Environmental Technology, 2014

http://dx.doi.org/10.1080/09593330.2014.911362

Micro-observations of different types of nano-Al2 O3 on the hydration of cement paste with

sludge ash replacement
Huan-Lin Luoa , Deng-Fong Lina∗ , Show-Ing Shiehb and Yan-Fei Youa
a Department of Civil and Ecological Engineering, I-Shou University, No. 1, Sec. 1, Syuecheng Rd., Dashu District, Kaohsiung City
84001, Taiwan, ROC; b Department of Liberal Education, Shu-Te University, Kaohsiung City 82445, Taiwan, ROC
(Received 1 December 2013; accepted 30 March 2014 )

In recent years, sewer systems and wastewater treatment plants have become important in developing countries. Consequently,
the amount of sewage sludge produced by these countries has been gradually increasing, and determining how to properly
recycle this sludge is becoming an important topic for researchers. In this study, to expand the recyclability of sewage
sludge ash (SSA) in engineering applications, two types of nano-aluminium oxides (Al2 O3 ), MC2A and MC2R, were added
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to SSA/cement paste and mortar specimens. The MC2R type (γ phase) had a smaller particle size and larger specific
surface area than the MC2A type (α phase). The results indicate that the addition of nano-Al2 O3 to SSA/cement paste
can effectively improve the hydration products of the paste. Moreover, the amount of hydration products increased as the
amount of nano-Al2 O3 added to the SSA/cement paste increased. The test results indicate that MC2A nano-Al2 O3 can more
uniformly distribute in the paste body and improve the hydration of cement than MC2R nano-Al2 O3 . Thus, more calcium-
silicate-hydrate (C-S-H) gel and calcium aluminate hydrate (C-A-H) salts were produced, and the strength of the specimens
was improved. This study suggests that MC2A nano-Al2 O3 is preferable to MC2R nano-Al2 O3 for SSA/cement specimen
applications.
Keywords: cement; micro-structure; nanomaterial; paste; sludge ash

Introduction
Sewage sludge ash
In recent years, numerous sewage and wastewater treatment
plants have been constructed in Taiwan, and household
connections and wastewater treatment have improved con-
siderably. As a result, large amounts of sewage sludge (SS)
are generated, which could become a serious environmental
problem if the sludge is not properly managed. To achieve
sustainable development in the eco-environment, proper
management of SS is gradually gaining attention world-
wide. Wang et al. [1] applied lignite, acid mine drainage
sludge, and coal fly ash to remove phosphate from dairy
wastewater. By using the Freundlich model, the authors
suggested that acid mine drainage sludge and coal fly
ash were the favourable adsorbents for column applica-
tions. Test results indicated that acid mine drainage sludge
and coal fly ash were potentially effective adsorbents if
applied separately at a ratio of 10 wt% or above for the
column application for phosphate removal. Masto et al.
[2] applied various amounts of fly ash (fluidized bed com-
bustion ash (FBCA) and lignite fly ash (LFA)) with SS
to form combined amendments and assess soil biologi-
cal quality changes with these amendments. They found
that pH was the most significant factor to soil quality and
microbial biomass carbon was a sensitive soil indicator for
the effects of the combined amendments. They suggested
that the soil biological quality was improved by the addi-
tion of 10–30% FBCA or LFA to SS. Dumping or landfilling
is the current method used for the final disposal of SS in
Taiwan. However, landfilling is not suitable for an island
where land is scarce, such as Taiwan. Moreover, activated
waste sludge contains high concentrations of organic mat-
ter, which decays easily. To avoid secondary pollution and
to choose a final disposal method for SS, establishing a
method for recycling sludge in a beneficial manner becomes
an urgent issue.
Research related to SS after calcination has been per-
formed worldwide. He et al. [3] noted that SS samples
calcined at temperatures greater than 1000 ◦ C were easily
broken into a considerable amount of powder. When the
samples were calcined between 600 ◦ C and 1000 ◦ C, they
were relatively hard and solid with less powder. Thus, cal-
cination at higher temperatures could be unfavourable for
the production using sewage sludge ash (SSA). After being
dewatered, dried and calcined (approximately 800 ◦ C),
Wang [4] ground these SS samples into ash. Then, he
mixed the sludge ash with different cementitious mate-
rials, such as cement, blast furnace slag, and fly ash,

