You are on page 1of 8

See

discussions, stats, and author profiles for this publication at: http://www.researchgate.net/publication/259678901

Influence of activated drinking-water


treatment waste on binary cement-based
composite behavior: Characterization and
properties
ARTICLE in COMPOSITES PART B ENGINEERING DECEMBER 2013
Impact Factor: 2.6 DOI: 10.1016/j.compositesb.2013.12.020

CITATION

DOWNLOADS

VIEWS

13

56

5 AUTHORS, INCLUDING:
Moiss Fras

Isabel S. De Soto Garca

Spanish National Research Council

Universidad Pblica de Navarra

163 PUBLICATIONS 1,283 CITATIONS

31 PUBLICATIONS 25 CITATIONS

SEE PROFILE

SEE PROFILE

Rosario Garca

Trino Baloa

Universidad Autnoma de Madrid

Central University of Venezuela

117 PUBLICATIONS 579 CITATIONS

12 PUBLICATIONS 9 CITATIONS

SEE PROFILE

SEE PROFILE

Available from: Trino Baloa


Retrieved on: 24 June 2015

Composites: Part B 60 (2014) 1420

Contents lists available at ScienceDirect

Composites: Part B
journal homepage: www.elsevier.com/locate/compositesb

Inuence of activated drinking-water treatment waste on binary


cement-based composite behavior: Characterization and properties
M. Fras a,, R. Vigil de la Villa b, I. de Soto c, R. Garca b, T.A. Baloa d
a

Eduardo Torroja Institute (CSIC), 28033 Madrid, Spain


Dpto de Geologa y Geoqumica, Unidad Asociada CSIC-UAM, Universidad Autnoma de Madrid, 28049 Madrid, Spain
c
Dpto de Ciencias del Medio Natural, Universidad Pblica de Navarra, 31006 Pamplona, Spain
d
Divisin de Estructuras y Materiales, IMME-Facultad de Ingeniera, Universidad de Central de Venezuela, Venezuela
b

a r t i c l e

i n f o

Article history:
Received 28 October 2013
Received in revised form 15 November 2013
Accepted 12 December 2013
Available online 23 December 2013
Keywords:
A. Recycling
B. Chemical properties
B. Mechanical properties
B. Microstructures
Blended cement

a b s t r a c t
Drinking water treatment plants regularly dispose of large volumes of industrial sludge in landll sites,
which often has negative environmental consequences. The calcination products of these kaolinite-based
sludges have properties that could make them appropriate supplementary cementing materials in the
production of blended binary cements.
This research analyses the pozzolanic and thermodynamic properties of a Venezuelan drinking water
sludge activated at 600 C for 2 h and its behavior in blended cement matrices prepared with 15% Activated Waste (AW) and 85% Ordinary Portland Cement (OPC). Our results show that this activated drinking water sludge presents high pozzolanic properties, mainly during the rst 24 h of reaction. The XRD,
SEM/EDX and thermodynamic studies conrm the formation of C2ASH8, CSH gels and C4AH13 as the
hydration products from the pozzolanic reaction. The binary mixture of 15% AW/85% OPC complied with
the physical and mechanical specications contained in current European cement standards.
2013 Elsevier Ltd. All rights reserved.

1. Introduction
Over recent years, fewer high-quality limestone quarries and
clays pits have been supplying raw materials to the cement industry, due fundamentally to the environmental policies introduced in
developed countries. This reduction coupled with an imperative
need to limit the CO2 emissions of the cement industry, has
prompted the search for supplementary cementing materials
extracted from industrial waste and its related sub-products
[110]. In consequence, research into binary and ternary cementbased composites is a priority research line in the cement sector
at present, due to energetic, economic and technical advantages,
stoked mainly by the present global economic crisis [1114].
In this area, scientic interest has recently been focused on kaolinite-based industrial waste, because it can be converted into a
highly pozzolanic product (metakaolinite-based pozzolan), having
undergone a process of thermal activation [1522]. The sludges
generated in drinking water treatment plants are among this class
of waste, generating signicant quantities of drinking water
sludges, which are normally taken to landlls for disposal, with
the ensuing environmental problems [23]. In general, a drinking Corresponding author. Tel.: +34 913020440; fax: +34 913020700.
E-mail address: mfrias@ietcc.csic.es (M. Fras).
1359-8368/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.compositesb.2013.12.020

water treatment plant of 1 m3/s of volume generates about


8300 kg/day of sludge [24], which means that the material is available in abundance, bearing in mind that there are 160,000 public
water systems in the United States alone. In some European countries, only 25% of drinking water sludges are re-used, mainly as raw
materials in the manufacture of Portland clinker as well as in various other industrial sectors [2528].
In a previous work by Fras et al. [29], the scientic bases were
established for the use of these siliceousaluminous sludges as a
pozzolanic material in activated waste systems/Ca(OH)2, which
highlighted suitable activation conditions at 600 C and 2 h retention in a laboratory furnace to transform this inert kaolinite-based
sludge into a metakaolinite based pozzolan.
However, there is a large gap in scientic and technical knowledge of the properties of binary cement-based composites prepared with these activated sludges. Hence, this present study
reports a novel study and a full characterization of industrial
sludge activated at 600 C, its pozzolanic behavior, the evolution
of its mineralogical phases and their inuence on the properties
of the new eco-cement composites. The results obtained from this
research are fundamental for the establishment of scientic
-technical knowledge bases for the manufacture of future commercial composites.

