Journal of Cleaner Production 231 (2019) 54e63

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Journal of Cleaner Production

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

Potential use of sugarcane bagasse and bamboo leaf ashes for

elaboration of green cementitious materials
Loïc Rodier a, *, Ernesto Villar-Cocin
~ a b, Julian Mejia Ballesteros a,
Holmer Savastano Junior a
a
Department of Biosystems Engineering, Faculty of Animal Science and Food Engineering, University of Sao Paulo, Duque de Caxias Norte Avenue, 225,
Jardim Elite, 13635-900, Pirassununga, SP, Brazil
b
Central University of Las Villas, Department of Physics, Santa Clara 54830, Cuba

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

Article history: The paper presents the study of pozzolanic activity and hydration of cement pastes containing sugarcane
Received 24 November 2018 bagasse (SCBA) and bamboo leaves ashes (BLA). Pozzolanic activity of binary and ternary mixtures of
Received in revised form ashes was investigated using electrical conductivity measurements. A kinetic-diffusive model was used
15 May 2019
to quantify the pozzolanic reaction between ashes and calcium hydroxide solution. The influence of
Accepted 18 May 2019
Available online 20 May 2019
ashes on hydration of cementitious pastes was also investigated using thermogravimetry analysis, X-Ray
diffraction, isothermal calorimetry and mechanical tests. The results showed that ternary mixtures of
SCBA and BLA have a higher pozzolanic activity than the binary mixture of SCBA. Binary and ternary
Keywords:
Pozzolanic materials
mortars have higher compressive strengths than the control mortar without mineral additives. Moreover,
Binary and ternary binder the replacement of cement by 10 wt% of SCBA and BLA leads to a decrease of the calcium hydroxide
Agroindustrial ashes content and the heat of hydration. The results also showed that the production of 1 ton of binder with
Kinetic parameters agro-industrial ashes needs lower energy than conventional cement. According to the results of the
Eco-efficient cement study, the use agro-industrial ashes in binary and ternary blend cements can bring economic, technical
and environmental benefits for the industrial sector including fiber cement industry, precast plants and
concrete producers.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction et al., 2009).

It is known that the cement industry consumes a lot of energy
and therefore produces a significant amount of greenhouse gas
(Hanle et al., 2004; Van Oss et al., 2002). One of the alternatives to
decrease the quantity of greenhouse is to partially replace the
cement by pozzolanic materials. Mineral additions are widely used
as partial replacement of cement because of their economic, envi-
ronmental and physico-mechanical interests. Agro-industrial
wastes such as rice husk ashes, sugarcane leaves and bagasse
ashes, bamboo leaves ashes, corn cob ashes, banana leaves, palm oil
ashes and elephant grass ashes have shown pozzolanic activity and
have been used as partial replacement in binary blend cements
(Singh et al., 2000; Ganesan et al., 2007; Adesanya, 2001; Zhang
and Malhotra, 1996; Cordeiro et al., 2009a,b; Sata et al., 2004;
Rodier et al., 2017; Dwivedi et al., 2006; Frías et al., 2012; Singh
* Corresponding author.
E-mail address: rodierloic@gmail.com (L. Rodier).
Brazil is the most important producer of sugarcane of the world
and has the greatest native bamboo reserves in the world, reaching
to 180 000 km2 (Judziewicz et al., 1999). In the case of sugarcane,
the production leads to a huge quantity of residue such as sugar-
cane bagasse. For bamboo, only the stalk is used and the leaves are
left on the planting area without interest for the industry. These
residues can be used as renewable energy source to produce elec-
tricity to supply all energy needed in the different factories and the
excess introduced in the public distribution lines (Hofsetz and Silva,
2012). The resulting ashes, from the combustion, can be used as
cement replacement to increase the physical and mechanical
properties of cementitious materials (Morales et al., 2009; Cordeiro
et al., 2009a,b).
In binary binders, the use of sugar cane bagasse and bamboo leaf
ashes was widely studied (Singh et al., 2000; Ganesan et al., 2007;
Cordeiro et al., 2009b; Rodier et al., 2017; Dwivedi et al., 2006; Frías
et al., 2012). The studies showed that the replacement of cement, by
these mineral additives, improves the physical, mechanical