∗ Corresponding author. Email: dflin@isu.edu.tw

© 2014 Taylor & Francis

 2 H.-L. Luo et al.
to manufacture modified artificial fine aggregates. The
compressive strength, workability, water absorption, and
abrasion resistance of the artificial fine aggregates were
improved. Tay and Show [5,6] found that the Strength
Activity Index (SAI) of SS after being ground was between
58% and 67%, which was close to the standards of C-
class pozzolanic materials, as determined by the American
Society for Testing and Materials (ASTM) C618. Khan-
bilvardi and Afshari [7] ground SS into ash and used it as
a pozzolanic admixture. They applied the ash to replace a
portion of Portland cement for soil stabilization treatment.
As stated above, researchers worldwide are applying SS
in civil and construction engineering applications with the
goal of manufacturing building materials with higher eco-
nomic values. Moreover, techniques for producing building
or construction materials are gradually improving.
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Nanomaterials
The development of nanotechnology has become an impor-
tant high-tech policy in many countries. The applications
of nanotechnology to different fields are gradually being
promoted and increased. In conventional civil engineering,
nanotechnology applications to building and construction
materials are well known and continuing to be developed
worldwide. Zeng et al. [8] noted that research on nano-
materials would become an important branch of materials
science. Because nanomaterials are characterized by very
small volumes with large surface areas, the characteris-
tics of the materials are dependent on the surface areas
of the nanomaterials. Lin and Sheen [9] investigated the
infiltration effects of nanosilicon powder on the proper-
ties of high-performance concrete. They observed that the
nanopowder can decrease the size of the cement paste
particles and make the interior of the paste body more
compact. As a result, the strength and durability of the high-
performance concrete was improved. Wang and Wang [10]
added nanomaterials to cement mortar to observe the result-
ing micro-structures using scanning electron microscopy
(SEM) and detect different phases using X-ray diffraction
(XRD); they also examined the effects of adding nanomate-
rials on the mechanical properties of the mortar specimens,
such as the compressive and bending strengths. These
researchers found that the optimal amount of nanomaterial
to be added to cement mortar specimens was between 5%
and 6%. Moreover, Phoo-ngernkham et al. [11] observed
that the elastic modulus, flexural strength, and compressive
strength of high calcium fly ash geopolymer paste were
improved by adding 1–2% nano-SiO2 or nano-Al2 O3 to
the pastes. However, the paste with the nano-SiO2 required
less setting time than that with the nano-Al2 O3 additive. A
shorter setting time is undesirable for construction applica-
tions. They also suggested that adding both nanomaterials
simultaneously can improve the shear and bonding strength
between the geopolymer and concrete substrate. Behfarnia
and Salemi [12] found that the compressive strength of
concrete was improved more by the nano-SiO2 than by the
nano-Al2 O3 additive. However, concrete with better frost
resistance was obtained using the nano-Al2 O3 additive.
Haruehansapong et al. [13] applied three sizes of nanosilica,
12, 20, and 40 nm, to cement mortars and then compared
their compressive strengths with those of cement mortar
containing silica fume. They found that nanosilica effec-
tively enhanced the compressive strength of the cement
mortar. The strength enhancement was correlated to the par-
ticle size of the nanosilica. Moreover, they observed that the
nanosilica particle size had a negligible effect on the opti-
mum replacement content of cement mortar. Shiri et al. [14]
studied the effect of reinforcement with nano-SiO2 particles
on the properties of cement pastes. When 1% nano-SiO2
particles was evenly distributed in the cement paste, they
observed that not only was the hydration process improved
but both the mechanical and physical properties of the paste
were also enhanced. As shown above, the nano-Al2 O3 addi-
tive was beneficial for construction applications and for
improving the frost resistance and compressive strength of
cementitious materials.
In this study, SSA and two types of nano-aluminium
oxides (Al2 O3 ) were added to cement paste and mortar
specimens. Through this investigation, we hope to extend
the uses of recycled SS and utilize these nanomaterials in
future engineering applications.
Materials and methods
To observe variations in the microproperties and com-
pressive strengths of cement paste, paste specimens were
manufactured by replacing 0% or 10% of the cement
with SSA and by adding different levels of two types of
nano-Al2 O3 additives. Note that the specimens with 0%
sludge ash replacement and no additives were considered
as the control group. Field-emission (FE)-SEM, XRD, and
nuclear magnetic resonance (NMR) tests were performed
to examine the micro-structures and chemical components
of the paste specimens.
Materials
Portland type I cement
Locally made Portland type I cement with a specific gravity
of 3.15 was used in this study. The chemical compositions
of the cement were CaO (62.33%), SiO2 (21.13%), Al2 O3
(4.39%), Fe2 O3 (3.17%), SO3 (3.2%), and MgO (3.15%).
Sewage sludge ash
Dewatered SS cake samples were collected at a municipal
wastewater treatment plant in Kaohsiung City and calcined
at 800 ◦ C for 20 h to generate ash in a brick kiln fac-
tory, as suggested by Luo and Lin.[15] The calcined SSA
was ground using a multi-spinning roller powder-grinding
machine until it passed through a #200 sieve and was then
 Environmental Technology 3

