Journal of Cleaner Production 185 (2018) 168e175

Contents lists available at ScienceDirect

Journal of Cleaner Production

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

One-part geopolymer cement from slag and pretreated paper sludge

Elijah Adesanya a, Katja Ohenoja a, Tero Luukkonen a, Paivo Kinnunen a, b,
Mirja Illikainen a, *
a
Faculty of Technology, Fiber and Particle Engineering Unit, PO Box 4300, 90014, University of Oulu, Finland
b
Department of Civil and Environmental Engineering, Imperial College London, London, SW7 2BU, United Kingdom

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

Article history: The aim of this study was the valorization of paper sludge waste from paper industry in designing one-
Available online 3 March 2018 part geopolymer cement using ground granulated blast furnace slag as main precursor. The effects of
increasing the amount of paper sludge pretreated with a constant amount of sodium hydroxide (2% of
slag) on mechanical strength, heat evolution, setting time and durability were analyzed. The reaction
products were characterized using X-ray diffraction and thermogravimetric analysis. The findings
showed that paper sludge can successfully be used as a secondary source of calcium carbonate in the
one-part (“just add water”) geopolymer. The compressive strength of the cured geopolymer increased
with increasing the amount of paper sludge, and the non-reacted sludge acted as a filler. The maximum
strength (42 MPa, 28 d) was reached at 18 wt-% paper sludge addition. The main reaction products were
calcium aluminate silicate hydrate and hydrotalcite-like cementitious gels. From the perspective of its
blast-furnace slag content, strength properties, water absorption and setting time, the one-part geo-
polymer cement could be classified as a CEM IIIC and Type 32.5N class cement under the European
standard EN-197.
© 2018 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND
license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction been active: such as alkali-activated cements based on alumino-

The increasing demand for environmentally friendly and sus-
tainable construction materials has necessitated finding alterna-
tives or substitutes for ordinary Portland cement (OPC).
Environmental impacts and emissions of greenhouse gases from
OPC production has been widely documented, and with the
increasing infrastructure development worldwide, the demand and
production of OPC cement as binder in concretes structures will
continue to increase (Cement Industry Energy an, 2017; Ali et al.,
2011; Schneider et al., 2011; Damtoft et al., 2008; Flatt et al.,
2012). Different alternatives for OPC in construction materials,
measures to reduce the reliance on its use and curbing the detri-
mental environmental impacts have been suggested by several
authors. Partial substitution of OPC with different supplementary
cementitious materials has been suggested and is already the norm
in many countries (Islam et al.,; Alex et al., 2016; Rissanen et al.,
2017; Vegas et al., 2009; Evaluation of paper industry,). In addi-
tion to this, the design and development of alternative binders has
* Corresponding author.
E-mail address: Mirja.illikainen@oulu.fi (M. Illikainen).
silicate materials (including industrial by-products or wastes, like
fly ash, slags and tailings (Adesanya et al., 2016; Kiventera € et al.,
2016; Yliniemi et al., 2015)) activated with alkaline solution (typi-
cally sodium silicate). These materials are called (two-part) geo-
polymers or alkali-activated materials, and the background,
chemical and elemental principles, reaction behavior and engi-
neering properties of them have been reviewed at length (Provis
et al., 2015; Garcia-Lodeiro et al., 2014; Puertas et al., 2011; Caijun
Shi, 2033; Wang et al., 1995; Davidovits, 2011; Duxson et al., 2007).
Geopolymers designed from two-part mix are comprised of alka-
line solutions and solid powdered precursors. However, the large-
scale production of geopolymers using this method makes it
scalability difficult due to handling issues and viscosity of the
alkaline solutions and are presently restricted to relatively small-
scale applications (Nematollahi et al., 2015).
One-part geopolymers are suggested to solve some of the short-
comings of conventional two-part geopolymer binder designs. One-
part geopolymers are made with blends of solid alkaline activators
and solid aluminosilicates precursors. Different synthesis routes in
designing one-part geopolymer cements have been proposed or
reviewed (Duxson and Provis, 2008; Abdollahnejad et al., 2015; Kim
et al., 2013; Luukkonen et al., 2017). In order to enable large-scale

