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
Downloaded from ascelibrary.org by CASA Institution Identity on 07/17/21. Copyright ASCE. For personal use only; all rights reserved.

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

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

© ASCE 04021123-1 J. Mater. Civ. Eng.

J. Mater. Civ. Eng., 2021, 33(6): 04021123

 Ataie and Riding 2013; Jenkins et al. 1998), studies on the use of as 800°C at a heating rate of 10°C=min. The analysis was carried
RSA as an SCM are very limited. For instance, earlier studies have out at an inert atmosphere of N2 at a flow rate of 50 mL=min. The
investigated the pozzolanic nature of RSA for its use as a pozzo- monitoring scan rate was set to one second. The TGA samples were
lanic material, and it was found to be sufficiently pozzolanic and kept in a platinum crucible. The morphology of the rice-straw sam-
composed of amorphous silica resembling the composition of the ples and the distinct components of the same were studied using an
ordinary glass (Jenkins et al. 1998). The lime consumption and FEI Apreo LoVac field emission scanning electron microscope
Frattini tests on rice-straw ash also indicated the pozzolanicity (SEM). Fourier transform infrared spectroscopy (FT-IR) was used
of RSA. Lime-RSA pastes were found to develop the pozzolanic to measure the absorbance spectra of the components of rice-straw
reaction product CSH after 7 and 28 days of curing (Roselló et al. samples.
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 Estimation of Kinetic Parameters of Rice-Straw
(Ataie and Riding 2016). It was also reported that the compressive Pyrolysis
Downloaded from ascelibrary.org by CASA Institution Identity on 07/17/21. Copyright ASCE. For personal use only; all rights reserved.

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

© ASCE 04021123-2 J. Mater. Civ. Eng.

J. Mater. Civ. Eng., 2021, 33(6): 04021123

     
ð1 − xÞ1−n − 1 AR 2RT E trichomes, dumbbell-shaped phytoliths, fibrous members with
ln ¼ ln 1 − − a; n≠1 vascular channels, and adaxial part of the leaves with intact stoma
ðn − 1ÞT 2 βEa Ea RT
are some of the well-defined features identified in the rice-straw
ð6Þ microstructure. Fig. 1(a) shows the phytoliths in the rice-straw
fibers.
Essentially, phytoliths are inorganic silicified structures in plants
Pyrolysis and Characterization of Rice-Straw Ash
that do not decay along with the plant. Plants absorb orthosilicic
A quartz U-tube was used to perform the pyrolysis experiments, acid and other minerals along with water in silica-rich soils. After
which was placed inside a tubular furnace. The reactions were car- the water is used for its digestive processes, the silica is polymer-
ried out in an inert N2 environment with a 200 mL=min flow rate. ized into amorphous silica and gets deposited as rigid structures in
The electric furnace was heated to the desired temperature, and the the plant stem or leaves. Phytoliths can remain intact long after the
finely ground biomass was dropped from the top of the heating plants decay and can become fossilized with the genetic material of
zone with a special arrangement. The experiments were carried the plant inside. This phenomenon has made phytoliths a topic of
Downloaded from ascelibrary.org by CASA Institution Identity on 07/17/21. Copyright ASCE. For personal use only; all rights reserved.

