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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.
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) 540–548 541
principles of developing UHPC have been established by Richard sand mostly fell in the range of 0.15–5 mm. The tailings were much
and Cheyrezy in 1995 [3]. finer with a range of 0.003–0.5 mm.
In the past few years, UHPC has been applied to coupling Fig. 2 shows scanning electron microscope (SEM) photos of the
beams in high-rise buildings, precast members, infrastructure re- two aggregates. Both of them had angular particle shapes. The tail-
pairs and special facilities like nuclear waste storage containers. ings had a highly rough and irregular surface while the natural
It is regarded as a promising material for the future but its high sand had a smoother surface.
cost restricts its wider application. In order to lower costs, indus- The crystalline phases in the two aggregates were examined by
trial by-products such as fly ash and slag have been used to par- X-ray diffraction (XRD) using Cu Ka radiation (40 kV, 30 mA). The
tially replace cement without significantly impairing the aggregates were each ground to a powder and then were tested
properties [4,5], and river sand has been employed successfully at a step size of 0.02° and a scanning rate of 6°/min with the 2h
as a substitute for the expensive quartz sand [6,7]. However, ranging from 5° to 70°. The XRD patterns given in Fig. 3 show that
the natural aggregate supply in many regions of China falls short the natural sand was mainly comprised of quartz, while the tailings
of market demand because of unprecedented large-scale con- contained, in addition to quartz, other minerals such as albite,
struction, and the price of natural aggregates goes up. Addition- diopside, clinochlore, calcite magnesium syn, meixnerite and mag-
ally, the continuous extraction of natural aggregates has been nesium ferrous oxide.
questioned due to a greater awareness of environmental protec- Nanoindentation was performed to investigate the intrinsic
tion. In light of this, finding a sustainable aggregate source has mechanical properties of the two aggregates. The test consists of
recently become a popular research topic [8–10]. With respect establishing contact between a sample and a diamond tip of known
to UHPC, using recycled glass cullet as fine aggregate has been geometry and then continuously measuring the applied load P and
studied and has been shown to lower the mechanical perfor- the indentation depth h. Two mechanical properties, the indenta-
mance by 15% [7]. tion modulus M and the indentation hardness H, can be derived
Iron ore tailings have the potential to be used as fine aggregate by analyzing the P–h curve. Proper sample preparation is critical
because they are relatively inert and the particle size of the tailings for the test in order to achieve as flat a surface as possible [12].
is significantly larger than that of cement. This paper investigated In this study, the aggregate was initially vacuum impregnated by
the use of iron ore tailings to replace natural sand as fine aggregate a low-viscosity epoxy resin. After the resin solidified, the sample
and studied the impact that various replacement levels had on the was first ground by successively finer-grained silicon carbide paper
mechanical properties of UHPC. Additionally, the pore structure and then was polished by water-based diamond suspensions of
and the microstructure were examined to interpret the macro- four successively finer particle sizes (9 lm, 3 lm, 1 lm and
performance of the material. 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-
2. Raw materials gate. The spacing between neighboring indentations was set to
be at least 10 lm to avoid potential interferences. For an individual
Ordinary Portland cement, with a strength class of 52.5 in accor- test, load was linearly increased from the initial contact of the dia-
dance with Chinese Standard GB 175-2007 [11] and two types of mond tip on the sample to 2 mN at a rate of 12 mN/min, and then
supplementary cementitious materials, type F fly ash and silica the load was held constant for 5 s to eliminate the creep effect be-
fume, were used as reactive powder. The physical and chemical fore unloading the sample at the same constant rate. Typical P–h
properties of the cementitious materials are given in Table 1. curves for both aggregates are plotted in Fig. 4 and the statistical
The steel fiber was brass-coated with a tensile strength higher mechanical properties of both aggregates are given in Table 2.
than 2000 MPa. The length of the fiber was 13 mm and the aspect From the micromechanical perspective, phases with different
ratio was 65. The mixing water was potable tap water. A polycar- mechanical properties could be differentiated by nanoindentation.
boxylate-based superplasticizer provided by Sika Ltd., was used. The natural sand showed homogeneous mechanical behavior due
Natural sand and iron ore tailings were used as aggregates. The to the dominant quartz phase while the tailings had relatively var-
natural sand was originally excavated from the lower reaches of ied mechanical properties because of responses from the distinct
Yangtze River and had an apparent density of 2.63 g/cm3. The tail- phases. These results are consistent with the XRD findings.
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 3. Mix proportions and specimen preparation
the natural sand and the tailings was tested by a sieve analysis
and a Microtrac S3500 laser particle size analyzer respectively, In this study, both UHPC mortars (the matrices of UHPC) and
and the results are given in Fig. 1. The particle sizes of the natural UHPC were produced and tested. The purpose of studying the
Table 1
Physical properties and chemical composition of cementitious materials and iron ore tailings.