https://doi.org/10.1016/j.jclepro.2018.03.007
0959-6526/© 2018 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
 E. Adesanya et al. / Journal of Cleaner Production 185 (2018) 168e175
application of geopolymer products and also to reduce the economic
cost in handling aqueous alkaline solution, developing one-part
geopolymer mix “just-add water” similar to OPC is necessary. That
being said, two-part geopolymers might be more useful in precast
work whereas one-part geopolymers could find applications espe-
cially in in situ casting (Provis, 1016). Since the introduction of one-
part geopolymers, several efforts in designs have been reported by
different authors. Ke et al. (2015) designed one-part geopolymers
blended with thermally treated red mud and sodium hydroxide. The
maximum compressive strength was 9.8 MPa after 7 days.
Nematollahi et al. (2015) made one-part geopolymer cement using
class F fly ash, slag and hydrated lime as aluminosilicates source
blended with anhydrous sodium silicate and sodium hydroxide. They
reported highest strength of 37 MPa for the hydrated one-part geo-
polymer cement, which was 5 MPa weaker than two-part geo-
polymer mix when compared. Peng et al. (2014) calcined low-quality
kaolin at temperatures between 650 and 1050
C with sodium hy-
droxide or sodium carbonate to make one-part geopolymer cement.
In comparison to two-part geopolymer mix with a compressive
strength of 16 MPa, they reported compressive strength of 63 and
48 MPa when the one-part mix was made with NaOH and Na2CO3
respectively. The energy consumption of some of the methods used in
making one-part geopolymer may limit its commercial viability and
also increase impact of production on environment. Also, alkali sili-
cate usage could be expensive and also has impacts on environment
from its production (Torres-Carrasco et al., 2015): sodium silicate is
estimated to account for about 75% of the carbon footprint of geo-
polymer concrete (Mellado et al., 2014). Therefore, there is a need for
sodium silicate-free one-part geopolymer, which leads to lower
environmental impacts and lowers the cost of raw materials. To this
end in some one-part geopolymer studies, synthetic sodium silicate
has been replaced with rice husk ash, maize cob ash, silica residue
from chlorosilane production, or geothermal silica (Hajimohammadi
et al., 2008; Peys et al., 2017; Sturm et al., 2015, 2016; Gluth et al.,
2013).
Meanwhile, in the pulp and paper industry a number of different
types of solid wastes and sludge are produced from pulping,
deinking processes and wastewater treatment at paper mills. In
2005, about 11 million tons of solid wastes were generated in
Europe alone (Mill Sludge Management,). According to the statistics
from CEPI (CEPI), a yearly production of paper mill sludge is more
than 4.7 million tons in Europe, and a global production has been
predicted to rise in the future (Mabee and Roy, 2003). Additionally,
Table 1
Chemical composition of paper sludge and GGBFS (weight-%).
CaO Al2O3 SiO2
GGBFS 38.5 9.58 32.33
Paper sludge 95.1 1.0 0.7
Fig. 1. Starting materials. a) As-received image of non-treated paper sludge. b) X-ray diffractograms of paper sludge and GGBFS (C e CaCO3).
169
about 300 kg of sludge is generated per 1 ton of recycled paper
(Utilization of Waste Pape, 2665). Sludge wastes have a high variety
of properties depending on the factory and process parameters, but
typically they have a chemical composition suggesting that they
could be utilized in concrete materials (Lightweight mortars,): they
contain different ratios of calcium, aluminum, sodium and silicon.
Paper sludge with and without calcination has been previously
used in concrete as a cement replacement material (Lightweight
mortars, ; Martínez-Lage et al., 2016; Valorization of paper mil,
2868), and it has been found that it possible to replace 20% of
OPC without significant loss in durability.
In earlier studies, chemical grade CaCO3 has been used in order
to achieve one and two-part geopolymer cements (Kim et al., 2013;
Abdel-GawwadA, 1016) (Mathur and Sharma, 2008). Here, we uti-
lized paper sludge as the CaCO3 source (i.e., as an activator) in
combination with a small amount of NaOH in the mix design of the
one-part geopolymer mortars. This paper sludge contains 58.4% dry
matter and 41.6% of water. We measured strength development,
durability, drying shrinkage and water absorption of the mortar
samples. Isothermal conduction calorimetry was used to analyze
the heat of hydration of the fresh-state samples, and X-ray
diffraction used in analyzing the mineralogy of starting materials
and reaction products.
2. Experimental program
2.1. Materials
Paper sludge obtained from Stora Enso Paper mill (Oulu,
Finland) was used in this study as a CaCO3 source. The dried paper
sludge contains 87.8% of CaCO3 and 12.2% of cellulose fibers and it is
a primary sludge originating from primary clarification at waste-
water treatment plant. Ground granulated blast furnace slag
(GGBFS) was supplied by Finnsementti (Finland). The median par-
ticle size (d50) of the slag was 10.21 mm as analyzed using a Beck-
mann Coulter LS 13320 laser diffraction particle size analyzer.
Oxide compositions of the materials as determined by X-ray fluo-
rescence (PANalytical Omnian Axiosmax) together with loss on
ignition (LOI, determined with PrepAsh, Precisa) results are shown
in Table 1. For the paper sludge, LOI at 525
C is due to fibers
degradation and at 950
C due to the decarbonation of calcite
[CaCO3 (s) / CaO (s) þ CO2 (g)]. X-ray diffractograms of the paper
sludge and GGBFS are shown in Fig. 1. In the XRD pattern of the raw
MgO Fe2O3 Others LOI (525
C) LOI (950
C)
10.24 1.23 8.11 N/A 1.3
0.8 0.1 2.3 12.2 50
170 E. Adesanya et al. / Journal of Cleaner Production 185 (2018) 168e175

materials, the raw paper sludge shows peaks which consists of

mainly calcite. The broad peak at 25e35
2q reflects the amorphous
structure of the slag. Alkaline solution was prepared by dissolving
sodium hydroxide (NaOH) pellets with 99% purity (Merck KGaA) in
distilled water. Standard sand in accordance with EN 196-1 (Nor-
mensand GmbH) was used as aggregates in the mortar samples
with a sand-to-binder weight ratio of 0.94.

2.2. Paper sludge pretreatment

Fig. 3. SEM images of (a) non-treated milled paper sludge (GP1) and (b) pretreated
milled paper sludge (GP5).
The paper sludge-based dry activators were prepared by mixing
6.3 M NaOH with increasing amount of paper sludge (see Table 2)
using a dispersing instrument (IKA T25 Ultra Turrax) for approxi- Table 3
mately 4 min. The mixed sludge were then dried in the oven at Mix composition of mortar samples.
95
C for two days. The resultant flakes as seen in Fig. 2, were then Dry activator (g) GGBFS (g) w/b s/b
milled using a tumbling ball mill (Germatec, Germany) to achieve
GP1a 29 421 0.31 0.94
an average d50 of 15 mm. GP2 29 421 0.31 0.94
The mineralogy of the samples after treatment with NaOH in GP3 56 393 0.31 0.94
Fig. 2 shows that Calcite (CaCO3) and Pirssonite (Na2Ca(CO3)2.2H2O) GP4 85 363 0.31 0.94
GP5 113 338 0.31 0.94
are the major phases and small quantities of Portlandite Ca(OH)2
a
and Natrite (Na2CO3) were also identifiable. The postulated chem- Contains only paper sludge.
ical reactions during the pretreatment are described below in
equations (1) and (2). The use of paper sludge as a source of calcium
carbonate serves a dual purpose: first reacting with NaOH to form powder mix was blended using a mechanical mixer for 3 min to
sodium carbonate and pirssonite and also as fillers. obtain a homogenized dry powder. Five mortar mixes (GP1eGP5)
were then fabricated using the blended geopolymer cement and
2NaOH þ CaCO3 / Na2CO3 þ Ca(OH)2 (1) mixed according to EN 196-1 (SFS-EN 196-1, 2011). The different
mix compositions have the same water-to-binder mass wight ratio
Na2CO3 þ CaCO3 þ 2H2O / Na2Ca(CO3)2.2H2O (2) (w/b) and sand-to-binder mass weight ratio (s/b).
After mixing, the fresh mortar samples for strength test were cast
The microstructures of paper sludge show cellulosic fibers into rectangular molds with dimension of 20  20  80 mm, while
(Fig. 3) in both non-treated and pretreated paper sludge. The the drying shrinkage samples were cast into 40  40  160 mm
observed fibers (arrowed) seem shorter after activating with NaOH molds. All samples were cured at 35 ± 3
C and demolded after 24 h.
and milling. Sample for shrinkage determination were placed in constant hu-
midity chamber (22
C and 50% ± 5 relative humidity), while the rest
of the samples were cured at 22
C and at 75% relative humidity until
2.3. Sludge-cement and mortar preparation
testing time.
In order to prepare one-part geopolymer cement, each dry
2.4. Sample analysis
activator was then blended with GGBFS according to Table 3. The