https://doi.org/10.1016/j.jclepro.2019.05.208
0959-6526/© 2019 Elsevier Ltd. All rights reserved.
 L. Rodier et al. / Journal of Cleaner Production 231 (2019) 54e63
properties and the durability of cementitious materials. Singh et al.
(2000) showed that sugarcane bagasse ashes can be considered to a
pozzolanic material due to the consumption of calcium hydroxide
and the increase of compressive strength. The authors showed that
the better percentage of substitution is 10 wt%. Ganesan et al.
(2007) showed that to obtain high early strength, a reduction of
the water permeability and a resistance to chloride penetration, the
cement must be replaced by sugarcane bagasse ashes up to 20 wt%.
Cordeiro et al. (2009b) used pozzolanic activity index and Chapel-
le's method to determine the pozzolanic activity of sugarcane
bagasse ashes. The authors showed that sugarcane bagasse ashes
have a high pozzolanic activity due to the presence of amorphous
silica. Rodier et al. (2017) showed that mortars containing 10 wt% of
sugar cane bagasse ashes provided higher compressive strength
than the control mortars without partial substitution of cement.
Dwivedi et al. (2006) evaluated the pozzolanic activity of
bamboo leaves ashes calcined at 600
C for a potential use in the
cement industry. The authors showed that the fixation of lime in-
creases with time and the pozzolanic activity of the ashes increases
with time and temperature. Frías et al. (2012) showed that the
partial replacement of cement by 10 and 20 wt% of bamboo leaf
ashes leads to mortars with similar mechanical properties than the
control mortars at 28 days. Moreover, the physical properties of
mortars containing bamboo leaf ashes meet the requirements of
standard specifications.
In the case of ternary binders, industrial by-products such as fly
ash (FA), silica fume (SF) and ground granulated blast-furnace slag
(GGBFS) were mainly used due to the synergetic action of both
materials on the properties of the cementitious material (Gesog lu
et al., 2009; Bagheri et al., 2012). Many studies showed that the
combination of FA, SF or GBFS in ternary blended cement materials
improves the compressive strength and the durability (Nochaiya
et al., 2010; Alexander and Magee, 1999). However, existing few
studies on the combination of by-products from agricultural wastes
such as sugar cane wastes, rice husk, bamboo leaf or bamboo culm
ashes in ternary blended cement materials. Cordeiro et al. (2012)
studied the use of rice husk and sugar cane ashes in binary and
ternary conventional and high strength concretes. The authors
showed that ternary concretes have intermediate values between
rice husk ashes (RHA) and sugarcane bagasse ashes (SCBA) binary
mixtures as well as a significantly decrease of the maximum
adiabatic temperature rise for conventional concretes. Ettu et al.
(2013) studied the potentiality of use rice husk and saw dust
ashes in binary and ternary blended cement concretes. From 10 wt%
of cement replacement, the authors showed that ternary concretes
elaborated with rice husk and saw dust ashes have higher
compressive strengths than binary concretes elaborated with saw
dust ashes. The authors explained this behavior is due to the pro-
duction of additional calcium silicate hydrates (CeSeH) produced
during the pozzolanic reaction between the amorphous silica and
the calcium hydroxide.
All studied cited showed that the pozzolanic activity of the ashes
is due to the capacity to react with calcium hydroxide, produced
during the cement hydration, to produce calcium silicate hydrates.
This reaction is also known as the pozzolanic reaction. To evaluate
the pozzolanic activity of a material, the electrical conductivity
method is commonly used (Luxa n et al., 1989; Paya et al., 2001;
Villar-Cocin~ a et al., 2003; Wansom et al., 2017). This method is
based on the variation of the electrical conductivity of a saturated
calcium hydroxide containing the material. The amorphous silica
present in the material reacts with the calcium hydroxide to pro-
duce CeSeH (Eqs. (1) and (2)). The fixation of calcium ions by the
material leads to the decrease of the electrical conductivity of the
solution, showing the pozzolanic behavior of the material.
55
Ca(OH)2 þ H4SiO4 / Ca2þ þ H2SiO2
4 þ 2H2O (1)
Ca2þ þ H2SiO2
4 þ 2H2O / CaH2SiO4.2H2O (2)
The aim of this study is to investigate quantitatively the pozzo-
lanic activity of the combination of sugar cane bagasse ashes (SCBA)
and bamboo leaf ashes (BLA) in saturated calcium hydroxide solu-
tion using a mathematical model. Secondly, the influence of these
ashes on the hydration of binary and ternary blend cement was
studied using X-Ray diffraction, isothermal calorimetry, thermog-
ravimetry analysis and compressive strength tests for a potential
application in cementitious materials. Finally, the environmental,
economic and technical impacts of these ashes on the production of
cement and cementitious materials were evaluated.
2. Materials and methods
2.1. Materials
The bamboo leaves were collected in the University of Saeo Paulo,
Pirassununga Campus, Brazil. Sugar cane bagasse was collected in
the Abengoa sugar cane factory (Pirassununga, Brazil).
Sugar cane bagasse and bamboo leaves were primarily calcined
in a muffle furnace (JUNG 10010, Brazil) at 400
C for 60 min to
remove organic matter. Then, calcined at 700
C for 60 min for
sugar cane bagasse (Cordeiro et al., 2008) and 600
C for 60 min for
bamboo leaves (Dwivedi et al., 2006; Villar-Cocin~ a et al., 2006) with
a heating rate of 10
C/min. For these temperatures, the pozzolanic
activity of the resulting ashes is the higher. A rapid cooling was
carried out from muffle furnace temperature (600 or 700
C) to
room temperature to obtain an amorphous structure. The ashes
obtained were passed through a sieve opening of 45 mm. According
to the curves of the particle size distribution of the ashes, deter-
mined using a laser diffraction particle analyzer (CILAS, Brazil) in
liquid mode, all ashes have a fine particle size with a median size of
6.41 and 21.41 mm for sugar cane bagasse ashes (SCBA) and bamboo
leaf ashes (BLA), respectively. The difference between the particle
sizes is mainly due to the nature of both grasses.
2.2. Methods
2.2.1. Chemical characteristics
The chemical composition of ashes and the cement was carried
out by the X-Ray Fluorescence (XRF), using the Philips Venus 100
minilab XRF Spectrometer. The mineralogical characterization was
carried out in a Rigaku Miniflex 600 X-Ray Diffractometer.
2.2.2. Pozzolanic activity in saturated calcium hydroxide solution
The pozzolanic reaction of ashes was evaluated by electrical
conductivity method. 250 mL of saturated Ca(OH)2 solution were
mixed with 5.25 g of ashes and magnetically stirred at 40
C. All
measurements began immediately after the introduction of ashes
in the saturated Ca(OH)2 solution. The mixture formulations are
shown Table 1.
Table 1
Mixtures of ashes-calcium hydroxide solution.
Samples SCBA (g) BLA (g) Saturated calcium hydroxide solution (mL)
50SCBA50BLA 2.625 2.625 250
60SCBA40BLA 3.150 2.100 250
70SCBA30BLA 3.675 1.575 250
100SCBA 5.250 0 250
100BLA 0 5.250 250
~a
A mathematical model is used to quantify the pozzolanic reaction (Villar-Cocin
et al., 2003). The model is presented in Eqs. (3) and (4).
56 L. Rodier et al. / Journal of Cleaner Production 231 (2019) 54e63