15

M. Fras et al. / Composites: Part B 60 (2014) 1420

2. Materials and methods


2.1. Materials
The Starting Waste (SW) for this research came from a Venezuelan drinking water treatment plant (Embalse La Mariposa), located at 8 km from Caracas. Its water content was initially
around 92%. After drying, the SW was activated at 600 C for 2 h
of retention in an electric laboratory furnace at a heating rate of
20 C/min, following the indications of a previous paper, [29] in
which these conditions were selected as the suitable activation
conditions from an economic and energetic point of view. The activated waste (AW), when cooled to room temperature in a desiccator, showed a reddish coloration (Fig. 1). The sample was ground in
an agate mortar and pestle and then sieved through a 63 lm sized
mesh. According to the laser granulometry analysis [30], 50% of the
particles were of a size below 9.8 lm, 60% below 12 lm and 97%
passed by 45 lm.
2.2. Blended cements
CEM I 52.5 R Ordinary Portland Cement (OPC) supplied from the
Lafarge Cement Companys plant at Villaluenga de la Sagra (Toledo,
Spain) was used. All the cement particles were under 63 lm and
47.41% passed through a 12 lm sieve mesh. The chemical composition and mineralogical of the OPC is given in Table 1.
The blended cements were prepared in a high-speed powder
mixer to guarantee homogeneity. The blends were calculated by
weight, with AW/OPC ratios of 0/100 and 15/85. This replacement
level corresponds to the standardized ratios for type II/A cements
(620%) [31].
2.3. Pozzolanic and thermodynamic methods
Pozzolanic activity method: the pozzolanic behavior in a pozzolan/calcium hydroxide (lime) system was studied using the solid
sludge waste after applying an accelerated chemical method. After
each period of 1, 7, 28 and 90 days of reaction, the sludge was
washed with acetone and dried in an electric oven at 60 C for
24 h, in order to stop the pozzolanic reaction. The content of xed
lime was calculated as the difference between the CaO concentration (mmol/l) in the original saturated lime solution (17.68 mmol/
L) and the content of this compound in the solution at each established time. Extra pure calcium hydroxide Ph Eur, USP, BP chemical
reagent was used.
PHREEQC geochemical software program version 2.18 was used
to evaluate the evolution of the hydrated phases formed in this

Table 1
Chemical and mineralogical composition of OPC.
Compositions

Chemical (%)

SiO2
Al2O3
Fe2O3
CaO
MgO
Na2O
K2O
TiO2
P2O5
S03
LOI

20.16
4.36
2.52
63.41
2.21
0.35
0.91
0.21
0.14
3.57
1.99

Mineralogical (%)

C2S = 8.95
C3S = 64.75
C3A = 7.29
C4AF = 7.65

study, in terms of their thermodynamic behavior [33]. The samples


entered an aqueous species concentration -AW/Ca(OH)2- at different ages (1, 7, 28 and 90 days of reaction). Even though the pH values were optimized with the geochemical PHREEQC code, due to
the various uncertainties of experimental analyses, rather than
using the PHREEQC database, our simulation used the THERMODDEM database [33] that lists all the minerals presented in this
study.
The saturation index of the strtlingite (Ca2Al2SiO2(OH)102.5H2O),
CSH phases with Ca/Si ratios 0.8, 1.2 and 1.6 (Ca0.8SiO2.81.54H2O,
Ca1.2SiO3.22.06H2O and Ca1.60SiO3.62.58H2O), C3AH6 (Ca3Al2(OH)12)
and C4AH13 [Ca4Al2(OH)146H2O], C3AH6 and portlandite Ca(OH)2 were
calculated with the simulation at different ages (1, 7, 28 and 90 days of
reaction), in order to study the stability and evolution of the minerals
(dissolution/precipitation) over time. The simulation also allowed us
to calculate the activities of the aqueous species. The concentrations
of aqueous species measured in the solution at different times were
introduced in the model at pH = 12. The aqueous carbonate (not experimentally determined in solution) was equilibrated with calcite in the
model.
2.4. Standardized methods
The rheological behavior of the blended cement pastes was assessed as described in standard EN 196-3 [34], using a Vicat apparatus to determine normal consistency and setting times. The
soundness of the blended cement pastes was tested with Le Chatelier apparatus, following the procedure specied in the current
European standard [34]. The effect of this addition on the mechanical behavior of new cements was ascertained as per standard EN
1961[35], which describes the methodology for testing mortar
components, and their preparation, curing and strength. Blended
cement mortar specimens measuring 4  4  16 cm were prepared
with a sand/binder ratio of 3/1 and a water/binder ratio of 0.5.
2.5. Characterization techniques

Fig. 1. Appearance of AW activated at 600 C for 2 h.