out at temperatures of 400°C–700°C with an interval of 50°C, extensive investigation in the fields of archaeology and paleoecol-
and the residual ash was collected at the bottom of the quartz re- ogy (Piperno 2006).
actor. The mineralogical and morphological evolution of the ash Although phytoliths have been observed to have various shapes,
samples across the temperature ranges were studied by subjecting the phytoliths in the rice plants collected in the study are observed
them to X-ray diffraction studies and SEM imaging. to be predominantly dumbbell shaped. The presence of silica in
phytoliths is visible from the energy-dispersive spectroscopic stud-
Performance Evaluation of Rice-Straw Ash in Cement ies conducted on rice samples. As can be seen from Fig. 1(b), the
Concrete elemental mapping study of rice-straw fibers using energy disper-
sive X-ray spectroscopy (EDS) revealed that the phytoliths were
The amorphous silica in RSA can aid in its usage as an alternative silica rich. Apart from the dumbbell-shaped structures, some globu-
cementitious material. The modification of the mechanical and lar structures were also found to be present on the surface of the rice-
durability properties of cement concrete upon the addition of RSA straw fibers, neatly aligned in rows, as seen in Fig. 1(c). Fig. 1(d)
was investigated in this study. The mechanical properties of shows the SEM-EDS analysis of these spherical structures, and it
the RSA blended concrete were determined by studying the varia- was found that these were also composed mostly of SiO2 .
tion in the 28-day compressive strength at different levels of Therefore, it can be concluded that the phytoliths in rice straw
replacement. The compressive strength of the RSA blended con- exist in both dumbbell and spherical structures. The variation in
crete specimens was conducted at three different levels of replace- the shape of the silica storing structures could be due to the lo-
ment (10%, 20%, and 30%). Concrete specimens of 150 × 150 × cation of the silica deposition. It has been proved in earlier studies
150 mm were made in accordance with IS 516-1959 (Bureau of that the shape of the phytoliths is influenced by the type of the
Indian Standards 2004) for compressive strength testing. The load- plants and the location of the silica storage in the plants (Anala
ing rate was set as 140 kg=cm2 =min. and Nambisan 2015). The presence of potassium in the phytoliths
The durability of blended concrete depends on the pore refine- as seen from Fig. 1(d) could be due to the occlusion and immo-
ment characteristics of the mineral admixture. Therefore, the water bilization of the potassium species (phytOK) at the time of silici-
penetration resistance of RSA blended concrete specimens was in- fication of the cell wall or the extracellular layers (Athira et al.
vestigated in this study following the DIN 1048 test procedure 2019). These silica-rich spherical structures are found in abun-
[DIN 1048: Part-5 (DIN 1991)]. Concrete cubes of 150 mm size dance in the rice straw microstructure and differ slightly in ap-
were used for the test procedure after 28 days of curing. The spec- pearance, as seen in Figs. 1(e and d). The surfaces of most of
imens were placed in the water permeability apparatus, and the the rice-straw fibers are filled with these spherical (and sometimes
cover plate was lowered on to the top surface of the specimen. bulbous) protrusions unless they are carbon-rich coarse particles
A rubber gasket was placed in between the top surface of the speci- with vascular channels. The needle-shaped structures present in
men and the cover plate to prevent the leakage of water. Water pres- the rice straw samples are epidermal appendages called trichomes,
sure of 0.5 N=mm2 was applied to the top surface of the specimens which also absorb water and biominerals. Trichomes can be found
for three consecutive days. After 72 h, the specimens were re- in the stem and leaves of the rice plant. The trichomes in the stem
moved, and they were split into two halves along the direction are short and stay close to the surface, whereas those on the
of the flow of water. The water penetration depth of all the spec- leaves are longer. As the water is transported along the stem to
imens was marked within 5 min before the specimens dried. The the leaves, the silica often gets left behind and hardens in the
average penetration depth of a set for each mix was reported as trichomes.
the final water penetration depth. Similarly, the resistance of the Fig. 1(g) shows the trichomes on the rice-straw fibers, along
blended concrete against chloride penetration was investigated with the bulbous phytoliths. The presence of silica in these struc-
by conducting a rapid chloride permeability test (RCPT) as per tures is evident from the EDS mapping analyses shown in Fig. 1(h).
ASTM C1202-19 (ASTM 2019).

