Construction and Building Materials 73 (2014) 754763

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Construction and Building Materials

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

Investigation of using hybrid recycled powder from demolished concrete

solids and clay bricks as a pozzolanic supplement for cement
Qiong Liu a,b, Teng Tong a, Shuhua Liu c, Dezhi Yang d, Qiang Yu a,
a

Department of Civil and Environmental Engineering, University of Pittsburgh, PA 15261, USA

Shanghai Research Institute of Building Science, 200032, China
c
State Key Laboratory of Water Resources and Hydropower Engineering Science, Wuhan University, 430072, China
d
Dujiangyan Recycled Construction Material Company, China
b

h i g h l i g h t s
 The pozzolanic property of hybrid recycled powder is systematically studied.
 The unique microstructure morphology of hybrid recycled powder is captured.
 Quantitative chemical analysis is carried out for hybrid recycled powder.
 Hybrid recycled powder changes the microstructure characteristics of cement paste.
 Hybrid recycled powder shows potential of being used as a supplement for cement.

a r t i c l e

i n f o

Article history:
Received 8 August 2014
Received in revised form 23 September
2014
Accepted 25 September 2014
Available online 31 October 2014
Keywords:
Construction and demolition wastes
Sintered clay brick
Hybrid recycled powder
Pozzolanic activity
Air pollution

a b s t r a c t
During recycling construction and demolition wastes containing both concrete solids and clay bricks, a
large amount of hybrid ne powder is generated. Finding a green way to dispose this hybrid recycled
powder not only promotes sustainable construction, but also benets the current effort to reduce the
human-produced aerosol, which triggers air pollution. To investigate the use of hybrid recycled powder
as a supplementary cementing material, the pozzolanic property of hybrid powder is comprehensively
studied here by utilizing advanced tools including SEM, AFM, LPS and XRD. Recycled powder of different
concreteclay brick ratios is rst studied with a focus on its neness, loss on ignition, strength activity
index and water requirement. Then, the microstructure characteristics and chemical composition of
the hybrid recycled powder, obtained directly from a dust collection system, are qualitatively and quantitatively probed. To develop a deeper understanding of the activity mechanism of hybrid powder, nanoscale characterization is employed to scan and analyze the microstructure of cement paste supplemented
with hybrid recycled powder. It is found that the activity mechanism of hybrid powder is strongly correlated with its unique microstructure morphology and chemical composition. The results show that if
the proportion of clay brick as well as the replacement percentage is well designed, hybrid powder from
dust collection systems has potentials of being used as a cement supplement for concrete.
2014 Elsevier Ltd. All rights reserved.

1. Introduction
The construction and demolition wastes (C&D wastes) generally
consist of materials used in civil construction, which typically
include concrete, clay brick, mortar, wood, plastic and steel. As
more and more civil structures are approaching the end of their
expected lifespan, nding economical and environment-friendly
strategies to manage the disposal of C&D wastes is an essential

Corresponding author. Tel.: +1 412 624 9899.

E-mail address: qiy15@pitt.edu (Q. Yu).
http://dx.doi.org/10.1016/j.conbuildmat.2014.09.066
0950-0618/ 2014 Elsevier Ltd. All rights reserved.

aspect of the current progress towards a sustainable built

environment.
A promising practice to meet this goal is to utilize C&D wastes
to generate recycled materials and then use them again to produce
green construction materials. After metals and organic materials
are removed, C&D wastes can be crushed into recycled aggregates,
which are then reused in construction based on their mechanical
and chemical properties. This practice, which signicantly reduces
the environmental and economic footprints of civil structures, has
been widely adopted around the world and many international and
national specications and standards [15] are developed to guide
and improve its implementations in practice.

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During the recycling process, a large amount of dust, as a

