Construction and Building Materials 133 (2017) 14–26

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Construction and Building Materials

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

Synergistic recycling of calcined clayey sediments and water

potabilization sludge as geopolymer precursors: Upscaling from binders
to precast paving cement-free bricks
F. Messina a,b,⇑, C. Ferone a,b, A. Molino a,b, G. Roviello a,b, F. Colangelo a,b, B. Molino c, R. Cioffi a,b
a
Dipartimento di Ingegneria, Università degli Studi di Napoli Parthenope, Centro Direzionale, Isola C4, 80143 Napoli, Italy
b
INSTM, Consorzio Interuniversitario per la Scienza e Tecnologia dei Materiali, Via G. Giusti, 9, 50121 Firenze, Italy
c
Department of Biotechnology and Territory, University of Molise, Campobasso 86100, Italy

h i g h l i g h t s

Calcined sediments and potabilization sludge were used as geopolymer precursors.

Precast geopolymer paving bricks were produced after upscaling process.

Significant results were obtained for sustainable production of building materials.

The proposed recycling route is very advantageous for reservoir management.

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

Article history: The building materials industry is facing relevant challenges in terms of sustainability requirements. The
Received 30 May 2016 same challenge is expected for other anthropogenic activities such as reservoir management. In this
Received in revised form 25 November 2016 study, in the light of industrial ecology approach, two wastes, namely clayey sediments and water pota-
Accepted 10 December 2016
bilization sludge, generated through reservoir life cycle, were used in a synergistic way in the synthesis of
Available online 22 December 2016
sustainable geopolymer binders. In order to guarantee a productive equilibrium between the different
yearly evolution of building materials demand and wastes production by the basin, precast materials
Keywords:
have been regarded as optimum potential application. In this regard, calcination conditions, mix design
Clay sediments
Water potabilization sludge
and curing conditions were preliminarily optimized. Particularly, geopolymerization kinetics were eval-
Geopolymer uated by means of mechanical and microstructural characterization of pastes to assess the influence of
Precast concrete early age curing conditions and mix design on the engineering performance and, afterwards, the product
Cement reduction was upscaled to a typical precast concrete element. The whole set of results demonstrated the feasibility
Bricks of the proposed recycling route, revealing highly promising perspectives for further studies and broader
application field.
Ó 2016 Elsevier Ltd. All rights reserved.

1. Introduction harbor, river and reservoir sediments was proposed in brick

production [4–6], sintered lightweight aggregate manufacturing
Recent updates in legislative approach in reservoir water and [7–12] and production of Portland cement [13]. Hence, summariz-
sediment management revealed the need to make supplementary ing the main results of the mentioned literature dealing with the
efforts in research towards the definition of possible reuses of pro- beneficial reuse of sediments, two main application-oriented
duced wastes [1–3]. Due to its high production volumes and simul- research trends can be detected, namely bricks and sintered light-
taneous need of increasing sustainability, building materials weight aggregates. In both cases, high temperature processes are
industry represents a highly promising solution to recycle the total required, implying a harmful environmental effect. In the latter
volume of sediments produced by silting in a reservoir. The use of case, more sustainable lightweight aggregates can be obtained
with alternative low temperature processes, such as cold bonding
pelletization [14–16]. In the case of bricks, and, generally, precast
⇑ Corresponding author at: Dipartimento di Ingegneria, Università degli Studi di elements, firing can be substituted by optimized calcination
Napoli Parthenope, Centro Direzionale, Isola C4, 80143 Napoli, Italy. treatment of clayey sources and proper mix design. The role of
E-mail address: [email protected] (F. Messina).

http://dx.doi.org/10.1016/j.conbuildmat.2016.12.039
0950-0618/Ó 2016 Elsevier Ltd. All rights reserved.
 F. Messina et al. / Construction and Building Materials 133 (2017) 14–26 15

