Rice-Straw Ash as a Potential Supplementary

Cementitious Material: Influence of Thermochemical

Conversion on Its Properties
G. Athira 1; A. Bahurudeen 2; and Srinivas Appari 3
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Abstract: Agro-waste ashes can be used as supplementary cementitious materials in concrete. Although many studies have been reported on
the use of rice husk ash as a pozzolan, only limited studies are attempted on the use of rice-straw ash in concrete. The composition of rice
straw and the influence of thermochemical processing on the amorphous nature and microstructure of rice-straw ash are reported in this study.
Moreover, compressive strength, water penetration test, and rapid chloride permeability tests were conducted for rice-straw ash blended
concrete. Results from the study indicate that rice-straw ash obtained from pyrolysis temperatures up to 700°C were amorphous and contained
reactive silica. From considerations of strength, workability, and durability, 10% rice-straw ash is observed to be the optimum level of
replacement. Rice-straw ash blended concrete with 20% replacement level exhibited better performance against water penetration and
chloride ingress than control concrete. DOI: 10.1061/(ASCE)MT.1943-5533.0003727. © 2021 American Society of Civil Engineers.
Author keywords: Rice-straw ash; Supplementary cementitious materials; Blended concrete; Pyrolysis; Durability.

Introduction fertility. However, to achieve the sustainable development goals

Research on agro-waste based construction products is gaining mo-
mentum due to the emphasis on cutting the carbon footprint of con-
struction industries. Rice straw is an abundantly available resource
from paddy cultivation, especially in Asian countries where rice is
the primary food for consumption. The quantity of global rice pro-
duction in 2018–2019 was about 494.8 million ton, of which 90.7%
is contributed by Asian countries such as China, India, Indonesia,
Thailand, Pakistan, and Japan (USDA 2020). Production of 1 t of
rice generates about 1.5 t of paddy straw (Binod et al. 2010). There-
fore, the total availability of rice straw globally comes to be around
742.2 million ton per annum.
In countries like India, farmers often adopt uncontrolled open-
field burning of rice straw as a method of disposal, producing sig-
nificant greenhouse gas emissions (Athira et al. 2019). Paddy straw
burning also reduces the soil fertility as it limits the nitrogen avail-
ability for plants by converting the available nitrogen in topsoil into
aromatic compounds. Moreover, burning of the topsoil is also found
to eliminate the microbiota in the soil critical for plant growth
(Yadav 2019). In countries like India, farmers often adopt uncon-
trolled open-field burning of rice straw as a method of disposal,
producing significant greenhouse gas emissions and reducing soil
1 the parent material and the influence of processing parameters such
Postdoctoral Researcher, Dept. of Civil Engineering, Indian Institute of
Technology Bombay, Mumbai 400076, India. ORCID: https://orcid.org
/0000-0001-6746-3198. Email: athira.nath36@gmail.com
2
Assistant Professor, Dept. of Civil Engineering, Birla Institute of
Technology and Science Pilani, Hyderabad Campus, Telangana 500078,
India (corresponding author). ORCID: https://orcid.org/0000-0002-8300
-2321. Email: bahurudeen.civil@gmail.com
3
Assistant Professor, Dept. of Chemical Engineering, Birla Institute
of Technology and Science Pilani, Pilani Campus, Rajasthan 333031, India.
Email: asrinu14@gmail.com
Note. This manuscript was submitted on July 10, 2020; approved on
October 27, 2020; published online on March 29, 2021. Discussion period
open until August 29, 2021; separate discussions must be submitted for
individual papers. This paper is part of the Journal of Materials in Civil
Engineering, © ASCE, ISSN 0899-1561.
(SDGs) put forth by the United Nations in 2015, most of the
OECD (Organisation for Economic Co-operation and Develop-
ment) countries are gradually transitioning from the traditional
coal-based energy economy to a more sustainable renewable en-
ergy economy. One of the most prominent sources of renewable
energy is biomass like rice straw, and its effective use as a fuel
feedstock can result in significant coal savings and greenhouse
gas (GHG) reduction. Pyrolysis and cogeneration are prominent
methods of thermochemical conversion processes and perhaps
the most beneficial (Varma and Mondal 2016). Therefore, rice
straw-based energy production is considered to be a very sustain-
able option and is implemented in developing countries. On the
other hand, the disposal of rice-straw ash (RSA), which is the by-
product of rice straw burning, has also increased considerably.
Similar to rice husk ash and sugarcane bagasse ash, RSA also
has significant potential to be used as supplementary cementitious
material (SCM). However, the use of RSA as a pozzolan is hindered
due to a lack of understanding of its characteristics. It is imperative
to study the influence of burning on rice straw and the character-
istics of RSA to enable its use as an SCM in concrete. The com-
position, type, and source of the agro-waste significantly influence
the properties of RSA and other end products. Since RSA is a
newly emerging material as an SCM, it is imperative to understand
as burning on the characteristics of RSA. It helps to evaluate the
changes in its properties with respect to thermochemical processes.
Further, the determination of the reaction kinetics of rice straw
under pyrolysis conditions is essential to understand the nature of
the residual ashes. Five rice-straw samples were collected, and an
attempt was made to assess the suitability of RSA for use as alter-
native cementitious materials in concrete based on their morpho-
logical and mineralogical investigations. Moreover, the strength
and durability properties of RSA blended concrete were also inves-
tigated in the study by conducting compressive strength, rapid chlo-
ride permeability, and water permeability tests.
Although the presence of significant quantity of silica in RSA
has been reported in previous research (Abou-Sekkina et al. 2010;