Different techniques were used for chemical, physical, mineralogical, morphological and microporosity characterization of the
sample. Its chemical composition was studied with a Philips PW1404 780 X-ray uorescence analyzer tted with a ScMo anticathode tube. Particle size was analyzed by laser ray diffraction
(LRD) on a Sympatec Helos 12 KA spectrometer using isopropyl
alcohol as the non-reactive liquid. Material mineralogy was determined with X-ray diffraction (XRD) using random powder mounts
for the bulk sample and oriented slides for the <2-lm fraction. The
samples were analyzed with a SIEMENS D-500 Cu anode diffractometer operating at 30 mA and 40 kV (2-mm divergence slit;
0.6-mm reception slit; 2h goniometer; step size: 0.04; count time:
3 s). The morphological observations and microanalysis of the samples were performed with a SEM/EDX, by using an INSPECT FEI

16

M. Fras et al. / Composites: Part B 60 (2014) 1420

COMPANY electron microscope, equipped with an energy dispersive X-ray analyzer (W source, DX4i analyzer and Si/Li detector).
The chemical composition was obtained by an average value of
ten analyses for each sample, in this case the value was the joint
standard deviation. These semi-quantitative analyses were
performed on clean surfaces to avoid any source of possible
contamination, such as high calcium oxide concentrations, which
might have perturbed the assignation of the mineral formula from
the EDX analysis. The results were expressed in oxides (wt%),
adjusted to 100%. The structural formulas were calculated from
these data, by considering 14 negative charges for C2ASH8
[Ca2Al2(SiO2)(OH)10].
An aqueous solution was used to measure the concentration of
aqueous species of interest for the simulation (Na, K, Mg, Ca, Al and
Si). These concentrations were determined by inductively coupled
plasma mass spectrometry (ICP-MS) with an Elan 6000 PerkinElmer Sciex analyzer.

Fig. 2. Evolution of pozzolanic activity vs hydration time: activated sludge paper


(APS), carbon mining waste (CMW) and y ash (FA).

3.21 (27.78 2h) and hematite (7%) (He) localized at 2.69


(33.30 2h)[35].

3. Results and discussion

3.2. Pozzolanic activity

3.1. Characterization of activated drinking water treatment waste


(AW)

The results of pozzolanic activity for this industrial waste activated at 600 C and two hrs of retention, expressed as a xed lime
percentage (%), are given in Fig. 2. The AW showed a high reaction
capacity for xing the available lime (70%), mainly after 24 h of
reaction time. Over longer times, the xed lime increased from
79.8% at 7 days of reaction to 84.1% at the end of test (90 days).
This pozzolanic activity of the AW was comparable, mainly after
7 days, to other thermally activated kaolinite-based wastes such
as coal mining wastes (CMW) and paper sludge (APS), and it
showed a higher activity than y ash (FA), a traditional pozzolan
in the cement industry, over the rst 28 days of reaction [19,38].

Table 2 shows the chemical compositions of SW and AW. The


AW waste was mainly composed of SiO2 (41.5%), Al2O3 (33.6%)
and Fe2O3 (11.1%), followed by K2O (3.7%), MgO (1.5%) and TiO2
(1.4%), and the other oxides were below 1%. The Starting Waste
(SW) presented a high Loss On Ignition (LOI) of 15.32% with respect
to that shown by AW (1.99%), which was due, mainly, to the presence of colloidal or dissolved organic matter in water (TOC = 2.3%),
kaolinite (11%) and water (1.3%) in the starting waste (SW) [29].
These chemical values differ from those values recently published
for a Spanish atomized sludge [24], the major oxide contents of
SiO2 (29.63%), Al2O3 (17.57%), and Fe2O3 (5.18%) of which were
lower than those reported in the present paper.
This kind of waste also presents traces of heavy metals in variable concentrations, mainly chlorides, barium, chromium, and
vanadium (Table 2), which could have a direct inuence on the initial setting behavior (accelerating or delaying the hydration reaction), once mixed with cements. Some of these minor elements
differed substantially from those quantied in a Portuguese sludge,
mainly in zinc, copper and chromium [36]. This nding implies
that the sludge characteristics depend on the source water type
(surface or groundwater) and the treatments that are employed.
The mineralogical composition obtained by XRD of the AW
(Fig. 2) shows the presence of phyllosilicates 2:1 (micas 47%) (M)
localised at 10.08 (8.76 2h), 4.48 (19.80 2h), 3.66 (24.28
2h), 3.35 (26.58 2h), 2.56 (35.02 2h) and 2.45 (36.64 2h),
quartz (17%) (Q) at 4.26 (20.82 2h), 3.34 (26.66 2h) and
1.81 (50.36 2h), cation-disordered CaMg carbonates (14%) (C)
in the d-spacing range 3.02 (29.54 2h) 2.99 (29.84 2h),
potassium-rich feldspars (Feld-K) (13%) at 13.25 (27.44 2h), plagioclases (2%) (Pl) in the d-spacing range 3.19 (27.96 2h)