The heat evolution during activation was observed with

Table 2 isothermal conduction calorimetry (TAM Air Instruments) at 20
C.
Mix composition of the dry activator preparation. The blended cement was mixed ex-situ before the heat of hydration
NaOH (6.3M) Paper sludge (g) % content was recorded. Setting time was determined using an automated
a Vicat apparatus (Matest E044N, Italy) at room temperature ac-
GP1 0 246 0:100
GP2 90 246 27:73 cording to EN196-3 standard for paste sample. The unconfined
GP3 90 486 16:84 compressive strength (UCS) and flexural strength was performed
GP4 90 726 11:89 on four replicate samples at 7, 28 and 50 days using a Zwick testing
GP5 90 960 9:91 machine with a maximum load of 100 kN and a loading force of
a
Contains only paper sludge. 2.4 kN/s for UCS and 0.05 kN/s for flexural strength. The average

Fig. 2. (L-to-R) Pretreated paper sludge after drying at 95
C, and XRD diffractograms of the pretreated paper sludge after drying (P¼Pirssonite, C¼Calcite, D ¼ Portlandite,
N¼Natrite).
 E. Adesanya et al. / Journal of Cleaner Production 185 (2018) 168e175
value was then reported as the UCS and flexural strength. Water
absorption of mortars was determined according to EN 5513 (SFS,
2009) after 28 days of curing.
Drying shrinkage measurements were carried out on duplicate
prism samples with dimensions of 40  40  160 mm, adapted ac-
cording to ASTM C596 (ASTM-C596,). The length measurement was
carried out at the age of 1, 3, 7, 14, 28 and 90 days. The length
change (LC) over time was then calculated using equation (3).
Li  Lx
LCð%Þ ¼  100;
G acceleration peak whose magnitude is lower than the initial peak.
where Li is the difference between the comparator reading and the
reference bar at 3 days, Lx is the length at each curing age of the
specimen and G is the nominal effective length.
X-ray diffraction (Rigaku SmartLab 9 kW) fitted with Co anode
was used to analyze the mineral phase of the paste samples using a
scanning rate of 0.02
2q/step from 10 to 60
2q, the mineral phase
identifications were then performed using PDXL2 software suite
with integrated access to the PDF-4 2015 database. Scanning elec-
tron microscope (SEM) analysis was conducted using a Zeiss Ultra
Plus microscope to analyze the surface morphology of the pre-
treated paper sludge. For thermogravimetric analysis, crushed
samples of similar mass were transferred to crucibles and heated
40e1000
C at 10
C/min in a nitrogen atmosphere.
3. Results and discussion
3.1. Heat release and setting time
Heat evolution curves in Fig. 4 from the conduction calorimeters
shows the effect of increasing paper sludge on the induction and
acceleration stages of the blended cements until 95 h of reaction.
The calorimetric curves for all samples except GP1 are similar to the
OPC heat of hydration stages (Jansen et al., 2012). Curves are sub-
divided into four stages including initial dissolution period, the
induction period, acceleration/deceleration period and the retar-
dation period (Shi and Day, 1995). For GP1, which was used as a
reference sample, alkali activation produced only an initial peak
due to wetting and dissolution of the blended cement. No other
peaks were logged until the end of the test at 96 h. This is com-
parable to previous study on GGBFS hydration (Shi and Day, 1995).
All other samples showed similar initial peaks followed by the in-
duction period, which was prolonged according to the amount of
Fig. 4. Heat evolution curve of blended cements.
171
Table 4
Setting time of blended cement pastes at room temperature.
Initial set (Ti) Final set (Tf)
GP2 2 h 20 min 3 h 25 min
GP3 10 h 50 min 12 h 30 min
GP4 11 h 10 min 12 h
GP5 12 h 14 h 10 min
pretreated paper sludge (from GP2 to GP5). This is trailed by an
(3)
The acceleration peak for GP2 appeared after 12 h of mixing while
GP5 acceleration peaked appeared after 80 h of mixing. This is due
to the higher alkalinity of the activator powder in GP2 than GP3,
GP4 and GP5. Presumably the higher alkalinity in GP2 aided in the
dissolution of the calcium alumino-silicate glass in the slag during
early stages of activation, contributing to the nucleation, growth
and precipitation of reaction products (i.e. C-(A)-S-H), which takes
place earlier and is seen as the heat release peak. The mortar
samples were cured at a higher temperature (35
C vs. 22
C), which
explains the faster setting time in the mortar samples compared to
the peaks in the heat release analyses.
The cumulative heat evolution of the different blended cements
is shown inset of Fig. 4. The increasing amount of pretreated paper
sludge from GP2 to GP5 delays the reaction as can be seen form this
figure. The initial increase is associated with the heat evolved
during the wetting and dissolution of the blended cement with
water. The subsequent period correlates to the induction while the
final increase is assigned to the acceleration period. Although
the reaction for GP5 was not completed before 96 h, it seems that
the increasing content of paper sludge in the sample correlates to
higher heat release from GP2 to GP5. Also, no other increment was
noticed with GP1 sample after the initial peak.
In addition, initial setting (Ti) and final setting (Tf) time tests
were done for each blended cement paste (see Table 4). The
retardation of setting time with increasing paper sludge in the mix
is partly due to lower alkalinity of formed carbonates (and sodium
carbonate during activation of the paper sludge), which are needed
to dissolve Ca2þ from the slag. When hydrated, the CO2 3 and Ca
2þ
released from the blended cements react to form carbonate salts