Elemental Analysis of Rice-Straw Samples

Results and Discussion
The ultimate analysis results for all the five samples of rice straw
are presented in Table 1, including the ash content as determined
Morphological Characterization of Rice Straw
from the thermogravimetric analyses. The oxygen content was de-
Compared to the numerous investigations conducted on rice husk termined by calculating the difference. The average ash content in
and its residual ashes, the morphology of rice straw is not very the samples was found to be about 22.8% as per the thermogravi-
well studied in the existing literature. Scanning electron micro- metric analysis.
graphs of Indian rice-straw samples obtained in this study reveal It can be seen that compared to other biomass materials such as
various distinct morphological features. Needle/thistle shaped bagasse, olive residues, and palm oil waste (Jindo et al. 2014;

© ASCE 04021123-3 J. Mater. Civ. Eng.

J. Mater. Civ. Eng., 2021, 33(6): 04021123

Downloaded from ascelibrary.org by CASA Institution Identity on 07/17/21. Copyright ASCE. For personal use only; all rights reserved.

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.

© ASCE 04021123-4 J. Mater. Civ. Eng.

J. Mater. Civ. Eng., 2021, 33(6): 04021123

 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-
Downloaded from ascelibrary.org by CASA Institution Identity on 07/17/21. Copyright ASCE. For personal use only; all rights reserved.

This is attributed to the significantly greater silica content in rice ligible. The residual mass after temperature Z is termed as the ash
straw. An average of 32% carbon, 4.5% hydrogen, 0.7% nitrogen, content in the material, and the mass loss that occurred in the in-
and 0.12% sulfur are present in the rice-straw samples. It is also terval between Y and Z is considered as the combustible material
interesting to note that the elemental compositions of all five content. The X, Y, and Z temperatures are not predefined in the case
rice-straw samples are similar, with only marginal differences. The of biomass materials. In order to understand the ranges of volatili-
low sulfur content of sample R5 makes it a better feedstock for the zation, rice straw was subjected to heating under both an inert (N2
production of value-added chemicals using in-situ catalytic fast atmosphere) and reactive (dry air) environments.
pyrolysis technique, as it can avoid the deactivation of catalysts Figs. 2(a and b) shows the thermograms of rice straw at a heat-
due to sulfur poisoning (Appari et al. 2014). 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.

© ASCE 04021123-5 J. Mater. Civ. Eng.

J. Mater. Civ. Eng., 2021, 33(6): 04021123

 Table 2. Zones of thermal decomposition and mass-loss rates at the peaks Table 3. Proximate analysis of rice straw from thermogravimetric data as
per ASTM E1131
Mass-loss rate
at the peak Highly volatile Medium volatile Combustible Ash
Peak Onset Offset
Sample matter (%) matter (%) material (%) content (%)
Item Zone temperature temperature temperature %=s %/°C
R1 8.42 58.33 7.61 25.66
In air I 62.3 30 126.8 −0.0288 −0.248
R2 8.94 59.96 8.45 22.67
II 285.75 171.1 335 −0.547 −0.496
R3 8.99 60.49 7.55 22.99
III 388.9 335 519.4 −0.0321 −0.244
R4 7.37 61.79 8.35 22.50
In N2 I 59.76 30 130 −0.0349 −0.246 R5 8.23 62.62 8.75 20.41
II 312.15 201.2 409.2 −0.0851 −0.609

oxygen promotes the mass decomposition at lower temperatures.

Downloaded from ascelibrary.org by CASA Institution Identity on 07/17/21. Copyright ASCE. For personal use only; all rights reserved.

