Waste Management 104 (2020) 60–73

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Waste Management
journal homepage: www.elsevier.com/locate/wasman

Recycling municipal solid waste incineration slag and fly ash as

precursors in low-range alkaline cements
Nuno Cristelo a,⇑, Luis Segadães b, João Coelho c, Benedita Chaves d, Nadine R. Sousa e,
Maria de Lurdes Lopes f
a
CQ-VR, Department of Engineering, University of Trás-os-Montes e Alto Douro, 5000-801 Vila Real, Portugal
b
Department of Engineering, University of Trás-os-Montes e Alto Douro, 5000-801 Vila Real, Portugal
c
Department of Civil Engineering, University of Minho, 4800-058 Guimarães, Portugal
d
LIPOR, Intermunicipal Waste Management of Greater Porto, 4435-996 Baguim do Monte, Portugal
e
LIPOR, Intermunicipal Waste Management of Greater Porto, 4435-996 Baguim do Monte, Portugal
f
CONSTRUCT, Department of Civil Engineering, University of Porto, 4200-465 Porto, Portugal

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

Article history: Application of municipal solid waste incineration (MSWI) products - fly ash (MSW-FA) and bottom ash
Received 7 October 2019 (MSW-BA), is increasingly popular, mostly due to the need to reintroduce it in the industrial chain, but
Revised 7 January 2020 also because its technical performance is constantly enhanced by a growing research effort. This paper
Accepted 10 January 2020
deals with the less popular application of these wastes without the addition of a more competent precur-
sor. Several pastes based on MSW-FA, MSW-BA or MSW-FA+MSW-BA were prepared, using sodium sil-
icate or sodium hydroxide. Their overall performance was then assessed through mechanical (uniaxial
Keywords:
compressive strength - UCS and seismic wave velocity), environmental (leaching) and durability tests
Municipal solid waste
Incineration waste
(freeze-thaw and wetting-drying). Cement stabilised MSW-BA pastes were also tested, for reference.
Alkali activation Results showed that a preliminary mechanical activation, achieved by milling, is fundamental; the acti-
Mechanical performance vation with silicate is more effective than with hydroxide, especially in the case of the MSW-BA pastes,
Durability when the UCS values are more than triplicated (3–10 MPa); the MSW-BA is a more competent precursor
Leaching than the MSW-FA and the durability and leachability of the alkali activated pastes is similar to that
obtained with cement. The most performing paste, in terms of UCS, was obtained with BA activated
exclusively with sodium silicate, with an activator/precursor weight ratio of 0.5. In general, the low-
cost solidification/stabilisation proposed in this study showed competitive with the alternative use of
up to 30% cement and should be regarded as a valid alternative for simple storage or low-range applica-
tions, in substitution of Portland cement.
Ó 2020 Elsevier Ltd. All rights reserved.

1. Introduction electricity (waste-to-energy principle) during the incineration pro-

The rapid increase in world population in the last century has
generated an ever-growing production of municipal solid waste
(MSW). Thousands of tonnes of MSW are produced each year –
in 2012, this number reached 1.3 billion tonnes, while 2.2 billions
are expected to be produced in 2025 (Hoornweg and Bhada-Tata,
2012). A common treatment of solid waste produced in urban
areas is incineration, with an energy recovery bonus resulting from
the calorific content of the wastes, which allows the production of
⇑ Corresponding author.
E-mail addresses: ncristel@utad.pt (N. Cristelo), al39036@utad.eu (L. Segadães),
id7225@uminho.com (J. Coelho), benedita.chaves@lipor.pt (B. Chaves), nadine.
sousa@lipor.pt (N.R. Sousa), lcosta@fe.up.pt (M. de Lurdes Lopes).
cess. This is a very effective procedure due to its capacity to reduce
the waste volumes and, at the same time, for the associated valori-
sation through energy production. Although the municipal solid
waste incineration (MSWI) rate varies significantly from country
to country and, most importantly, between different areas of the
globe, it can reach as high as 50–58% in some northern Europe
countries (Dou et al., 2017). However, significant volumes of fly
ash (FA) and, especially, bottom ash (BA) are still produced by this
method, with the inevitable financial and environmental costs
associated with the landfilling of these by-products. Even though
the volumes of BA + FA are much lower than that of the original
waste, representing a weight reduction of about 80% (Tillman
et al., 1989; Wei et al., 2011), their recycling, by integration in
any industrial process, constitutes an attractive possibility (Quina