b ¼ (X0  Xt)/X0 (3) Table 3

Mix proportions of mortars.

b ¼ 1 e [(0.23 * Exp(-3t/ t)*(-1 þ Exp(t/ t)) * (1/ t)) / (X0 * De* Samples Cement (%) SCBA (%) BLA (%) Sand/Cement Water/Binder
rs)] þ [0.23 * Exp(-t/ t) * (1/ t) / (X0 *K * rs)] (4) Control 100 0 0 3 0.5
BLA10 90 0 10 3 0.5
Where, De is the effective diffusion coefficient, K is the reaction SCBA10 90 10 0 3 0.5
rate constant, t is a constant of time and b represents the relative BLA20 80 0 20 3 0.5
SCBA20 80 20 0 3 0.5
loss of conductivity of the solution, rs is the initial radius of the
BLA5SCBA5 90 5 5 3 0.5
particle and X0 and Xt are the conductivity of the solution at t ¼ 0 BLA10SCBA10 80 10 10 3 0.5
and time t, respectively.
More details about the model are presented in Villar-Cocin ~a
et al. (2003). Table 4
Chemical composition of the materials.
2.2.3. Study of blended cementitious pastes
Components (%) SCBA BLA Cement CPV ARI
Thermogravimetric analysis was performed in a simultaneous
thermal analyzer NETZSCH STA 409 PC/PG. The mix proportions MgO 4.750 1.840 2.340
Al2O3 12.300 0.632 3.670
and water amount for cementitious pastes were summarized in SiO2 36.200 70.500 15.900
Table 2. P2O5 5.420 1.670 0.204
All cementitious pastes were cured in water at room tempera- SO3 4.380 2.870 4.750
ture for 28 days. After curing, the hydration of cement pastes was Cl 0.171 0.851 0.040
K2O 12.800 5.140 1.260
stopped using acetone, then the samples were dried in a oven at
CaO 7.100 7.860 67.700
60
C up to constant weight and putted in a desiccator under vac- TiO2 1.980 0.063 0.283
uum atmosphere before testing. Cementitious pastes were MnO 0.303 0.345 0.079
analyzed under nitrogen atmosphere as a purge gas at a flow rate of Fe2O3 8.760 0.468 2.990
40 mL/min and protective gas at a flow rate of 20 mL/min. The CuO 0.028 0.010 0.008
ZnO 0.085 0.010 0.034
heating rate was 10
C/min from 30 to 1000
C. LOI 5.370 7.790 e
The mineralogical phases of cementitious pasted was deter-
mined in a Rigaku Miniflex 600 X- Ray Diffractometer using the
random power method operating from 5
to 65
2q at a rate of 2
/
component following by K2O, Al2O3, Fe2O3, CaO, P2O5, MgO, SO3
min.
and TiO2. In bamboo leaf ashes (BLA) the major component is SiO2
The isothermal calorimetry study in the pastes was conducted in
following by CaO, K2O, SO3, MgO and P2O5.
an isothermal calorimeter TAM Air (TA Instruments). The dried
The presence of silica in both ashes is due to the absorption of
cement powder was added to the flask and the water added with a
the silicic acid from the soil and then the deposition, in amorphous
syringe, keeping a water/binder ratio equal to 0.4. The monitoring
form, in all parts of plant such as stem and leaves (Norsuraya et al.,
of the heat released during the hydration of the binder was carried
2016). The sum of SiO2, Al2O3, and Fe2O3 for SCBA, and BLA are 57.26
out for 48 h. The temperature of the calorimeter was maintained at
and 71.66% respectively. The difference between the chemical
25
C during the experiment.
composition of SCBA and BLA is due to the difference of the nature
of grass precursors, the maturity and the nature of the soil where
2.2.4. Study of blended mortars
they were collected. SCBA has the highest content of K2O (12.80% by
Cylindrical specimens of mortar (diameter ¼ 4 cm,
mass); the presence of K2O in the ashes is due to the use of fertil-
length ¼ 8 cm) were elaborated using cement, sand and agro-
izers for the sugarcane cultivation. The alkaline ions can lead to the
industrial ashes (Table 3).
alkali-aggregate reaction, which is a reaction between the silica
After casting, mortars were kept in molds for 24 h. Then, mor-
present in the aggregate and the alkaline ions (Kþ, Naþ). This re-
tars were cured in water at room temperature for 7 and 28 days.
action (Eq. (5)) causes severe deteriorations by producing silica-
After curing, the compressive strength of mortars was determined
rich gels capable of swelling and cracking the cementitious mate-
using a universal testing machine EMIC DL3000 with load speed of
rial such as concrete structures (West, 1996). However, some au-
0.5 mm/min. Four specimens for each mixture were tested to
thors already showed that sugarcane bagasse ashes with high K2O
determine the compressive strength. The water/cement ratio was
content (9 wt%) can be used as mineral additive in cementitious
fixed according to NF EN 196-1 (2016).
materials (Cordeiro et al., 2009a,b).