3.3. Reaction kinetics and thermodynamic modelling


XRD analysis of the AW/ Ca(OH)2 system (Fig. 3) at 1, 7, 28 and
90 days of reaction showed that, in all cases, the main crystalline
reaction product detected by XRD was the formation of strtlingite
(C2ASH8)(St), with reections at 12.61 (7.0 2h), 6.28 (14.08
2h), 4.15 (21.38 2h) and 2.87 (31.14 2h); followed by tetracalcium aluminate hydrate (C4AH13) in minor proportions (5%), localized at 7.9 (11.18 2h), 2.88 (31.02 2h) and 2.86 (31.24 2h).
The chemical reactions involved when calcined MK based clays are
used as pozzolans for cements and concretes have been discussed
previously [39,40]. This reaction between MK and calcium hydroxide produced during the cement hydration forms additional
phases: aluminum containing CSH gel, together with crystalline
products, which include metastable phase such as: calcium aluminate hydrates and alumina-silicate hydrates (C4AH13, C2ASH8,), and
stable phases (C3AH6C3ASH6), belonging to the hydrogarnet family. The crystalline products formed depend principally on the MK/
CH ratio and the reaction temperature [4144].
In alkaline solutions, Al and Si solubilities increase with pH. Dissolved aluminum can be existed in several forms in solution. In the

Table 2
Chemical composition of the starting and activated waste.
Main oxides (%)

SW
AW

SiO2

Al2O3

Fe2O3

CaO

MgO

Na2O

K2O

TiO2

P2O5

SO3

MnO

LOI

36.24
41.54

29.46
33.60

10.05
11.09

0.98
0.42

1.23
1.51

0.83
0.98

3.31
3.67

1.23
1.36

0.67
0.74

0.29
0.31

0.38
0.42

15.32
3.31

Minor elements (ppm)

SW
AW

Cl

Sr

Cu

Ni

Co

As

Ba

Cr

Zn

Zr

663
211

64
65

26
51

76
81

25
27

20
21

233
226

137
130

275
263

82
77

M. Fras et al. / Composites: Part B 60 (2014) 1420

17

C2ASH8 during the whole reaction, which agreed with the experimental observations obtained by SEMEDX and XRD. The simulation also conrmed that the precipitation of C4AH13 due to the
positive saturation index calculated at 1 and 7 days reaction
(Fig. 6). The thermodynamic analysis predicted under-saturation
conditions (negative saturation indexes) for portlandite, CSH
gels and C3AH6 phases, according to the experimental data.
3.4. Chemical composition of the blended cement

Fig. 3. Evolution of mineralogical phases during pozzolanic reaction.

absence of other ligands, the most important are Al3+, AlOH


2,
Al(OH)2+, Al(OH)3, and Al(OH)4. At high pH (pH > 10), Al(OH)4
is the dominant specie in solution, these ions start to combine with
the readily available Ca2+ ions via metastable phases forming
C3AH6. The total dissolved silica concentration in equilibrium with
quartz or amorphous silica will increase at high pH values
(pH > 10). At these pH values, the total dissolved silica concentration will be the sum of the ionized and un-ionized species

2
(H4SiO4, H3 SiO4 and H2 SiO4 ). If the total silica concentration in
the solution becomes supersaturated with respect to amorphous
silica, begins to form polymers which combine with the Ca2+ ions
forming CSH gels [45,46].
These ions react with the C3AH6 initially formed, forming
C2ASH8. High MK contents, relative to those with low MK contents,
was attributed, in part, to the formation of increased amounts of
C2ASH8 and reduced amounts of C4AH13 as the MK content increased [47]. In this study, after activation process of AW at
600 C 2 h, the presence of high metakaolinite (MK) content favored the formation of stratlingite C2ASH8 as the main reaction
product at all times of the pozzolanic reaction.
The appearance of C4AH13 is attributed to supersaturation of the
aqueous phase with respect to calcium hydroxide and low MK contents. High concentrations of Ca2+ and OH in the solution, created
by the Ca(OH)2 dissolution, maintain a composition that enables
precipitation of C4AH13 [45,46]. In this study, 1 and 7 days of the
pozzolanic reaction enables precipitation of C4AH13.
The laminar phases corresponding to C2ASH8 may be observed
in the AW/CaOH)2 system by means of SEM. The existence of laminar mica and laminar microaggregates of silica enriched composition may also be observed and material deposits on the surface
(Fig. 4).
The study of the evolution of the aqueous chemistry of the samples provides useful information on the new hydrated phases
formed in this study. Ca and Si concentrations decreased throughout the reaction and Al concentration decreased at 28 days reaction, due to the incorporation of Ca, Si and Al formed in the main
phase (strtlingite and C4AH13) (Fig. 5).
In contrast, an increase of Na and K concentrations over time in
the aqueous solution was studied after the pozzolanic reaction.
This constant increase showed a continuous dissolution of the
phyllosilicates in the pozzolanic reaction over time (Fig. 5). Finally,
Mg concentrations were very low throughout the reaction (Fig. 5).
Saturation indexes of the phases formed in the pozzolanic reaction were obtained with PHREEQC [32]. Positive saturation index
values (oversaturation conditions) were obtained for stratlingite