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 Ataie and Riding 2013; Jenkins et al. 1998), studies on the use of
RSA as an SCM are very limited. For instance, earlier studies have
investigated the pozzolanic nature of RSA for its use as a pozzo-
lanic material, and it was found to be sufficiently pozzolanic and
composed of amorphous silica resembling the composition of the
ordinary glass (Jenkins et al. 1998). The lime consumption and
Frattini tests on rice-straw ash also indicated the pozzolanicity
of RSA. Lime-RSA pastes were found to develop the pozzolanic
reaction product CSH after 7 and 28 days of curing (Roselló et al.
2017). The pozzolanic nature of RSA was also confirmed by the
Chapelle test, where RSA burned at 650°C and 500°C both showed
almost comparable CaðOHÞ2 fixation values as that of silica fume
(Ataie and Riding 2016). It was also reported that the compressive
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as 800°C at a heating rate of 10°C=min. The analysis was carried
out at an inert atmosphere of N2 at a flow rate of 50 mL=min. The
monitoring scan rate was set to one second. The TGA samples were
kept in a platinum crucible. The morphology of the rice-straw sam-
ples and the distinct components of the same were studied using an
FEI Apreo LoVac field emission scanning electron microscope
(SEM). Fourier transform infrared spectroscopy (FT-IR) was used
to measure the absorbance spectra of the components of rice-straw
samples.
Estimation of Kinetic Parameters of Rice-Straw
Pyrolysis

strength of RSA blended mortar at 10% was higher than that of The thermal decomposition of biomass under pyrolysis conditions
control, attributed to the production of additional C─S─H gel from follows the general Arrhenius temperature dependence
the pozzolanic reaction between RSA and calcium hydroxide
(Roselló et al. 2017). However, a detailed study on the performance dx
¼ kðTÞfðxÞ ð1Þ
of RSA as an alternative cementitious material in concrete is not dt
available in the literature. Therefore, evaluation of the mechanical
and durability properties of RSA blended cement systems is nec- where x = degree of reaction; t = reaction time; and kðTÞ =
essary for recognizing RSA as a viable SCM. This study is an at- Arrhenius rate constant, which is also expressed as k ¼ Ae−E=RT .
tempt to bridge these gaps in knowledge by assessing the influence A = preexponential factor; Ea = Activation energy in kJ/mol;
of processing conditions on residual ashes and by evaluating the R = universal gas constant; and T = absolute temperature in K.
mechanical and durability performance of RSA blended concrete. fðxÞ = reaction model. Considering β as the rate of heating,
The detailed investigation adopted in the present study contributes β ¼ dT=dt. Then Eq. (1) is written as
to the scientific understanding of RSA and its acceptance for use as Z x Z
a pozzolan in concrete. dx A T −Ea
¼ e RT dT ð2Þ
0 fðxÞ β T0

Materials and Methods As there is no exact solution available for the left-hand side of
the equation, the Ozawa–Flynn–Wall (OFW) method considers
Five rice-straw (Oryza sativa) samples were collected from differ- Doyle’s approximation (Doyle 1961) for solving the temperature
ent parts of Kerala, a southern state in India. These samples were integral. Considering the approximation and re-arranging the terms,
oven dried at 100°C for 24 h to remove any moisture and were Eq. (2) is transformed into Eq. (3) (Ounas et al. 2011)
ground to a fine size of 150 μm. The five rice-straw samples in-
vestigated in the study are designated R1, R2, R3, R4, and R5.  
AEa E
The influence of thermochemical conversion was investigated lnðβÞ ¼ ln − 5.331 − 1.052 a ð3Þ
RcðxÞ RT
for all rice-straw samples R1–R5. The residual ash from the com-
bustion of rice straw is used as a mineral admixture in concrete. The where cðxÞ = integral form of the biomass conversion function.
rice straw ash used in the current study was processed using a com- From Eq. (3), it is evident that the plots between ln (β) and
bination of sieving and grinding. The RSA was sieved through a (1=T) will yield parallel lines for different conversion rates ‘x.’ The
150 μm sieve to remove the carbon-rich fibrous particles. After slope of the line is used to calculate the activation energy at a speci-
sieving, grinding was conducted using a laboratory scale ball mill. fied conversion. Similarly, the Kissinger–Akahira–Sunose (KAS)
Based on different trials, the grinding duration of RSA was opti- method uses the Coats–Redfern approximation (Coats and Redfern
mized to three hours to match the fineness of ordinary portland ce- 1964), and the Eq. (2) is transformed to
ment (OPC) (300 m2 =kg) used in the study and to avoid the filler
   
effect. The same source of cement (OPC 53 grade) and the same β RA E
source of RSA were used for all the concrete-related experiments ln 2 ¼ ln − a ð4Þ
T cðxÞE a RT
adopted in the study.
where the plots between lnðTβ2 Þ and T1 are used to calculate the ap-
Characterization of the Five Rice-Straw Samples parent activation energy at various degree of biomass conversion.
The ultimate analysis of the rice-straw samples was conducted us- The overall activation energy of the conversion process over a
ing a carbon-hydrogen-nitrogen-sulphur (CHNS) elemental ana- range of conversion is determined by the Coats–Redfern method. In
lyzer (Elementar Vario Microcube). The volatile components, this study, a temperature range of 270°C–600°C is considered as the
combustible materials, and char content were determined from biomass conversion range as most of the volatilization occurs in
the thermogravimetric data of rice straw, based on the method de- that interval. While the OFW and KAS methods are model-free
scribed in ASTM E1131-08 (ASTM 2015). As per ASTM E1131, and do not assume any particular reaction kinetics for the biomass
three different temperature regimes were determined for creating a conversion, the Coats–Redfern method is a model-fitting method.
heating profile in the thermogravimetric analysis. The temperature The activation energy (Ea ), pre-exponential factor (A), and appar-
regimes were determined based on the thermal decomposition pat- ent reaction order (n) are determined from the Coats–Redfern mod-
terns of rice-straw biomass under inert N2 and reactive atmospheres els, as shown in Eqs. (5) and (6)
(dry air). A Shimadzu DTG-60 thermogravimetry/differential ther-     
mal analysis (TG/DTA) apparatus was used for the thermal analy- − lnð1 − xÞ AR 2RT E
ln ¼ ln 1− − a; n¼1 ð5Þ
sis. The target temperature for all the rice-straw samples was fixed T2 βEa Ea RT