byproduct, is generated. The dust obtained from collection systems
is usually called recycled micro-powder and how to reuse it is a
challenge attracting increasing interests in recent years. Similar
to many other countries, a signicant portion of C&D wastes is sintered clay brick in China, especially for those collected in towns
and villages. Due to the nancial burden resulting from the high
demands for labor and time, there are usually no screening procedures implemented to separate concrete solids and clay bricks
from C&D wastes in the current recycling practice. Consequently,
the recycled powder obtained in collection systems is a hybrid of
concrete and clay brick. A recent report shows that the percentage
of clay brick can be up to more than 50% in C&D wastes collected in
Chinese cities [6,7]. This unique composition of C&D wastes leads
to more dust obtained in collection systems, because sintered clay
brick has lower strength compared to concrete and thus is easier to
be pulverized during recycling [8,9].
This hybrid recycled powder of a large number of ne particles,
if not correctly collected and disposed, can spread and suspend in
air to increase the level of human-produced aerosol, which triggers
air pollution causing respiratory system diseases and other disorders, e.g., asthmas and lung cancer. In many developing countries,
the particulate-induced air pollution imposes a severe threat to
public health, which is exemplied by the increasing air quality
warnings issued in Chinese cities. Therefore, nding a green
way to dispose the waste dust generated in the recycling of C&D
wastes is of great importance for reducing the ne particulates suspended in air, and thus contributes to both public health and environmental sustainability.
An environment-friendly way is to reuse it like y ash to produce green construction materials. It is widely reported that sintered clay brick, after comminuted, can be used as a pozzolanic
supplement like y ash because of the rich pozzolanic ingredients
in its mineral composition [10,11]. Thus, it can be added to concrete to replace part of cement, as well as to suppress the expansion induced by the possible alkalisilica reaction [12]. In a
recent research [13], different types of clay bricks from different
European countries were collected and then ground into powder
to replace the cement. Chemical tests for pozzolanic activity conrmed that all the brick types investigated displayed good pozzolanic activity and this conclusion was further supported by
strength development data based on the mortar bars [14].
It is found if the proportion of the recycled clay brick powder in
the concrete mix is well designed, the concrete strength is not signicantly compromised. In an investigation by Kartini et al. [15],
recycled clay brick powder is used to replace part of cement in concrete samples. The test results show corresponding to 10%, 20% and
30% replacement, the average strength of samples, when compared
with the benchmark samples containing no recycled clay brick
powder, is 4.4%, 8.4% and 14.9% lower, respectively. In another
investigation, it is reported that no signicant effect is found on
the water demand and the setting time even the replacement is
up to 25% [16].
The effect of recycled clay brick powder is also investigated in
mortar. It is documented that when it replaces 10% of cement,
the values of compressive and exural strength at 90 days are similar to the companion samples, whose mix does not include any
supplements [17]. Besides proportion, the grain size of brick powder shows a signicant impact on the mortar strength. A recent test
on mortar samples containing recycled clay brick powder graded
by 4 different grain sizes, namely, 0.04, 0.06, 0.1 and 0.3 mm,
shows that the grain size of 0.06 mm gives the highest strength
among all the samples tested [18].
Similar to recycled clay brick powder, recycled concrete powder
can also be used as a supplement in concrete because of its pozzolanic property. Both Chen et al. [19] and Sun et al. [20] studied the

recycled micro-powder collected from the dust collection systems

used for recycling demolished concrete solids. In their studies, the
recycled micro-powder collected is mainly ne particles of
hardened cement paste, mixed with a very small portion of stone
powder from aggregate. By comparing the strength of samples containing recycled concrete powder with those containing none, they
found that the recycled concrete powder showed about 70% pozzolanic activity.
The pozzolanic properties exhibited in both recycled clay brick
powder and recycled concrete powder imply that it is possible to
use the hybrid recycled powder obtained from dust collection systems as a cement supplement. Motivated by this, research to
explore the use of the recycled powder from a hybrid of demolished concrete and clay brick attracts increasing interests. However, despite the progress has been made, information of the
activity mechanisms of hybrid recycled powder and their correlation with concrete macro- and micro-properties is limited and further systematic study is much needed. To respond to this need, the
objective of this study is to comprehensively investigate hybrid
powder with a focus on microstructure characteristics and chemical compositions. A general study on hybrid powder of different
concreteclay brick ratios is rst carried out to investigate the correlations of clay brick content with the properties of hybrid powder. Then, mortar samples supplemented with hybrid powder
from a dust collection system are examined. The result found in
this study provides qualitative and quantitative information to
deepen the understanding of the activity mechanisms of hybrid
recycled powder, and thus aids the current efforts to develop
guidelines for its green application in practice.

2. Properties of hybrid powder of different concreteclay brick

ratios
As demonstrated by the measured bulk density of coarse solids
(Table 1), clay brick is weaker than concrete because of its more
porous meso-structure. This leads to lower strength for aggregates
recycled from clay bricks. However, after ground into powder, clay
brick shows an apparent density similar to concrete (Table 1). This
implies the disadvantage related to the higher porosity in mesostructure is suppressed after clay brick is ground. Furthermore,
after grinding, clay brick powder may show more active pozzolanic
property because of the increase in surface area.
However, the similarity in porosity does not mean recycled clay
brick powder is same as recycled concrete powder when used as a
pozzolanic supplement to replace cement. This is due to their difference in mechanical property and mineral composition. To systematically characterize the properties of their mix, powder
containing different weight proportions of concrete and clay brick
is examined here. In addition to pure clay brick powder and pure
concrete powder, hybrid powder with the percentage of clay brick
increasing by a 10% interval is mixed. Thus, total 11 concreteclay
brick ratios are used for mixing the hybrid powder. Here the powder is collected by using a vacuum equipped with a proper sieve
when the clay bricks and concrete solids are being ground in a
lab ball mill.