such as calcite and pirssonite, which are proposed to lengthen the
induction period together with the lower pH of the pretreated
paper sludge. This interaction is proposed to take place before the
precipitation of the Ce(A)eSeH gel (Bernal et al., 2015; Garcia-
Lodeiro et al., 2015; Ke et al., 2016). Over a period of time, the
excess CO23 in the blended cement slowly reacts in the system
which may have influenced the later high strength achieved with
GP5 matrix (see Fig. 5) (Ke et al., 2016; Fern andez-Jime nez and
Puertas, 2001). Also, it should be noted that all samples set be-
tween 3 and 8 h when they were cured at slightly elevated tem-
perature (i.e. at 30e35
C). For GP1, the setting time was not
recorded because the sample did not harden after three days.
3.2. Mechanical properties and water absorption
The effect of increasing the amount of dry activators in the
blended geopolymer cement on mechanical strength at 7, 28 and 50
days can be seen in Fig. 5. At 7 days, the compressive strength
(Fig. 5a) was highest with GP2 and lowest with GP5. The alkaline
carbonates/bicarbonates (sodium carbonate and pirssonite) from
the dry activator are proposed to be concentrated in GP2 than in
GP5. And might have ensured increase dissolution of slag particles
at early age of the mortars and directly influencing the 7 days
strength of GP2. This is also consistent with the setting time and
heat release of the samples previously discussed. Xu et al.
172 E. Adesanya et al. / Journal of Cleaner Production 185 (2018) 168e175
(a)
Fig. 5. Compressive (a) and flexural strength (b) of the mortars at 7, 28 and 50 days.
(Characterization of Aged Slag Concretes,) also explained that in
Na2CO3-activated slag binders, the long term activation reaction is a
recurring process in which the Na2CO3 creates buffered alkaline
environment. The amount of CO2 3 available in the system would be
sustained by the gradual dissolution of CaCO3 slowly increasing the
pH. The Ca released during this period would react with the dis-
solved silicate from the BFS forming new reaction products pro-
posed as a C-A-S-H type product thereby increasing the strength
later on. This assertion correlates with the delayed strength
development of the samples in this study with increasing amount
of pretreated paper sludge. On the other hand, the flexural strength
(Fig. 5b) development of the mortars during the curing period has
similar trend with minor difference observed with GP3. Overall,
other samples (except GP3) had a similar flexural strength of
11 MPa at 50 days.
Total water absorption for the blended geopolymer mortars at 3,
7 and 14 days of water immersion are shown in Fig. 6. The water
absorption values increase slightly with time for each mortar after
prolonged immersion until 14 days. The increase in the amount of
paper sludge in mortar resulted in reduction of water absorption
values. All samples had water absorption below 5%, GP5 mortars
present the lowest absorption at 4.1%, while GP2 had the highest
with 4.8% at 14 days. This may be partly due to the filler effect of the
paper sludge in the mortar resulting in the reduction of the pore
sizes. Since absorption is a measure of the total water required to fill
open voids within the net volume of a mortar, it can be concluded
Fig. 6. Water absorption variation with time for GP-mortars.
(b)
that the porosity of the GP-mortars also reduces from GP2 to GP5.
This is similar to previous findings using limestone dusts (Ghosh,)
and calcium carbonate in geopolymerization (Abdel-GawwadA,
1016). Based on its blast-furnace content, strength properties, wa-
ter absorption and setting time recorded, the one-part geopolymer
cements could be classified as a CEM IIIC and Type 32.5N class
cement under European standard EN-197 (E. Standards,).
3.3. Drying shrinkage
Drying shrinkage of all four blended geopolymer cement mor-
tars with different pretreated paper sludge incorporated were
observed up to 90 days (Fig. 7). A higher content of pretreated paper
sludge in the mortar resulted in higher drying shrinkage, with
lowest shrinkage of 0.14% (GP2), and highest of 0.39% (GP5) at 90
days. The increase in drying shrinkage at higher paper sludge levels
is consistent with the literature data on carbonate mineral addition
to metakaolin (Yip et al., 2008). Contrary to the strength properties
of the GP-mortars, there is no correlation between drying
shrinkage and strength gain. According to Law et al. (2012), no
correlation between durability properties and strength exists and
the former are dependent on factors such as resistance to chloride
ingress and carbonation, both of which can initiate undesirable
effects on the mortars. However, none of the specimens showed
noticeable shrinkage cracks when observed visually.
Fig. 7. Drying shrinkage of the mortar samples.
 E. Adesanya et al. / Journal of Cleaner Production 185 (2018) 168e175
3.4. Reaction product analysis
X-ray diffraction (XRD) and derivative thermal analysis (DTG/
TGA) analysis were undertaken for all paste samples to determine
the degree of activation and the phase composition of the main re-
action products. XRD curve for GP1 shows an amorphous hump and
crystalline peaks corresponding to similar diffraction in GGBFS and
non-treated paper sludge XRD (see Fig. 8 and Fig. 1). In other sam-
ples, the introduction of the dry activator in the mix modifies the
diffraction pattern: a new phase was identified at 13.5
2q as the peak
of hydrotalcite (Mg6Al2CO3(OH)16.4H20). Hydrotalcite is commonly
observed as a part of the main reaction products of alkali-activated
GGBFS when the slag has MgO content higher than 5 weight-%