Table 3 shows the chemical composition by XRF analysis of the


blended cement prepared with 15% AW replacement. This blended
cement consisted primarily of CaO (54.1%), SiO2 (23.7%), Al2O3
(8.5%), Fe2O3 (3.9%) and SO3 (3.74.2%); followed by MgO (1.9%)
and K2O (1.22%). The content of the other oxides was below 0.5%.
Table 3 also compares the sulfate and chloride contents in the
AW blended cement analyzed according to the specications in
the current European standard for type CEM II/A cements [31].
The cements prepared with 15% activated drinking water treatment waste proved to be standard-compliant.
3.5. Physical properties of the blended cements
Tests on physical properties in line with European standards focused on water content at normal consistency, the determination
of setting times and volume stability [34]. The incorporation of
AW substantially modied the water content needed to reach a
normal consistency in the blended cement paste with respect to
the control paste (Table 4). Dening OPC water content as 100%,
water content demand increased by 50% following the addition
of 15% AW. This fact will be related to a higher neness of the
AW than the OPC (as mentioned above), and to the clayey nature
of this activated waste which presents strong water retention
powers.
With respect to the results obtained for setting times (10 min),
it was clearly detected that the incorporation of AW in the cement
pastes neither substantially modied the initial nor the setting
times. Compared to the control paste, the values found were similar in both cements and the slight variations that were observed
would be related to testing error. This behavior is contrary to the
ndings reported by Fras et al. [48,49] for the cements elaborated
with 20% activated coal mining wastes, 10% rice husk ash, 1020%
sugar cane bagasse ash, which delayed the initial setting times.
Hence, it is important to note that the presence of low heavy
metals concentrations such a barium, chromium, vanadium and
zinc in AW ash (Table 2) did not affect the setting times of blended
cement, possibly due to very low Zn content in the sample, element well known to delay the start of initial setting (<82 ppm).
The expansion test was conducted as specied in EN 196-3 [34].
The ndings for the three blended cements (average of three measurements with a 0.5-mm test error) given in Table 4 show that the
addition of AW had no effect on cement paste soundness.
3.6. Mechanical properties of blended cements
The effect of the addition of AW on the compressive strength of
blended cement mortar (average of six specimens), including the
standard deviation intervals, is depicted in Fig. 7. The AW blended
cement mortars exhibited lower compressive strength than the
OPC mortar, a similar tendency to that shown for most pozzolans
used in the manufacture of blended cements (y ash, natural pozzolan, SiMn slag, ceramic waste) [48,50]. Fig. 8 shows the relative
losses in compressive strength in greater detail.
The blended cement mortars containing 15% AW maintained
relative strength losses of about 12% during the rst 24 h of reaction, and subsequently, this loss was reduced by up to 9% with re-

18

M. Fras et al. / Composites: Part B 60 (2014) 1420

Fig. 4. Morphological aspects of laminar stratlingite, mica aggregates and mica with surface depositation.

Fig. 5. Evolution of the aqueous ions as a function of time.

Table 4
Values of water content (g), setting times (10 min) and volume stability (mm).

OPC
OPC + 15% AW
Requirements

Fig. 6. Saturation indices of the AW/Ca(OH)2 system over time.

spect to the control specimen, at 7 days of curing. For longer hydration times, 15% ASW blended cement mortars increased their relative losses, reaching 16% and 18% with respect to the control
mortar at 28 and 60 days of reaction, respectively. Strength loss
in AW blended mortars with rising hydration time may be re-