Table 1
Density of recycled clay brick, recycled concrete and natural aggregate.

Bulk density (kg/m3) of coarse solid

Apparent density (kg/m3) of ne
powder

Clay
brick

Concrete

Natural
aggregate

1920
2521

2270
2594

2610
2645

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Q. Liu et al. / Construction and Building Materials 73 (2014) 754763

carbonation, which produces calcium carbonate in concrete. This

will be further veried in the subsequent Thermo-Gravimetric
and Differential Thermal Analysis (TG-DTA).
2.2. Strength activity index and water requirement

Fig. 1. The neness and LOI of the hybrid powder for different concreteclay brick
ratios.

2.1. Fineness and Loss on Ignition (LOI)

The powder neness, characterizing the surface-to-volume
ratio, has a signicant effect on the cement paste when the powder
is added as a supplement. For the hybrid powder used in this study,
its neness is measured based on the standard method recommended for y ash in Chinese specications [21] and ASTM standard test methods [22]. According to the specications and ASTM
recommendation, the neness of powder is characterized by the
percentage of grains of size larger than 45 lm. Obviously, the
lower this percentage, the ner is the powder.
The neness of the hybrid powder of different concreteclay
brick ratios is obtained by tests using negative pressure sieving
method here. As shown in Fig. 1, the hybrid powder becomes ner
with the growth of the percentage of clay brick. For pure clay brick
powder or hybrid powder containing more than 70% clay brick,
almost all the solids are ground into ne grains smaller than
45 lm (Fig. 1).
To use supplements (e.g. y ash) to replace cement in concrete,
the carbon content in the powder must be controlled because it
detrimentally inuences the properties of concrete [21]. For hybrid
powder, it usually contains some organic ne particles, which are
from the organic materials in C&D wastes, for instance, wood, plastic and so on. So, carbon content criterion must be satised if
hybrid powder is used as an additive in concrete. Generally, the
carbon content can be characterized by LOI, which is the mass loss
after the material is heated to a high temperature. Since there are
no specications available for hybrid powder, the standards for y
ash will be used here as a reference. Based on ASTM, the material
under test is heated from 105 C to 750 C, while in Chinese standards, it is from 105 C to 950 C. In this test, the recycled powder
is heated to 950 C. To ensure the concrete quality, LOI must be
lower than a limit, for example, less than 8% for Class II y ash in
Chinese standards [21] and less than 6% for Class F y ash in ASTM
recommendation [23].
Fig. 1 shows that the value of LOI decreases as the percentage of
clay brick in the hybrid powder increases. This means the recycled
clay brick powder contains less carbon ingredients than the recycled concrete powder. For the pure concrete powder used in this
test, its LOI is about 11%, beyond the limits allowed in Chinese
and ASTM standards respectively. However, if the proportion of
clay brick reaches 20%, the LOI of the hybrid powder drops within
the limit required by Chinese specications.
For hybrid powder, one source of LOI is organic materials.
Another contribution is the decomposition of calcium carbonate,
which decomposes at about 740 C. As a result, CO2 is released
and the powder mass decreases [24]. The higher LOI exhibited
in the recycled concrete powder is mainly due to the concrete

The effect of additives on compressive strength of concrete is

generally called strength activity index. Generally, the strength
activity index of cement supplements is measured by the ratio of
the compressive strength between benchmark mortars containing
no supplements and mortar samples with certain amount of
cement being replaced.
In this study, the compression test is run on a standard MTS
loading frame. Following Chinese recommendations [25], for each
type of hybrid powder, 3 mortar cubes of size 40 mm are cast and
then cured for 28 days before test. The mix proportion for mortar
samples is cement:recycled powder:sand:water = 0.7:0.3:3:0.5, for
benchmark samples, it is cement:sand:water = 1:3:0.5. Note, the
mix proportion based on Chinese standard is slightly different
from that of ASTM, for which 20% replacement is used and
waterbinder-ratio is 0.484 for control samples. The test results
are plotted in Fig. 2. It shows the compressive strength generally
rises up as the percentage of clay brick in the hybrid powder
increases. When the percentage of clay brick reaches 40% in the
hybrid powder, the strength activity index reaches 70%, which is
the strength limit required by Chinese specications for Class II
y ash [21] (75% is required for Class F y ash in ASTM [23]). If
pure recycled clay brick power is used, the strength activity index
jumps to 82%. This is consistent with the tests by Kartini et al.
[15].
If part of the cement is replaced by y ash or other supplements, the amount of water required to remain the concrete
workability may differ. In both Chinese specications and ASTM
standards, the workability of concrete containing powder as an
additive is characterized by the water requirement based on
the mortar ow method. Here the water requirement is the ratio
of water quantity to remain 130140 mm ow in mortar samples
containing 30% additive powder to that of the benchmark mortars without any cement replacement. As shown in Fig. 2, to
achieve the same degree of workability, extra water is needed
for all hybrid powder. The extra water does not monotonically
increase with the clay brick content. It reaches its peak at 6%
when the percentage of clay brick is about 70%. Then it is gradually reduced to 4% for pure clay brick powder. This unique trend
is closely related to the microstructure morphology of hybrid
powder, which will be shown in the subsequent microscopic
characterization.