3. Results and discussion

SiO2þ 2NaOH þ H2O / Na2SiO3.2H2O (5)

3.1. Characterization of ashes

The equation can be also written replacing sodium (Na) by po-
tassium (K).
Table 4 shows the chemical composition of the cement and
The sum of SiO2, Al2O3, and Fe2O3 of both ashes is higher than
ashes. In sugar cane bagasse ashes (SCBA), silica (SiO2) is the major
the minimum value (50%) specified by ASTM C618 (2012), which is
a condition to be considered as a pozzolanic material for use as
Table 2 partial replacement of cement.
Mix proportions of cementitious pastes. Moreover, the loss of ignition of all ashes is less than 10 wt%,
which indicates that the temperature of calcination adopted is
Samples Cement (%) SCBA (%) BLA (%) Water
sufficient to remove organic matter and volatile compounds.
Control 100 0 0 0.5
The XRD patterns of SCBA and BLA are shown in Fig. 1. All ashes
80CEM20SCBA 80 20 0 0.5
80CEM20BLA 80 0 20 0.5 have a broad band localized between 2q ¼ 15
and 2q ¼ 35
, which
80CEM10SCBA10BLA 80 10 10 0.5 is characteristic of amorphous material (Morales et al., 2009; Villar-
 L. Rodier et al. / Journal of Cleaner Production 231 (2019) 54e63 57

Silvite
16000
Quartz
14000 Calcite

12000

10000
Intensity (u.a.)

8000

6000

4000 SCBA

2000
BLA
0
10 20 30 40 50 60 70
2 (°)

Fig. 1. X-Ray Diffraction (XRD) patterns of SCBA and BLA.

Cocin~ a et al., 2011). 3.2. Pozzolanic activity

Moreover, quartz is the main crystalline phase present in all
ashes. The presence of quartz is due to the temperature of calci-
nation of both sugarcane bagasse and bamboo leaves. Indeed,
depending of the temperature, silicon dioxide has three poly-
morphs and each transformation has two transformations (a and
b). The stable form of silicon dioxide is the quartz in a-form at
573
C and b-form up to 870
C (Guthrie and Heaney, 1995).
The percentage of amorphous phase (%AP) is determined ac-
cording to Eq. (6) (Saleki-Gerhardt et al., 1994):
%AP ¼ AP / (CP þ AP)
Where AP is the area of amorphous phase and CP is the area of each
crystalline phases.
In BLA and SCBA, the amorphous phase represents 32.26% and
9.84% respectively.
Fig. 2 shows the conductivity versus time for 100SCBA, 100BLA,
70SCBA30BLA, 60SCBA40BLA, 50SCBA50BLA. A decrease of the
electrical conductivity of the ashes/calcium hydroxide system is
observed for all samples. The greater the change in the electrical
conductivity of saturated solution with the mineral addition is, the
higher pozzolanic activity the mineral has.
This behavior is attributed to the pozzolanic reaction between
amorphous silica and lime, which produce CeSeH (Villar-Cocin ~a
et al., 2011). The electrical conductivity is related to the concen-
(6) ~ a et al., 2003). The
tration of ions Ca2þ in the solution (Villar-Cocin
decrease of the concentration of Ca2þ in the solution leads to a
decrease of the electrical conductivity.
From 0 to 10h, the fixation of calcium hydroxide is higher for
100BLA followed by 60SCBA40BLA, 50SCBA50BLA, 70SCBA30BLA
and 100SCBA. For binary mixtures, 100BLA has a higher fixation of
calcium hydroxide than 100SCBA. This result shows that, in ashes/