together with C-(A)-S-H (Ben Haha et al., 2011; van Jaarsveld et al.,
1997; Wang and Scrivener, 1995; Provis and Bernal, 2014). The
main crystalline peak was that of calcite, and some remnants of
Portlandite and pirssonite could also be found. Amorphous phase
was also present, and the hump indicating amorphous phases re-
duces from GP1 to GP5. This could be due to the increasing crystal-
line calcite content from GP1 to GP5 which are undissolved in each
matrix decreasing the relative amorphous content of the mix. Similar
observations was reported when calcite content was increased in
metakaolin geopolymer (Yip et al., 2008).
Thermogravimetric analysis of the hydrated slag and the de-
rivatives of the analysis corroborated the XRD findings for the
most part. With all the samples, a distinct peak is noticeable at
105
C (peak a), which indicates the removal of free water
and the decomposition of C-A-S-H type reaction products
(Wang and Scrivener, 1995; Sha and Pereira, 2001; Ismail et al.,
2013) and subsequently at 200
C (see Fig. 9) (Ben Haha et al.,
Fig. 8. XRD of paste samples at 28 days curing age (P¼Pirssonite, C¼Calcite, D ¼ Por-
tlandite, H¼Hydrotalcite). For comparison, XRD graph of GP1 is also shown in the
figure. Horizontal dashed lines are used to indicate the area of the amorphous hump.
Fig. 9. TGA/DTG of blended cements after 28 days of activation.
173
2011; Taylor, 1997). The broad peak at 300e400
C (peak b) can
be attributed to hydrotalcite-type phases, which corresponds to
release of structural water and CO2 (Wang and Scrivener, 1995).
The beginning of calcium carbonate decomposition (peak c) is
observed between 550 and 620
C and continues subsequently at
the temperature range of 680e760
C (peak d). This indicates
the decomposition of carbonate-containing phases including
calcite and sodium carbonate originating from the pretreated
paper sludge (Jin et al., 2014; Sha, 2002; Ismail et al., 2014).
Portlandite was not identified or does it correlate with any of the
peaks.
3.5. Further discussion
This study shows that within the current mix-design one-part
geopolymer concrete can be designed from NaOH pre-treated pa-
per sludge and GGBFS conforming with CEM IIIC and Type 32.5N
class cement under the European standard EN-197 (E. Standards,).
This study also highlights the possibility of reducing the environ-
mental footprints of geopolymer concrete that comes from the use
of sodium silicate. Furthermore, in order to replace OPC, the
packaging and marketability of geopolymer cement could be
improved using the methods proffered in this study. Thirdly, using
the described method of pretreating and utilizing paper sludge in
the blended geopolymer design, reduces the disposals and the
associated environmental and economic impacts of paper sludge
waste streams. On the contrary, the energy consumption from
drying and milling of the treated activator can potentially have an
economic impact, though it is estimated to be lower than sodium
silicate activated geopolymer or OPC. In industrial scale, energy
consumption can be further reduced by milling GGBFS with treated
paper sludge instead of separate milling.
Although the sample without NaOH (GP1) contains calcite and
completely amorphous slag, the 7 days strength was not possible to
measure and that mortar sample was therefore not analyzed
further. Also, from the calorimetry study in Fig. 4, no heat peak was
recorded throughout the duration of the analysis. GGBFS cemen-
titious properties is known to be latent, except when it is blended
with chemical activator such as OPC, gypsum, alkali activators, etc.
(Shi and Day, 1995; Kumar et al., 2005; Richardson, 2000). There-
fore, under the NaOH pre-treated paper sludge environment, the
cementitious properties of the blended cement can however be
improved.
The content of the paper sludge in each mortar has an effect on
the amount of produced sodium carbonate (Na2CO3) when its pre-
treated with NaOH. This pretreatment reaction involves release of
carbonates ions on contact with Naþ from the activator that readily
form pirssonite (Na2Ca(CO3)2.2H2O) and sodium carbonate (see
reaction 1 and 2). This could explain the increase in the amount of
carbonates seen in the XRD and TGA of the samples and the
strength performance as paper sludge amount increased. Further-
more, the strength gain is probably due to better packing as paper
sludge content increased in the samples: during pre-treatment the
unreacted calcite forms crystalline precipitates like Ca(OH)2 (Yip
et al., 2008) and possibly act as fillers in the geopolymer system.
As would be expected, the unreacted calcite content increases from
GP2 to GP5 (Fig. 2). Additionally, previous work done by Yip et al.
(2008) have demonstrated that in a metakaolin-based geo-
polymer optimum content of calcite, without an adverse effect on
the strength, is achieved at 20% content of calcite. They also
postulated that the increased long-term strength may be due to
surface binding of the geopolymer gel phase on the carbonate
mineral. In the current study, the maximum amount of paper
sludge quantify in GP5 is 18% and minimum of 4% in GP2.
Drying shrinkage increment with increasing paper sludge
174 E. Adesanya et al. / Journal of Cleaner Production 185 (2018) 168e175
content is likely due to the evaporation of water absorbed on the
organic matter of the paper sludge. Free water in the matrix is
probably absorbed into structure of the dry activator and when
exposed to air it evaporates contributing to the drying shrinkage as
seen in Fig. 7.
TG/DTG of the activated geopolymer cement indicated the