https://doi.org/10.1016/j.wasman.2020.01.013
0956-053X/Ó 2020 Elsevier Ltd. All rights reserved.
 N. Cristelo et al. / Waste Management 104 (2020) 60–73
et al., 2018). Targeting the BA is more interesting than targeting the
FA. Not only the intrinsic properties of the former (higher silica and
alumina contents) are more suited for the demands of the produc-
tion of aluminosilicate-based pastes, but also because the volume
of BA represents approximately 85% of the total incineration resi-
due (Alam et al., 2017; Zhu et al., 2018). Although the BA is signif-
icantly less polluting than FA (Li et al., 2012; Liu et al., 2018), it still
possesses a considerable heavy metal content. furthermore, there
are several already widespread methods commonly used to deal
with MSWI fly ash, namely treating and landfilling as a hazard, sta-
bilisation/solidification and removal of heavy metals (Bie et al.,
2016).
Several studies focused on the use of traditional Portland
cement (OPC) to stabilise these by-products resulting from the
MSWI, either for solidification/stabilisation (Caprai et al., 2019;
Chen and Yang, 2017; Weng et al., 2015; Yang et al., 2018), with
or without previous washing (to remove excess chlorides and sul-
phates, allowing the resulting material to be safely landfilled); or
to be used in specific applications, such as an artificial aggregate
(Cioffi et al., 2011; Li et al., 2018; Saikia et al., 2015; Tang et al.,
2015; Tang and Brouwers, 2017), as a road basement layer
(Colangelo et al., 2012) or as a partial cement replacement (Li
et al., 2017, 2016; Lin, 2005). However, the application of OPC adds
to the overall environmental toll, due to the high CO2-eq associated
with the manufacturing of clinker and cement. At the same time, a
recent study focusing on the long-term behaviour of cement-
solidified MSWI fly ash (Du et al., 2018) was able to determine that,
after aging for 6 years, the evolution of the heavy metals in the sta-
bilised material still includes several worrying drawbacks. Alterna-
tive methods for immobilization-stabilisation-removal involve, for
instance, the sieving and washing of the material (Alam et al.,
2017). Other alternatives include the dechlorination of the BA
using superheated steam, at 420 °C (Suda et al., 2016); or calcina-
tion, at 1000 °C (Yang et al., 2014); the mixing with sodium car-
bonate to both stabilise the leaching of heavy metals and to
separate the soluble salts (Atanes et al., 2019); accelerated carbon-
ation to form stable carbonate mineral forms and, thus, reduce the
leaching in BA (Lin et al., 2015); or the increase in reactivity by
milling and heat treatment (Tang et al., 2016). Other authors
(Ghouleh and Shao, 2018) used the incineration step to produce
a cleaner cement, with the incinerator operating temperature
(1000 °C), lower than the required for clinker production
(1400 °C), capable of synthetizing a high-strength binder from
MSW.
Another important alternative to Portland cement for the stabil-
isation/solidification of the MSWI residues are alkaline cements,
obtained with the alkaline activation (AA) technique. Although
AA is already well-known for its capacity to stabilise heavy metals
and other environmental treats in different hazardous wastes, only
recently it is becoming a solution for MSWI, with only a few – but
promising – published papers on the subject. The inclusion of BA or
FA in alkaline activation reactions is becoming an increasingly
viable option, with most studies focusing on blends of MSWI prod-
ucts with other well-known wastes/precursors (coal incineration
fly ash, blast furnace slag, red mud and glass powders) (Huang
et al., 2018b; Monich et al., 2018; Wongsa et al., 2017; Ye et al.,
2016; Yi et al., 2014), or more noble precursors, like metakaolin
(Jin et al., 2016; Lancellotti et al., 2013) or dehydrated pyrophyllite
(Shiota et al., 2018; Shiota et al. (2017a)). In some cases, the stud-
ied pastes included fillers (Gao et al., 2017) or mortars (Huang
et al., 2019). Alkaline activation has also proved very effective for
removal of metallic aluminium in BA, by simply increasing the
pH of the solution, which will then dissolve the different shape
and size metallic aluminium particles. This will enhance the poz-
zolanic effect of the BA and, after mixed with cement, produces
higher compressive strength levels, very similar to those obtained
61
with cement pastes (Liu et al., 2018; Xuan and Poon, 2018). Other
possible application of AA treatment is the transformation of the
vitrified fraction of the BA either into glass-ceramic foams, using
low-concentration activators (Rincon Romero et al., 2018) or into
high strength binders (Zhu et al., 2019). The vast majority of these
studies used NaOH-based activators, although activators composed
by NaOH and sodium silicate (Huang et al., 2018c; Lancellotti et al.,
2013; Shiota et al., 2017b; Zhu et al., 2019, Zhu et al., 2018) or
sodium silicate alone (Huang et al., 2019; Li et al., 2019) were also
applied. So far, the most relevant drawback associated with the AA
of the MSWI residues is carbonation (Huang et al., 2018c; Huang
et al. (2018a)), which was reported to be higher than that regis-
tered with OPC. However, reduced additions of lime or OPC can
drastically mitigate the carbonation of the AA paste, by accelerat-
ing and, thus, offsetting the production of Ca(OH)2, relatively to
the polymerization stage. The concern with carbonation is mostly
related with aesthetic reasons, as the main application of alkali
activated MSWI residues is probably related with the production
of non- metallic reinforced pieces, like building blocks or urban
furniture. The mechanical properties are not affected, there is only
the matter of ‘cleaning’ the efflorescence from the surface of the
material, if indeed the aesthetic is a potential issue.
The present study targets the stabilisation, using alkaline acti-
vation, of the products resulting from MSWI (FA and/or BA), with-
out the addition of any additional precursor. Very few studies
focused on the exclusive use of BA or FA as the sole source of silica
and alumina in AA. One exception was produced by Qiao et al.
(2008), although, in this case, the BA was cumulatively submitted
to a mechanical (milling) and thermal (up to 880 °C) pre-
treatment, with the latter proving much more effective than the
former. In the present study, the BA and the FA resulting from a
Portuguese MSWI plant were chemically and mechanically acti-
vated, independently or combined, in order to assess its adequacy
to act as precursors in alkali activated reactions and, thus, become
the main element of a binding paste that could then be used to pro-
duce non-reinforced materials. To establish a reference, Portland
cement was also used, and the quality of the pastes was monitored
by uniaxial compression strength (UCS) test, ultrasonic pulse
velocity measurements, mineralogical and microstructural charac-
terisation (using Scanning Electron Microscopy, Energy Dispersive
Spectroscopy and X-ray Diffraction), environmental tests (leach-
ing) and durability tests.
2. Materials and methods
2.1. Materials
The residues resulting from Municipal Solid Waste Incineration
(MSWI) – fly ash (FA) and bottom ash (BA) (Fig. 1) – were supplied
by LIPOR - Intermunicipal Waste Management of Greater Porto,
responsible for the management, recovery and treatment of the
municipal solid waste produced in its 8 associated municipalities
from the greater Porto area, in northern Portugal. The air pollution
control system used in the incinerator uses urea, in a initial phase,
to reduce emissions, followed by a wet-scrubbing treatment with
the addition of activated coal, to absorb organochlorine com-
pounds, and lime slurry, which evaporates and condenses existing
heavy metals and neutralises acids. Finally, the gases are pushed
through a filter bag for particle removal.
Commercially available Portland cement (OPC) type II/B-L, class
32.5 N, was used to establish threshold results in the several tests
that were designed to study the behaviour of the FA and BA.
The chemical composition of the two residues, obtained by X-
ray fluorescence (XRF) on a PHILIPS PW-1004 X-ray spectrometer,
is shown in Table 1. Silica is the main element of the BA, although a
62 N. Cristelo et al. / Waste Management 104 (2020) 60–73

Fig. 1. Original BA (a) and FA (b) as received.