100SCBA 100BLA 30BLA70SCBA 40BLA60SCBA 50BLA50SCBA

9

7
Conductivity (mS/cm)

1
0 10 20 30 40 50 60 70
Time (hours)

Fig. 2. Electrical conductivity of the solutions containing ashes.

58 L. Rodier et al. / Journal of Cleaner Production 231 (2019) 54e63

Table 5
Kinetic parameters of the pozzolanic reaction.

Samples t (h) Reaction rate constant K (h-1) Correlation coefficient (r) Coefficient of multiple determination (R2) Residual sum of squares

50SCBA50BLA 5.6 ± 0.2 (3.83 ± 0.02).10-1 0.9880 0.9863 0.062

60SCBA40BLA 3.6 ± 0.1 (6.18 ± 0.03).10-1 0.9810 0.9780 0.041
70SCBA30BLA 4.5 ± 0.2 (2.89 ± 0.03).10-1 0.9875 0.9810 0.042
100SCBA 5.3 ± 0.06 (1.85 ± 0.004).10-2 0.9970 0.9952 0.003
100BLA 2.9 ± 0.07 (10.02 ± 0.03).10-1 0.9902 0.9873 0.057

calcium hydroxide system, the dominant factor that dictates the
pozzolanic reaction is the degree of amorficity of the material and
the amount of reactive SiO2. As seen in session 3.1, BLA has a high
content of silica and amorphous phase.
For ternary mixtures, the higher reactivity is obtained by
60SCBA40BLA followed by 50SCBA50BLA, 70SCBA30BLA. Theoret-
ically, the higher content of silica is, the higher fixation of calcium
hydroxide. However, 60SCBA40BLA has a higher fixation of calcium
hydroxide than 50SCBA50BLA. This result can be explained by the
presence of higher fine particles in SCBA than BLA, which increases
the fixation of calcium hydroxide.
Table 5 indicates the results of kinetic parameters of the
pozzolanic reaction in ashes/calcium hydroxide system. The K value
directly reflects the reactivity of ashes and is a direct index of the
pozzolanic activity. According to the results of Table 5, the lower
reactivity is obtained for sugar cane bagasse ashes (100SCBA) and
the higher for bamboo ashes (100BLA). These results are compa-
rable with those obtained for sugar cane bagasse ashes and bamboo
leaf ashes found in the scientific literature (Villar-Cocin ~ a et al.,
2003; 2009). For ternary mixtures, 60SCBA40BLA has the highest
reactivity.
3.3. Thermogravimetry analysis (TG)
band between 105 and 200
C is higher for 80CEM20BLA at 28 days
of curing, which means a higher amount of products of hydration
such as CeSeH and ettringite in the sample.
The band between 350 and 550
C is related to the decompo-
sition of calcium hydroxide (Ca(OH)2) formed during hydration (Eq.
(7)) (Alarcon-Ruiz et al., 2005):
Ca(OH)2 ¼ CaO þ H2O (7)
All bands of 80CEM20SCBA, 80CEM20BLA and 80CEM50SC-
BA50BLA have a lower intensity than that of the Control, which
means the amount of calcium hydroxide in these specimens, is
lower than the one of the Control. According to the weight losses
determined from TG data (Table 6), the replacement of cement by
20 wt% of ashes in binary and ternary binders leads to a decrease of
about 32% of the amount of calcium hydroxide. The reduction of the
calcium hydroxide content is interesting for applications in fiber
cement industry for example. Indeed, the calcium hydroxide
decrease the durability the cementitious composites, the partial
substitution of cement by sugarcane bagasse or bamboo ashes
could be a solution to improve the durability of these materials.
The third stage of decomposition, between 600 and 850
C, is
related to the decarbonation of calcium carbonate (CaCO3) in the
cementitious paste (Eq. (8)) (Alarcon-Ruiz et al., 2005):

The results of TG/DTG of blended cementitious pastes contain- CaCO3 ¼ CaO þ CO2 (8)
ing SCBA and BLA are given in Figs. 3 and 4.
TG curves indicate 3 stages in the decomposition of cementi- Two peaks can be observed in the stage of decarbonation of
tious pastes. Temperatures from 105 to 200
C induce the thermal CaCO3, the first (between 600 and 700
C) is related to the decar-
decomposition of CeSeH gel, ettringite and gypsum, from 200 to bonation of poorly crystalline CaCO3 and the second (between 700
350
C the thermal decomposition of C3A and C4AF. In Fig. 4, the and 770
C) to well crystalline CaCO3.