Fig. 2. SEM images of natural sand (a and b) and iron ore tailings (c and d).
S. Zhao et al. / Construction and Building Materials 50 (2014) 540–548 543
4. Experimental program
Fig. 3. XRD patters of natural sand (a) and iron ore tailings (b). 5.1. Mechanical behavior
Table 3
Mix proportions and flowability of UHPC mortars and UHPC.
Cementitious components (%) Aggregate to binder ratioa Water to binder ratiob Superplasticizer Flow diameter (mm)
(% solid by weight of binder)
Cement Fly ash Silica fume Natural sand Iron ore tailings Mortars UHPC
T0 50 35 15 1.2 – 0.16 0.98 190 175
T20 50 35 15 0.96 0.24 0.165 0.98 180 165
T30 50 35 15 0.84 0.36 0.17 0.98 180 160
T40 50 35 15 0.72 0.48 0.175 0.98 195 180
T50 50 35 15 0.6 0.6 0.18 0.98 195 180
T100 50 35 15 – 1.2 0.20 0.98 160 150
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 to features/defects in the microstructure, like micro-cracks in the
compressive strength [20]. The rough surface of the tailings could material, than compressive strength [21,22]. Therefore, as shown
improve the grip between the aggregates and the paste, which is in Figs. 7 and 8, the flexural strength results showed higher scatter
beneficial to strength development. Therefore, this could help mit- due to the complex microstructure of concrete materials.
igate the strength loss to some extent. Based on the experimental The flexural strengths of the UHPC mortars that underwent dif-
results shown in Fig. 5, we can see that, generally, the strength- ferent curing regimes are presented in Fig. 7. With standard curing,
impairing effect outweighs the strength-beneficial effect. With the incorporation of the tailings into the mix showed no impair-
standard curing, the compressive strength of T0 was 93.1 MPa at ment on the flexural strength at early ages. T20, T30 and T100 even
28 days, and the tailings mixes showed a strength loss of less than had higher flexural strengths than T0 at 3 and 7 days. At 28 days,
10% when the tailings content was no more than 50%. At 90 days, however, the control mix had a flexural strength of 18.6 MPa,
the compressive strengths of T20, T30 and T40 were even higher and all the tailings mortars showed a strength loss of 1017%. At
than that of the control mix. T20 showed the highest strength of 90 days, the flexural strength of T0 increased to 22.5 MPa, and
118.2 MPa, which was almost 10% higher than the strength of T0. the strength gap between T0 and the tailings mortars became even
This indicates that a higher rate of strength increase is achieved more significant. The flexural strength decreased by about 20%
from 28 to 90 days for these three mortars than that of the control when the tailings content ranged from 20% to 50% and decreased
mix. The compressive strength of T100 is about 14% lower than T0 by 29% for T100. For steam curing, the control mix had a similar
at both 28 and 90 days. With steam curing, the strength loss with flexural strength compared to its 28-day standard cured counter-
an increase of the tailings content was more significant compared part; however, all the tailings mortars exhibited higher strengths
to standard curing. The control mix showed a compressive strength than their 28-day standard cured counterparts and had strengths
of 116.8 MPa, and every 10% increase in the tailings content caused comparable to the control mix.
a 4% compressive strength drop when the tailings content in- The introduction of fibers into cementitious materials is more
creased from 0% to 40%. T50 showed similar compressive strength effective at enhancing the flexural strength than the compressive
to T30, and T100 had a strength loss of 26%. strength of the materials when the fiber content is higher than a
The compressive strengths of UHPC mixes are given in Fig. 6. The critical value [23]. For example, comparing Figs. 5–8, the increase
introduction of 2% steel fiber remarkably increased the compressive in the flexural strengths when fibers were added was about 70%
strength. The basic trend of the influence of the curing and tailings while the increase in the compressive strengths was only about
content on the compressive strength was similar to the trend shown 50% for the 90-day standard cured mixes. In Fig. 8, for the standard
in Fig. 5. The major difference was that, with steel fibers, the com- cured UHPC at early ages, there was no obvious trend of the flex-
pressive strengths of the steam cured mixes were higher than that ural strength development versus the tailings content. At 28 days,
of their 90-day standard cured counterparts. This indicates that the flexural strength of the control mix was 29.65 MPa, and the
the strength enhancing effect of steel fiber might be more signifi- flexural strength decreased with an increase of the tailings content.