presence of C-A-S-H-like reaction product, hydrotalcite which
accrued as a result of the magnesium content of the slag and also
carbonated matrix. Considering the increase in strength at later
ages, it is possible that carbonation may have contributed to the
strength gain of the mortars at later curing ages. The observed
formation of C-A-S-H like products is characteristic of alkali-
activated geopolymer.
4. Conclusion
We have investigated the use of paper sludge as a waste-based
source of calcite in one-part geopolymer cement, and found it to
be suitable for that purpose. After pretreatment with sodium hy-
droxide, paper sludge can act as a slag activator and also as a filler.
The increasing amount of the pretreated paper sludge had a signif-
icant effect on the mechanical and durability properties of the pre-
pared mortars. It was found to increase the compressive strength up
to 48 MPa at 50 days. Additionally, the sample with the lowest
amount of paper sludge had considerable strength gain (40 MPa) at
50 days and lowest drying shrinkage value. It is considered that
rheology studies of these cement should be made to define how to
improve the workability. In conclusions, the final material is >98%
side-stream based, and CO2 emissions can be avoided per ton of
paper sludge used assuming that it would have been incinerated.
Acknowledgements
The research was funded by the European Regional Develop-
ment Fund (A70189) under the auspices of the MINSI project and
the following companies: SSAB Europe Oy, Ekokem Oy, Stora Enso
Oy, Pohjolan Voima Oy and Oulun Energia. The authors would like
€
to thank Jarno Karvonen and Jani Osterlund for their contribution to
the laboratory work. Lubica Kriskova and Antigoni Katsiki of KU
Leuven and VUB Brussels respectively for helping with isothermal
calorimetry.
References
ASTM-C596 j Standard Test Method for Drying Shrinkage of Mortar Containing
Hydraulic Cement j Document Center, Inc., (n.d.). https://www.document-
center.com/standards/show/ASTM-C596 (Accessed 27 November 2016).
H.A. Abdel-Gawwad, S.A. Abo-El-Enein, A novel method to produce dry geopolymer
cement powder, HBRC J. (n.d.). doi:10.1016/j.hbrcj.2014.06.008.
Abdollahnejad, Z., Pacheco-Torgal, F., Aguiar, J.B., Jesus, C., 2015. Durability perfor-
mance of fly ash based one-part geopolymer mortars. Key Eng. Mater. 634,
113e120. https://doi.org/10.4028/. www.scientific.net/KEM.634.113.
Adesanya, E., Ohenoja, K., Kinnunen, P., Illikainen, M., 2016. Alkali activation of ladle
slag from steel-making process. J. Sustain. Metall 1e11. https://doi.org/10.1007/
s40831-016-0089-x.
Alex, J., Dhanalakshmi, J., Ambedkar, B., 2016. Experimental investigation on rice
husk ash as cement replacement on concrete production. Construct. Build.
Mater. 127, 353e362. https://doi.org/10.1016/j.conbuildmat.2016.09.150.
Ali, M.B., Saidur, R., Hossain, M.S., 2011. A review on emission analysis in cement
industries, Renew. Sustain. Energy Rev. 15, 2252e2261.
Ben Haha, M., Le Saout, G., Winnefeld, F., Lothenbach, B., 2011. Influence of activator
type on hydration kinetics, hydrate assemblage and microstructural develop-
ment of alkali activated blast-furnace slags. Cement Concr. Res. 41, 301e310.
https://doi.org/10.1016/j.cemconres.2010.11.016.
Bernal, S.A., Provis, J.L., Myers, R.J., Nicolas, R.S., van Deventer, J.S.J., 2015. Role of
carbonates in the chemical evolution of sodium carbonate-activated slag
binders. Mater. Struct. 48, 517e529. https://doi.org/10.1617/s11527-014-0412-6.
P.V.K. Caijun Shi, Alkali-activated cements and concretes, Taylor & Francis Ltd, n.d.
https://www.dawsonera.com/abstract/9780203390672 (Accessed 27 May
2015).
Cement Industry Energy and CO2 Performance, World Bus. Counc. Sustain. Dev.
(n.d.). http://www.wbcsd.org/Projects/Cement-Sustainability-Initiative/
Resources/Getting-the-Numbers-Right (Accessed June 22, 2017).
Characterization of Aged Slag Concretes, ResearchGate. (n.d.). https://www.
researchgate.net/publication/287723316_Characterization_of_Aged_Slag_
Concretes (Accessed 20 March 2017).
Damtoft, J.S., Lukasik, J., Herfort, D., Sorrentino, D., Gartner, E.M., 2008. Sustainable
development and climate change initiatives. Cement Concr. Res. 38, 115e127.
https://doi.org/10.1016/j.cemconres.2007.09.008.
Davidovits, J., 2011. Geopolymer Chemistry and Applications, 3. Ed, Inst.
Ge opolyme re, Saint-quentin.
Duxson, P., Provis, J.L., 2008. Designing precursors for geopolymer cements. J. Am.
Ceram. Soc. 91, 3864e3869. https://doi.org/10.1111/j.1551-2916.2008.02787.x.
Duxson, P., Fern andez-Jime nez, A., Provis, J., Lukey, G., Palomo, A., Deventer, J., 2007.
Geopolymer technology: the current state of the art. J. Mater. Sci. 42,
2917e2933. https://doi.org/10.1007/s10853-006-0637-z.
Evaluation of paper industry wastes in construction material applications, (n.d.).
http://www.scielo.br/scielo.php?script¼sci_arttext&pid¼S1516-
14392001000400013 (Accessed 1 June 2017).
Fern andez-Jime nez, A., Puertas, F., 2001. Setting of alkali-activated slag cement.
Influence of activator nature. Adv. Cement Res. 13, 115e121. https://doi.org/
10.1680/adcr.13.3.115.39288.
Flatt, R.J., Roussel, N., Cheeseman, C.R., 2012. Concrete: an eco material that needs to
be improved. J. Eur. Ceram. Soc. 32, 2787e2798. https://doi.org/10.1016/
j.jeurceramsoc.2011.11.012.
Garcia-Lodeiro, I., Palomo, A., Fern andez-Jime nez, A., 2014. An overview of the
chemistry of alkali-activated cement-based binders. In: Handb. Alkali-act. Cem.
Mortars Concr, pp. 19e47.
Garcia-Lodeiro, I., Palomo, A., Ferna ndez-Jime nez, A., 2015. 3-Crucial insights on the