W. content

Initial set

Final set

Soundness

150
225

150
130
P45

202
216

0
0
610

garded as an exception among other activated kaolinite based


wastes (paper sludge, coal mining) [48,49] that showed similar
and/or slightly higher compressive strengths than the control mortar from 7 to 28 days of curing. However, this same tendency was
also observed in a previous work when drinking water treatment
sludge (activated at 700 C) was used as an active addition for
the blended mortars manufacture [38]. The addition of 10% Portuguese activated sludge produced a compressive strength loss of the
14.4% at 7 days of reaction, although no justication was given to
explain it.
According to the results shown in the present paper (chemical
composition, mineralogy, pozzolanic activity, setting times), no scientic explanation for this unfavorable behavior can presently be
put forward because of the novelty of the research and the absence
of prior studies. A possible explanation of the important compressive
strength losses of 15% AW blended cement mortars could be related
to the high water demand needed to reach a normal consistency. As
mentioned above, a 15% AW replacement increased the water content of blended pastes by 50%. However, the blended cement mortars

Table 3
Chemical composition of blended cement.
Chemical composition (%)

15% OPC

SiO2

Al2O3

Fe2O3

CaO

MgO

Na2O

K2O

TiO2

P2O5

SO3

Cl

LOI

23.70

8.48

3.90

54.10

1.89

0.41

1.22

0.39

0.24

3.01

0.01

15.32

European standard requirements (%)


SO3: 63.5

Cl: 60.1

M. Fras et al. / Composites: Part B 60 (2014) 1420

19

effect of addition of 15% of AW on microprorosity of mortars cured


at 60 days. The total porosity results (Table 5) showed that the
addition of 15% AW did not affect practically to the microporosity
of the cement mortars; the 15% AW blended mortar (12.9%) obtaining a slightly higher value than the control mortar (11.8%) in
mortar cured at 60 days. The distribution density curves (Fig. 9)
conrmed this tendency, in which there is a well dened maximum in each case, localised at 0.11 and 0.13 lm for the OPC and
15% AW mortars, respectively. These ndings are totally in agreement with the average pore diameter results (4 V/A), showing values of 0.067 and 0.084 lm for percentages of 0 and 15% of
activated waste.
Fig. 7. Evolution of compressive strength up to 60 days of curing.

4. Conclusions
The conclusions drawn from the experimental results are as
follows.

Fig. 8. Relative compressive strength losses (%).

Table 5
Porosity values at 60 days of curing.

OPC
OPC + 15% AW

P. total (%)

Av. pore diam. (lm)

11.80
12.93

0.067
0.084

Fig. 9. Comparison of pore-size distribution of OPC and 15% AW blended cement


mortars at 60 days of reaction.

had a consistency (tested in ow table) of 15% prepared with a constant water/binder ratio (w/b = 0.5) [37]. Notwithstanding the above,
all the AW blended mortars had 28-day compressive strength values
that were above the requirements of the existing European standard
(P52.5 MPa) for class 52.5 R cements.
3.7. Microporosity of cements
Total porosity, average pore diameter and pore size distribution
were analysed by mercury porosimetry, in order to determine the

1. The drinking water treatment waste activated at 600 C for 2 h


showed a siliceousaluminous nature with a Fe2O3 content of
about 11% and minor elemental contents of over 100 ppm (Cl,
Ba, Cr, V). Mineralogically, the AW is formed by phyllosilicates
2:1 (micas), quartz, cation-disordered CaMg carbonates,
potassium-rich feldspars, plagioclases and hematite.
2. The AW activated at 600 C and 2 h of retention showed
maximum pozzolanic activity during the rst 24 h of reaction,
taking the xed lime percentages (70% of available lime) into
account.
3. Strtlingite (C2ASH8) was the main crystalline reaction product
detected through XRD and tetracalcium aluminate hydrate
(C4AH13) in minor proportions (5%) throughout the pozzolanic
reaction. The laminar phases corresponded to C2ASH8 and
SEM analysis revealed the existence of laminar mica and laminar micro-aggregates of silica enriched composition with supercial deposits.
4. The precipitation of strtlingite during the pozzolanic reaction
was calculated with PHREEQC. The results indicate that stratlingite was the main mineral phase produced during the pozzolanic reaction, according with the experimental XRD and
SEM data.
5. The addition of 15% AW to the cement paste raised the water
demand by 50% and a consistency reduction of about 38% in
blended mortars.
6. The 15% AW cement pastes complied with standardized chemical requirements in terms of sulfate and chloride content of the
cements type CEM II/A, and with physical requirements (initial
setting time and volume stability).
7. The addition of 15% AW in the blended cement mortars manufacture produced compressive strength losses of between 12%
and 18% in function of the cured age. In spite of this, all 15%
AW blended cement mortars complied with the mechanical
requirements specied in the existing standards.
8. In general, the incorporation of AW affected slightly to the total
microporosity and the average size diameter values of the
blended cement mortars. A small increase in the average diameter was observed for the 15% AW cement mortar with respect
to the control mortar, passing from 0.067 lm for the OPC to
0.084 lm for the 15% AW blended mortar.
In summary, the use of activated drinking water treatment
waste as an active pozzolanic addition to blended cements is a solid scientic option that is technically viable. Further research (into
durability, higher AW percentages, and the use of water reducer
agents) is necessary before this knowledge may be transferred to
the industrial sector.