calcination is crucial in the development of proper performance of were considered in alternative civil engineering applications such
clay-based binders, and this was clarified since the first pioneering as soil improvement and other geotechnical works [43]. In a recent
works [17–21], where calcined clays were employed as pozzolanic study [44], the pozzolanic potential of calcined water potabiliza-
admixture in cementitious systems. One of the main problem con- tion sludge (CWPS) was investigated in a deeper way than prelim-
cerning the recovery of sediments is represented by the hetero- inary literature studies. In this work, Chapelle test was applied by
geneity of clay sources, as highlighted in Table 1. As it can be preparing cementitious blends with lime and CWPS (alumina con-
observed in this table, the structural performance can vary in a tent equal to 16.47% according to XRF results) as pozzolan, after a
very wide range due to different chemistry and reactivity, going calcination process carried out at 400–900 °C for 2 h. The highest
from load-bearing elements (laterite/pure kaolinite) down to amounts of fixed lime were found at 700 and 800 °C, with a detri-
non-structural materials (nature impure clays/Illite/etc.). Starting mental effect of further temperature increase associated with the
from this consideration, it is clear that a proper and economically initiation of crystallization processes of amorphous silica [44].
feasible recycling track for dredged sediments cannot be associated The use of CWPS and calcined clay sediments (CCS) can only
a priori to high performance structural materials. In this scenario, partially reduce the environmental impact of cement, mainly asso-
the production of bricks and other precast non-structural elements ciated with the content of clinker, whose production is responsible
can be proposed with higher reliability and elasticity respect to on a global scale for 5–8% CO2 emissions. Hence, in order to further
periodical oscillations in raw material availability. Another main increase the sustainability of the recycling process of both CWPS
technological issue is represented by calcination parameters. Three and CCS, cementitious blends should be avoided. In this frame-
main calcination equipment can be found nowadays in clay pro- work, the use of alternative low-energy and low-CO2 binders such
cessing, with different operating conditions: rotary furnace, multi- geopolymers (also called ‘‘alkali activated binders” or, more
ple earth furnace and flash calcination plants. The latter one gained recently, ‘‘hybrid cements”) is highly promising. Geopolymers
a lot of research attention due to increased sustainability in terms were proposed for a wide range of engineering applications such
of energy demand [22] and higher efficiency in particle treatment. as: production of geopolymer concrete [45,46]; production of
In the work by San Nicolas et al. [23], a description of the process is bricks and other non-structural elements starting from ‘‘poor” solid
provided. After a preliminary drying process, the clay-based raw precursors [47,48]; waste stabilization/solidification [49,50]; fire
mix is crushed and coarse particles and quartz are eliminated. A resistant binders [51,52]; and other functional applications [53,54].
secondary drying process is then performed at 100 °C. Afterwards, The idea of finding a common solution for sustainability issues
a stream of hot air takes clays to 200 lm sieving just before feed- of two fundamental anthropic activities such as reservoir manage-
ing. The calcination phase is carried out for few tenths of seconds ment and building materials production through the geopolymer-
of 1000–1200 °C. The process ends with air cooling cyclones and ization of CCS was already proposed in literature [55–57]. In [55], a
material storage in silos. preliminary investigation proved that sediments from two Italian
The same study provides an evaluation of influence on rheolog- reservoirs located in Southern Italy had the potential to be
ical properties is carried out by producing mortars with paste com- employed as aluminosilicate solid precursors for the synthesis of
posed by cement and different metakaolin sources with fractions geopolymers after calcination at 650 and 750 °C, considering that
equal to 75 and 25%, respectively. The rheological measurements sufficient mechanical performance for non-structural components
used was LCL flow test (EN 196-1) and the reduction in flow time was already achieved. In a subsequent study [56], FTIR and NMR
due to provided by flash calcination for different clay source was in analysis confirmed that, in the range 400–750 °C, the dissolution
the range 38.0–62.5% [23]. These results contribute to clarify the of both Al and Si increased with temperature, revealing also that
need of optimizing calcination process. the addition of blast furnace slag as secondary component of the
Alumina-containing water potabilization sludge (WPS) is blend can significantly increase the reactivity. More recently,
another fundamental residue produced by reservoir management Peirce et al. [57] considered the possibility to use an aluminate
activities. This waste is accumulated after treatment processes alkaline solution to activated CCS in place of typical silicate solu-
for water potabilization, which are based on flocculation- tions, achieving good mechanical performance.
clarification using alumina-based coagulant [24]. The amount of In this study, for the first time, the synergistic recycling of CCS
generated sludge and its chemical composition mainly depend on and CWPS to produce precast geopolymer concrete elements was
the following parameters: (i) water chemical and physical charac- proposed. Particularly, starting from characterization of clayey
teristics; (ii) efficiency of removal process; (iii) type and dose of sediments and water potabilization sludge, the effect of calcination
coagulant. The amount of sludge can be approximately estimated was evaluated and an evaluation of optimal sediment/sludge ratio
to be in the range 1–5% of the total untreated water quantity was provided by testing geopolymer pastes from a mechanical and
[24]. This waste was investigated in literature only in few studies, microstructural point of view. Afterwards, a gradual manufactur-
mainly concerning the potential reuse in building materials indus- ing upscaling from paste to mortars up to real scale elements (pav-
try. Particularly, WPS was proposed in the production of bricks ing bricks) was carried out, and main rheological and mechanical
[25–27], ceramics [28,29], cement manufacturing with role of issues were highlighted. Significant insight into several key param-
alternative raw material [30–34], inorganic binder-based compos- eters were obtained, particularly mix design, calcination parame-
ites [35–40], lightweight aggregates [41,42]. Furthermore, WPS ters, workability, curing conditions, mechanical properties, were