Fig. 2. The strength activity index and water requirement for different concrete
clay brick ratios.

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Q. Liu et al. / Construction and Building Materials 73 (2014) 754763

Table 2
The chemical composition (wt, %).

SiO2
Al2O3
Fe2O3
CaO
MgO
K2O
Na2O
TiO2
SO3
P2O5
Cl

Hybrid recycled powder

Brick powder [13]

Recycled powder from concrete [19]

Fly ash [20]

Cement [13]

43.85
12.64
6.15
17.86
2.58
2.05
1.10
0.67
2.01
0.22
0.032

66.54
16.88
6.62
4.24
2.73
2.41
1.03
_
0.46
_
_

38.61
7.13
3.19
41.22
1.35
1.57
2.01
_
1.04
_
0.04

35.4
18.9
7.1
25.9
1.6
_
1.1
_
2.4
_
_

21.33
4.99
3.65
62.48
1.16
0.65
0.38
_
2.60
_
_

3. Recycled powder obtained from dust collection systems

Knowing these general properties, one can estimate the performance of the hybrid recycled powder obtained from dust collection
systems based on the proportion of clay brick, which can be evaluated from the neness and LOI described in Fig. 1. However, to
develop deeper understanding of the activity mechanisms of
hybrid recycled powder, qualitative and quantitative characterization based on micro-scale probe and high-resolution chemical
analysis is necessitated because the effects of hybrid recycled powder on cement paste are strongly correlated to its microstructure
and chemical composition.
In this study, the hybrid recycled powder used for microcharacterization and chemical analysis is obtained directly from a
dust collection system. The C&D wastes are collected from the
demolished structures in Dujiangyan, a typical Chinese city where
clay brick is widely used together with concrete for buildings. An
initial investigation based on the weight of bricks and concrete solids picked out from the C&D wastes shows that the weight percentage of clay brick is about 50%.
3.1. Chemical and mineral composition
The chemical composition of this hybrid recycled powder is
quantitatively analyzed with Axios X Ray Fluorescence (XRF),
which takes advantage of the emission of the characteristic
secondary X-ray from a material that is excited by high-energy
X-ray. During the test, voltage 3060 kV and current 50100 mA
are employed. The results are shown in Table 2, where the typical

Fig. 3. The mineral composition of the hybrid recycled powder based on XRD
spectrum.

chemical compositions of y ash, cement, brick powder and concrete powder are also shown for comparison.
According to Table 2, the dominant element in the hybrid powder is Si, followed by Ca and Al. These 3 elements count for over
70% of the total weight of the hybrid recycled powder. Compared
with y ash, cement, brick powder and concrete powder, the
hybrid recycled powder displays a wider spectrum of chemical
composition.
In addition to the chemical element analysis, the mineral compounds are also investigated. X-ray diffraction (XRD) measurements are performed to analyze the mineral constituents of the
hybrid recycled powder. XRD is a popular tool used for determining the atomic and molecular structure of a crystal whose crystalline atoms cause a beam of X-ray to diffract into many specic
directions. Here a diffractometer equipped with a graphite monochromator is used to scan the hybrid recycled powder with Cu K
radiation under an operation condition of 40 kV and 20 mA. In
order to achieve high scan resolution, a scan speed of 2 /min is
adopted in this study.
The mineral compounds identied by XRD scan are shown in
Fig. 3. Based on the diffraction peaks shown on the spectrum, the
main mineral compounds in the hybrid powder are Gismondine
(Ca(Al2Si2O8)
4H2O), Illite (KAl2Si3AlO10(OH)2), Anorthite (CaS2)
aSiO2, and CaCO3, which are common in both hardened cement
paste and clay brick. Among them, aSiO2 is found related to pozzolanic activity [26], and CaCO3 is reported to participate in the hydration of C 3 A to generate monocarboaluminate (C3A
CaCO3
11H2O)
[27]. In the XRD spectrum, there are some small diffraction peaks
showing the hybrid powder contains rutile (TiO2), which is also
found in Zheng et al.s work [18]. The existence of TiO2 is from clay
brick. In the process of producing clay brick, TiO2 is commonly used
as colorant to enhance the mechanical properties of brick.
Surprisingly, neither ettringite nor calcium hydroxide from the
hardened paste is found in the XRD spectrum. The disappearance

Fig. 4. Grain size distribution of the hybrid recycled powder obtained by LPS.