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ð1 − xÞ1−n − 1 AR 2RT E trichomes, dumbbell-shaped phytoliths, fibrous members with
ln ¼ ln 1 − − a; n≠1
ðn − 1ÞT 2 βEa Ea RT
ð6Þ
Pyrolysis and Characterization of Rice-Straw Ash
A quartz U-tube was used to perform the pyrolysis experiments,
which was placed inside a tubular furnace. The reactions were car-
ried out in an inert N2 environment with a 200 mL=min flow rate.
The electric furnace was heated to the desired temperature, and the
finely ground biomass was dropped from the top of the heating
zone with a special arrangement. The experiments were carried
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out at temperatures of 400°C–700°C with an interval of 50°C,
and the residual ash was collected at the bottom of the quartz re-
actor. The mineralogical and morphological evolution of the ash
samples across the temperature ranges were studied by subjecting
them to X-ray diffraction studies and SEM imaging.
Performance Evaluation of Rice-Straw Ash in Cement
Concrete
The amorphous silica in RSA can aid in its usage as an alternative
cementitious material. The modification of the mechanical and
durability properties of cement concrete upon the addition of RSA
was investigated in this study. The mechanical properties of
the RSA blended concrete were determined by studying the varia-
tion in the 28-day compressive strength at different levels of
replacement. The compressive strength of the RSA blended con-
crete specimens was conducted at three different levels of replace-
ment (10%, 20%, and 30%). Concrete specimens of 150 × 150 ×
150 mm were made in accordance with IS 516-1959 (Bureau of
Indian Standards 2004) for compressive strength testing. The load-
ing rate was set as 140 kg=cm2 =min.
The durability of blended concrete depends on the pore refine-
ment characteristics of the mineral admixture. Therefore, the water
penetration resistance of RSA blended concrete specimens was in-
vestigated in this study following the DIN 1048 test procedure
[DIN 1048: Part-5 (DIN 1991)]. Concrete cubes of 150 mm size
were used for the test procedure after 28 days of curing. The spec-
imens were placed in the water permeability apparatus, and the
cover plate was lowered on to the top surface of the specimen.
A rubber gasket was placed in between the top surface of the speci-
men and the cover plate to prevent the leakage of water. Water pres-
sure of 0.5 N=mm2 was applied to the top surface of the specimens
for three consecutive days. After 72 h, the specimens were re-
moved, and they were split into two halves along the direction
of the flow of water. The water penetration depth of all the spec-
imens was marked within 5 min before the specimens dried. The
average penetration depth of a set for each mix was reported as
the final water penetration depth. Similarly, the resistance of the
blended concrete against chloride penetration was investigated
by conducting a rapid chloride permeability test (RCPT) as per
ASTM C1202-19 (ASTM 2019).
Results and Discussion
Morphological Characterization of Rice Straw
Compared to the numerous investigations conducted on rice husk
and its residual ashes, the morphology of rice straw is not very
well studied in the existing literature. Scanning electron micro-
graphs of Indian rice-straw samples obtained in this study reveal
various distinct morphological features. Needle/thistle shaped
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vascular channels, and adaxial part of the leaves with intact stoma
are some of the well-defined features identified in the rice-straw
microstructure. Fig. 1(a) shows the phytoliths in the rice-straw
fibers.
Essentially, phytoliths are inorganic silicified structures in plants
that do not decay along with the plant. Plants absorb orthosilicic
acid and other minerals along with water in silica-rich soils. After
the water is used for its digestive processes, the silica is polymer-
ized into amorphous silica and gets deposited as rigid structures in
the plant stem or leaves. Phytoliths can remain intact long after the
plants decay and can become fossilized with the genetic material of
the plant inside. This phenomenon has made phytoliths a topic of
extensive investigation in the fields of archaeology and paleoecol-
ogy (Piperno 2006).
Although phytoliths have been observed to have various shapes,
the phytoliths in the rice plants collected in the study are observed
to be predominantly dumbbell shaped. The presence of silica in
phytoliths is visible from the energy-dispersive spectroscopic stud-
ies conducted on rice samples. As can be seen from Fig. 1(b), the
elemental mapping study of rice-straw fibers using energy disper-
sive X-ray spectroscopy (EDS) revealed that the phytoliths were
silica rich. Apart from the dumbbell-shaped structures, some globu-
lar structures were also found to be present on the surface of the rice-
straw fibers, neatly aligned in rows, as seen in Fig. 1(c). Fig. 1(d)
shows the SEM-EDS analysis of these spherical structures, and it
was found that these were also composed mostly of SiO2 .
Therefore, it can be concluded that the phytoliths in rice straw
exist in both dumbbell and spherical structures. The variation in
the shape of the silica storing structures could be due to the lo-
cation of the silica deposition. It has been proved in earlier studies
that the shape of the phytoliths is influenced by the type of the
plants and the location of the silica storage in the plants (Anala
and Nambisan 2015). The presence of potassium in the phytoliths
as seen from Fig. 1(d) could be due to the occlusion and immo-
bilization of the potassium species (phytOK) at the time of silici-
fication of the cell wall or the extracellular layers (Athira et al.
2019). These silica-rich spherical structures are found in abun-
dance in the rice straw microstructure and differ slightly in ap-
pearance, as seen in Figs. 1(e and d). The surfaces of most of
the rice-straw fibers are filled with these spherical (and sometimes
bulbous) protrusions unless they are carbon-rich coarse particles
with vascular channels. The needle-shaped structures present in
the rice straw samples are epidermal appendages called trichomes,
which also absorb water and biominerals. Trichomes can be found
in the stem and leaves of the rice plant. The trichomes in the stem
are short and stay close to the surface, whereas those on the
leaves are longer. As the water is transported along the stem to
the leaves, the silica often gets left behind and hardens in the
trichomes.
Fig. 1(g) shows the trichomes on the rice-straw fibers, along
with the bulbous phytoliths. The presence of silica in these struc-
tures is evident from the EDS mapping analyses shown in Fig. 1(h).
Elemental Analysis of Rice-Straw Samples
The ultimate analysis results for all the five samples of rice straw
are presented in Table 1, including the ash content as determined
from the thermogravimetric analyses. The oxygen content was de-
termined by calculating the difference. The average ash content in
the samples was found to be about 22.8% as per the thermogravi-
metric analysis.
It can be seen that compared to other biomass materials such as
bagasse, olive residues, and palm oil waste (Jindo et al. 2014;
J. Mater. Civ. Eng.
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Fig. 1. (a and b) Individual phytoliths and mapped silica content; (c and d) a row of phytoliths and EDS analysis; (e and f) spherical phytoliths; and
(g and h) trichomes, and mapped silica.