Table 1
Data collection related to mechanical strength variations due to heterogeneities in clay sources (adapted from [21]).

Clay source Mineralogical description Compressive strength [MPa] Strength loss

Laterite Kaolinite (55%); quartz; iron oxides 27.1 /
Pure kaolinite Kaolinite (>98%); quartz (<2%) 26.9 0.74%
Tropical soils Kaolinite (33  44%) 15–23 15.1  44.6%
Montmorillonite Montmorillonite (>90%); quartz 12.6 53.5%
Natural impure clays Kaolinite (30%); illite (30%); quartz 8–9 66.8  70.5%
Illite Illite (>85%); quartz 7.8 71.2%
Slate waste Chlorite (29%); muscovite (46%); quartz (24%) 2.1 92.2%
Black colliery spoil Kaolinite + Illite/mixed layer clay; quartz 0.6 97.8%
16 F. Messina et al. / Construction and Building Materials 133 (2017) 14–26

provided, achieving the successful production of paving blocks 200 mg of KBr in an agate mortar and then pressed into 200 mg
demonstrating the feasibility of the proposed highly sustainable pellets of 13 mm diameter. The spectrum of each sample repre-
process. sents an average of 32 scans.
Calcination treatment was carried out by means of a laboratory
2. Materials and methods muffle. The calcination process was carried out at 750 °C for two
hours according to previous optimization studies [55–57], and
2.1. Raw materials characterization and calcination cooling of CCS was performed also in a fast way. The fast-cooled
CCS were employed in the production of precast concrete bricks,
Clayey sediments and water potabilization sludge were as clarified in the next sections. The alkaline activating solution
obtained from Liscione (Italy) reservoir (Fig. 1). Particularly, the for the synthesis of geopolymer systems was a blend of sodium sil-
clayey sediments were collected from a site very close to a bridge icate solution (SSS) supplied by Prochin (Italy) with R = 3.2 and
(Fig. 2). In Italy, the potential rate of silting in large reservoirs sodium hydroxide 14 M solution (SHS).
ranges from 0.1% to 1% of total storage volume depending on
several environmental boundary conditions (e.g., agricultural land 2.2. Mix design, curing and testing of paste, mortars and precast
use). elements
In medium and small size reservoirs, the range of silting is equal
to 0.3% and 2% of total storage volume. Considering both scales of After calcination process was carried out, CCS and CWPS were
reservoirs, the annual average loss of storage capacity would be used in an explorative mix design in order to understand major
about 1.6%. The hydraulic sustainability and safety of reservoirs trends in strength development and curing influence. Three differ-
is not the only issue. Often, the process of silting threatens also ent pastes were designed, whose compositions were reported in
adjacent structures and infrastructures. In Fig. 2, it is possible to Table 2. The chemical composition of the pastes is represented in
observe a roadway bridge which presents a very high submersion terms of main oxides, namely SiO2, Al2O3, CaO, Fe2O3 and Na2O,
risk, determining that in many periods of the year the infrastruc- in order of decreasing content. The solution to precursors (S/P)
ture is out of service with several arising management problems. mass ratio was fixed at 0.93, since the water demand of precursors
Three cores of sediments were sampled from the reservoir similar to metakaolin is generally close to a unitary S/P ratio [58].
when the water level was low enough. The cores were 10 cm in The solution blend was realized using SSS and 14 M SHS in a mass
diameter and 1 m in height. The three cores coming from the Lis- ratio equal to 2.32.
cione site were crushed, milled in a ball mill (330 rpm for 3 min) The pastes were mixed using a laboratory Hobart mixer. The
and mixed to get a homogeneous sample. After drying at 105 °C dry powders were mixed for 1 min at low speed. At the same
in an oven, the characterization of each sample was performed speed, the solution blend was slowly and continuously added in
by means of chemical (quantitative), mineralogical, thermal and about 30 s. Afterwards, the mixing was continued for 3 min at
spectroscopic analyses. medium speed and, finally, after scrapping the edges of the mix-
X-ray fluorescence (XRF) analysis was carried out by means of ing bowl for 30 s, at fast speed for 1 min. The fresh pastes were
Bruker Explorer S4 apparatus, in order to obtain chemical compo- cast in small cylindrical (d = 2.7 cm; h = 6 cm) polyethylene
sitions in terms of main oxides. Thermogravimetric analysis (TGA) molds, preparing three samples for each paste. Two curing cycles
was performed using a TGA-DSC apparatus provided by Mettler were programed, considering different curing temperatures on
Toledo (weight of the sample, 10 mg; heating rate, 10 °C min1; the first day after casting. Particularly, temperature was fixed at
atmosphere, nitrogen and air). X-ray diffraction (XRD) analysis 20 °C and 60 °C for the first 24 h, respectively. Afterwards, sam-
was carried out by means of Miniflex 600 supplied by Rigaku (Cu ples were stored under sealed conditions in a high relative
Ka radiation, 40 kV, 15 mA, 2h range from 3 to 90°, step size humidity environment through a climatic chamber operating at
0.020° 2h, 0.5° slit width). Rigaku PDXL2 software and ICSD data- 20 °C and RH > 90%. Finally, the samples were placed in room
base were used for mineral identification and semi-quantitative conditions for supplementary 21 days to reach typical four weeks
evaluation. The FTIR absorption spectra were recorded in the curing. This curing cycle was intended to replicate properly
4000–400 cm1 range using a Nicolet system, Nexus model, the traditional cycle of precast concrete industry, for which in
equipped with a DTGS KBr (deuterated triglycine sulfate with the first phases (i.e., from casting up to 48 h) the material can
potassium bromide windows) detector. A spectral resolution of be cured at highly controlled conditions, with subsequent phases
2 cm1 was chosen. Each test sample (2.0 mg) was mixed with of storage and final transport.