Table 1. Leached metal concentrations obtained from the TCLP test.

Item As Pb Cu Cd Zn Cr Hg Cr6+ Se Ba

Sludge ash (mg/L) 0.42 < 0.2 7.94 < 0.2 11.3 < 0.2 ND ND ND < 0.2
TCLP standard (mg/L) 5.0 5.0 15.0 1.0 25.0 5.0 0.2 2.5 1.0 100

Table 2. Chemical SSA components obtained from EDX analysis.

Elements C O Na Mg Al Si K Ca Ti Fe Ni Zr Total

Sludge ash Weight (%) 16.8 32.42 0.29 0.74 10.99 21.36 2.85 1.14 0.74 9.43 2.26 0.98 100

Table 3. Physical properties of MC2A and MC2R nano-Al2 O3 .

Type MC2R MC2A

Purity (%) 99.99 99.99

Lattice structure γ phase α phase
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Average particle size (nm) 30 ± 5 < 150

Specific surface area (m2 /g) 180 ± 20 10 ± 5
Apparent specific gravity (g/cm3 ) 0.2–0.4 0.3–0.5
Impurity content (ppm) Si < 50 Na < 8 Mg < 10 Cu < 5 Cr < 5 Fe < 20 K < 8 Cl< 1

sealed in a plastic bag to be applied for the manufacturing
of paste and mortar specimens. The specific gravity of the
calcined SSA was 2.13. The leached metal concentrations
obtained from the toxicity characteristic leaching procedure
(TCLP) test, as given in Table 1, met the standards required
by the Environmental Protection Agency of the Republic of
China. Furthermore, Table 2 presents the chemical compo-
nents of the SSA obtained from the energy-dispersive X-ray
spectroscopy (EDX) analysis.
Nano-Al2 O3
Two types of nano-Al2 O3 , MC2A and MC2R, were used
as additives in the specimens. The physical properties of
these two types of nano-Al2 O3 are listed in Table 3, and
the micro-structures of these nanomaterials are revealed in
two SEM images (×10, 000) shown in Figure 1. As shown,
MC2A was composed of separated small particles, whereas
MC2R consisted of very fine acicular particles that clustered
together. Moreover, the particle sizes of MC2R were smaller
than those of MC2A.
Fine aggregates
Local natural river sand with a specific gravity, fineness
modulus (FM), and water absorption equal to 2.58, 2.84,
and 2–3%, respectively, was applied and oven-dried for 24 h
before use in this study.
Specimen mix design and manufacture
Two types of specimens were prepared in this study.

Figure 1. Micro-structures of two nano-Al2 O3 types, MC2A and MC2R.