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 Table 1. Ultimate analysis (in percentage by dry weight) of biomass Compositional Analysis of Rice-Straw Samples as per
samples ASTM E1131-08
Sample C H N S Asha O The proximate analysis defined in the ASTM E1131-08 is based on
R1 32.77 4.51 0.705 0.217 25.66 36.138 the thermogravimetric data of energy fuels. It includes the heating
R2 32.60 4.48 0.885 0.142 22.67 39.223 up of rice straw at a particular heating rate in an inert atmosphere up
R3 34.32 4.57 0.470 0.082 22.99 37.568 to the initial mass-loss plateau, indicating the release of moisture.
R4 30.73 4.20 0.940 0.104 22.5 41.526 This temperature is indicated as X. Further, it is heated at a con-
R5 32.72 4.48 0.665 0.088 20.41 41.637
stant heating rate up to the next mass-loss plateau at temperature Y,
a
From thermogravimetric analysis. indicating the volatilization of medium volatile matter including the
hemicellulose, cellulose, and lignin contents [ASTM E1131-08
(ASTM 2015)]. After rest for a brief duration at Y, the inert atmos-
phere is switched to a reactive atmosphere and heated at a constant
Ounas et al. 2011), the ash content in rice straw is much higher. heating rate till temperature Z beyond which the mass loss is neg-
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This is attributed to the significantly greater silica content in rice
straw. An average of 32% carbon, 4.5% hydrogen, 0.7% nitrogen,
and 0.12% sulfur are present in the rice-straw samples. It is also
interesting to note that the elemental compositions of all five
rice-straw samples are similar, with only marginal differences. The
low sulfur content of sample R5 makes it a better feedstock for the
production of value-added chemicals using in-situ catalytic fast
pyrolysis technique, as it can avoid the deactivation of catalysts
due to sulfur poisoning (Appari et al. 2014).
ligible. The residual mass after temperature Z is termed as the ash
content in the material, and the mass loss that occurred in the in-
terval between Y and Z is considered as the combustible material
content. The X, Y, and Z temperatures are not predefined in the case
of biomass materials. In order to understand the ranges of volatili-
zation, rice straw was subjected to heating under both an inert (N2
atmosphere) and reactive (dry air) environments.
Figs. 2(a and b) shows the thermograms of rice straw at a heat-
ing rate of 10°C from ambient temperature to 900°C in dry air and

Fig. 2. (a and b) TGA and (c and d) DTG curves of rice straw at reactive and inert atmospheres.