Fig. 1. Water potabilization sludge (A) and clayey sediment (B) from Liscione reservoir.
 F. Messina et al. / Construction and Building Materials 133 (2017) 14–26 17

Fig. 2. Collection site for clayey sediments in proximity of a critical infrastructure.

Table 2
Compositions of investigated pastes.

Binder composition SiO2 Al2O3 CaO Fe2O3 Na2O Na2O/Al2O3 (molar) SiO2/Al2O3 SiO2/Na2O H2O/Na2O S/P SSS/SHS
(% w/w) (molar) (molar) (molar)
P1 70WPS/30CCS 48.89 31.09 6.70 6.43 0.45 0.75 3.64 4.83 14.22 0.93 2.32
P2 50WPS/50CCS 51.35 27.63 7.34 6.66 0.54 0.85 4.25 4.97 14.12 0.93 2.32
P3 30WPS/70CCS 53.81 24.18 7.97 6.88 0.56 0.98 5.03 5.11 14.03 0.93 2.32

Table 3
Compositions of mortar mixtures.

M1 M2 M3 M4 M5 M6 M7 M8
CCS/WPS 30/70 50/50 30/70 50/50 30/70 50/50 30/70 50/50
Binder/sand (mass) 1.88 1.88 1.25 1.25 0.94 0.94 0.63 0.63
Sand type EN-Standard EN-Standard EN-Standard EN-Standard EN-Standard EN-Standard EN-Standard EN-Standard

Fig. 3. Comparison of industrial aggregates distribution with Fuller and Bolomey model curves.

According to the results presented in next section, the paste mass ratios were investigated, namely 1.88, 1.25, 0.94 and 0.63,
samples were upscaled to produce mortars, by means of the addi- gradually increasing sand content. Mortar samples were cast in
tion of European standard sand (grain size range: 0–4 mm). The 4 cm size small cubes in steel molds. The mortar mixtures are
mixing process for mortars was the same programed for the pastes, reported in Table 3.
except for the sand content which was added together with the Since several workability problems were encountered with the
solid precursors (i.e., CCS and CWPS) in the preliminary dry mixing use of P3 binding system, the final upscaling to prototype precast
phase. One of the paste, namely P1, was excluded by this second paving eco-bricks was carried out by using only P2, i.e. the paste
part of the research work for the results discussed in the next sec- with CCS/CWPS ratio equal to 1. In this third mixture design phase,
tion and for the management observation that the produced natural aggregates were used in place of standard sand, in order to
amounts of potabilization sludge are much less than clayey sedi- get more reliable comparison with an industrial reference provided
ments. Hence, it is quite difficult to organize a feasible industrial by a local company. The same aggregate distribution of the indus-
production with a 70/30 sludge to sediment ratio. For the two trial reference was used, as shown in Fig. 3. Furthermore, one of the
remaining pastes, namely P2 and P3, four different binder to sand mixes was realized using CE-marked recycled aggregates provided
18 F. Messina et al. / Construction and Building Materials 133 (2017) 14–26