20

M. Fras et al. / Composites: Part B 60 (2014) 1420

References
[1] Siddique A. Waste materials and by-products in concrete. Berlin: Springer;
2008.
[2] Fras M, Vegas I, Vigil R, Garca R. Recycling of paper sludge in cements:
characterization and behaviour of new eco-efcient matrices. In: Kumar S,
editor. Integrated Waste Management. vol II. Croatia: 2011, p. 301318.
[3] Ibrahim R, Hamid R, Taha MR. Fire resistance of high volume y ash mortars
with nanosilica addition. Const Build Mater 2012;36:77986.
[4] Arizzi A, Cultrone G. Aerial lime-based mortars blended with a pozzolanic
additive abd different admixture: a mineralogical, textural and physical
mechanical study. Constr Build Mater 2012;31:13543.
[5] Fras M, Snchez de Rojas MI. Microstructural alterations in y ash mortars:
study on phenomena affecting particle and pore size. Cem Concr Res
1997;27(4):61928.
[6] de Lomas M, Snchez de Rojas MI, Fras M. Pozzolanic reaction of a spent uid
catalytic cracking catalyst in FCC cement mortars. J Therm Anal Calorim
2007;35(11):213742.
[7] Vigil R, Fernndez R, Rodriguez R, Garca R, Villar E, Fras M. Evolution of the
pozzolanic activity of a thermally treated zeolite. J Mater Sci
2013;48:321324.
[8] Najigivi A, Khaloo A, Iraji A, Abdul S. Investigating the effects of using different
types of SiO2 nanoparticles on the mechanical properties of binary blended
concrete. Composites Part B 2013;54:528.
[9] Sanjuan MA, Argiz C. The new European standard on common cements
specications EN 197-1:2011. Construcc Mater 2012;62(307):42530.
[10] Argiz C, Menndez E, Sanjuan MA. Effect of mixes made of coal bottom ash and
y ash on the mechanical strength and porosity of Portland cement. Construcc
mater 2013;63(309):4964.
[11] Fras M, Goi S. Accelerated carbonation effect on behaviour of ternary
Portland cements. Composites Part B 2013;48(may):1228.
[12] Goi S, Fras M, Vegas I, Garca R, Vigil R. Quantitative correlations among
textural characteristics of CSH gel and mechanical properties: case of ternary
Portland cements containing activated paper sludge and y ash. Cem Concr
Comp 2012;34(8):9116.
[13] Medina C, Banll PFG, Snchez de Rojas MI, Fras M. Rhelogical and
colorimetric behaviour of cements blended with containing ceramic sanitary
ware
and
construction/demolition
waste.
Constr
Build
Mater
2013;40(march):82231.
[14] Madani M, Shao Y, Whalen JK. Biocement production from silicon-rich plant
residues: perspectives and future potential in Canada. Biosyst Eng
2011;110:35162.
[15] Lin DF, Huang LS, Luo HL, Weng RS. Effects on cement after partial replacement
with burned joss paper ash. Environ Technol 2012;33(22):2595601.
[16] Yan S, Sagoe-Crentsil K, Shapiro G. Reuse of de-inkg sludge from wastepaper
recycling in cement mortar products. J Environ Manage 2011;92:208590.
[17] Banll PFG, Fras M. Rheology and conduction calorimetry of cement modied
with clacined paper sludge. Cem Concr Res 2007;37(2):18490.
[18] Vegas I, Urreta J, Fras M, Garca R. Freezethaw resistance of blended cements
containing calcined paper sludge. Constr Build Mater 2009;23(8):28628.
[19] Fras M, Vigil R, Sanchez de Rojas MI, Medina C, Juan A. Scientic aspects of
kaolinite based coal mining wastes in pozzolan/Ca(OH)2 system. J Am Ceram
Soc 2012;95(1):38691.
[20] Fras M, Martnez S, Blasco T, Fras-Rodrguez M. Evolution of mineral phases
by 27Al and 29Si NMR in MK-Ca(OH)2 system cured at 60 C. J Am Ceram Soc
2013;96(7):230610.
[21] Fras M, Villar E, Savastano H. Brazilian sugar cane bagasse ashes from the
cogeneration industry as active pozzolans for cement manufacture. Cem Concr
Comp 2011;33(4):4906.
[22] Resmini C, Anglioletto E, Gracher H, Peterson M, Rocha MR, Resmini A, et al.
Production of MK from industrial cellulose waste. J Therm Anal Calorm
2012;109:13415.
[23] Kyncl M. Opportunities for water treatment sludge re-use. GeoSci Eng
2008;54(1):1122.
[24] Verlicchi P, Masotti L. Reuse of drinking water treatment plants sludges in
agriculture: Problems, perspectives and limitations. Google website:
www.ramiran.net/doc; 2012.