Table 1
°2h (FA) and 18 to 35 °2h (BA), approximately. The OPC diffrac-
Chemical composition of the BA and FA. togram, as expected, shows traces of calcite, alite, belite quartz
and gypsum.
Element BA FA
Sodium hydroxide (SH) or sodium silicate (SS), both in solution
(wt%) (wt%) form, were used as activator. The sodium hydroxide was supplied
Al2O3 6.81 2.31
CaO 22.77 38.70
in pellets, with a specific gravity of 2.13 at 20 °C (99 wt%), which
Cl 2.42 27.06 was then dissolved in deionised water to previously defined con-
Cu2O – 0.13 centrations of 4, 6, 8 and 12 molal. The SS presented a unit weight
Fe2O3 2.03 0.39 of 1.464 g/cm3 (at 20 °C), a SiO2/Na2O weight ratio of 2.0 (molar
K2O 3.12 8.35
oxide ratio of 2.063) and a Na2O concentration in the solution of
MgO 5.11 1.67
Na2O 7.00 11.57 13.0%.
P2O5 3.91 1.06
SO3 2.43 4.59
2.2. Optimisation of the particle size
SiO2 43.75 3.25
TiO2 – 0.39
ZnO 0.65 0.54 From the beginning of the experimental work, it was decided to
study the influence of the particle size distribution (PSD) of the BA
on the uniaxial compressive strength (UCS), so that all the speci-
mens tested would be prepared with the most effective PSD. Such
significant calcium oxide content is also present (22.8%). The main option was based on previous research (Cristelo et al., 2016), which
element of the FA was calcium oxide (38.7%), but it also presented concluded that reducing the particle size should improve the reac-
a very significant chlorine content (27.1%) which, considering that tivity of the precursor. Therefore, the BA was submitted to a thor-
chlorides are soluble in water, represented an immediate concern, ough milling process, using a Los Angeles abrasion test machine
especially regarding the durability of the pastes with a high FA (LAM) and a benchtop ball mill, with a 500 ml ceramic closed bowl
content. The presence of high Cl contents in the finer particles and 27 zirconia balls of different diameters. The original material
resulting from the incineration was expected, based on the work was initially screened on a 25 mm sieve to remove large particles,
of Yang et al. (2014) and Suda et al. (2016), among others. not greatly affected by the incineration stage. The passing material
The original materials (FA and BA) and the resulting pastes were was then submitted to 15 min on the Los Angeles, and screened
characterised using X-Ray Diffraction (XRD), on a PANalytical again, this time on the 4 mm sieve. The particles smaller than
X’Pert Pro diffractometer, using CuKa radiation. The scans covered 4 mm were milled on the ball mill (280 g of material on each
a 2h range of 10 to 60°, with a nominal step size of 0.017° and run), for 15 min, at 300 rpm. The resulting material was screened
100 s/step. The FA diffractogram showed the main presence of syl- on the 0.250 mm, and the smaller particles were again submitted
vite, halite and calcite, with traces of portlandite, anhydrite (cal- to 30 min on the ball mill (300 rpm), but this time only 140 g were
cium sulphate) and lime (Atanes et al., 2019; García-Lodeiro milled on each run. All the material that resulted from this final
et al., 2016); while the diffractogram of the BA revealed mostly stage was included in the final volume of the BA, which was then
quartz, calcite, clinozoisite and akermanite (García-Lodeiro et al., divided in five different size fractions (Table 2), obtained by siev-
2016; Wei et al., 2011). The former belongs to the melilite group, ing. Each fraction was then used as a precursor and activated with
which has been found to be the single most relevant mineral in a 12 molal sodium hydroxide solution, with an activator/BA weight
MSW bottom ash (Alam et al., 2019). The amorphous content of ratio of 0.4. These pastes were cured for 24 h, at 80 °C, and submit-
both precursors is evidenced by a halo between angles 25 to 33 ted to uniaxial compressive strength tests soon after.
 N. Cristelo et al. / Waste Management 104 (2020) 60–73
Table 2
BA fractions prepared at the initial stage of the experimental work.
Fraction Passing
(BA) (mm)
Fa 1.0
Fb 0.50
Fc 0.250
Fd 0.125
Fe 0.063
Based on the preliminary study addressing the influence of the
particle size in the UCS of the pastes (presented and discussed fur-
ther ahead), it was necessary to mill significant quantities of the
precursors. Therefore, 20 kg of the original BA or FA were milled
on the Los Angeles machine, for 24 h, until approximately 80%
and 70% of the particles became smaller than 63 and 50 lm,
respectively. The final PSD of both precursors (Fig. 2), after milling,
were determined by laser granulometry, using a Sympatec Helos
BF analyser (size range between 0.9 and 175 lm) and Fraunhofer
diffraction theory. A preliminary 5-minute ultra-sonic bath on a
water-ethanol solution was included, to particle dispersion.
2.3. Preparation and testing of the definitive pastes
Four different sets of paste were fabricated and tested (Table 3).
The PaB pastes used only the BA precursor, with activators based
on SH (4 and 12 molal) or SS. The PaF pastes used only the FA pre-
cursor, with activators also based either on SH (4, 6 and 8 molal) or
SS. The third set was a mix of BA and FA, with a BA/FA weight ratio
of 70/30 and a 4 molal SH activator. Finally, pastes PaC were pre-
pared with BA, Portland cement and water. Preliminary UCS tests
were developed to assess the most interesting SH concentrations,
using purposely fabricated specimens that were cured for only
2 days.
Preparation of the fresh pastes started with the definition of the
best liquid/solid weight ratios, for each precursor, by trial and
error. This proved to be a complex task, not only because a slight
variation in the composition of the precursor or activator would
significantly change the ideal ratio, but also because the BA pastes
showed a strong tendency to expand when higher liquid/solid
ratios were used. As an example, the evolution shown in Fig. 3,
Fig. 2. Particle size distribution of the milled BA and FA, as used throughout the experimental work.
63
for the paste with a 0.50 ratio, took only 4 min. This was probably
caused by an increase in the pore volume produced by the forma-
Retained tion of hydrogen, occurring when the metallic aluminium dust par-
(mm) ticles present in the original MSWI reacted with the water, after
0.50 the oxide film covering the aluminium layer was previously dis-
0.250 solved by the alkaline aqueous solution (Ilyukhina et al., 2012;
0.125 Nithiya et al., 2018). A similar behaviour was described by
0.063
–
Larraza et al. (2014), which obtained a significant expansion when
activating fly ash with sodium hydroxide, with the addition of
hydrogen peroxide with the specific aim of causing this expansion
and, as a result, obtain a highly porous and lightweight material. To
mitigate such behaviour, the reduction of the liquid/solid ratio was
successfully tested and complemented with an extended waiting
period, of approximately 10 min, for the pastes to cool down,
before being casted into 40
40
40 mm moulds.
For the initial 72 h, specimens for all types of test were cured
while still inside the moulds, under constant temperature and
humidity of 30 °C and 25% RH, respectively. After demoulding, they
were kept under the same conditions (30 °C and 25% RH) until the
test, which was scheduled to occur 7 days after fabrication.
A servo-hydraulic testing machine, fitted with a 25 kN capacity
load cell, was used for the uniaxial compressive strength tests.
These tests were carried out under monotonic displacement con-
trol, at a rate of 0.2 mm/min. Each UCS result presented is the aver-
age of 9 tested specimens.
Non-destructive ultrasonic pulse velocity (P-wave) measure-
ments were taken on purposely built cubic specimens
(100x100x100 mm) of pastes PaB4, PaF5 and PaC3, throughout
their respective curing period. Measurements were taken for each
of the 3 axes of the cubic specimens, to evaluate their respective
anisotropy. A commercially available equipment was used, which
included a pair of axially aligned piezoelectric broadband trans-
ducers, with a nominal frequency of 54 kHz. The measurements
started as soon as the specimens were demoulded (i.e. after
3 days), and were further taken after 5, 7, 10, 14, 21, 32 and
122 days. Since the rheology of the specimens evolved with curing
time, the emitted wave frequency was adapted to each stage. The
values of 24, 54, 150, 250 and 500 kHz were used whenever possi-
ble (initial measurements were only possible using lower frequen-
cies of 24 and 54 kHz), and the values presented are the average of
all frequencies taken. The model proposed by the American Con-
crete Institute (ACI Committee 209, 2008) to predict the strength
64 N. Cristelo et al. / Waste Management 104 (2020) 60–73