by IPS company (Benevento, Italy), with commercial labels bricks are reported in Table 4. The mixtures are also reported in
Ò Ò
SABB1-L (maximum aggregate size 4 mm) and SABB2-L (maxi- order of preparation (from B1 to B5), with binder to aggregates
mum aggregate size 6 mm). In order to realize prototypes of paving ratio gradually reducing in order to obtain desired workability,
eco-bricks, a pressure forming was applied after casting to repli- which is very low in precast paving bricks. The five brick mixtures
cate the operating conditions of industrial plants high pressure were cured at 20 °C for seven days.
forming bricks equipment is usually employed (Fig. 4). The forming After curing, the realized prototypes of paving bricks, were
load was applied by means of a mechanical testing frame model tested from a mechanical point of view according to European
50-C5600 provided by Controls. The forming load was fixed equal standard EN 1338 [59]. Particularly, the splitting tensile strength
to 0.4 MPa and was applied after casting and vibratory operations. (T) was evaluated, by means of the following formula:
Additionally, the CCS fraction was subjected also to a fast cooling
F
procedure in order to check potential effects in terms of increased T ¼ 0:637  k  ð1Þ
reactivity in alkaline environment. The compositions of paving aspl t

Fig. 4. Pressure forming equipment used by the industrial reference (A) and laboratory equipment (B).

Table 4
Compositions of bricks mixtures.

B1 B2 B3 B4 B5
CCS/WPS 50/50 50/50 50/50 50/50 50/50
Binder/sand (mass) 0.79 0.72 0.63 0.43 0.66
CCS cooling Slow Slow Slow Fast Fast
Aggregates type Natural Natural Natural Natural Recycled

Fig. 5. Scheme of upscaling process from binder optimization to prototype realization.

Table 5
Chemical compositions of the investigated wastes.

Waste SiO2 Al2O3 CaO Fe2O3 K2O MgO TiO2 Na2O SO3 P2O5 LOI
Clayey sediments 50.95 16.86 7.90 6.39 2.37 1.98 0.77 0.70 0.21 0.15 12.40
WP sludge 34.64 28.07 4.41 4.67 1.47 1.44 0.50 0.23 0.55 0.42 23.80
 F. Messina et al. / Construction and Building Materials 133 (2017) 14–26 19