N2 atmospheres. The early thermal degradation patterns at both the This is in line with earlier findings reported for other biomass com-
atmospheres are found to be similar, indicating the removal of bustion (Chen et al. 2011; Ma et al. 2018). However, when biomass
highly volatile matter such as moisture and other impurities that conversion was calculated with respect to the temperature incre-
are not part of the lignocellulosic structural matrix of rice straw. ment across the range of 202°C–409°C, slightly higher mass loss
Figs. 2(c and d) shows the derivative thermograms of rice-straw was observed at the peak temperature (312°C) under the nitrogen
degradation in dry air (combustion) and nitrogen (pyrolysis) envi- environment. The difference arising in the mass-loss rates with re-
ronment. The initial mass-loss curve from 30°C–120°C is attributed spect to time and temperature is because mass-loss rate is calculated
to the release of highly volatile materials after which a mass-loss per second in the case of DTG curves with respect to time, whereas
plateau is achieved at around 110°C–125°C (X) for rice straw at mass-loss rates with respect to temperature are calculated per de-
both the atmospheres. Beyond this temperature, a region of rapid gree Celsius (or six seconds as β ¼ 10°C=min). Therefore, instan-
volatilization of biomass is observed from 217°C to 480°C, as de- taneous mass changes can be seen from mass loss plotted with
scribed by the sharp slopes of the thermogravimetric curves. respect to time, while mass changes with respect to a broader time
The thermal decomposition pattern of rice straw in this temper- range can be seen from mass loss plotted with temperature.
ature interval differs with respect to the environment. For instance, A third zone of mass loss is observed in the case of air atmos-
there is a distinct and steep mass-loss curve from 217°C to 323°C phere, starting at 335°C and ending at around 520°C, centered
for rice straw under the reactive atmosphere. Further, a second stage at 388°C. This zone is not significant or is entirely absent in the
of decomposition is observed, which continues till 480°C. How- derivative thermograms under a nitrogen environment. Therefore,
ever, under the nitrogen atmosphere, the steep mass loss is observed it can be assumed that the mass loss in this temperature range is due
till 358°C, beyond which the decomposition trend is unchanged to char combustion and the devolatilization of the combustible
until the target temperature is reached (900°C). The residual ash materials in the presence of oxygen.
content of the rice straw under the inert atmosphere was found From the thermogravimetric studies, the volatilization behavior
to be about 31%. However, the ash content under the reactive envi- of rice straw was studied, and the switchover points for the TGA
ronment is about 22%. The exact mass loss rate and zones of bio- based proximity analyses were determined. The initial temperature
mass conversion can be observed from the derivative thermograms to determine the moisture content (X) was fixed as 120°C based on
as depicted in Figs. 2(c and d). Fig. 2(c) shows the derivative ther- the TGA curves. Then, 600°C was considered as the final temper-
mogravimetric (DTG) curve of rice straw mass decomposition with ature for the decomposition of volatile materials (Y), as all the steep
respect to temperature. As discussed, the initial temperature region mass losses under pyrolysis conditions occur before that temper-
where the highly volatile materials decompose are similar in both ature. The temperature to determine the ash content (Z) was taken
the atmospheres, as the presence of oxygen does not affect the re- as 900°C.
lease of moisture. However, the second volatilization peaks in both Based on these parameters, the composition of rice-straw
atmospheres differ as there is an apparent right shift of peak mass- samples collected in this study (R1–R5) is determined and given
loss rate in the case of inert conditions. It was also observed that the in Table 3. An average of about 8.4% highly volatile materials were
peak mass-loss rate with respect to temperature in this zone is found to be present in the rice-straw samples. Similarly, the
slightly more for decomposition under pyrolysis than combustion. medium volatile material components constituted an average of
Table 2 shows the characteristics of each of the identified devola- 60.6%. The fixed carbon/combustible material in the samples came
tilization zones of rice straw under inert and reactive environments. out to be around 8.14%. The ash content in all the samples was
Three distinct biomass decomposition zones are observed in the above 20%. This is significantly greater than other biomass mate-
air atmosphere, whereas only two zones can be identified in the rials such as bagasse, wood, or other agricultural wastes (Dhyani
case of an inert atmosphere. The initial mass-loss curves have peaks and Bhaskar 2018; Gopinath et al. 2018). The higher ash content in
at 62.3°C and 59.7°C and a mass-loss plateau at around 126°C–130° rice straw is attributed to the higher amounts of inorganic silica
C under reactive and inert atmospheres, respectively. The mass-loss present in the phytoliths of rice straw, as is confirmed from the mor-
rates at both peaks are also similar. The second zone of thermal phological studies.
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 Structural Composition of Rice-Straw Samples from
of N2 . While the shift in the onset temperature for the second vola- TGA and FT-IR Studies
tilization curve is only about 30°C, the right shift in the offset tem- The thermogravimetric data obtained for the rice straw samples are
perature is quite significant (∼75°C). Considering the derivative of a superposition of the decomposition of their individual fiber com-
mass loss with respect to time, a significantly higher mass-loss rate ponents such as hemicellulose, cellulose, and lignin. Therefore, in
can be seen in the case of biomass decomposition under a reactive order to determine the relative decomposition of each of these indi-
atmosphere. Therefore, it can be assumed that the presence of vidual components, a deconvolution method is adopted, through