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 Table 2. Zones of thermal decomposition and mass-loss rates at the peaks
Mass-loss rate
at the peak
Peak Onset Offset
Item Zone temperature temperature temperature %=s %/°C
In air I 62.3 30 126.8 −0.0288 −0.248
II 285.75 171.1 335 −0.547 −0.496
III 388.9 335 519.4 −0.0321 −0.244
In N2 I 59.76 30 130 −0.0349 −0.246
II 312.15 201.2 409.2 −0.0851 −0.609
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N2 atmospheres. The early thermal degradation patterns at both the
atmospheres are found to be similar, indicating the removal of
highly volatile matter such as moisture and other impurities that
are not part of the lignocellulosic structural matrix of rice straw.
Figs. 2(c and d) shows the derivative thermograms of rice-straw
degradation in dry air (combustion) and nitrogen (pyrolysis) envi-
ronment. The initial mass-loss curve from 30°C–120°C is attributed
to the release of highly volatile materials after which a mass-loss
plateau is achieved at around 110°C–125°C (X) for rice straw at
both the atmospheres. Beyond this temperature, a region of rapid
volatilization of biomass is observed from 217°C to 480°C, as de-
scribed by the sharp slopes of the thermogravimetric curves.
The thermal decomposition pattern of rice straw in this temper-
ature interval differs with respect to the environment. For instance,
there is a distinct and steep mass-loss curve from 217°C to 323°C
for rice straw under the reactive atmosphere. Further, a second stage
of decomposition is observed, which continues till 480°C. How-
ever, under the nitrogen atmosphere, the steep mass loss is observed
till 358°C, beyond which the decomposition trend is unchanged
until the target temperature is reached (900°C). The residual ash
content of the rice straw under the inert atmosphere was found
to be about 31%. However, the ash content under the reactive envi-
ronment is about 22%. The exact mass loss rate and zones of bio-
mass conversion can be observed from the derivative thermograms
as depicted in Figs. 2(c and d). Fig. 2(c) shows the derivative ther-
mogravimetric (DTG) curve of rice straw mass decomposition with
respect to temperature. As discussed, the initial temperature region
where the highly volatile materials decompose are similar in both
the atmospheres, as the presence of oxygen does not affect the re-
lease of moisture. However, the second volatilization peaks in both
atmospheres differ as there is an apparent right shift of peak mass-
loss rate in the case of inert conditions. It was also observed that the
peak mass-loss rate with respect to temperature in this zone is
slightly more for decomposition under pyrolysis than combustion.
Table 2 shows the characteristics of each of the identified devola-
tilization zones of rice straw under inert and reactive environments.
Three distinct biomass decomposition zones are observed in the
air atmosphere, whereas only two zones can be identified in the
case of an inert atmosphere. The initial mass-loss curves have peaks
at 62.3°C and 59.7°C and a mass-loss plateau at around 126°C–130°
C under reactive and inert atmospheres, respectively. The mass-loss
rates at both peaks are also similar. The second zone of thermal
decomposition of rice straw has a peak at 285°C and 312°C under
air and N2 gas. It can be seen that the onset and offset temperature
for the devolatilization curve has also shifted to the right in the case
of N2 . While the shift in the onset temperature for the second vola-
tilization curve is only about 30°C, the right shift in the offset tem-
perature is quite significant (∼75°C). Considering the derivative of
mass loss with respect to time, a significantly higher mass-loss rate
can be seen in the case of biomass decomposition under a reactive
atmosphere. Therefore, it can be assumed that the presence of
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Table 3. Proximate analysis of rice straw from thermogravimetric data as
per ASTM E1131
Highly volatile Medium volatile Combustible Ash
Sample matter (%) matter (%) material (%) content (%)
R1 8.42 58.33 7.61 25.66
R2 8.94 59.96 8.45 22.67
R3 8.99 60.49 7.55 22.99
R4 7.37 61.79 8.35 22.50
R5 8.23 62.62 8.75 20.41
oxygen promotes the mass decomposition at lower temperatures.
This is in line with earlier findings reported for other biomass com-
bustion (Chen et al. 2011; Ma et al. 2018). However, when biomass
conversion was calculated with respect to the temperature incre-
ment across the range of 202°C–409°C, slightly higher mass loss
was observed at the peak temperature (312°C) under the nitrogen
environment. The difference arising in the mass-loss rates with re-
spect to time and temperature is because mass-loss rate is calculated
per second in the case of DTG curves with respect to time, whereas
mass-loss rates with respect to temperature are calculated per de-
gree Celsius (or six seconds as β ¼ 10°C=min). Therefore, instan-
taneous mass changes can be seen from mass loss plotted with
respect to time, while mass changes with respect to a broader time
range can be seen from mass loss plotted with temperature.
A third zone of mass loss is observed in the case of air atmos-
phere, starting at 335°C and ending at around 520°C, centered
at 388°C. This zone is not significant or is entirely absent in the
derivative thermograms under a nitrogen environment. Therefore,
it can be assumed that the mass loss in this temperature range is due
to char combustion and the devolatilization of the combustible
materials in the presence of oxygen.
From the thermogravimetric studies, the volatilization behavior
of rice straw was studied, and the switchover points for the TGA
based proximity analyses were determined. The initial temperature
to determine the moisture content (X) was fixed as 120°C based on
the TGA curves. Then, 600°C was considered as the final temper-
ature for the decomposition of volatile materials (Y), as all the steep
mass losses under pyrolysis conditions occur before that temper-
ature. The temperature to determine the ash content (Z) was taken
as 900°C.
Based on these parameters, the composition of rice-straw
samples collected in this study (R1–R5) is determined and given
in Table 3. An average of about 8.4% highly volatile materials were
found to be present in the rice-straw samples. Similarly, the
medium volatile material components constituted an average of
60.6%. The fixed carbon/combustible material in the samples came
out to be around 8.14%. The ash content in all the samples was
above 20%. This is significantly greater than other biomass mate-
rials such as bagasse, wood, or other agricultural wastes (Dhyani
and Bhaskar 2018; Gopinath et al. 2018). The higher ash content in
rice straw is attributed to the higher amounts of inorganic silica
present in the phytoliths of rice straw, as is confirmed from the mor-
phological studies.
Structural Composition of Rice-Straw Samples from
TGA and FT-IR Studies
The thermogravimetric data obtained for the rice straw samples are
a superposition of the decomposition of their individual fiber com-
ponents such as hemicellulose, cellulose, and lignin. Therefore, in
order to determine the relative decomposition of each of these indi-
vidual components, a deconvolution method is adopted, through
J. Mater. Civ. Eng.
 Table 4. Properties of the deconvolved DTG curves for each rice-straw sample
DC1—peak DC2–peak
Sample temperature (°C) temperature (°C)
R1 61.48 300.6
R2 64.97 294.0
R3 62.64 296.9
R4 59.12 295.3
R5 63.21 285.5
which the underlying mass-loss peaks for individual components
may be observed. For this, the peaks in the original TGA curves
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were identified for all the rice-straw samples, and a Levenberg–
Marquardt algorithm was used for the deconvolution with a Gaus-
sian fitting function. The iterations were continued till convergence.
The temperature ranges for hemicellulose, cellulose, and lignin
decomposition in various biomass materials are identified to be
260°C–300°C, 330°C–370°C, and 200°C–600°C in the literature
(Bryś et al. 2016; Yang et al. 2007).
Following deconvolution of the derivative thermograms, similar
peaks were also observed for all the rice-straw samples investigated
in the study, as can be seen from Table 4. After the initial moisture
release peak, another peak centered at around 300°C was observed
for the first deconvolved curve. Another noticeable peak was ob-
served in the range of 317°C–325°C. Even though not clearly dis-
cernible from the original DTG curves, another deconvolution
curve with broad peaks at around 405°C–420°C was also revealed,
which is attributed to the decomposition of lignin. The deconvolu-
tion of the DTG of each rice-straw sample in the study is shown in
Fig. 3, and it can be seen that the simulated DTG curve is an exact
fit to the observed derivative thermogram in all five cases.
The third curve corresponding to lignin degradation appeared to
be the broadest of all, with almost all samples reporting a mass-loss
Fig. 3. Deconvolved thermogravimetric curves for all five rice-straw samples.
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DC3–peak DC4–peak
temperature (°C) temperature (°C) R2
325.9 405.6 0.99
316.4 406.0 0.99
319.2 420.1 0.99
317.1 419.1 0.99
301.1 377.4 0.99
peak at a temperature range of 405°C–420°C, except for R5 which
had a peak for the lignin deconvolved curve at around 377°C. From
the deconvolution procedure adopted in the study, the area under
the fitted curves was calculated, which were remarkably similar for
all the rice-straw samples. FT-IR is an effective tool in the identi-
fication of the lignocellulosic components in biomass species. The
rice-straw samples in this study were subjected to attenuated total
reflectance (ATR) infrared spectroscopy, and the observed absorb-
ance spectra are presented in Fig. 4.
The most significant absorbance peak was observed at a
wavenumber of 1,035–1,036 cm−1 , which is related to the C─O
and C─C─O stretching of cellulose, hemicellulose, and lignin
(Nybacka 2016). In addition, the peaks at 789 cm−1 may also
correspond to the vibrations in hemicellulose and/or lignin. The
increase in the intensity at the ∼897 cm−1 region is a distinct fea-
ture of glycosidic CH deformation with ring vibration, which is
a typical structure of amorphous cellulose (Nelson and O’Connor
1964). Moreover, the absorbance peak at 1,160 cm−1 is ascribed to
C─O─C asymmetrical stretching of cellulose and hemicellulose
(Shi et al. 2012). A peak at the band in the region of 1,327 cm−1
indicates the C─O of the syringyl ring of lignin (Traoré et al. 2016).
Intensity at ∼1,369 cm−1 is related to CH deformation in cellulose
and hemicellulose. The two absorption bands at 1,465 cm−1 and
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Fig. 4. Rice-straw FT-IR curves: (a) the whole spectra; and (b) the fingerprint region.
1,423 cm−1 are attributed to the C─H deformation of lignin. Sim-
ilarly, the band at around 1,633 cm−1 is characteristic of absorbed
O─H (Cao and Tan 2004) and conjugated lignin or cellulose,
whereas absorbance peak ∼1,730 cm−1 indicates the C═O stretch
of hemicellulose.
Reaction Kinetics of Rice-Straw Pyrolysis
Model-Free ISO-Conversional Kinetic Models for Rice-Straw
Pyrolysis: OFW and KAS
In order to determine the reaction kinetics of the rice-straw pyroly-
sis process, thermogravimetric analysis was conducted under vari-
ous heating rates (from 10°C=min to 50°C=min). In this study, the
pyrolysis kinetics are evaluated using the thermogravimetric data
based on model-free kinetics. The thermogravimetric curves
of the rice-straw samples under various heating rates are given in
Fig. 5(a). The derivative thermograms of the samples at various
heating rates are also shown in Fig. 5(b). The thermal degradation
pattern is similar for all the five heating rates adopted in the study.
The only differences were in the final residual ash content. The
OFW method of determining apparent activation energy depends
on the assumption that the natural logarithm of heating rate
(ln β) has a linear relationship with the reciprocal of temperature
(K) at various heating rates for the same conversion percentage.
Fig. 5(c) shows the relationship between lnβ and 1=T for a rice-
straw sample at conversion percentages from 10% to 70% for five
heating rates from 10°C=min to 50°C=min. The slopes of the lines
were found to be almost similar initially; however, at later conver-
sion percentages, the slopes were found to increase. The increase in
slope indicates the higher activation energy which is required to
decompose the lignin content in the rice straw. Therefore, for
the range of conversion studied, it was observed that the reactions
that occur at the later stages of biomass pyrolysis (at a higher tem-
perature) require greater activation energy to result in products. The
calculated apparent activation energies at a specified conversion
percentage and the Pearson coefficient are described in Table 5.
It is observed that almost all the coefficient of correlation is above
0.95, except for some at the higher conversion rates. The average
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apparent activation energy calculated from the OFW method for
rice straw is thus found to be 155.83 kJ=mol. Similarly, another
isoconversional method employed in this study for the determina-
tion of apparent activation energy is the Kissinger–Akahira–Sunose
(KAS) method. This method is similar to the OFW method in its
data requirements. However, the relationship between the heating
rates and temperature for specific conversion rates is different. KAS
method is based on the linear relationship between lnðβ=T 2 Þ and
(1=T) as shown in Fig. 5(d).
Table 5 also shows the apparent activation energies calculated as
per the KAS method for various conversion percentages. It can be
seen that as in the OFW method, the activation energies at higher
conversion percentages tend to be higher. The average apparent ac-
tivation energy for conversion from 10% to 75% is calculated to be
about 155.38 kJ=mol. This is very close to the activation energy as
obtained from the OFW method. The coefficient of correlation (r)
values were also found to be reasonable and in most cases were
higher than 0.95.
Coats–Redfern Kinetic Model for Rice-Straw Pyrolysis
The overall apparent activation energies, preexponential factors,
and apparent reaction orders of the Arrhenius equation cannot
be estimated using the isoconversional models used previously.
Therefore, the overall apparent activation energy for the medium
volatilization region, preexponential factors, and apparent reaction
orders of rice-straw pyrolysis were determined based on the Coats–
Redfern equation.
The apparent reaction order and the preexponential factors were
selected based on the best fit according to the coefficient of deter-
mination values. The fit statistics for a heating rate of 20°C=min
and apparent reaction orders from n ¼ 1 to n ¼ 2.8 are shown
in Table 6. It can be seen that the highest R2 value is for a reaction
order of 2.1, and the corresponding overall apparent activation en-
ergy for the temperature range of medium volatiles decomposition
was found to be 63.56 kJ=mol. Similarly, the apparent reaction or-
ders and activation energy for rice straw at various heating rates
were determined, as shown in Table 7.
The overall apparent activation energy (averaged at different
heating rates) for rice-straw pyrolysis, therefore, comes to be
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Fig. 5. (a and b) TGA and DTG curves of rice straw at different heating rates, activation energy slopes based on (c) OFW; and (d) KAS methods.