mix design of alkali-activated cement-based binders. In: Pacheco-Torgal, F.,
Labrincha, J.A., Leonelli, C., Palomo, A., Chindaprasirt, P. (Eds.), Handb. Alkali-act.
Cem. Mortars Concr. Woodhead Publishing, Oxford, pp. 49e73. http://www.
sciencedirect.com/science/article/pii/B9781782422761500034. (Accessed 18
January 2016).
Gluth, G.J.G., Lehmann, C., Rübner, K., Kühne, H.-C., 2013. Geopolymerization of a
silica residue from waste treatment of chlorosilane production. Mater. Struct.
46, 1291e1298. https://doi.org/10.1617/s11527-012-9972-5.
Hajimohammadi, A., Provis, J.L., van Deventer, J.S.J., 2008. One-Part Geopolymer
mixes from geothermal silica and sodium aluminate. Ind. Eng. Chem. Res. 47,
9396e9405. https://doi.org/10.1021/ie8006825.
S.Ghosh, Effect of Lime Stone Dust on Geopolymerisation and Geopolymeric
Structure, Ijetae.com. (n.d.). http://www.academia.edu/3469555/Effect_of_
Lime_Stone_Dust_on_Geopolymerisation_and_Geopolymeric_Structure
(Accessed 14 April 2017).
Ismail, I., Bernal, S.A., Provis, J.L., Hamdan, S., van Deventer, J.S.J., 2013. Drying-
induced changes in the structure of alkali-activated pastes. J. Mater. Sci. 48,
3566e3577. https://doi.org/10.1007/s10853-013-7152-9.
Ismail, I., Bernal, S.A., Provis, J.L., San Nicolas, R., Hamdan, S., van Deventer, J.S.J.,
2014. Modification of phase evolution in alkali-activated blast furnace slag by
the incorporation of fly ash. Cement Concr. Compos. 45, 125e135. https://
doi.org/10.1016/j.cemconcomp.2013.09.006.
Jansen, D., Goetz-Neunhoeffer, F., Lothenbach, B., Neubauer, J., 2012. The early hy-
dration of Ordinary Portland Cement (OPC): an approach comparing measured
heat flow with calculated heat flow from QXRD. Cem. Concr. Res. 42, 134e138.
https://doi.org/10.1016/j.cemconres.2011.09.001.
Jin, F., Gu, K., Al-Tabbaa, A., 2014. Strength and drying shrinkage of reactive MgO
modified alkali-activated slag paste. Construct. Build. Mater. 51, 395e404.
https://doi.org/10.1016/j.conbuildmat.2013.10.081.
Ke, X., Bernal, S.A., Ye, N., Provis, J.L., Yang, J., 2015. One-Part Geopolymers based on
thermally treated red mud/NaOH blends. J. Am. Ceram. Soc. 98, 5e11. https://
doi.org/10.1111/jace.13231.
Ke, X., Bernal, S.A., Provis, J.L., 2016. Controlling the reaction kinetics of sodium
carbonate-activated slag cements using calcined layered double hydroxides.
Cement Concr. Res. 81, 24e37. https://doi.org/10.1016/j.cemconres.2015.11.012.
Kim, M.S., Jun, Y., Lee, C., Oh, J.E., 2013. Use of CaO as an activator for producing a
price-competitive non-cement structural binder using ground granulated blast
furnace slag. Cement Concr. Res. 54, 208e214. https://doi.org/10.1016/
j.cemconres.2013.09.011.
Kiventera €, J., Golek, L., Yliniemi, J., Ferreira, V., Deja, J., Illikainen, M., 2016. Utiliza-
tion of sulphidic tailings from gold mine as a raw material in geo-
polymerization. Int. J. Miner. Process. 149, 104e110. https://doi.org/10.1016/
j.minpro.2016.02.012.
Kumar, R., Kumar, S., Badjena, S., Mehrotra, S.P., 2005. Hydration of mechanically
activated granulated blast furnace slag. Metall. Mater. Trans. B 36, 873e883.
https://doi.org/10.1007/s11663-005-0089-x.
Law, D.W., Adam, A.A., Molyneaux, T.K., Patnaikuni, I., 2012. Durability assessment
of alkali activated slag (AAS) concrete. Mater. Struct. 45, 1425e1437. https://
doi.org/10.1617/s11527-012-9842-1.
Lightweight mortars containing expanded polystyrene and paper sludge ash, (n.d.).
http://www.sciencedirect.com/science/article/pii/S0950061814002827
(Accessed 1 June 2017).
Luukkonen, T., Abdollahnejad, Z., Yliniemi, J., Kinnunen, P., Illikainen, M., 2017. One-
part alkali-activated materials: A review. Cem. Concr. Res. https://doi.org/
10.1016/j.cemconres.2017.10.001.
Mabee, W., Roy, D.N., 2003. Modeling the role of papermill sludge in the organic
carbon cycle of paper products. Environ. Rev. 11, 1e16. https://doi.org/10.1139/
 E. Adesanya et al. / Journal of Cleaner Production 185 (2018) 168e175
a03-001.
Martínez-Lage, I., Velay-Lizancos, M., Va zquez-Burgo, P., Rivas-Fern andez, M.,
Vazquez-Herrero, C., Ramírez-Rodríguez, A., Martín-Cano, M., 2016. Concretes
and mortars with waste paper industry: biomass ash and dregs. J. Environ.
Manag. 181, 863e873. https://doi.org/10.1016/j.jenvman.2016.06.052.
Mathur, R., Sharma, S.K., 2008. Magnesium oxysulphate cement: change in prop-
erties on admixing sodium bicarbonate as an additive. Rasayan J Chem. 1,
620e630.
Mellado, A., Catala n, C., Bouzo n, N., Borrachero, M.V., Monzo  , J.M., Paya, J., 2014.
Carbon footprint of geopolymeric mortar: study of the contribution of the
alkaline activating solution and assessment of an alternative route. RSC Adv. 4,
23846e23852. https://doi.org/10.1039/C4RA03375B.
Nematollahi, B., Sanjayan, J., Shaikh, F.U.A., 2015. Synthesis of heat and ambient
cured one-part geopolymer mixes with different grades of sodium silicate.
Ceram. Int. 41, 5696e5704. https://doi.org/10.1016/j.ceramint.2014.12.154.
SFS, 2009. Online, SFS 5513-Brick Tile Testing (Finnish Standard). https://online.sfs.
fi/fi/index/tuotteet/SFS/SFS/ID2/5/119637.html.stx. (Accessed 22 December
2015).
Peng, M.X., Wang, Z.H., Shen, S.H., Xiao, Q.G., 2014. Synthesis, characterization and
mechanisms of one-part geopolymeric cement by calcining low-quality kaolin
with alkali. Mater. Struct. 48, 699e708. https://doi.org/10.1617/s11527-014-
0350-3.
Peys, A., Arnout, L., Blanpain, B., Rahier, H., Acker, K.V., Pontikes, Y., 2017. Mix-design
parameters and real-life considerations in the pursuit of lower environmental
impact inorganic polymers. Waste Biomass Valorization 1e11. https://doi.org/
10.1007/s12649-017-9877-1.