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Q. Liu et al. / Construction and Building Materials 73 (2014) 754763

(a) Magnified by 200 times

(c) Magnified by 5000 times

(b) Magnified by 2000 times

(d) Magnified by 10000 times

Fig. 5. The SEM images of the hybrid recycled powder.

3.2. Grain size distribution and microstructure morphology

Fig. 6. Curves obtained based on TG-DTA analysis.

of calcium hydroxide may result from carbonation. After the hardened paste is ground into ne particles, calcium hydroxide is
released from the paste and its direct exposure to CO2 in the air
leads to accelerated carbonation [28]. Thus, part of the CaCO3 in
the XRD spectrum is from the carbonate generated after grinding,
which increases LOI of hybrid recycled powder. As for the ettringite, its absence may stem from its decomposition at temperature
above 80 C [29,30]. The hybrid powder is produced in a dry grinding system and the local temperature during crushing can easily
rise beyond 80 C.

The grain size distribution of the hybrid powder is quantied by

laser diffraction spectroscopy (LPS), a technology that utilizes diffraction patterns of a laser beam passing through any particle ranging from nanometers to millimeters in size to quickly measure its
geometrical dimensions. A Laser Diffraction Particle Size Analyzer
(LPS) is used in this study. For this hybrid recycled powder
obtained from a dust collection system, its grain size distribution
(solid line) and cumulative distribution (dotted line) are displayed
in Fig. 4. It can be seen that most of the grains have a size smaller
than 45 lm and the neness of the hybrid powder is about 8%. As
demonstrated by the plateau in the size distribution curve (solid
line), the distribution of grain size ranging from 6 to 25 lm is relatively uniform. Based on the cumulative distribution, the percentage of particles of size less than 10 lm is about 40%, which benets
the strength activity due to the increased surface-volume ratio.
The morphology of the grain particles is then studied by SEM
scan. Before test, the hybrid recycled powder is cleaned with acetone for better surface exposure. After it dries, the hybrid recycled
powder is sprinkled on a conductive adhesive tape for scanning by
a high resolution SEM. During the SEM scan, the general shape and
surface texture of the particles are shown at different degrees of
magnication; see Fig. 5. It is found that unlike the y ash, the particles in the hybrid recycled powder are neither spherical nor
smooth. Instead, they contain sharp corners and irregular edges,
which form slits and V-notches. Under the highest magnication,
ner particles are found staying in the slits and V-notches of larger

Table 3
Mix design and compression test for samples with a higher waterbinder-ratio.
Mix proportion
Cement (g)

Hybrid powder (g)

Sand (g)

Water (g)

550
385

0
165

1650
1650

320
336

28-day strength (kN)

Strength activity index

37.22
53.51

70%

Q. Liu et al. / Construction and Building Materials 73 (2014) 754763

Fig. 7. AFM image of Region I.

759

The exothermic peak at 340 C corresponds with the burning of

cellulose particles. When the waste clay brick is ground into powder, the cellulose particles are released. The accelerated drop on TG
curve at 740 C corresponds to the decomposition of CaCO3, agreeing with the endothermic valley on the DTA curve. At the same
time, the decomposition of Illite may also contribute to the endothermic valley at 740 C. It can be found that the exothermic peaks
and endothermic valleys are small on the DTA curve shown in
Fig. 6.
According to Chinese specications and ASTM standards, in LOI
test for y ash, the temperature is raised to 950 C and 750 C,
respectively. While, for the hybrid recycled powder, the calcium
carbonate decomposes at 740 C, which can be demonstrated by
the steeper drop of TG curve and the valley of DTA curve around
740 C. Unlike the organic materials, calcium carbonate in the
powder is reported to contribute to the pozzolanic property [27].
Since both the TG and DTA curves are shown to be stabilized after
800 C, there should be no further decomposition after it. Thus, for
hybrid recycled powder, it may be more appropriate to set the ignition temperature from 105 C to 730 C, before the decomposition
of calcium carbonate.
3.4. Strength activity index

Fig. 8. AFM image of Region II.