Table 3
Identification and composition of the pastes submitted to UCS tests (shaded rows indicate pastes further submitted to microstructural analyses and durability and environmental
tests).

ID BA FA OPC Liquid/Solids Liquid type

(wt.%) (wt.%) (wt.%) (wt. ratio) and concentration
PaB1 100 – – 0.35 SH (4 m)
PaB2 100 – – 0.40 SH (4 m)
PaB3 100 – – 0.40 SH (12 m)
PaB4 100 – – 0.50 SS
PaB5 100 – – 0.50 0.8SS + 0.2Water
PaF1 – 100 (*) – 0.45 SH (4 m)
PaF2 – 100 – 0.45 SH (4 m)
PaF3 – 100 – 0.45 SH (6 m)
PaF4 – 100 – 0.45 SH (8 m)
PaF5 – 100 – 1.50 SS
PaBF1 70 30 – 0.35 SH (4 m)
PaBF2 70 30 – 0.40 SH (4 m)
PaBF3 70 (*) 30 (*) – 0.40 SH (4 m)
PaC1 90 – 10 0.30 Water (deonised)
PaC2 80 – 20 0.30 Water (deonised)
PaC3 70 – 30 0.30 Water (deonised)

(*) Precursors submitted to an additional milling period of 60 min

(EDS), on a FEI Quanta 400 scanning electron microscope, with

30 kV, in low vacuum mode (1.3 mbar), avoiding the deposition
of a conductive layer, coupled with a EDS analyser, from EDAX
(the quantitative chemical analysis used a ZAF correction model).
The durability of selected pastes (PaB2, PaF1 and PaC3) was
assessed using two different procedures: wetting and drying and
freeze-thaw, based on the contents of the standards (ASTM D559,
2011) and (BSi PAS 8820, 2016), respectively. Both tests assess
the accumulated mass loss throughout the sequential cycles to
which the specimens are submitted. Two cylindrical specimens
with 100 mm in diameter and 116 in height were produced for
each wet-dry test, with each cycle corresponding to an initial
weighting, followed by 5 h under water and 42 h in an oven at
71 °C ± 2 °C. One of the specimens was then submitted to several
strokes (on all areas) with a wire scratch brush.
The freeze-thaw test (Method B) also required cylindrical spec-
imens, with 150 mm in diameter and 120 mm in height, from
which a 50 mm thick slices were sawn and tested (Fig. 4). After
submitted to a strict conditioning procedure, the specimens were
stored in the test chamber, which then automatically applied a
total of 56 freezing and thawing cycles, each lasting 24 h and rang-
ing between + 24 °C to 20 °C and back to + 24 °C. After 7, 14, 28,
42 and 56 cycles, the material detached from the exposed surface
of each specimen was dried and weighted, sometime between
the 20th and the 24th hour of the respective cycle.
The same pastes selected for the durability tests were also sub-
mitted to an environmental leaching test, described in standard EN
12457-4 (BSi EN 12457-4, 2002). It is a one stage batch test, with a
Fig. 3. Expansion of the 0.50 liquid/solids weight ratio paste (time lapse indicated
refers to the end of the mixing stage).
liquid/solid weight ratio of 10 l/kg, performed on particles below
10 mm. The specimens used in this test were identical to those
already described for the UCS tests, i.e. 40 mm cubes, cured for
development rate in cementitious binders (Eq. (1)) was applied to 7 days. Element concentration on the eluate was determined fol-
the 3 sets of data. lowing the standard BSi EN 16192 (2011), and the values obtained
were compared with the limits imposed, for each waste category,
t by the Council Decision 2003/33/EC (EU, 2003).
f c ðtÞ ¼ f c ð28Þ  ð1Þ
aþbt