 4 H.-L. Luo et al.
SSA/cement paste specimens
According to ASTM C311, the water–binder ratio was set at
0.485. Cement was partially replaced with calcined SSA at
0% and 10%. Moreover, two types of nano-Al2 O3 , MC2A
and MC2R, were added as additives, and the amounts of
MC2A and MC2R added were set at 0%, 1%, 2%, and
3%. Different types and amounts of nano-Al2 O3 were well
mixed with water in a mixer at low speed while 0% or 10%
of sludge ash was mixed with cement in another mixer.
Next, the specimens were prepared by adding water/nano-
Al2 O3 into the sludge ash/cement mixture in a mixer at
low speed. After 30 s, the speed of the mixer was increased
to the intermediate setting for an additional 30 s. After
the mixer was stopped, the paste around the mixer was
scrapped off for 15 s, and then the paste was allowed to
sit for an additional 75 s. Then, the mixer was turned to
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the intermediate-speed setting to blend the paste for 60 s.
Finally, the mixer was stopped and the process of cast-
ing the paste into moulds was initiated. The specimens
were produced using two mould sizes. One of the moulds
produced specimens for micro-structure observations and
was a 2.5-cm3 -cube mould; the other was for produc-
ing specimens to measure length and weight changes and
was a rectangular mould with dimensions of 2.54 × 2.54 ×
28.5 cm.
SSA/cement mortar specimens
The mix design was the same as that for the SSA/cement
paste and the water–binder ratio for the mortar specimens
was also set at 0.485. Specimens were manufactured with
a mix ratio of SSA/cement and fine aggregate equal to
1:2.75. Again, different types and amounts of nano-Al2 O3
were well mixed with water in a mixer at low speed
while 0% or 10% of sludge ash was mixed with cement
in another mixer. Next, the specimens were produced by
adding water/nano-Al2 O3 into the sludge ash/cement mix-
ture in a mixer at low speed. Sand was slowly added to
the mix within 15 s after the process began. After 30 s, the
speed of the mixer was increased to the intermediate set-
ting for an additional 30 s. After the mixer was stopped,
the mortar around the mixer was scraped off for 15 s,
and then the mortar was allowed to sit for an additional
75 s. Then, the mixer was turned to the intermediate-
speed setting to blend the mortar for 60 s. Finally, the
mixer was stopped, and the process of casting the mortar
into moulds was initiated. Then, the mixture was poured
into a 5-cm3 mould and compacted to obtain the mortar
specimens.
The two types of specimens were cured at different des-
ignated curing ages of 1, 3, 7, 14, and 28 days. Moreover,
before proceeding with the different tests, all specimens
were left in saturated limewater to cure until the designated
curing ages. Three identical specimens were manufactured
for each test.
Methods
Weight test
A weight test was conducted to determine the weight
changes of specimens with different levels of SSA replace-
ment and with different types of nano-additive additions
when cured at various ages.
Compressive strength
The compressive strengths were obtained for mortar speci-
mens cured at different designated ages, and the tests were
regulated by the Chinese National Standard (CNS) 1010
(R3032) and ASTM C109 standards.
XRD analysis
The SSA/cement paste samples were stored in methanol
and then ground into powder. This powder was left in an
oven at a temperature of 105 ◦ C for 24 h before being used
in the XRD analysis. For the powder XRD measurements,
data were recorded from 20 ◦ and 80 ◦ 2θ at a scan speed of
2 ◦ /min. The XRD results were compared to the Joint Com-
mittee on Powder Diffraction Standards (JCPDS) database
to determine the chemical components in the SSA/cement
paste samples.
FE-SEM analysis
Through observations of the surface micro-structure images
of the SSA/cement samples, the shapes of the crystalline
phase for products of samples with different mix designs
were determined. These images can provide information
about the interior pore structure distributions and crystalline
structure arrangements and can support macrotest results,
such as compressive strength.
NMR analysis
In the 29 Si NMR spectra, different bonding formations for
the silicon (Si) atom could provide hydration information
about the SSA/cement samples with different nanomaterial
additives and various curing times.
Results and discussion
Weight changes
Table 4 presents the results of weight changes for paste spec-
imens with different levels of calcined SSA replacements
and various amounts of MC2A and MC2R nano-Al2 O3
additives at designated curing times. The weights of the
specimens increased with increasing amounts of added
nano-additives for both types of nano-Al2 O3 . The increases
in the weight of the specimens with 0% SSA replacement
and with 1%, 2%, and 3% MC2A nano-Al2 O3 added were
1.65, 2.27, and 2.44 g, respectively, when cured at 1 and
3 days. For the specimens with 1%, 2%, and 3% MC2R
 Environmental Technology 5