[25] Chen H, Ma X, dai H. Reuse of water purication sludge as raw material in


cement production. Cem Concr Comp 2010;32(6):4369.
[26] Husillos N, Martnez S, Blanco MT, Guillem M, Puig J, Larrotcha E, et al.
Evaluation of spary dried sludge from drinking wter treatment plants as a
prime material for clinker manufacture. Cem Concr Comp 2011;33(2):26775.
[27] Liang Ch, Tseng DH, lin TT. Characterization of eco-cement paste produced
from waste sludges. Chenosphere 2011;84(2):2206.
[28] Lin KL, Lin CY. Hydration characteristics of waste sludge ash utilized as raw
cement material. Cem Concr Res 2005;35:19992007.
[29] Frias M, Vigil R, Garca R, Snchez de Rojas MI, Baloa TA. Mineralogical
evolution of kaolin based drinking water treatment waste for use as
pozzolanic material. The effect of activation conditions. J Am Ceram Soc
2013;96(10):318895.
[30] Fras M, Snchez de Rojas MI, Lxan MP, Garca N. Determination of specic
surface area by the laser diffraction technique. Comparison with the Blaine
permeability method. Cem Concr Res 1991;21(5):70917.
[31] UNE-EN 197-1. Cement Part 1: composition, specications and conformity
criteria for common cements, 2011.
[32] Parkhurst DL, Appelo CAJ. Users guide to PHREEQC (Version 2) a computer
program for speciation, batch-reaction, one-dimensional transport, and
inverse geochemical calculations.US Geological Survey, Reston, VA. 1999.
[33] Blanc P, Lassin A, Piantone P. Thermoddem a database devoted to waste
minerals. Orlans, France: BRGM. <http://thermoddem.brgr.fr>. 2007.
[34] UNE EN 196-3. Methods of testing cement. Part 3: Determination of setting
time and sounness; 2005.
[35] UNE EN 196-1. Methods of testing cement. Part 1: Determination of strength;
2005.
[36] Goncalves A, Esteves A, Carvalho M. Incorporation of sludges from a water
treatment plant in cement mortars. In: Proceeding of Inter Conference on the
Use of Recycled Materials in Building and Structure, vol. 1, Edited by RILEM,
Barcelona, 2004, p. 347350.
[37] Brindley GW, Brown G. Crystal structures of clay minerals and their X-ray
identication. Mineralogical Society Monograph no. 5. London, 1980.
[38] Rodrguez O, Fras M, Snchez de rojas MI. Inuence of the calcined paper
sludge on the development of hydration heat in blended cement mortars. J
Therm Anal Calorim 2008;92(3):86571.
[39] de Silva PS, Glasser FP. Hydration of cements based on metakaolin:
thermochemistry. Adv Cem Chem 1990;3(12):16777.
[40] Dunste AM, Parsonage JR, Thomas MJK. The pozzolanic reaction of metakaolin
and its effects on PC hydration. J Mater Sci 1993;28:134550.
[41] Fras M, Sanchez de Rojas MI. The effect of high curing temperature on the
reaction kinetics in MK/lime and MK-blended cement matrices at 60C. Cem
Concr Res 2003;33:6439.
[42] Fras M. Study of hydrated phases present in a MK-lime system cured at 60 C
and 60 months of reaction. Cem Concr Res 2006;36(5):82731.
[43] Wild S, Khatib J, Roose LJ. Chemical and autogenous shrinkage of Portland
cement-metakaolin pastes. Adv Cem Res 1998;10(3):10919.
[44] Khatib JM, Sabir BB, Wild S. Some properties of metakaolin paste and mortar.
In: Dhir RK, Dyer TD, editors. International congress, concrete in the service of
Mankind-concrete for environmental enhancement and protection. Theme 6
waste materials and alternative product. London: E & F N Spon; 1996. p.
63744.
[45] McBride MB. Environmental chemistry of soils. New York, Oxford: Oxford
University Press; 1994.
[46] Drever JI. The geochemistry of natural waters. 2nd ed. New Jersey
07632: Prenyice Hall. Englewood Cliffs; 1988.
[47] Sabir BB, Wild S, Bai J. Metakaolin and calcined clays as pozzolans for concrete:
a review. Cem Concr Comp 2001;23:44154.
[48] Fras M, Snchez de Rojas MI. Natural and articial pozzolans in eco-efcient
concrete. In: Pacheco F, Jalali S, Labrincha J, John VM, editors. Eco-efcient
concrete. Cambridge: Woodhead Publishing Limited; 2013. p. 10522 [chapter
5].
[49] Fras M, Snchez de Rohas MI, Garca R, Juan A, Medina C. Effect of activated
coal mining wastes on the properties of blended cement. Cem Concr Comp
2012;34(5):67883.
[50] Taylor HFW. In: Cement chemistry. Thomas Telford Publishing. Thomas
Telford Services Ltd.: London; 1997.