where fc(t) and fc(28) are the compressive strength at time t and the
reference 28-day compressive strength, respectively; and a (in
days) and b are experimental coefficients, defined so that the ratio
a/b is the age of concrete (in days) at which one half of the ultimate
compressive strength of the concrete is reached. The ranges of a and
b are 0.05–9.25 and 0.67–0.98, respectively.
After curing, the pastes were further characterized by Scanning
Electron Microscopy (SEM) and Energy Dispersive Spectrometry
3. Results
3.1. Influence of particle size on UCS
Uniaxial compressive strength results on pastes prepared with
different BA particle sizes, presented in Fig. 5, clearly stated the
influence of such parameter on the mechanical behaviour of the
material and highlighted the importance of a thorough milling pre-
 N. Cristelo et al. / Waste Management 104 (2020) 60–73
Fig. 4. Freeze-thaw test specimens from pastes PaB2 (a), PaF1 (b) and PaC3 (c).
liminary stage, before fabrication of the pastes. Based on these
results, it became obvious that such step will always be required
if this material is to be introduced in industrial applications. A
study by (Loginova et al., 2019), on the particle size distribution
of a bottom ash recovered from a Dutch MSW incinerator plant,
discover that the Si content on the course particles (greater
than22.4 mm) can be approximately the double found in the finer
particles (<63 lm), reinforcing the importance of breaking the big-
ger particles to gain better access to their core silicon. Moreover,
the fitted power model seems to indicate that a slight decrease
in the maximum particle size will generate significant gains.
Whether such gains justify the financial and logistical cost of the
additional milling is a question that needs to be addressed in fur-
ther research, as it was beyond the scope of the present paper.
The results now presented were merely used to design the milling
stage of the present study. It is relevant to point out that, although
this laboratory scale process was significantly time-consuming,
producing a mere 20 kg of ready-to-use precursor per 24 h, the cor-
responding industrial scale process is presumably much more
effective, both in terms of time and cost.
65
3.2. Uniaxial compressive strength
Uniaxial compressive strength (UCS) after 7 days is shown in
Fig. 6. It is notorious that the activation of the BA with sodium sil-
icate produced significantly higher UCS than sodium hydroxide.
Curiously, the preliminary addition of 20% water (by weight) to
the sodium silicate solution (paste PaB5), although decreasing
the sodium concentration and, thus, the pH of the paste during
the mixing stage, produced a higher compressive strength than
paste PaB4. Regarding the activation with SH, a higher liquid/solids
ratio produced a higher UCS, while the opposite occurred with the
SH concentration, i.e. an increase in concentration produced
slightly lower UCS.
The FA-based pastes reinforced the importance of the particle
size, as the PaF1 paste showed a UCS value 1.48 higher than
PaF2, with the only difference between being the additional milling
for 60 min. Contrary to what was observed with the BA-based
pastes, the increase in SH concentration, from 6 to 8 molal, repre-
sented a 53% strength increase. The activation of FA with SS,
although significantly more effective than the FA pastes activated
with SH, didn’t produce a strength increase as significant as the
one obtained when SS was used to activate the BA. This is some-
how surprising, given that the FA has a low silica content, meaning
that this precursor should greatly benefit from the addition of the
soluble silicon (from the SS).
Although the UCS values obtained by the mixed pastes (includ-
ing both BA and FA), were higher than most of the BA or FA-based
pastes (with the exception of PaB2), the difference doesn’t seem to
justify the extra cost of mixing two precursors.
As expected, an increase in cement content represented a
strength increase. However, the highest cement content used in
the present work (30 wt%) produced a compressive strength simi-
lar to the strength generated by the 4 molal paste, i.e. PaB2. This
result is very significant, since the low SH concentration of the
paste PaB2, which represents a low alkali content (4 molal corre-
sponds to a mere 160 g of SH per litre of water), implies that the
financial and environmental cost of the activator used is very com-
petitive with cement. Additionally, this paste included a higher
waste content (BA = 100%) than the cement-based paste
(BA = 70%).
The UCS results are well in line with those obtained by Luna
Galiano et al. (2011), when stabilising MSWI fly ash with low cal-
cium coal fly ash activated with potassium-based activators. The
study included also the use of OPC and sodium-based activators.
The latter resulted in similar UCS values to those now obtained,
but the UCS values obtained from the latter were significantly
lower, especially considering that the MSWI waste proportion in
every paste was only approximately 25%, by weight.
Moreover, the excellent behaviour of the SS-activated pastes
was also registered by Huang et al. (2019), when developing MSWI
bottom ash mortars, reaching UCS values of more than 50 MPa (liq-
uid SS) and 30 MPa (solid SS). However, the mortars included 40%
of granulated blast furnace slag (GGBFS), relatively to the total BA
+ GGBFS weight.
It is also important to highlight the fact that the curing time
adopted for these tests might slightly favour the pastes prepared
with SS, relatively to the pastes prepared with SH, since the time
required for the silicon ions to become available, after the dissolu-
tion phase, and participate in the aluminosilicate new matrix is
usually higher than 7 days. This would represent an advantage
for the pastes prepared with sodium silicate, which provides sol-
uble silicon right from the start of the reactions. This, together with
the higher financial cost associated with SS than SH, expressed in
both the unity price and the total volumes of SH and SS consumed
by each paste (Table 3), justified the option for pastes PaB2 and
66 N. Cristelo et al. / Waste Management 104 (2020) 60–73

Fig. 5. UCS of the preliminary pastes, fabricated with different BA particle size fractions.

Fig. 6. UCS of the main pastes after 7 days curing (values presented are the average
of 9 specimens).

PaF1 to be further studied, in terms of microstructure and durabil-

ity and environmental tests.