Table 4. Results of weight changes for paste specimens with different levels of calcined SSA replacements and
various amounts of MC2A and MC2R nano-Al2 O3 additives at assigned curing times.

1 day 3 day 7 day 14 day 28 day

Amount of sludge Nano-Al2 O3 Amount of
ash replacement (%) type nano-additive (%) Weight (g)

0 – 0 327.51 328.57 330.51 331.24 332.00

MC2A 1 330.12 331.77 333.18 334.78 335.73
2 330.25 332.52 334.18 335.72 336.20
3 332.37 334.81 335.71 337.15 338.65
MC2R 1 329.57 331.93 332.26 334.56 335.08
2 330.22 332.50 334.55 335.17 336.06
3 332.29 334.67 335.30 337.52 338.44
10 – 0 326.69 327.43 329.80 330.39 331.11
MC2A 1 328.53 330.18 331.58 333.99 334.11
2 329.49 331.52 332.22 334.06 335.46
3 329.79 331.69 332.78 334.79 335.89
MC2R 1 328.41 329.89 331.08 332.74 333.85
2 327.99 330.40 332.97 333.19 333.76
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3 329.17 330.30 331.83 334.42 335.19

for specimens with the MC2R nano-Al2 O3 additive. More-

over, when nano-Al2 O3 particles were in full contact with
the SSA/cement particles and because nano-Al2 O3 contains
a large amount of Al2 O3 , the nanoparticles could trigger the
generation of hydration products. Therefore, the weights of
the SSA/cement paste specimens increased with increasing
levels of nano-Al2 O3 additive.

Figure 2. Weight growth rates for specimens with 0% and 10%
SSA replacements and 0%, 1%, 2%, and 3% MC2A and MC2R
nano-Al2 O3 additives.
Compressive strength
Figure 3 illustrates the compressive strengths for mortar
specimens with 0% and 10% SSA replacements and with
0%, 1%, 2%, and 3% nano-Al2 O3 additives when cured for
28 days. The compressive strength of the mortar specimens
in the control group (0% SSA replacement and nano-Al2 O3