Table 5. Activation energy (Ea) and correlation coefficient (R) of rice Table 6. The apparent activation energy and preexponential factors
straw pyrolysis based on OFW and KAS methods determined for various reaction orders for rice-straw samples
(β ¼ 20°C=min)
Ozawa-Fynn-
Wall method KAS method Apparent Adj. Activation
reaction order R-square energy (kJ/mol) lnðAÞ
Component Conversion (%) Ea R Ea R
n¼1 0.9077 20.67 1.06
Hemicellulose 15 137.85 0.965 136.13 0.96
n ¼ 1.2 0.9514 26.26 2.48
20 137.98 0.988 139.97 0.989
n ¼ 1.4 0.9748 32.56 4.01
25 137.94 0.992 140 0.989
n ¼ 1.6 0.9861 39.52 5.65
30 140.72 0.985 138.95 0.99
n ¼ 1.8 0.9905 47.06 7.39
35 142.49 0.986 140.2 0.984
n ¼ 1.9 0.9906 55.10 9.21
40 144.27 0.975 141.93 0.971
n¼2 0.9910 59.28 10.15
45 148.8 0.971 146.57 0.967
n ¼ 2.1 0.9913 63.56 11.10
Cellulose 50 151.67 0.963 149.45 0.958 n ¼ 2.2 0.9895 67.92 12.07
55 157.97 0.946 155.93 0.939 n ¼ 2.3 0.9886 72.36 13.05
60 164.92 0.916 163.07 0.905 n ¼ 2.4 0.9876 76.87 14.04
65 180.92 0.867 179.66 0.853 n ¼ 2.5 0.9865 81.44 15.04
70 181.6 0.936 190.44 0.901 n ¼ 2.6 0.9855 86.06 16.05
75 198.69 0.838 197.73 0.822 n ¼ 2.7 0.9845 90.74 17.07
n ¼ 2.8 0.9836 95.46 18.10
Note: A: Preexponential factor (min−1 ).
around 63.4 kJ/mol. The model-predicted conversion values for the
temperature range of biomass conversion along with the observed
values are given in Fig. 6. The kinetic model predictions are found the thermal degradation behavior of Indian rice straw with a good
to agree with the observed values at various heating rates. degree of accuracy. It is interesting to note that a slight lack of
Therefore, the activation energy and apparent reaction order of fit is observed in the model for rice straw conversion at temperature
rice straw obtained from the Coats–Redfern equation can predict regions 650–750 K.