3.3. Seismic waves

Fig. 7 presents the results of the P-wave velocity measurements

performed on cubic specimens fabricated with pastes PaB2, PaF1
and PaC3. Data from the vertical axis and both horizontal axes is
included, as well as the ACI model fit which, since the curves
Fig. 7. Ultrasonic pulse velocity (P-wave) measurements over the 3 axes, on
obtained for each of the 3 axes are very similar, was only fitted
specimens fabricated with pastes PaB2, PaF1 and PaC3, up to122 days curing.
to the vertical axis.
Paste PaF1 showed the lowest propagation velocities of the 3
pastes, throughout the curing period, suggesting a faster curing
process. The cement-based paste (PaC3) clearly showed the highest ysed in detail further ahead. Moreover, paste PaB2 only failed to
initial value of the 3 pastes. However, its increase rate was similar achieve the highest value of the test due to its low initial value,
to that shown by PaF1, and significantly lower than that shown by similar to paste PaF1, but its increase rate was the highest of the
PaB2. This result is in accordance with the durability tests, anal- 3 pastes analysed. After 122 days, pastes PaB2 and PaC3 showed
 N. Cristelo et al. / Waste Management 104 (2020) 60–73
very similar velocities, which mostly results from the decrease,
with time, of the cement-based material.
The ACI model helps to illustrate that, although the initial
consistency development of the pastes prepared with an alkaline
activator is significantly lower than that presented by the
cement-based paste, the latter presented a progressive degrada-
tion, which can be a consequence of secondary chemical reactions
between the complex chemical composition of the waste and the
binder. The FA-based paste showed also some slight degradation
after 122 days, especially regarding the vertical axe. On the con-
trary, the BA-based paste appears to be more consistent and ade-
quate to stabilise the complex and broad spectrum (in terms of
chemical composition) residues generated by the incineration of
municipal waste, since an increase in velocity was registered for
all 3 axes. Although the referred model was developed for concrete
applications, it does fit reasonably well in the experimental results.
3.4. Mineralogy and microstructure
Fig. 8 shows the diffraction patterns obtained with the anhy-
drous materials (FA, BA and OPC) and some selected pastes
(PaB2, PaF1 and PaC3), after 7 days curing. The PaB2 reflections
showed only a slight evolution relative to the anhydrous BA,
produced by the disappearance of the clinozoisite phase, with most
phases remaining mostly unchanged (e.g. calcite, quartz,
oligoclase, akermanite), indicating they were not involved in
alkaline activation reactions. Also relevant is the fact that the halo
indicating the presence of amorphous matter, detected in the BA
diffractogram, showed a slight increase, which is compatible with
the formation of an essentially amorphous aluminosilicate gel
(Fernández-Jiménez et al., 2017; Garcia-Lodeiro et al., 2015).
Reflections for paste PaF1 showed a peak intensity decrease of
the Ca(OH)2 (calcium hydroxide) and CaCl2 (calcium chloride)
phases detected in the anhydrous FA diffractogram, suggesting
the participation of the calcium element in the composition of
Fig. 8. XRD diffractograms of the original anhydrous materials (BA, FA and OPC) and the resulting pastes PaB2, PaF1 and PaC3 after 7 days curing (A: alite; B: belite; C: calcite;
E: clinozoisite; F: Potassium aluminium silicate; G: gypsum; H: halite; K: akermanite; L: Ca(OH)2; M: anhydrite; N: partheite; O: oligoclase; Q: quartz; S: sylvite; V: CaCl2).
67
the aluminosilicate gel formed during alkaline activation reactions.
Alternatively, it could also be a consequence of carbonation, since
the intensity of the calcite peaks detected in this paste seam
slightly higher than those detected in the original FA. A significant
intensity decrease of the KCl peaks (sylvite) was also registered,
relatively to the FA reflection. Similarly to the PaB2 paste, several
crystalline phases remained unchanged, like calcite, quartz and
anhydrite. A significant intensity increase of the NaCl (halite) and
CaSO4 (anhydrite) peaks was registered after the reactions. The for-
mation of the CaSO4 compound suggests the participation of the Ca
element in the final matrix. García-Lodeiro et al. (2016), when con-
ducting a similar study on hybrid cements using fly and bottom ash
from a municipal solid waste incinerator, added CaSO4 to a paste
composed by clinker (60%), incinerated fly ash (10%) and bottom
ash (50%) to improve setting properties, and attributed several
new phases to this admixture, something that was not corrobo-
rated in the present case, since the only new phase found after acti-
vation was potassium aluminium silicate.
The OPC diffractogram showed several peaks attributed to typ-
ical crystalline phases found in clinker, like alite and belite. Consid-
ering the dilution resulting from the addition of BA, is it normal
that the intensity of such phases is reduced. However, several
peaks disappeared after the PaC3 reactions, which is always to be
expected in cement hydration. However, portlandite, another com-
mon phase resulting from cement hydration, was not detected,
most likely because it carbonated. The PaC3 diffractogram shows
phases resulting from both anhydrous materials (OPC and BA).
The phases resulting from the BA appear mostly unchanged, with
the exception of the clinozoisite, which disappeared (similarly to
what happened with paste PaB2). At the same time, a new zeolite
called partheite (calcium aluminium silicate) was formed.
SEM micrographs and selected EDS spectra of the PaB2, PaF1
and PaC3 pastes are presented in Fig. 9. The morphology of the
paste PaB2 seams to reveal a fairly compacted material, with less
voids than pastes PaF1 and PaC3, which might help explain the
68 N. Cristelo et al. / Waste Management 104 (2020) 60–73

Fig. 9. SEM micrographs and representative EDS spectra of pastes PaB2, PaF1 and PaC3 after 7 days curing.

higher strength of this paste – obviously, the type and quality of
the gel developed in each case plays also a very significant role
in this matter. Nevertheless, all pastes showed a uniform spreading
of the cementitious gel, with no apparent unreacted particles.
The EDS spectra presented were chosen as to represent the
overall trend of the gel precipitated in each paste. The compact
and regular morphology of the pastes substantially increased the
difficulty in finding and separate the gel zones from the precursor
particles. Such distinction was mostly made by trial-and-error,
using the EDS analyser, considering that higher Na contents would
be found in the gel phase. The most abundant element found in
paste PaB2 was Si, with lower (and similar between them) contents
of Ca, Al and Na contents. This proportion was found to be very
stable across the analysed sample, suggesting the predominant for-
mation of a (N,C)-A-S-H gel. A slightly different scenario was found
in paste PaF1, with a very significant presence of Ca in the reaction
products. The Si and Cl contents were very similar, followed by
even smaller percentages of Al and Na. The predominance of Ca
in this paste and the poor incorporation of Al suggests the main
precipitation of a C-S-H gel type. Finally, elements Ca, Si and Al
presented the most relevant contents in the reaction products of
paste PaC3, suggesting the classification of its reaction gel as a
 N. Cristelo et al. / Waste Management 104 (2020) 60–73 69