100

Control
95
80CEM20SCBA

80CEM20BLA
90 80CEM10SCBA10BLA
Mass (%)

85

80

75
0 100 200 300 400 500 600 700 800 900 1000
Temperature (°C)

Fig. 3. TGA of binary and ternary cementitious pastes containing SCBA and BLA at 28 days.
 L. Rodier et al. / Journal of Cleaner Production 231 (2019) 54e63 59

0 100 200 300 400 500 600 700 800 900 1000
0

-0.2

-0.4
DTG (%/min)

-0.6
Control

-0.8
80CEM20SCBA

-1 80CEM20BLA

80CEM10SCBA10BLA
-1.2
Temperature (°C)

Fig. 4. DTG of binary and ternary cementitious pastes containing SCBA and BLA at 28 days.

Table 6
Weight losses (%) of the cementitious pastes at different temperatures.

Temperature (
C) Control 80CEM20SCBA 80CEM20BLA 80CEM10SCBA10BLA

60e350 11.03 11.40 11.70 11.61

350e550 24.45 16.20 16.61 16.18
600e700 3.27 3.72 4.28 4.08
700e770 3.54 3.27 3.25 3.32

3.4. X-ray diffraction
Fig. 5 shows the mineral phases present in Control,
80CEM20SCBA, 80CEM20BLA and 80CEM10SCBA10BLA after 28
days of curing. In Control, calcium hydroxide, quartz, calcite, alite
and CeSeH are identified.
The same phases are identified in binary and ternary blended
pastes. In comparison to the control specimen, a decrease of the
intensity of all peaks related to calcium hydroxide is observed in all
samples containing mineral additives and is more pronounced for
80CEM20BLA. This result is consistent to the reduction of the
amount of calcium hydroxide in the thermogravimetry analysis.
3.5. Isothermal calorimetry
Fig. 6 shows the heat of hydration of all cementitious pastes for
48 h. In the case of binary and ternary cementitious, all specimens
indicate a decrease of total heat of hydration. The higher reduction
is obtained by the paste containing 20 wt% of SCBA (25% in com-
parison to Control), whereas the combination of SCBA and BLA with

Calcium hydroxide
Quartz
Calcite
Alite/CSH 80CEM10SCBA10BLA
Intensity (u.a.)

80CEM20BLA

80CEM20SCBA

Control

0 10 20 30 2 (°) 40 50 60 70

Fig. 5. X-Ray Diffraction (XRD) patterns of binary and ternary cementitious pastes containing SCBA and BLA at 28 days.
60 L. Rodier et al. / Journal of Cleaner Production 231 (2019) 54e63

0.01

Control
0.008
80CEM20SCBA

Heat of hydration (W/g) 80CEM20BLA

0.006 80CEM10SCBA10BLA

0.004

0.002

0
0 12 24 36 48
Time (hours)

Fig. 6. Heat of hydration of cementitious pastes.

cement leads to a decrease of 12% of the heat of hydration in
comparison to Control (without mineral addition). This behavior is
mainly due to the dilution effect when pozzolanic materials
partially replace cement. The decrease of the heat of hydration can
be explained by the modification of the chemical composition of
blended cement. Several constituents of cement such as C3A, C3S
and gypsum significantly influence the heat evolution of cement
(Graham et al., 2011; Bahurudeen et al., 2015). The lower quantity of
these constituents in the binder, due to the replacement of cement
by the ashes, justifies the reduction of the heat of hydration of the
cementitious pastes. A high heat of hydration can cause thermal
cracking in massive structure such as bridges. The use of agro-
industrial residues as partial replacement of cement can reduce
this negative effect.
3.6. Compressive strength
Fig. 7 shows the compressive strength of binary mortars at 7 and
28 days. The compressive strength of mortars increases with the
curing time and the percentage of substitution of cement. This
behavior is mainly due to the formation of hydrates compounds
such as CSH during the hydration reaction of cement and the
pozzolanic reaction (Rodier et al., 2017).
At 7 and 28 days, the mortars containing 20 wt% of sugarcane
bagasse ashes have a higher compressive strength with an increase
of 19 and 31% in comparison to Control (without mineral additives),
respectively. This disagrees with the pozzolanic test (section 3.2)
showing that the bamboo leaf ashes have the higher pozzolanic
activity. This behavior can be due to the effect of the particles of
sugarcane ashes, finer than bamboo leaf ashes, which improve the
packing density of the blend. Indeed, SCBA particles occupy the
space between the larger particles (cement) that leads to an in-
crease of the density and the compressive strength of mortars.
The substitution of cement by pozzolanic materials is known to
decrease the initial strength of cementitious materials due to the
dilution effect, which dilute the cement at early ages (Massazza,