where k¼
1:3
2 t > 180 mm ; F=
(ITZ) on mechanical properties. In literature, it was highlighted
1:3  30 0:18  1000t
40 mm 6 t 6 180 mm that geopolymer matrices might form a strongly reduced ITZ in
failure load; aspl = splitting length; t = thickness of the sample. terms of thickness and, so, improve the adhesion between matrix
The general upscaling procedure is summarized in Fig. 5. The and aggregates [60].
main knowledge inputs of each step are highlighted. The process
is composed by three main phases (pastes, mortars, blocks). Since 3. Experimental results and discussion
the goal of the upscaling procedure is to develop a prototype of
paving bricks, it needs to be clarified which are the main features 3.1. Results of chemical characterization of sediments and sludge and
of this composite material: (i) no-flow fresh concrete behavior in effects of calcination
order to keep the shape pre-formed by means of vibro-
compacting equipment; (ii) sufficient mechanical performance at Chemical compositions of both sediments and sludge obtained
early age in order to favor plant operation and subsequent trans- by means of XRF were reported in Table 5. Clayey sediments had
port; (iii) low cost in terms of raw materials and process parame- a very different composition respect to typical values of commer-
ters. In order to satisfy the latter aspect, it is clear that avoiding the cial metakaolin, which generally exhibits SiO2 + Al2O3 > 90%. A sig-
use of expensive raw materials (e.g. chemical admixtures, special nificant amount of CaO and Fe2O3 was also detected. In the case of
cements, fibers, etc.) and energy intensive curing patterns (e.g., water potabilization sludge, the alumina content is quite relevant,
T P 40 °C) would represent a clear advantage, and the designed reaching a Si/Al ratio equal to 1.05, which is significantly lower
upscaling procedure is able to describe properly all these aspects. than value detected for sediments (Si/Al = 2.58). Minor contents
Furthermore, passing from binding pastes to mortars (adding EN- of CaO and Fe2O3 were detected also for sludge, even if the sum
standard sand) and, finally, to concrete bricks (considering both was lower than the case of sediments by 57.4%. Analysis of con-
natural and CE-marked recycled aggregates), it is possible to taminants (heavy metals and organic compounds) revealed no sig-
understand better the influence of interfacial transition zone nificant issues respect to environmental legislation in force, hence
it was not reported in the present work. The sediments can be clas-
sified as non-hazardous wastes.
In Fig. 6, the TGA results were reported. Mass loss cannot be
only associated to dehydroxylation of kaolinite, but it also depends
on other processes such as calcination of other alumino-silicate
species or oxidation of algae and other organic residues. In Figs. 7
and 8, the results of XRD analyses were reported. In the case of
clayey sediments (Fig. 7), the main detected mineralogical phases
were: quartz, calcite, kaolinite, illite, smectite and albite. In the
case of water potabilization sludge (Fig. 8), the main detected
phases were: quartz, calcite, kaolinite, smectite, muscovite and
magnetite.
In Figs. 9 and 10, results of FTIR analysis for calcined sediments
and sludge, respectively, were reported. In Fig. 5, related to sedi-
ments, a peak at 3697 cm1 can be observed, which is associated
to another peak at 912 cm-1. This distribution can be attributed
to the presence of kaolinite and it was not found after calcination.
A similar observation can be done for the distribution of peaks
(namely, 1429 cm1 and 875 cm1) which is associated to calcium
Fig. 6. TGA of sediments and sludge. carbonate. These results are in good agreement with other litera-
ture studies [55–57]. On the other hand, the interpretation of

Fig. 7. XRD analysis of clayey sediments.

20 F. Messina et al. / Construction and Building Materials 133 (2017) 14–26

Fig. 8. XRD analysis of water potabilization sludge.

Fig. 9. FTIR analysis of sediments as-received and after calcination at 750 °C.

results related to the sludge is more complex and no consistent temperature to check if potential mechanical improvement could
observations can be deduced. be obtained. Results were reported in Fig. 12. It was observed that
the range of compressive strength values was similar respect to
3.2. Mechanical properties and upscaling from binders to precast eco- previously obtained ones (Fig. 11), except that for P1 system,
bricks where CCS/WPS ratio was equal to 30/70. P1-60 exhibited a
reduced mechanical performance respect to P1-20. For this reason,
In Fig. 11, the mechanical properties of specimens were and considering that from a reservoir management perspective it is
reported. Three different CCS/WPS were tested for two different not frequent to have greater volumes of sludge respect to
curing periods. Two main observations can be deduced. First, sediments, this binding system was excluded from subsequent
for all the designed binders, significant mechanical strength upscaling phases. Supplementary experiments will be carried out
development after first week can be detected for the proposed to assess this peculiar behavior.
application. In Figs. 13–15, the SEM images related to all the investigated
Secondly, the compressive strength values were in a narrow paste samples were presented. These images were taken on frac-
range, namely 17.9–22.9 MPa. The observed mechanical perfor- ture surface of samples after curing for 7 days.
mance allowed to move to the second step of upscaling process. The system P2 showed limited microcracking patterns for the
Before considering upscaled materials, the mechanical tests related sample cured at 20 °C. This result is not in agreement with
to paste samples were repeated considering a higher curing mechanical results but can be associated with sample preparation.
 F. Messina et al. / Construction and Building Materials 133 (2017) 14–26 21

Fig. 10. FTIR analysis of sludge as-received and after calcination at 750 °C.