C-A-S-H type. This analysis is supported and discussed in greater PaB2 seems low, given that the BA was constituted by more than
detail below. 22% of calcium. A possible explanation might be associated with
The ternary diagrams presented in Fig. 10 are a graphical and the fact that, although the presence of Ca degrades the N-A-S-H
quantitative presentation of the SEM/EDS presented above, aiming gel in favour of a C-A-S-H precipitation, with the Ca displacing
a more comprehensive understanding of the relative content of Si, the Na ions, this happens only until the available Ca is exhausted
Al, Ca and Na. The point distribution variability in the CaO-Al2O3- (García-Lodeiro et al., 2011). What is common to all pastes is the
SiO2 diagram clearly shows the heterogeneity between the three
pastes. Furthermore, the Na2O-Al2O3-SiO2 diagram shows that
the composition of paste PaB2 is less variable than PaC3 and, espe-
cially, PaF1. Paste PaB2, which produced a gel that was already
classified as type (C,N)-A-S-H, showed the lowest Ca content of
the test. The remaining two pastes showed higher scatters in their
composition but revealed a prevalence of Si (PaC3) or Ca (PaF1).
This is an indication that the higher Ca content of the PaF1, which
was only used in the composition of this paste (pastes PaB2 and
PaC3 were prepared with bottom ash as the sole precursor) was
mostly incorporated in the final matrix. This paste also revealed
the highest Na content. Nevertheless, the Ca content found in

Fig. 11. Molar ratios obtained from the EDS analysis of the pastes PaB2, PaF1 and
PaC3, cured for 7 days.