60

50
Compressive strength (MPa)

40

30 7 days
28 days

20

10

0
Control BLA10 BLA20 SCBA10 SCBA20
Fig. 7. Compressive strength of binary mortars at 7 and 28 days.
 L. Rodier et al. / Journal of Cleaner Production 231 (2019) 54e63 61

50

45

40

Compressive strength (MPa)

35

30

25 7 days
28 days
20

15

10

0
Control BLA5SCBA5 BLA10SCBA10
Fig. 8. Compressive strength of ternary mortars at 7 and 28 days.

1993). This phenomenon can be observed for the mortars con-
taining 10 wt% of bamboo leaf ashes at 7 days.
Fig. 8 shows the compressive strength of ternary mortars. As
seen for binary mortars, the compressive strength of ternary mor-
tars increases with the curing time and the percentage of substi-
tution of cement.
At 7 and 28 days, the mortars containing 20 wt% of BAM and
SCBA have the highest compressive strengths with an increase of
14% and 25% in comparison to Control mortars, respectively. It can
be observed that, at 28 days, the ternary mortars present inter-
mediate values of compressive strength between both binary
mortars. The increase of the compressive strength of mortars
containing ashes in comparison to mortars without ashes is mainly
due to the pozzolanic activity of the ashes observed in section 3.2.
The reaction between the silica or aluminosilica and the calcium
hydroxide forms additional CeSeH, which fills the capillary pores.
The densification of the matrix leads to an increase of the me-
chanical properties of the material (Taylor, 1997).
The strength activity index of mortars was calculated following
Eq. (9):
SAI ¼ (A/B) * 100
Where, SAI is the strength activity index (%), A is the compressive
strength of mortars containing mineral admixtures (MPa), B is the
compressive strength of mortars without mineral admixtures
(MPa).
At 7 and 28 days, all binary and ternary mortars have SAI su-
perior to 75% (Table 7), which is the minimum value preconized by
ASTM C618 for the use of mineral additions in concrete.
Table 7
Strength activity index of mortars at 7 and 28 days.
Samples SAI (%) 7 days
BLA10 88
SCBA10 98
BLA20 111
SCBA20 119
BLA5SCBA5 93
BLA10SCBA10 114
3.7. Environmental, economic and technical aspects
In Brazil, the sugarcane production reaches an average of
600*106 tons per year (Conab, 2018) and the consumption of
bamboo, used only for paper production for example, is about
500*103 tons per year (Villar-Cocin~ a et al., 2011). However, if all the
growing area of the country was used, this number should reach
1.35*109 tons per year (Judziewicz et al., 1999).
Considering that one ton of sugarcane leads to about
200e280 kg (average 240 kg) of sugarcane bagasse (with 50% of
relative humidity), whose calcination produces 1e4 wt% (average
2.5 wt%) of ashes (Dantas Filho, 2009), there is a potential pro-
duction of 3.6*106 tons of sugarcane bagasse ashes per year.
In the case of bamboo, considering that the leaves represent
7 wt% of the biomass (Liese, 1985), whose calcination produces
about 2 wt% of ashes (Villar-Cocin~ a et al., 2003), there is a potential
production of 1.89*106 tons of bamboo leaf ashes.
In Brazil, the use of the biomass for production of energy rep-
resents more than 15% of the national energy matrix, losing only to
petrol (EPE, 2013). The management of the residue produced
(ashes) became a strategic point for the cogeneration plants. For
(9) economic reasons, the ashes are mainly used as soil amendments.
Nevertheless, the use of high doses of ashes can lead to an envi-
ronmental contamination by heavy metals (Rautaray et al., 2003).
Another solution is the use of the ashes as partial replacement of
cement. This is possible due to the high content of silica and alu-
minosilica present in the residue.
In the country, the most important consumer of cement is the
industrial sector (including fiber cement industry, precast concrete
plants and concrete producers), with a consumption of 21*106 tons
of cement per year (Viana et al., 2014). According to the data, in
term of quantity of materials, the use of these mineral additions as
substitution of cement up to 20 wt% is viable.
Moreover, the use of agro-industrial ashes can be a solution to
reduce the environmental impact of the industrial sector. Indeed,
SAI (%) 28 days the partial replacement of cement reduces the quantity of cement
110 used for the elaboration of cementitious materials. Considering that
110 the production of 1 ton of cement produces about 1 ton of carbon
119 dioxide and by not taking account the CO2 emissions linked to
131
transport, the ashes can be a solution to reduce CO2 emissions.
111
125 Indeed, the carbon dioxide produced during the calcination of the
62 L. Rodier et al. / Journal of Cleaner Production 231 (2019) 54e63
biomass burning does not contribute to the increase of the con-