© ASCE 04021123-6 J. Mater. Civ. Eng.

J. Mater. Civ. Eng., 2021, 33(6): 04021123

 Table 4. Properties of the deconvolved DTG curves for each rice-straw sample
DC1—peak DC2–peak DC3–peak DC4–peak
Sample temperature (°C) temperature (°C) temperature (°C) temperature (°C) R2
R1 61.48 300.6 325.9 405.6 0.99
R2 64.97 294.0 316.4 406.0 0.99
R3 62.64 296.9 319.2 420.1 0.99
R4 59.12 295.3 317.1 419.1 0.99
R5 63.21 285.5 301.1 377.4 0.99

which the underlying mass-loss peaks for individual components peak at a temperature range of 405°C–420°C, except for R5 which
may be observed. For this, the peaks in the original TGA curves had a peak for the lignin deconvolved curve at around 377°C. From
Downloaded from ascelibrary.org by CASA Institution Identity on 07/17/21. Copyright ASCE. For personal use only; all rights reserved.

were identified for all the rice-straw samples, and a Levenberg– the deconvolution procedure adopted in the study, the area under
Marquardt algorithm was used for the deconvolution with a Gaus- the fitted curves was calculated, which were remarkably similar for
sian fitting function. The iterations were continued till convergence. all the rice-straw samples. FT-IR is an effective tool in the identi-
The temperature ranges for hemicellulose, cellulose, and lignin fication of the lignocellulosic components in biomass species. The
decomposition in various biomass materials are identified to be rice-straw samples in this study were subjected to attenuated total
260°C–300°C, 330°C–370°C, and 200°C–600°C in the literature reflectance (ATR) infrared spectroscopy, and the observed absorb-
(Bryś et al. 2016; Yang et al. 2007). ance spectra are presented in Fig. 4.
Following deconvolution of the derivative thermograms, similar The most significant absorbance peak was observed at a
peaks were also observed for all the rice-straw samples investigated wavenumber of 1,035–1,036 cm−1 , which is related to the C─O
in the study, as can be seen from Table 4. After the initial moisture and C─C─O stretching of cellulose, hemicellulose, and lignin
release peak, another peak centered at around 300°C was observed (Nybacka 2016). In addition, the peaks at 789 cm−1 may also
for the first deconvolved curve. Another noticeable peak was ob- correspond to the vibrations in hemicellulose and/or lignin. The
served in the range of 317°C–325°C. Even though not clearly dis- increase in the intensity at the ∼897 cm−1 region is a distinct fea-
cernible from the original DTG curves, another deconvolution ture of glycosidic CH deformation with ring vibration, which is
curve with broad peaks at around 405°C–420°C was also revealed, a typical structure of amorphous cellulose (Nelson and O’Connor
which is attributed to the decomposition of lignin. The deconvolu- 1964). Moreover, the absorbance peak at 1,160 cm−1 is ascribed to
tion of the DTG of each rice-straw sample in the study is shown in C─O─C asymmetrical stretching of cellulose and hemicellulose
Fig. 3, and it can be seen that the simulated DTG curve is an exact (Shi et al. 2012). A peak at the band in the region of 1,327 cm−1
fit to the observed derivative thermogram in all five cases. indicates the C─O of the syringyl ring of lignin (Traoré et al. 2016).
The third curve corresponding to lignin degradation appeared to Intensity at ∼1,369 cm−1 is related to CH deformation in cellulose
be the broadest of all, with almost all samples reporting a mass-loss and hemicellulose. The two absorption bands at 1,465 cm−1 and