ones. This unique conguration denitely increases the water

requirement and hinders the workability of concrete when hybrid
recycled powder is used as a supplement. Since clay brick is easier
to be ground into ner particles, the amount of smaller particles
attached on larger ones increases with the proportion of clay brick.
This explains the growth of water requirement with the content of
clay brick. However, if the percentage of concrete is too small,
there are no enough coarse particles in the hybrid recycled powder
to host the ner ones. Consequently, the water requirement drops,
see Fig. 2.
3.3. Thermo-Gravimetric and Differential Thermal Analysis (TG-DTA)
Thermo-gravimetric (TG) is a method of thermal analysis in
which the mass loss is measured as a function of temperature
during heating. Differential thermal analysis (DTA) is a thermoanalytic technique to investigate the energy adsorption and
release. In DTA, the material under study and an inert reference
are made to undergo identical thermal history and any temperature difference between them is recorded and then compared.
The TG-DTA results of the hybrid recycled powder are shown in
Fig. 6, where the solid line shows TG measurement and the dotted
line is DTA measurement. A constant heating rate (10 C/min) is
applied to the hybrid recycled powder to obtain the mass loss
curve. The tests are carried out using approximately 50 mg of powder sample in dry nitrogen. Although the temperature is heated to
1100 C, TG curve shows the mass loss of powder is stabilized at
12% after 800 C.

The neness and LOI tests show that this hybrid powder has
neness = 8% and LOI = 7.41%. Further standard test nds that its
water requirement is about 105%. According to the measured neness, LOI and water requirement, the percentage of clay brick in
this hybrid recycled powder obtained from a dust collection system should be about 50%, which agrees with the initial estimation
based on the weight of bricks picked out from the C&D wastes
before recycling.
For hybrid powder containing 50% clay brick, Fig. 2 shows the
strength activity index is about 75% when waterbinder-ratio is
0.5 and replacement is 30%. However, to remain same workability
of concrete, extra water is needed when hybrid powder is used as a
pozzolanic supplement. As it is well known, high water content has
deleterious effects on concrete strength and other mechanical
properties. Therefore, to ensure the higher water requirement of
this hybrid powder does not compromise its strength activity
index signicantly, compressive strength of mortar samples containing this hybrid powder with a higher waterbinder-ratio is
tested. Since this hybrid powder from a dust collection system
shows a water requirement of 105%, 5% more water is added in
the mix to achieve the same level of workability. As shown in
Table 3, although the waterbinder-ratio is higher, the strength
activity index of the hybrid powder still satises the Chinese specications, 70% (for Class F y ash, ASTM requires the strength activity index be higher than 75% for 20% replacement).
4. Microstructure of cement paste containing hybrid recycled
powder
After the microstructure morphology and chemical composition
are probed, this hybrid recycled powder obtained from a dust collection system is used to replace 30% of cement in casting mortar
samples. The waterbinder-ratio is chosen as 0.5. After curing for
28 days, the mortar samples with and without hybrid recycled
powder are cut into small blocks. Then the small blocks are cast
in epoxy resin and polished with care to prepare samples for
AFM tests.
In order to study the effect of hybrid recycled powder on
cement paste by AFM, a representative region containing the
hybrid recycled particles must be identied for the nano-scale
probe. This can be accomplished by searching for the clay brick

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Q. Liu et al. / Construction and Building Materials 73 (2014) 754763

(a) Region Ia

(b) Region Ib

(c) Region Ic
Fig. 9. AFM images of CSH gels in different regions.

particles in the hybrid powder, which display a color very different

from other constituents in the mortar. Considering that ner concrete powder prefers to be attached on coarser clay brick particles,
it is more appropriate to treat them as hybrid particles here than
just as pure clay brick particles. In this study, a representative
region containing 1 hybrid particle and 1 ne aggregate (sand),
which is denoted as Region I, is selected (Fig. 7). For comparison,
another region containing no hybrid recycled particles and no ne
aggregates, denoted as Region II, is also selected to represent the
normal cement paste (Fig. 8). Both Region I and Region II have
the identical scanning size of 30  30 lm.
4.1. Quantitative evaluation of microstructure roughness
It is suggested that the intrinsic roughness of cement paste,
which is generally expressed by root-mean-squared (RMS)
roughness, should be within a range for properly prepared mortar
samples. Based on Trtik et al. [31], the average intrinsic RMS roughness of motar paste ranges from 115 to 492 nm, and a RMS out of
this range may indicate surface damage or articial polishing.
According to Mondal [32], the RMS roughness of motar sample is
about from 40 to 200 nm, corresponding to 10  10 lm and
50  50 lm scanning sizes, respectively. The reason why the value
is lower in Mondals test is that special polish method is employed
by her [32].
Here the surface of the two selected representative regions is
quantitatively scanned by AFM under tapping mode. Fig. 7 shows
the surface topography of Region I, where the ne aggregate is
enclosed by a dashed curve and the hybrid particle by a solid curve.