centration of greenhouse gases in the atmosphere, since the carbon
liberated was absorbed during the life of the plants.
Beyond the reduction of carbon emissions, the use of mineral
additions such as ashes results in an increase of the mechanical
properties the material due to the pozzolanic reaction (section 3.6).
To quantify the impact of the agro-industrial ashes on the
elaboration of binary and ternary blend cements, the energy
necessary to produce the cement (En) and the energy performance
(Ep) of mortars were calculated according to Eqs. (10) and (11)
(Hamidi et al., 2013):
En (kWh/t) ¼ XC (Epro þ Egri) þ XA (Epro þ Egri) (10)
Ep (kWh/t/MPa) ¼ En / s (11)
Where XC and XA are the percent by mass (%) of cement and ashes
in the matrix respectively, Epro and Egri are the energy (kWh/t)
necessary for the manufacturing process and the grinding of
cement respectively, s is the compressive strength of the mortars.
En and Ep are calculated for binary and ternary mortars pre-
senting the highest compressive strength at 28 days. For the cal-
culations, the following data is used:
- the total energy needed (Epro þ Egri) to produce cement is
112 kWh/t (Bilitewski et al., 2012),
- the ashes are considered as a residue (Epro ¼ 0 kWh/t),
- the energy necessary to obtain the required particle size is about
40% of the total energy needed to produce cement (Harder,
2003).
Table 8 shows that to produce 1 ton of binder with agro-
industrial ashes it is necessary lower energy than conventional
cement (Control). Moreover, in term of energy performance, to
obtain the same mechanical behavior than the conventional
mortar, it is necessary lower energy.
Concerning the economic aspect, the average cost of 1 ton of
cement in Brazil is R$ 122 (US$ 32) (CBIC, 2019). Taking account that
the average electricity price is R$ 0.561/kWh (ABRADEE, 2019), the
cost of the production of 1 ton of ashes is estimated to around R$ 90
(US$ 24). This value includes 50% of Brazilian taxes and labor (IBPT,
2019), as well as 8% of the profit margin of the Brazilian industrial
sector (Receita Federal, 2009). The use of ashes as partial replace-
ment of cement can reduce the cost of cement in civil construction
industry.
4. Conclusion
Based on the experimental results obtained in this study, the
following conclusions can be drawn:
1. X-Ray fluorescence analysis shows that SCBA and BLA have a
content of silica of 36 and 70%, respectively.
2. X-Ray diffraction patterns of both ashes show a halo between 15
and 35
2q, suggesting the presence of amorphous silica. In BLA
Table 8
The energy necessary to produce the cement (En) and the energy performance (Ep)
of mortars at 28 days.
En (kWh/t) Ep (kWh/t/MPa)
Control 112 3.07
BLA20 98.56 2.06
BLA10SCBA10 98.56 2.16
and SCBA, the amorphous phase represents 32.26% and 9.84%,
respectively.
3. Electrical conductivity tests of ashes/calcium hydroxide solution
showed the high reactivity of BLA. Moreover, combinations of
SCBA and BLA showed higher reactivity than SCBA.
4. The kinetic-diffusive model permitted to describe quantitatively
the pozzolanic reaction between ashes and calcium hydroxide.
5. A decrease of 32% of calcium hydroxide content is observed
when SCBA and BLA are used in binary and ternary blended
pastes.
6. A ternary binder composed of 80 wt% of cement, 10 wt% of
bamboo leaves ashes and 10 wt% of sugar cane bagasse ashes
shows a decrease the total heat of hydration in comparison of
control at 48 h.
7. Binary and ternary mortars have SAI superior to 75% as pre-
conized by ASTM C618 at 7 and 28 days.
8. To produce 1 ton of binder with agro-industrial ashes it is
necessary lower energy than conventional cement (Control).
The use of ashes as partial replacement of cement in binary and
ternary binder offers environmental, technical and economic ad-
vantages in comparison to conventional cement without mineral
additives.
Compliance with ethical standards
Funding: This study was funded by Conselho Nacional de
Desenvolvimento Cientifico e Tecnolo  gico (CNPq) PVE grant
401704/2013-0, Post-doctoral grant 150336/2015-2, Fundaça ~o de
Amparo  a Pesquisa do Estado de S~ao Paulo (FAPESP) Thematic
Project 2012/51467-3, Post-doctoral grant 14331/2016-7 and
Agence nationale de la recherche (ANR) Project no 12-IS09-0002-
01.
Declarations of interest
None.
Acknowledgements
The author would like to thank Conselho Nacional de Desen-
gico (CNPq) PVE grant 401704/
volvimento Cientifico e Tecnolo
~o de Amparo a 
2013-0, Post-doctoral grant 150336/2015-2, Fundaça
~o Paulo (FAPESP) Thematic Project 2012/
Pesquisa do Estado de Sa
51467-3, Post-doctoral grant 14331/2016-7 and Agence nationale
de la recherche (ANR) Project no 12-IS09-0002-01 for the Financial
support.
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