J.L. Provis, Alkali-activated materials, Cem. Concr. Res. (n.d.). doi:10.1016/
j.cemconres.2017.02.009.
Provis, J.L., Bernal, S.A., 2014. Geopolymers and related alkali-activated materials.
Annu. Rev. Mater. Res. 44, 299e327. https://doi.org/10.1146/annurev-matsci-
070813-113515.
Provis, J.L., Palomo, A., Shi, C., 2015. Advances in understanding alkali-activated
materials. Cement Concr. Res. 78 (Part A), 110e125. https://doi.org/10.1016/
j.cemconres.2015.04.013.
Puertas, F., Palacios, M., Manzano, H., Dolado, J.S., Rico, A., Rodríguez, J., 2011.
A model for the C-A-S-H gel formed in alkali-activated slag cements. J. Eur.
Ceram. Soc. 31, 2043e2056. https://doi.org/10.1016/j.jeurceramsoc.2011.04.036.
Recent Advances in Paper Mill Sludge Management, ResearchGate. (n.d.). https://
www.researchgate.net/publication/221927329_Recent_Advances_in_Paper_
Mill_Sludge_Management (Accessed 1 June 2017).
Richardson, I.G., 2000. The nature of the hydration products in hardened cement
pastes. Cement Concr. Compos. 22, 97e113. https://doi.org/10.1016/S0958-
9465(99)00036-0.
Rissanen, J., Ohenoja, K., Kinnunen, P., Illikainen, M., 2017. Partial replacement of
portland-composite cement by fluidized bed combustion fly ash. J. Mater. Civ.
Eng. 29 https://doi.org/10.1061/(ASCE)MT.1943-5533.0001899.
Schneider, M., Romer, M., Tschudin, M., Bolio, H., 2011. Sustainable cement pro-
ductiondpresent and future. Cem. Concr. Res. 41, 642e650. https://doi.org/
10.1016/j.cemconres.2011.03.019.
SFS-EN 196-1, 2011. Methods of Testing Cement. Part 1: Determination of Strength.
Sha, W., 2002. Differential scanning calorimetry study of the hydration products in
portland cement pastes with metakaolin replacement. In: Adv. Build. Technol.
Elsevier, Oxford, pp. 881e888. http://www.sciencedirect.com/science/article/
pii/B978008044100950111X. (Accessed 10 March 2017).
Sha, W., Pereira, G.B., 2001. Differential scanning calorimetry study of hydrated
ground granulated blast-furnace slag. Cement Concr. Res. 31, 327e329. https://
175
doi.org/10.1016/S0008-8846(00)00472-5.
Shi, C., Day, R.L., 1995. A calorimetric study of early hydration of alkali-slag cements,
Cem. Concr. Res. 25, 1333e1346. https://doi.org/10.1016/0008-8846(95)00126-
W.
G.M.S.Islam, M.H.Rahman, N.Kazi, Waste glass powder as partial replacement of
cement for sustainable concrete practice, Int. J. Sustain. Built Environ. (n.d.). doi:
10.1016/j.ijsbe.2016.10.005.
Sturm, P., Greiser, S., Gluth, G.J.G., J€
ager, C., Brouwers, H.J.H., 2015. Degree of reaction
and phase content of silica-based one-part geopolymers investigated using
chemical and NMR spectroscopic methods. J. Mater. Sci. 50, 6768e6778. https://
doi.org/10.1007/s10853-015-9232-5.
Sturm, P., Gluth, G.J.G., Brouwers, H.J.H., Kühne, H.-C., 2016. Synthesizing one-part
geopolymers from rice husk ash. Construct. Build. Mater. 124, 961e966.
https://doi.org/10.1016/j.conbuildmat.2016.08.017.
E. Standards, EN 197e1 ed. 2, Httpswwwen-Stand. (n.d.). https://www.en-standard.
eu/csn-en-197-1-ed-2-cement-part-1-composition-specifications-and-confor-
mity-criteria-for-common-cements/(Accessed 11 July 2017).
Taylor, H.F.W., 1997. Cement Chemistry. Thomas Telford Publishing. http://www.
icevirtuallibrary.com/doi/abs/10.1680/cc.25929.fm. (Accessed 8 December
2016).
Torres-Carrasco, M., Rodríguez-Puertas, C., del, M., Alonso, M., Puertas, F., 2015.
Alkali activated slag cements using waste glass as alternative activators.
Rheological behaviour. Bol. Soc. Esp. Cera mica Vidr. 54, 45e57. https://doi.org/
10.1016/j.bsecv.2015.03.004.
Utilization of Waste Paper Pulp by Partial Replacement of Cement in Concrete,
ResearchGate. (n.d.). https://www.researchgate.net/publication/266503174_
Utilization_of_Waste_Paper_Pulp_by_Partial_Replacement_of_Cement_in_
Concrete (Accessed 1 June 2017).
Valorization of paper mill sludge as a partial replacement of Portland cement in
mortar: The impact of incineration conditions on the strength of mortars,
ResearchGate. (n.d.). https://www.researchgate.net/publication/286807432_
Valorization_of_paper_mill_sludge_as_a_partial_replacement_of_Portland_
cement_in_mortar_The_impact_of_incineration_conditions_on_the_strength_
of_mortars (Accessed 1 June 2017).
van Jaarsveld, J.G.S., van Deventer, J.S.J., Lorenzen, L., 1997. The potential use of
geopolymeric materials to immobilise toxic metals: Part I. Theory and appli-
cations. Miner. Eng. 10, 659e669. https://doi.org/10.1016/S0892-6875(97)
00046-0.
Vegas, I., Urreta, J., Frías, M., García, R., 2009. Freezeethaw resistance of blended
cements containing calcined paper sludge. Construct. Build. Mater. 23,
2862e2868. https://doi.org/10.1016/j.conbuildmat.2009.02.034.
Wang, S.-D., Scrivener, K.L., 1995. Hydration products of alkali activated slag cement.
Cement Concr. Res. 25, 561e571. https://doi.org/10.1016/0008-8846(95)00045-
E.
Wang, S.-D., Pu, X.-C., Scrivener, K.L., Pratt, P.L., 1995. Alkali-activated slag cement
and concrete: a review of properties and problems. Adv. Cement Res. 7, 93e102.
Welcome to CEPI - Confederation of european paper Industries j CEPI - Confeder-
ation of european paper industries, (n.d.). http://www.cepi.org/(Accessed 1
June 2017).
Yip, C.K., Provis, J.L., Lukey, G.C., van Deventer, J.S.J., 2008. Carbonate mineral
addition to metakaolin-based geopolymers. Cement Concr. Compos. 30,
979e985. https://doi.org/10.1016/j.cemconcomp.2008.07.004.
Yliniemi, J., Pesonen, J., Tiainen, M., Illikainen, M., 2015. Alkali activation of recov-
ered fuelebiofuel fly ash from fluidised-bed combustion: stabilisation/solidifi-
cation of heavy metals. Waste Manag. 43, 273e282. https://doi.org/10.1016/
j.wasman.2015.05.019.