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 Table 7. The kinetic parameters of rice straw as estimated from the Coats– are sintered together, whereas the globular phytoliths are enlarged.
Redfern equation These morphological changes at high temperatures are visible in
Heating Activation energy (Ea ) Preexponential factor the SEM images [Figs. 7(c and d)] of the RSA obtained from
rate (β) (in kilojoules) [ln (A)] (in min−1 ) Order (n) pyrolysis carried out at 700°C. The enlargement of the silica-rich
10 62 11.136 2.5 spherical structures could be due to the volatilization of occluded
20 63 11.103 2.1 phosphorous species in the silicified and hardened structures. There
30 64 11.423 2.2 has been evidence for the surface disruption of hardened structures
40 64 11.638 2.2 in the fiber matrix due to the escape of occluded gaseous species
50 64 11.744 2.0 (Bharadwaj et al. 2004). Higher temperatures could completely dis-
integrate the RSA structure and also result in the crystallization of
silica in the phytoliths.

Mineralogy of Rice-Straw Ash

Characterization of Rice-Straw Ash
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Morphology of the Rice-Straw Ash
Figs. 7(a and b) shows the morphological composition of RSA
from pyrolysis at 400°C. Compared to the raw rice-straw mor-
phology, fewer fibers with vascular channels are present in the
ash. The craters and protrusions on the fiber surfaces signifying
the silica depositions are retained in the char, as is visible from the
figure.
At higher pyrolysis temperatures, the morphologies of these
siliceous bodies are evolved, and the dumbbell-shaped phytoliths
The ash samples from the pyrolysis of rice straw at various temper-
atures from 400°C to 700°C were collected. It was observed that the
ash content is directly related to the heating rate adopted. The ash
content was found to increase with an increase in the heating rates.
For instance, the ash percentage of the rice-straw sample when β ¼
50°C=min was found to be 25.31%, whereas it was 21.73% at
β ¼ 10°C=min. The high char content at β ¼ 50°C=min is attrib-
uted to the heat and mass transfer resistances during the heating
stage. The variation in char content with respect to heating rate
is shown in Fig. 8(a). As evident from the morphology and elemen-
tal composition of these materials as discussed in the previous

Fig. 6. Model-predicted and observed values of rice straw decomposition.