the possibility of obtaining a properly developed geopolymeric

microstructure starting from calcination of very poor natural waste
materials, and the results are in good agreement with mechanical
testing outcomes.
In Fig. 16, the results related to mortars were reported. Four dif-
ferent binder/sand mass ratios were investigated, namely 1.88 (M1
and M2), 1.25 (M3 and M4), 0.94 (M5 and M6) and 0.63 (M7 and
M8). For the highest binder/sand ratio (i.e., 1.88 associated to M1
and M2), the observed compressive strength values were quite
similar to ones observed for the same pastes (i.e., P2 and P3) after
7 days curing at 20 °C. Particularly, compressive strength values
equal to 17.4 and 16.9 MPa were detected for M1 (CCS/
WPS = 70/30) and M2 (CCS/WPS = 50/50), respectively. These val-
ues were modified according to changes in binder/san ratio. Red
and blue lines indicate a similar trend for the same CCS/WPS ratio.
The worst packing conditions were observed for binder/sand
ratios equal to 1.25 and 0.63. In all the cases, mortars realized
Fig. 11. Compressive strength at 7 and 28 days of geopolymer specimens after starting from binder P2 (CCS/WPS = 50/50) exhibited higher values
curing at 20 °C.
of compressive strength, even if a significant reduction of mechan-
ical performance was observed.
For the final upscaling step, only 50/50 CCS/WPS ratio was con-
sidered. The precast paving brick realized in laboratory by means
of vibro-compacting operations was reported in Fig. 17 together
with the standard geometry used for the construction of pave-
ments. The produced concrete bricks were tested according to EN
1338 for splitting tensile strength. Results were reported in
Fig. 18. Splitting tensile strength values ranged from 0.82 to
2.01 MPa. EN 1338 requires a minimum characteristic tensile split-
ting strength equal to 3.6 MPa, which could be converted to mean
tensile strength equal to 3.9 MPa [61]. These values can be
achieved after 28 days with cement-based bricks. In our case,
results related to geopolymer-based bricks after 7 days curing at
20 °C were reported. Soutsos et al. [61] reported values ranging
from 1.5 to 3.8 MPa after 28 days curing for standard blocks real-
ized by only substituting natural aggregates with recycled concrete
aggregates. Gencel et al. [62] obtained splitting tensile strength
values ranging from 3.7 to 5.4 MPa after 28 days curing for a set
Fig. 12. Compressive strength at 7 and 28 days of geopolymer specimens after
of cement-based bricks realized with a high content of cement,
curing at 60 °C for 1 d. namely 400 kg/m3, and substituting part of the natural aggregates
with wastes of marble industry. Uygunoğlu et al. [63] observed
In the case of system P3, deductions are quite similar to the case of splitting tensile strength values ranging from 3 to 5 MPa after
P1, with very limited modifications of the microstructure at 7 days. 28 days curing for blocks realized substituting part of the cement
Generally, it can be stated that microstructural analysis confirms with fly ash. Hence, it can be observed that characteristic and mean
22 F. Messina et al. / Construction and Building Materials 133 (2017) 14–26

Fig. 13. SEM images (5000 magnification) for system P1 cured at different temperature.

Fig. 14. SEM images (5000x magnification) for system P2 cured at different temperature.

Fig. 15. SEM images (5000x magnification) for system P3 cured at different temperature.

splitting tensile values are not easy to be obtained. In the case of former case natural aggregates and in the latter one CE-marked
the present study, cement-free bricks are realized and, addition- recycled ones.
ally, the curing is limited to 7 days and curing temperature is The effect of rapid cooling is beneficial for the produced bricks,
reduced at 20 °C. In this scenario, obtained values can be consid- since a significant strength increase at the early age is observed.
ered a satisfactory prototype for final industrial upscaling after fur- The results related to B4 and B5 allow to propose these materials
ther optimization of the processes and the materials. Rapid cooling for effective use in a more sustainable building materials industry.
of CCS was carried out for prototypes B4 and B5, considering in the In the case of B5, an additional benefit was represented by the use
 F. Messina et al. / Construction and Building Materials 133 (2017) 14–26 23

Fig. 16. Compressive strength at 7 d of geopolymer mortars in function of binder/ Fig. 18. Compressive strength at 7 d of geopolymer mortars in function of binder/
sand and CCS/WPS ratios. sand and CCS/WPS ratios.