nano-Al2 O3 additives, the increases in weight were 1.36,

2.28, and 2.38 g, respectively. These results indicate that
the weights of the specimens increased with the curing time
when cured in saturated limewater. Furthermore, for spec-
imens with 10% SSA replacement, the weight increased
with increasing amounts of added nano-Al2 O3 additives.
However, the increments in weight change were relatively
smaller. As shown in Figure 2, the weight increases in spec-
imens with MC2A nano-Al2 O3 additives were larger than
those with MC2R nano-Al2 O3 additives. This result could
be because the MC2R nano-Al2 O3 particles were more eas-
ily clustered together than the MC2A nano-Al2 O3 particles.
Thus, MC2A nano-Al2 O3 particles became more uniformly
distributed in the SSA/cement paste than the MC2R nano-
Al2 O3 particles, which led to an increase in contact area
between the MC2A nano-Al2 O3 and SSA/cement parti- Figure 3. Compressive strengths for mortar specimens with 0%
cles. As a result, the hydration efficiency for specimens with and 10% SSA replacements and 0%, 1%, 2%, and 3% nano-Al2 O3
MC2A nano-Al2 O3 additive was more improved than that additives when cured for 28 days.
 6 H.-L. Luo et al.
Figure 4. The pozzolanic SAIs for mortar specimens with 0% and 10% SSA replacements and 0%, 1%, 2%, and 3% nano-Al2 O3 additives
when cured for 7 and 28 days.
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additive) was approximately 38.1 MPa, whereas it was 34.8
MPa for mortar specimens with 10% SSA replacement (0%
nano-Al2 O3 additive). This result indicates that the com-
pressive strengths of mortar specimens decreased with SSA
replacement, which could be due to the SS samples being
calcined at inadequate or non-uniform temperatures. More-
over, the addition of nano-Al2 O3 additives could increase
the compressive strengths of cement mortar specimens.
Type MC2A showed better improvement in compressive
strength than type MC2R. MC2R, which contained smaller
particles, had a higher specific surface area than MC2A.
Theoretically, MC2R would activate the hydration process
more than would MC2A. Hence, the compressive strengths
of the specimens containing MC2R would be higher than
those containing MC2A, which is inconsistent with the
result obtained above. Two possible reasons could lead
to this conflict. First, during the mixing process, although
the MC2R nano-Al2 O3 particles were uniformly distributed
over the water, the very fine particles were easily clustered
together, which affected the hydration process and strength
development of the specimens. Second, MC2A nano-Al2 O3
belongs to the α phase and has a high hardness, which aids
in the strength development of the specimens. However, the
improvements in the compressive strengths of mortar spec-
imens with 10% SSA replacement were not noticeable for
the addition of either type of nano-Al2 O3 additive. Because
more calcium sulphoaluminate was produced during the
hydration process after 10% of the cement was replaced
by SSA, the extra generation of calcium sulphoaluminate
influenced the calcium hydroxide to form more calcium-
silicate-hydrate (C-S-H) gel in the continuing hydration
process. As a result, improvements in the compressive
strengths were not noticeable.
Figure 4 shows the pozzolanic SAIs for mortar speci-
mens with 0% and 10% SSA replacements and 0%, 1%,
2%, and 3% nano-Al2 O3 additives when cured for 7 and
28 days. As shown in this figure, when cured for 7 days,
the largest SAIs were observed for specimens with 2%
nano-Al2 O3 additives added and were slightly reduced for
specimens with 3% nano-Al2 O3 additives added. Moreover,
when cured for 28 days, the SAIs of the specimens increased
with as the amount of nano-Al2 O3 additives increased.
This result implies that the higher level of nano-Al2 O3
additives could lead to an insufficient initial hydration reac-
tion in the specimens. As the curing times increased, the
pozzolanic reaction in the specimens was progressed and
the hydration products filled the pores in the specimens.
Thus, the compressive strengths of the specimens improved
with the longer curing time and higher levels of added
nano-Al2 O3 additives. Moreover, the figure shows that the
SAIs for specimens with MC2A nano-Al2 O3 additives were
higher than those with MC2R nano-Al2 O3 additives when
cured for 28 days. Therefore, MC2A nano-Al2 O3 additives
increased the improvement in the hydration efficiency in the
specimens.
XRD analysis
Figure 5 shows the XRD results for paste specimens
with 0% and 10% SSA replacements and 0%, 1%, 2%,
and 3% nano-Al2 O3 additives. After being compared with
the JCPDS database, four compositions, C-S-H gel, cal-
cium aluminate hydrate (C-A-H) salts, calcium hydroxide
(Ca(OH)2 ), and Al2 O3 , were clearly observed in the speci-
mens. As shown in Figure 5(a) and 5(b), when comparing
the peak values of the hydration products for specimens
with 0% (NA0S0) and 10% (NA0S10) SSA replacement
at approximately 34 ◦ 2θ , the specimens with 10% SSA
replacement displayed a lower amount of hydration prod-
ucts, which implies that less C-S-H gel and C-A-H salts
were generated after 10% cement was replaced by SSA.
Furthermore, as can be observed from Figure 5(b) and 5(d),
the peak values of the hydration products increased with
increasing level of added nano-Al2 O3 additives. Thus,
 Environmental Technology