The vertical deviation of the surface is illustrated by the given color

scale, in which dark grade means a valley and bright one means a
protrusion. In Region I the height varies from +2.2 to 2.2 lm.
Using the scan results, it can be found that the RMS roughness of
Region I reaches 595 nm, a relatively high value due to the existence of sand and hybrid recycled particle. However, if one only
considers the cement paste, the RMS roughness drops within the
range given by Trtik et al. [31]. The surface topography of Region
II is shown in Fig. 8. In this region, the main constituent is CSH
gel. Based on the quantitative measurement, the RMS roughness
of Region II is 470 nm, a value within the limit given by Trtik
et al. [31]. Based on the quantitative measurement in Regions I
and II, it seems that although the addition of hybrid recycled powder increases the microstructure roughness of cement paste, the
change is still at an acceptable level when compared to normal
cement paste.
4.2. Microstructure topography of CSH
To investigate the effect of hybrid recycled powder on the formation of CSH, 3 sub-regions, enclosed by dashed rectangles, are
selected in Region I; see Fig. 7. The sub-regions, labeled as Regions
Ia, Ib and Ic respectively, all have a same size of 4.1  4.1 lm. As
shown in Fig. 7, Region Ia is selected in the vicinity of the ne aggregate, Region Ib close to the hybrid particle, and Region Ic at a location away from both the sand and the hybrid particle.
The microstructure topography of the cement paste in these 3
sub-regions is shown in Fig. 9. Based on the topographical features
shown in the AFM images, one can estimate the size of CSH gel

Q. Liu et al. / Construction and Building Materials 73 (2014) 754763

761

(a) Region I

Fig. 11. Fitted probability distributions representing four phases: (a) Region I and
(b) Region II.

(b) Region II
Fig. 10. Nanoindentation results showing elastic modulus at each node of a 7  7
grid (unit: GPa).

in these 3 sub-regions. For the CSH gels in Region Ia, the size of
CSH gels ranges from 200 to 900 nm, in Region Ib, it is from 200
to 1200 nm, and in Region Ic, it is from 800 to 1400 nm; see Fig. 9.
The CSH gels in Region Ic are more uniform than those in
Regions Ia and Ib, which are inuenced by the sand an hybrid powder respectively. In addition to the size, the boundary between the
CSH gels is different in these 3 sub-regions. In Region Ic, a discrete boundary can hardly be found between the CSH gels, while
in Regions Ia and Ib, the boundary between CSH gels is conspicuous (Fig. 9). This indicates a stronger bond of CSH gels in Region
Ic. According to the AFM images, it transpires that the CSH gels
in Region Ia are more uniform than those in Region Ib. This may be
induced by the unique microstructure morphology of the hybrid
recycled powder shown in Fig. 5. Considering the locations of these
2 sub-regions, the AFM images represent the topographical properties of CSH gels in the interfacial transition zones (ITZ) surrounding ne aggregate and hybrid recycled powder, respectively.
4.3. Modulus based on nanoindentation
The mechanical properties of the CSH gels are further quantied by nanoindentation based on Hertz model [33]. In order to
characterize the distribution of elastic modulus, both Regions I
and II are mapped by a 7  7 grid, based on which nanoindentation
is carried out. The details of calculating elastic modulus can be
referred to the work by Tan et al. [34].

Following the methodology proposed by Mondal [32], fully

hydrated cement paste can be classied by 4 distinct phases in
order of increasing elastic modulus: porous phase, low stiffness
CSH, high stiffness CSH and calcium hydroxide. For Region I,
2 extra phases, namely, recycled particle and sand, exist. The nanoindentation is carried out at each node of the 7  7 grid, and the
measured elastic modulus is labeled at the corresponding location
(Fig. 10).
The average modulus of the cement paste in Region II is
32.7 GPa, within the range from 10 to 30 GPa as reported by Mondal [32]. The average modulus of Region I is 25.6 GPa, here the
moduli of sand and hybrid particle are not considered. The lower
modulus in Region I is due to the existence of ITZ around the sand
and the recycled particle. In Fig. 10, it shows extremely high moduli (60 GPa or higher) at some nodes in the cement paste. This is
related to the unhydrated cement particles and they are not used
in the analysis.
In Fig. 10a, the nodes close to the ITZs are marked out with a circle. The average modulus of ITZ around sand is about 9.0 GPa, and
for the recycled particle it is about 8.7 GPa. This means that the
hybrid recycled particle has a similar effect on the formation of
CSH around its interface. The marginal difference may result
from the unique morphology of the hybrid powder, in which the
ner particles are attached in the slits and notches of larger ones
and thus attract more water during hydration.
As proposed by Mondal [32], the measured modulus at different
nodes can be used to estimate the distribution of different phases
in the cement paste based on statistical analysis. If the interval is
set as 5 GPa and Gaussian distribution is assumed, the probability

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Q. Liu et al. / Construction and Building Materials 73 (2014) 754763

Table 4
Change of elastic modulus and volume fraction of different phases.
Region I

Porous phase
Low stiffness CSH
high stiffness CSH
Calcium hydroxide

Region II

Elastic modulus (GPa)

Volume fraction (%)