of recycled aggregates, thus reducing the embedded environmental environment, where a very aggressive environment with intensive
impacts related to quarrying activities. The worst packing condi- water washing/abrasion phenomena can occur. Anyway, prelimi-
tion was observed in correspondence of B1 mixture for which a nary evaluation of potential harmful durability issues can be pro-
binder/aggregates ratio equal to 0.79 was used. Despite what vided by visual inspection of samples stored for six months at
observed for mortars, in the case of geopolymer concrete bricks, 20 °C ± 1 and RH = 50% ± 2 (Fig. 20). The sample exhibited no crack-
the effect of pressure-forming of the material is able to mitigate ing neither efflorescence. In a recent publication [64], efflorescence
and even invert the detrimental effect of reduction of binder/sand was presented as one of the main potential durability problems for
ratio. alkali activated metakaolin geopolymeric materials. In the case of
In Fig. 19, XRD analysis related to two differently cooled CCS the present study, a poorer aluminosilicate source, namely CCS
samples were reported in order to provide insight into the from dredging activities, was employed allowing to achieve inter-
improvement of mechanical performance in bricks brought by esting engineering performance. The role of WPS was quite rele-
rapid cooling (see Fig. 18). It can be observed that, due to dramatic vant in polycondensation kinetics, since the regulation of Na2O/
reduction in cooling period (from 2 hours down to few minutes), a Al2O3 molar ratio allowed to properly bind sodium cations in
general reduction of peak intensity can be detected and, in some geopolymeric structure by means of charge balancing. Particularly,
cases, the disappearance of some peaks can be assessed. These this ratio is equal to 0.85 for P2, representing an optimized choice
results provide a partial clarification of results related to splitting at the present state of the research. The reduction of efflorescence
tensile testing. was also favored by low calcium content of sediments [65]. Fur-
Starting from the main outcomes of this study, several improve- thermore, in all the samples as in Fig. 20, a general reduction in
ments can be achieved with future studies. First, dealing with mix plastic/drying shrinkage cracking was observed and this represents
design, beneficial strategy to obtain a strength gain from 7 to an important advantage respect to other systems with higher early
28 days needs to be found, and a solution might derive from the age reactivity, such as metakaolin-based ones, which usually exhi-
introduction in the mix of a secondary aluminosilicate source to bit significant shrinkage phenomena [66].
improve reactivity. A more articulate curing cycle might be It can be finally observed that several technologies are already
designed to obtain higher reactivity after early age. Secondly, dura- available for an improved sediment management but enhance-
bility assessment needs to be carried out since the main use of the ment of environmental legislation is needed to favor the rise of
designed precast geopolymer concrete paving bricks is outdoor practical outcomes [67].

Fig. 17. Prototype of paving eco-brick realized to synergistic use of geopolymerized CCS and CWPS.
24 F. Messina et al. / Construction and Building Materials 133 (2017) 14–26

Fig. 19. XRD analysis of CCS samples with different cooling velocities.

usually characterized according to EN 1338 standard. These mate-

rials are generally realized in many factories operating on Italian
territory, and the recipe is quite simple and relies on a cementi-
tious binder, water and aggregates. The mixture is tailored on a
cost-oriented basis since the produced materials need to be sold
at low prices, hence, no particular raw materials or special
chemical admixtures can be used. In our case, we propose the
use of residues coming from hydraulic reservoir management,
which are usually destined to landfill. The process presents the
following advantages:

The hydraulic storage capacity of the reservoir (e.g., dam) is

resumed.

The structural safety and serviceability of threatened infrastruc-
tures is ensured (see Fig. 2).

The residues are recovered in an economically productive way
in order to produce building materials.

The production of precast elements allows to overcome differ-
ent evolutions of raw materials production (mainly associated
Fig. 20. Surface morphology of P2-20 sample after 6 months exposure at room
conditions.
to dredging activities, which are periodical) and building mate-
rials demand, which is associated to demographic/economic
growth.

The total substitution of cement with calcined residues repre-
4. Conclusions sents a milestone environmental benefit since clinker produc-
tion is one the main highly polluting anthropic activities, and
In this study, the innovative synergistic use of calcined water tremendous research effort was produced in the last years to
potabilization sludge (CWPS) in combination with calcined clay minimize these effects.
sediments (CCS) as solid precursors for geopolymer materials
was proposed. Particularly, starting from the chemical characteri-
zation of residues and analysis of calcination effects, an upscaling Acknowledgements
process was carried out in order to carefully observe all the
aspects related to a specific potential application field. This is The authors acknowledge Prochin and IPS companies for
intended in order to give an effective contribution to the lack of sodium silicate solution and CE-marked recycled aggregates sup-
industrial activities related to the geopolymers in Italy and other ply, respectively. Special thanks are due to engineers Augusta De
European countries. The case study considered is the production Santis, Mario Elefante and Fulvio Pannone for assistance in labora-
of paving concrete bricks for non-structural elements, which are tory procedures.
 F. Messina et al. / Construction and Building Materials 133 (2017) 14–26 25

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