a good bond
between the paste and the aggregates. However, around
some tailings particles, oriented crystalline CH could be
observed in the ITZ, which is harmful to the material
properties.
Acknowledgments
Financial support from China Railway No. 3 Engineering Group
Co., Ltd., is gratefully acknowledged. The authors would also like to
thank Emily Van Dam, a graduate student from University of Illi-
nois at Urbana-Champaign, for helping to improve the manuscript.
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