Fig. 3. Deconvolved thermogravimetric curves for all five rice-straw samples.

© ASCE 04021123-7 J. Mater. Civ. Eng.

J. Mater. Civ. Eng., 2021, 33(6): 04021123

Downloaded from ascelibrary.org by CASA Institution Identity on 07/17/21. Copyright ASCE. For personal use only; all rights reserved.

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- apparent activation energy calculated from the OFW method for
ilarly, the band at around 1,633 cm−1 is characteristic of absorbed rice straw is thus found to be 155.83 kJ=mol. Similarly, another
O─H (Cao and Tan 2004) and conjugated lignin or cellulose, isoconversional method employed in this study for the determina-
whereas absorbance peak ∼1,730 cm−1 indicates the C═O stretch tion of apparent activation energy is the Kissinger–Akahira–Sunose
of hemicellulose. (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
Reaction Kinetics of Rice-Straw Pyrolysis method is based on the linear relationship between lnðβ=T 2 Þ and
(1=T) as shown in Fig. 5(d).
Model-Free ISO-Conversional Kinetic Models for Rice-Straw Table 5 also shows the apparent activation energies calculated as
Pyrolysis: OFW and KAS per the KAS method for various conversion percentages. It can be
In order to determine the reaction kinetics of the rice-straw pyroly- seen that as in the OFW method, the activation energies at higher
sis process, thermogravimetric analysis was conducted under vari- conversion percentages tend to be higher. The average apparent ac-
ous heating rates (from 10°C=min to 50°C=min). In this study, the tivation energy for conversion from 10% to 75% is calculated to be
pyrolysis kinetics are evaluated using the thermogravimetric data about 155.38 kJ=mol. This is very close to the activation energy as
based on model-free kinetics. The thermogravimetric curves obtained from the OFW method. The coefficient of correlation (r)
of the rice-straw samples under various heating rates are given in values were also found to be reasonable and in most cases were
Fig. 5(a). The derivative thermograms of the samples at various higher than 0.95.
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. Coats–Redfern Kinetic Model for Rice-Straw Pyrolysis
The only differences were in the final residual ash content. The The overall apparent activation energies, preexponential factors,
OFW method of determining apparent activation energy depends and apparent reaction orders of the Arrhenius equation cannot
on the assumption that the natural logarithm of heating rate be estimated using the isoconversional models used previously.
(ln β) has a linear relationship with the reciprocal of temperature Therefore, the overall apparent activation energy for the medium
(K) at various heating rates for the same conversion percentage. volatilization region, preexponential factors, and apparent reaction
Fig. 5(c) shows the relationship between lnβ and 1=T for a rice- orders of rice-straw pyrolysis were determined based on the Coats–
straw sample at conversion percentages from 10% to 70% for five Redfern equation.
heating rates from 10°C=min to 50°C=min. The slopes of the lines The apparent reaction order and the preexponential factors were
were found to be almost similar initially; however, at later conver- selected based on the best fit according to the coefficient of deter-
sion percentages, the slopes were found to increase. The increase in mination values. The fit statistics for a heating rate of 20°C=min
slope indicates the higher activation energy which is required to and apparent reaction orders from n ¼ 1 to n ¼ 2.8 are shown
decompose the lignin content in the rice straw. Therefore, for in Table 6. It can be seen that the highest R2 value is for a reaction
the range of conversion studied, it was observed that the reactions order of 2.1, and the corresponding overall apparent activation en-
that occur at the later stages of biomass pyrolysis (at a higher tem- ergy for the temperature range of medium volatiles decomposition
perature) require greater activation energy to result in products. The was found to be 63.56 kJ=mol. Similarly, the apparent reaction or-
calculated apparent activation energies at a specified conversion ders and activation energy for rice straw at various heating rates
percentage and the Pearson coefficient are described in Table 5. were determined, as shown in Table 7.
It is observed that almost all the coefficient of correlation is above The overall apparent activation energy (averaged at different
0.95, except for some at the higher conversion rates. The average heating rates) for rice-straw pyrolysis, therefore, comes to be