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Figure 5. XRD for paste specimens with 0% and 10% SSA replacements and 0%, 1%, 2%, and 3% nano-Al2 O3 additives.
the addition of nano-Al2 O3 additives helped to improve
the hydration efficiency of the specimens. Moreover, the
peak values for specimens with type MC2A nano-Al2 O3
additives (Figure 5(b)) were higher than those with type
MC2R nano-Al2 O3 additives (Figure 5(d)) at approxi-
mately 34 ◦ 2θ. Similar results were obtained when compar-
ing Figure 5(a) and 5(c). Again, MC2A nano-Al2 O3 addi-
tives increased the improvement in the hydration efficiency
of the specimens.
FE-SEM analysis
Figure 6 presents the results obtained from the FE-SEM
analysis of paste specimens with 0% and 10% SSA replace-
ments and 0% and 3% nano-Al2 O3 additives when cured
for 28 days. As observed in Figure 6(a) and 6(b), more
ettringite and monosulphate were produced in the spec-
imens with 10% SSA replacement. These products were
not helpful for the growth of the paste structure, which led
to a reduced development of the compressive strength in
specimens. With the addition of 3% nano-Al2 O3 additives
7
to the paste specimens, Figure 6(c)–6(f) shows that the
nano-Al2 O3 additive particles were mainly found around
the C-S-H gel and C-A-H salts. These nanoparticles could
be inserted in the pores of C-S-H gel and C-A-H salts
by van der Waals forces. As a result, the paste structure
became more compact and the compressive strengths were
improved. Moreover, for the SSA/cement paste specimens,
as shown in Figure 6(b), 6(d), and 6(f), the addition of 3%
nano-Al2 O3 additives reduced the generation of monosul-
phate and increased the amount of C-S-H gel and C-A-H
salts produced, which improved the development of the
paste structure. By comparing Figure 6(c) and 6(d) with
Figure 6(e) and 6(f), the MC2A nano-Al2 O3 additives had
a superior inserted effect on C-S-H gel and C-A-H salts
and were more uniformly distributed in the paste than the
MC2R nano-Al2 O3 additives. This result could be because
the MC2R nano-Al2 O3 additives were more easily clus-
tered together, which made achieving a uniform distribution
of the nanoparticles more difficult. As a result, MC2A
nano-Al2 O3 additives increased the improvement in the
hydration efficiency in the specimens.
 8 H.-L. Luo et al.
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Figure 6. FE-SEM analysis for paste specimens with 0% and 10% SSA replacements and 0% and 3% nano-Al2 O3 additives when cured
for 28 days.
NMR analysis
The Si atom plays an important role during the hydration
process in cement paste or mortar specimens. In this study,
the 29 Si nucleus was selected for NMR analysis. In the 29 Si
NMR spectra, different Qn sites comprise separate regions
of 29 Si chemical shifts in solid silicates. The Q represents the
silicate tetrahedron, and n refers to the number of other tetra-
hedra to which it is linked by the sharing of oxygen atoms,
with n = 0, 1, 2, 3, and 4. In He and Hu’s research,[16]
they suggested that C2 S and C3 S were observed at the Q0
site and that the hydration products of the C-S-H gel were
observed in the chemical shifts between the Q1 and Q2 sites.
The effects of nano-Al2 O3 additives on the SSA/cement
paste specimens were investigated by studying the struc-
tural changes of silicate tetrahedra. Figure 7 shows the NMR
spectra for cement paste specimens that were cured for 28
days with different types and levels of nano-Al2 O3 addi-
tives added. As shown in Figure 7, peaks were observed
between −78 and −80 ppm, and the intensities of the peaks
increased as the amount of the added nano-Al2 O3 additive
increased. Among these peaks, the increase in the Q1 inten-
sity for specimens with the MC2A nano-Al2 O3 additive
was relatively noticeable; the MC2R nano-Al2 O3 additive
exhibited a lower increase in the Q1 intensity.
Figure 8 presents the NMR spectra for 10%
SSA/cement paste specimens that were cured for 28 days
with different types and levels of nano-Al2 O3 additives
added. As shown in this figure, adding a greater amount
of the nano-Al2 O3 additives to the specimens resulted in
greater intensity peaks. These results were similar to those
obtained for specimens with no SSA replacement. Thus, the
Q1 peak increased with increasing amounts of nano-Al2 O3
additive added.
By comparing Figures 7 and 8 for specimens with 0%
and 10% SSA replacement and various amounts of the
MC2A nano-Al2 O3 additive, the specimens with 10% SSA
replacement were observed to have relatively smaller peaks
and wider peak band widths. This finding implies that these
specimens had less chemical shifting in the Q0 site. This
phenomenon also explains why specimens with 10% SSA
replacement had smaller compressive strengths than those
with 0% SSA replacement.
By comparing the peaks for the 0% SSA replacement
specimens with those that had added MC2A and MC2R
nano-Al2 O3 additives, the peaks for the MC2A additive
were slightly higher than those for the MC2R type. This
finding indicates that larger amounts of C-S-H gel were
produced and that relatively better compressive strengths
were obtained for specimens with MC2A type. However,
when the 10% SSA replacement specimens were consid-
ered, slight differences in the peaks of both MC2A and
MC2R types were observed. Therefore, no clear variations
 Environmental Technology 9