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Fig. 7. (a and b) SEM images of RSA obtained after pyrolysis at 400°C; (c) Sintered; and (d) bulged phytoliths on the fiber surfaces
at 700°C.

sections, it can be seen that at higher temperature pyrolysis, most of
the carbon fibrous particles are volatilized, leaving the siliceous
phytoliths behind in the char as residue. The nature of the silica
present in this char and the mineralogical phases contained in it
are investigated by carrying out X-ray diffraction (XRD) studies
on these samples.
The X-ray diffractograms of RSA obtained from pyrolysis of rice
straw at 400°C, 450°C, 500°C, 550°C, 600°C, and 700°C are shown
in Fig. 8(b). The XRD patterns were mostly amorphous in nature
(∼89%), with distinctive peaks superimposed on the amorphous
hump at 28.44° and 40. 68° 2-theta. These peaks correspond to
the quartz mineral. Pyrolysis of rice straw at 500°C results in another
peak at around 29.58° 2-theta, which could be due to the formation of
cristobalite. The same peak is observed in the XRD patterns of RSA
at all temperatures above 500°C. This indicates a gradual crystalli-
zation of the amorphous silica present in the phytoliths at higher tem-
peratures. The broad humps in the XRD pattern from 15° − 30°
2-theta for all the ashes show that the silica in the material is
mostly amorphous in nature. Therefore, RSA can also be treated
as a source of amorphous silica and with proper processing can be
effectively used as SCMs in concrete.
Rice-Straw Ash as an Alternative Cementitious Material
in Concrete
Compressive Strength of RSA Blended Cement Concrete
Compressive strength test of RSA blended concrete specimens was
carried out as per the standard specifications after 28 days of curing.
The results are presented in Fig. 9. It can be seen that at 10%
replacement of cement with RSA, the compressive strength of
RSA blended concrete is greater than that of the control concrete.
The increment in the compressive strength with the addition of
RSA can be attributed to its pozzolanic reactivity and the produc-
tion of additional calcium–silicate–hydrate products, densifying the
pore structure. However, for 20% replacement of ordinary Portland
cement with RSA, the compressive strength was observed to be
slightly less than that of control concrete, although still greater than
the target strength as per the mix design.
As for 30% RSA replacement, the compressive strength reduced
by 19.8% compared to control concrete. The reduction in compres-
sive strength at higher replacement percentages is attributed to the
dilution effect induced by the higher volume of RSA powder in the
cement concrete mix. This is also in line with the findings for rice

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Fig. 8. (a) Variation in char content with respect to the heating rate (β); and (b) X-ray diffraction patterns of residual ashes obtained at different
pyrolysis temperatures.
Fig. 9. Compressive strength of RSA blended concrete at various re-
placement levels.
Fig. 10. Water penetration depth of RSA blended concrete specimens.
© ASCE
J. Mater. Civ. Eng., 2021, 33(6): 04021123
husk ash, where in many studies, 10% by weight of the binder is
found to be the optimum level of replacement (Ramasamy 2012).
Water Penetration Depth of RSA Blended Concrete
The resistance of the RSA blended concrete specimens against
water penetration was studied by carrying out the DIN 1048 water
permeability test. The average water penetration depth for three
specimens after 28 days of curing was reported as the water pen-
etration depth. The results of the test conducted on RSA blended
concrete at three (10%, 20%, and 30%) different replacement levels
are shown in Fig. 10. The average water penetration depth of 10%
RSA blended concrete specimens showed a noticeable reduction
(∼20.9%) compared to the control concrete specimens.
At 20% replacement, the water penetration depth was found to
be greater than 10% RSA; nevertheless, it was still less than the
control concrete. At 30% replacement, however, the water penetra-
tion depth was greater than the control concrete. The significant
reduction in water penetration depth of concrete on the addition
of RSA up to 20% level of replacement implies densification of
the concrete matrix due to the formation of additional reaction
products.
Chloride Penetration Resistance of RSA Blended Concrete
The chloride penetration resistance of the RSA blended concrete
was investigated as per the rapid chloride permeability test. A sud-
den decrease in charge passed was observed for 10% RSA blended
concrete specimens compared to the control specimens. The total
charge passed was found to be reduced by 30% for 10% RSA
blended concrete compared to the control concrete, as shown in
Fig. 11. For further replacement up to 20%, the charge passed value
increased relative to 10% RSA but was still less than that of control.
At 30% RSA, however, the total charge passed in the test was
found to be higher than that of control, indicating a poor binder
matrix with interconnected pores. The higher charge passed values
for the higher level of replacement indicate that after an optimum
replacement level, the dilution effects overcome pore refinement.
According to the classification given in ASTM C1202-19 (ASTM
2019), the control specimens fall under the “Moderate chloride ion
penetrability” category whereas 10% RSA falls under the “Low
chloride ion penetrability” category. Even though 20% RSA has
a lower total charge passed value than control, it still falls under
the “Moderate chloride ion penetrability” category, along with
04021123-12 J. Mater. Civ. Eng.

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Fig. 11. Total charge passed values from RCPT test of RSA blended
cement concrete.
30% RSA. The chloride permeability, as measured by RCPT of
RSA blended concrete at different replacement levels, followed
the same trend as that of the water permeability. Therefore, at
10% level of replacement, RSA blended cement can produce better
concrete than control in terms of compressive strength and
durability.
Conclusions
The suitability of the rice straw from the thermochemical conver-
sion of rice straw as a pozzolanic material has been described in this
paper. The investigations into the mineralogical and morphological
profiles of raw rice-straw samples proved its amorphous nature and
the presence of distinct dumbbell-shaped phytoliths in the rice-
straw matrix. The RSA obtained from various pyrolytic tempera-
tures was silica rich and amorphous. Concrete specimens blended
with RSA showed about a 6.3% increase in compressive strength
compared to control concrete at a level of replacement of 10%. The
resistance of concrete against water penetration and chloride in-
gression was found to be significantly enhanced upon the addition
of RSA up to a level of replacement of 20%. However, the maxi-
mum reduction in water penetration (20.9%) and chloride penetra-
tion (29.6%) compared to control was observed for specimens at
10% level of cement replacement.
Data Availability Statement
Some or all data, models, or code that support the findings of this
study are available from the corresponding author upon reasonable
request.
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