Elastic modulus (GPa)

Volume fraction (%)

8.2 2.75
18.3 3.16
28.3 2.16
46.4 3.80

37
36
15
12

8.94 2.8
19.0 2.7
30.0 10.1
53.4 3.89

17
24
48
11

distribution of elastic modulus can be obtained for the Region I and

Region II respectively (solid lines with square symbols in Fig. 11a
and b). Taking advantage of peak analysis, the overall probability
distribution of elastic modulus can be decomposed into individual
probability distribution for the 4 different phases of cement paste
[32], which is represented by the dashed curves in Fig. 11. This
individual probability distribution is further validated by the goodness of tting based on Chi-square test [35]; see the solid curves in
Fig. 11a and b.
In Fig. 11, the volume fraction of each phase can be calculated
based on the area under the dashed curve representing its
individual probability distribution. The volume fraction of each
phase is presented in Table 4. It can be seen that under the inuence of the hybrid recycled powder and sand, there is a substantial
change in the microstructure of cement paste. If compared with
Region II, one can nd that in Region I volume fraction of high stiffness CSH drops from 48% to 15%, while those of porous phase
and low stiffness CSH rise from 17% and 24% to 37% and 36%,
respectively. Considering the high active surface area and unique
morphology of the hybrid recycled powder, the locally high
waterbinder-ratio contributes signicantly to this phase distribution change.

powder contribute to the pozzolanic property. However, due to

the accelerated carbonation and elevated temperature during
grinding, ettringite and calcium hydroxide in hardened paste
disappear from hybrid recycled powder.
4. AFM scan reveals that hybrid recycled powder affects the
microstructure of cement paste around it. The size and
morphology of CSH gels in the vicinity of hybrid powder
are similar to those close to sand, but very different from the
normal CSH gels. The increased surface roughness and conspicuous boundary indicates a weaker bond of CSH gels
around hybrid recycle powder.
5. Nanoindentation test shows that a weaker ITZ, with an average
modulus similar to that surrounding sand, is produced to form
the cement paste-recycled particle interface. The unique microstructure morphology of hybrid recycled powder is deemed as
the main contributor to this ITZ.
6. Using the elastic modulus at each node of the nanoindentation
grid, the probability distribution of different constituent phases
of the cement paste can be estimated based on statistical analysis. It transpires that the existence of hybrid recycled powder
signicantly changes the volume fractions of the constituents,
characterized by a substantial increase of porous phase and
low stiffness CSH.

5. Conclusion
In the present study, a comprehensive investigation on the
properties and microstructure characteristics of hybrid recycled
powder is carried out. Based on the qualitative and quantitative
analysis of its morphology, chemical composition and effects on
cement paste, the following conclusions can be drawn for the
hybrid recycled powder when it is used as a cement supplement:
1. For C&D wastes containing concrete solids and clay bricks, a
large amount of hybrid recycled powder is collected from dust
collection systems during recycling. Characterized by the
concreteclay brick ratio, the hybrid recycled powder obtained
from dust collection systems displays different levels of
pozzolanic activity. With the increase of clay brick, tests show
that the powders LOI drops and neness and strength activity
index rise. If the proportion of clay brick reaches 40%, the
strength activity index approaches 70% for 30% replacement.
2. Hybrid recycled powder exhibits a unique microstructure morphology, which leads to higher water requirement to maintain
concrete workability. The water requirement increases with
clay brick until its proportion in the hybrid powder reaches
around 70%. Compression tests based on 30% replacement show
that the extra water reduces strength activity index, but not signicantly. Thus, by controlling the replacement percentage and
adjusting the clay brick content, concrete supplemented with
hybrid recycled powder can meet both the strength and workability requirements.
3. Quantitative chemical analysis nds that hybrid recycled powder displays a wider spectrum of chemical composition, primarily inherited from both hardened paste and clay brick. The
mineral compounds of aSiO2 and CaCO3 found in hybrid recycled

This study reveals that the microstructure morphology and

chemical composition of hybrid recycled powder are closely
related to its activity mechanism, and thus have a strong effect
on the microstructure of cement paste around it. Like ne aggregates, similar ITZs form around hybrid recycled particles. Thus, if
the proportion of clay brick and replacement percentage are well
controlled, hybrid recycled powder can be used as a pozzolanic
supplement to replace part of the cement in concrete. Of course,
to establish a complete guideline for the green use of hybrid
recycled powder, deeper understanding of its role in cement
hydration is indispensable. Therefore, further investigation is
needed to study its effects on the packing density, chemical composition and morphology of CSH gels. In addition, the increase
of porous phase and low stiffness CSH demands research efforts
on durability (e.g., freeze and thaw) and time-dependent properties (e.g., creep and shrinkage) for concrete supplemented with
hybrid recycle powder.

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