Figure 7. NMR spectra for cement paste specimens cured for 28 days with different types and levels of nano-Al2 O3 additives added.
Downloaded by [Northeastern University] at 21:05 06 January 2015

Figure 8. NMR spectra for 10% SSA/cement paste specimens cured for 28 days with different types and levels of nano-Al2 O3 additives
added.

in the compressive strength were observed for specimens
with these two types of nano-Al2 O3 additives.
Conclusions
In this study, the effects of two types of nano-Al2 O3 addi-
tives, MC2A and MC2R, on SSA/cement paste and mortar
were investigated. We drew the following conclusions from
the results:
(1) For specimens with 10% SSA replacement, the
weight of the specimens increased as the amount
of added nano-Al2 O3 additives increased. Further-
more, the weight of specimens increased with the
curing time.
(2) The addition of nano-Al2 O3 additives could
improve the compressive strengths of the cement
mortar specimens, and the strength of the spec-
imens increased as the amount of added nano-
Al2 O3 additives increased. However, a less sig-
nificant increase in the compressive strength of
the specimens was observed when the cement
was replaced by SSA. Furthermore, although the
MC2R nano-Al2 O3 particle sizes were finer than
that of MC2A nano-Al2 O3 , the fine particles of
MC2R were easily clustered together in water. On
the contrary, MC2A particles were easier to uni-
formly distribute in the specimens. Hence, MC2A
increased the contact area with cement. More
hydration products and better improvements in
compressive strength were obtained for specimens
containing MC2A nano-Al2 O3 .
(3) The XRD results show that the peak values of the
C-S-H gel, C-A-H salts, calcium Ca(OH)2 , and
Al2 O3 relatively increased with increasing levels
of both MC2A and MC2R nano-Al2 O3 additives.
This finding implies that the addition of nano-Al2 O3
additives helped to improve the hydration efficiency
of the specimens. Moreover, the amounts of C-S-H
gel and C-A-H salts produced in specimens with the
MC2A nano-Al2 O3 additive were relatively higher
than those with the MC2R nano-Al2 O3 additive.
(4) The results obtained from the FE-SEM analysis
show that both MC2A and MC2R nano-Al2 O3
particles can be incorporated in the pores of C-S-H
gel and C-A-H salts by van der Waals forces. As
 10 H.-L. Luo et al.
a result, the structure of the specimens became
more compact and integrated. Moreover, when
SSA replaced part of the cement in the specimens,
there was an increased amount of monosulphate
generated, which affected the structure of the spec-
imens. However, the addition of nano-Al2 O3 addi-
tives reduced the generation of monosulphate and
increased the amount of C-S-H gel and C-A-H salts
production, which improved the development of the
structure of the specimens.
(5) The micro-observations obtained from NMR indi-
cate that the increase in the Q1 intensity for speci-
mens with the MC2A nano-Al2 O3 additive was rel-
atively noticeable, whereas that for the specimens
with the MC2R nano-Al2 O3 additive was com-
paratively less obvious. This observation implies
that the MC2A nano-Al2 O3 additive increased the
Downloaded by [Northeastern University] at 21:05 06 January 2015
hydration efficiencies of the specimens more than
the MC2R nano-Al2 O3 additive.
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