Fig. 10. Na2O-Al2O3-SiO2 and CaO-Al2O3-SiO2 ternary phase diagrams for pastes Fig. 12. Wetting and drying test performed on pastes PaB2, PaF1 and PaC3 (ASTM
PaB2, PaF1 and PaC3, after 7 days curing. D559, 2011).
70 N. Cristelo et al. / Waste Management 104 (2020) 60–73
Fig. 13. General view of the brushed specimens submitted to the wetting and drying test, before the first cycle (a1 - PaB2, a2 - PaF1, a3 - PaC3) and after 12 cycles (a2, b2, c2).
low Al content, which will increase the difficulty to classify each
gel type, as demonstrated ahead.
To further analyse the elemental composition, the Al2O3/SiO2
and CaO/SiO2 molar ratios of the three pastes were plotted and pre-
sented in Fig. 11. The plot is divided in three areas which, according
to several authors (Fernández-Jiménez et al., 2019, 2013; Garcia-
Lodeiro et al., 2015; García-Lodeiro et al., 2011), translate the com-
positional ranges that should be expected for different types of
cementitious gel. In this case, only the areas corresponding to C-
S-H, C-(A)-S-H, C-A-S-H and (C,N)-A-S-H gels are plotted, i.e. areas
below the Al2O3/SiO2 molar ratio = 0.5, since all EDS points regis-
tered were contained by this upper limit.
The low Al precipitation is clear. According to the above-
mentioned authors, the minimum Al2O3/SiO2 molar ratio for the
gel to be considered as a N-A-S-H gel is 0.5, and no point in the
PaB2 paste showed a value above 0.2. However, Zheng et al.
(2010), when studying the immobilisation of heavy metals in
MSWI fly ash through AA, found an optimum Al2O3/SiO2 molar
ratio of 0.5. The authors concluded also that a decrease of this ratio
would produce larger pores, given the excessive soluble silicon
content, suggesting that an Al correction could drastically improve
the UCS results obtained during the present study, an idea that was
reinforced by Zheng et al. (2016).
The Ca content was significant for all pastes, as a result of the
presence of this element in both precursors. All points obtained
with paste PaB2 clustered in an area which, although well inside
the CaO/SiO2 range corresponding to the N-A-S-H and (C,N)-A-S-
H gel areas, has a Al2O3/SiO2 molar ratio significantly below the
minimum threshold required for the (C,N)-A-S-H gel. Paste PaF1
showed most points well inside the C-S-H area, and some points
in the C-(A)-S-H gel area, which is a bridging stage evolution
between the C-S-H and C-A-S-H gels, produced by an increasing
Al content. Furthermore, although almost all PaF1 points show
CaO/SiO2 values well above 2, which is the axis limit presented
in the literature above mentioned. This is mostly related with the
Ca content of the FA (40%) and the FA content of this paste
(100%). For instance, the study presented by Fernández-Jiménez
et al. (2013) also included a high-calcium precursor (ground gran-
ulated blast-furnace slag with 40% Ca), but the resulting paste had
a slag content of only 40%. Regarding paste PaC3, it showed most
points in the C-S-H area and also some points in the CaO/SiO2
range corresponding to the C-A-S-H gel. However, the Al2O3/SiO2
molar ratios were below the C-A-S-H minimum of 0.3.
3.5. Durability tests
The accumulated loss of mass (ALM) registered for specimens
prepared with pastes PaB2, PaF1 and PaC3, after 12 wetting and
drying cycles, is presented in Fig. 12. Somehow surprisingly, the
paste PaF1 showed the lowest ALM throughout the test, even con-
sidering the substantial losses suffered by pastes PaB2 (during the
7th cycle) and PaC3 (during the 10th and 11th cycles). Paste PaF1
itself also suffered a substantial loss during the 12th cycle,
although it wasn’t enough to alter the overall relative performance
of the three pastes. These substantial losses occurred as a conse-
quence of bigger and intact pieces being separated from the main
 N. Cristelo et al. / Waste Management 104 (2020) 60–73
Fig. 14. Freeze-thaw test performed on pastes PaB2, PaF1 and PaC3 (BSi PAS 8820,
2016).
body of the specimen, instead of a gradual, dusty-like mass loss.
Although relevant, such sudden increases in ALM are usually more
related with structural flaws in the specimen, which are enhanced
as the test progresses, and less related with durability, defined as
the gradual particle release as the material is exposed to adverse
conditions. Paste PaB2 showed a higher ALM rate than the remain-
ing two pastes during the first 4 cycles. After that, and excluding
the 7th cycle, it showed an ALM rate similar to the rate showed
Fig. 15. Element concentrations in the leaching solution obtained from pastes P2B (EN 12,457 test) and comparison with the acceptance limits defined in 2003/33/EC for
inert, non-hazardous and hazardous wastes.
71
by PaC3 (excluding, obviously, cycles 10 and 11). This initial beha-
viour is most likely related with the slower curing process demon-
strated by the PaB2 paste during the seismic wave measurements
presented in Fig. 7. The performance showed by paste PaF1, clearly
with a lower ALM rate than the BA-based pastes, can also be
related with the faster curing process demonstrated during the
seismic wave analysis. This is an interesting result, which shows
that the proposed binders are competitive with the use of 30%
Portland cement. The general aspect of the specimens, after cured
for 7 days and submitted to the full 12 cycles, is presented in
Fig. 13. Visually, it is also clear that paste PaF1 produced the most
resilient specimen.
The accumulated loss of mass registered during the freeze–
thaw tests (ALMft) performed on specimens fabricated with pastes
PaB2, PaF1 and PaC3 cured for 7 days, is presented in Fig. 14. After
mere 14 cycles, and contrary to the overall trend obtained during
the wetting and drying tests, the performance of PaF1 was clearly
the least effective of the three pastes tested. Such scenario was
maintained after 28 cycles, with the PaF1 and PaC3 showing the
highest and lowest degradation at this stage, respectively. How-
ever, after 42 cycles, a significant ALMft increase was registered
for the PaF1 specimen which, as referred above, is caused by the
loss of bigger and intact pieces. However, the present test, contrary
to what can be expected from the wetting and drying test, targets
this kind of fragmentation, meaning that the performance of the
PaF1 paste can be seen as poor or inadequate. Nevertheless, the
other paste prepared with the alkaline activation technique
(PaB2) showed a similar behaviour to the paste (PaC3) prepared
with the current solution (Portland cement), which is another pos-
itive indication of the potential of this more sustainable
alternative.
3.6. Leaching tests
The environmental performance of the pastes PaB2, PaF1 and
PaC3 was assessed through the compliance test standardized by
BSi EN 12457-4 (2002). Leachable concentrations obtained from
eluate recovered from the solid pastes were compared with the
threshold values presented in the Council Decision 2003/33/EC,
for inert waste, non-hazardous waste and hazardous waste
(Fig. 15). Given the original element composition of both residues,
and the information gathered from previous research (Alam et al.,
72 N. Cristelo et al. / Waste Management 104 (2020) 60–73
2019; Jin et al., 2016; Tang et al., 2015; Yang et al., 2018), the study
focused on the elements Cu, Zn, Cl, F and SO4, as well as the total
dissolved solids content.
All concentrations measured were below the hazardous and
non-hazardous waste threshold. The Cl and SO4 concentrations
in the eluate collected from paste PaF1 were the only cases when
the inert waste threshold was crossed, a behaviour that was pre-
viously reported by other authors, especially concerning the Cl
(Alam et al., 2017). Nevertheless, given the very high Cl (27%)
and SO3 (5%) contents found in the original FA precursor, it can
be inferred that the proposed stabilisation was able to effectively
immobilise these ions. Paste PaF1 showed the highest concentra-
tions in almost every case, with the exception of the Cu and Zn
elements found in the PaB2 eluate. It is important to notice that
paste PaC3 had only 70% of the waste content incorporated in
the remaining pastes, and still showed very similar concentra-
tions, which is an indication of the adequacy of the alkaline acti-
vation reactions to stabilise slag and fly ash resulting from the
incineration of municipal solid waste. This is in accordance with
García-Lodeiro et al. (2016), which performed a toxic characteris-
tic leaching procedure (better known as a TCLP test) to similar
waste and, although this test uses an acidic, more aggressive lea-
chant, the concentrations measured were still well below the haz-
ardous limit values. The same authors also found the chlorine to
be the element with the highest concentration in the eluate, and
point out that the values found, as in the case of the present
study, are well above the Cl content limit for high-cements estab-
lished by BSi EN 197–1 (2011), due to the durability concerns
associated with the steel reinforcement.
4. Conclusions
The present paper describes the results obtained with the alkali
activation of BA and FA generated by the incineration of the munic-
ipal solid waste collected in the Greater Porto (Portugal) area. Both
residues were previously submitted to a mechanical activation
step, and later activated with sodium hydroxide or sodium silicate,
without the addition of a second, more effective precursor. The
effectiveness of the stabilisation of the bottom ash with Portland
cement was also tested, to establish a reference, by mixing up to
30% (weight) of OPC and 70% bottom ash.
The fabrication process of the pastes depends on the use of the
BA alone or combined with a second precursor (e.g. coal fly ash). If
the BA is the only precursor, the activation will generate hydrogen,
thus affecting the consistency and even the structural integrity of
the pastes. To overcome this, it was necessary to wait for the pastes
to cool down. The use of a second precursor, in combination with
the BA, allowed to avoid this step.
Regarding the mechanical behaviour, the influence of a prelim-
inary mechanical activation is very clear, with the <0.063 mm frac-
tion showing a UCS which is an order of magnitude higher than
that of the 0.5–1.0 mm fraction. The activation with sodium silicate
proved significantly more effective than with sodium hydroxide,
especially in the case of the BA-based pastes, when the UCS values
more than triplicated. Based on the compressive strength, the BA is
a more effective residue than the FA for the production of cemen-
ted pastes, although the FA pastes clearly presented the most effec-
tive performance in the wetting and drying durability tests, which
might be related with its faster curing, as shown by the seismic
wave patterns, i.e. the stiffness of the FA paste after 10–15 days
was very similar to the values obtained after 122 days. The seismic
wave velocity showed that, although the initial stiffness of the
cement-based pastes was superior, the stiffness evolution of the
BA pastes evolved at a faster rate, reaching similar values after
4 months curing.
In terms of environmental performance, the BA and OPC pastes
presented similar performances in terms of leachability, while the
only situations of non-compliance with the inert waste landfill
threshold were registered with the FA-based paste.
In general, the low-cost MSWI waste solidification/stabilisation
proposed in this study showed a very competitive performance
with the alternative use of up to 30% cement, and should therefore
be regarded as a valid alternative for simple storage or for low-
range applications, like road bases or non-structural use, where
the material’s performance is less demanding, in substitution of
cement stabilised BA or FA.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgments
The authors would also like to acknowledge the contribution of
the Electronic Microscopy Unit of the University of Trás-os-Montes
e Alto Douro (Dr. Lisete Fernandes), for the microstructural
analysis.
Funding
This work was funded by the R&D Project PRJ-0127, financed by
the company LIPOR - Intermunicipal Waste Management of
Greater Porto, Portugal.
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