cant when heat treatment is applied. For the steam cured UHPC, FT20 only showed a strength loss of 2.0% while FT100 showed the
the control mix showed the highest strength of 174.6 MPa, and lowest strength of 24.29 MPa (18% drop). At 90 days, the flexural
FT20, FT30, FT40, FT50 and FT100 showed a strength loss of 3.3%, strength fluctuated with the tailings content and the variation
6.1%, 10.8%, 19.1% and 24.4%, respectively. For the 28-day standard range was below 8% compared to the control. Note that FT100
cured UHPC, the compressive strength of FT20 was close to that of showed the highest flexural strength of 32.85 MPa at 90 days. For
FT0, but with the tailings content further increased from 20% to the steam cured UHPC, some of them showed higher flexural
100%, the compressive strength decreased linearly from 139.2 to strengths than their 90-day standard cured counterparts, and it is
97.2 MPa. The strength loss of FT50 and FT100 was 12.6% and interesting that all of the tailing mixes showed higher flexural
29.3% compared to FT0, respectively. For the 90-day standard cured strengths than the control mix. The flexural strength increased
UHPC, however, the compressive strengths of the tailings mixes from 30.17 to 33.18 MPa with an increase in the tailings content
were comparable to that of the control mix when the tailings con- from 0% to 50%, and then the strength decreased to 31.42 MPa
tent ranged from 20% to 50%. FT0, FT20, FT30, FT40 and FT50 for 100% tailings content. For UHPC, fibers bridge the cracks in
showed compressive strengths of 147.0, 144.0, 149.0, 148.9 and the matrix and continue to carry load after the matrix reaches its
140.5 MPa, respectively. The strength loss of FT100 was 19.5%. This peak load. Therefore, the ultimate flexural strength of UHPC is
again indicates that a higher rate of strength gain is obtained for the dominated by the dispersion of the fibers and the interaction be-
tailings mixes in the later curing period. tween the fibers and matrix. This interaction is further related to
the microstructure of the fiber–matrix interfacial zone and the
5.1.2. Flexural strength homogeneity of the matrix, which affect the fiber debonding
Both compressive strength and flexural strength are a function behavior. The tailings, with a smaller average particle size than
of the porosity of a material, but flexural strength is more sensitive 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.
T40, T50 and T100 had porosities of 3.8%, 4.7%, 5.3%, 5.7%, 6.4%
and a more homogeneous matrix, which are beneficial to the flex- and 7.3%, respectively. This could be explained by the increased
ural strength. w/b with an increase of the tailings content. In Fig. 10b, it is ob-
From the strength results shown above, we can see that the served that all the mixes showed almost the same threshold pore
addition of the tailings into the UHPC generally decreased the diameter (20 nm), which implies that the addition of tailings does
mechanical properties of the UHPC matrix. However, with the not significantly affect the transport property and durability of the
introduction of fibers, the UHPC tailings mixes exhibited compara- material. But with an increase of the tailings content, the pore size
ble mechanical properties to the control mix when the tailings con- distribution curve shifted toward larger pore size. So we can con-
tent ranged from 20% to 40%. Specifically, for the 90-day standard clude that under standard curing, the addition of the tailings into
cured UHPC tailings mixes, the mechanical properties were close to the UHPC had little impact on the threshold pore size, but tended
those of the control mix, and for the steam cured mixes, the com- to increase the total porosity and slightly coarsen the micro-pore
pressive strengths decreased by less than 11% while the flexural structure of the material.
strengths increased by up to 8% as compared with the control In general, compressive strength is closely related to the total
mix. Therefore, based on the mechanical behavior, it can be con- porosity of cementitious materials. Fig. 11 shows the compressive
cluded that iron ore tailings can be used to partially replace natural strength of the 28-day standard cured specimens versus the total
sand to produce UHPC. 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. Micro-analysis
Fig. 8. Flexural strength results of UHPC mixes under different curing regimes.
Fig. 11. Correlation between compressive strength and porosity of UHPC mortars at
Fig. 9. Pore size distribution of T30 (the mortar using 30% iron ore tailings as fine
28 days.
aggregate) at ages of 3, 7 and 28 days.
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- tailings particle in T100. Though the surface of the particle was
ible pores in this zone and the bond between the sand and the angled to the plane surface, a dense ITZ surrounding the particle
paste seemed to be very strong. Previous nanoindentation work could still be observed. However, a different case in T100 is pre-
confirmed that the micro-mechanical properties were similar be- sented in Fig. 12h. Oriented crystalline calcium hydroxide (CH)
tween the interfacial zone and the bulk paste of the UHPC [26]. was observed in the ITZ, which is harmful to strength because
This is mainly attributed to the use of silica fume, which densifies CH is prone to fracture and thereby can initiate cracks under load.
the packing in the ITZ [27]. Moreover, the dense ITZ is related to As described above, some tailings particles with a porous surface
the high water-retention ability and high homogeneity of the fresh could absorb extra water during mixing, which provides adequate
UHPC, without which the bleeding water could gather around the room for the growth of CH during hydration and hence form the
aggregate and result in a porous and weak ITZ. Fig. 12g shows a porous ITZ.
548 S. Zhao et al. / Construction and Building Materials 50 (2014) 540–548
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