© ASCE 04021123-8 J. Mater. Civ. Eng.

J. Mater. Civ. Eng., 2021, 33(6): 04021123

Downloaded from ascelibrary.org by CASA Institution Identity on 07/17/21. Copyright ASCE. For personal use only; all rights reserved.

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.

© ASCE 04021123-9 J. Mater. Civ. Eng.

J. Mater. Civ. Eng., 2021, 33(6): 04021123

 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
Downloaded from ascelibrary.org by CASA Institution Identity on 07/17/21. Copyright ASCE. For personal use only; all rights reserved.

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

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

© ASCE 04021123-10 J. Mater. Civ. Eng.

J. Mater. Civ. Eng., 2021, 33(6): 04021123

Downloaded from ascelibrary.org by CASA Institution Identity on 07/17/21. Copyright ASCE. For personal use only; all rights reserved.

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

© ASCE 04021123-11 J. Mater. Civ. Eng.

J. Mater. Civ. Eng., 2021, 33(6): 04021123

Downloaded from ascelibrary.org by CASA Institution Identity on 07/17/21. Copyright ASCE. For personal use only; all rights reserved.

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.

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
Fig. 9. Compressive strength of RSA blended concrete at various re- reduction in water penetration depth of concrete on the addition
placement levels. 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
Fig. 10. Water penetration depth of RSA blended concrete specimens.
the “Moderate chloride ion penetrability” category, along with

© ASCE 04021123-12 J. Mater. Civ. Eng.

J. Mater. Civ. Eng., 2021, 33(6): 04021123

 biogas: An experimental investigation.” Int. J. Hydrogen Energy 39 (1):
297–304. https://doi.org/10.1016/j.ijhydene.2013.10.056.
ASTM. 2015. Standard test method for compositional analysis by thermog-
ravimetry. ASTM E1131-08. West Conshohocken, PA: ASTM.
ASTM. 2019. Standard test method for electrical indication of concrete’s
ability to resist chloride ion penetration. ASTM C1202-19. West
Conshohocken, PA: ASTM.
Ataie, F. F., and K. A. Riding. 2013. “Thermochemical pretreatments for
agricultural residue ash production for concrete.” J. Mater. Civ. Eng.
25 (11): 1703–1711. https://doi.org/10.1061/(ASCE)MT.1943-5533
.0000721.
Ataie, F. F., and K. A. Riding. 2016. “Influence of agricultural residue ash
on early cement hydration and chemical admixtures adsorption.”
Constr. Build. Mater. 106 (Mar): 274–281. https://doi.org/10.1016/j
Downloaded from ascelibrary.org by CASA Institution Identity on 07/17/21. Copyright ASCE. For personal use only; all rights reserved.

.conbuildmat.2015.12.091.
Athira, G., A. Bahurudeen, and S. Appari. 2019. “Sustainable alternatives
to carbon intensive paddy field burning in India: A framework for
cleaner production in agriculture, energy, and construction industries.”
Fig. 11. Total charge passed values from RCPT test of RSA blended
J. Cleaner Prod. 236 (Nov): 117598. https://doi.org/10.1016/j.jclepro
cement concrete. .2019.07.073.
Bharadwaj, A., Y. Wang, S. Sridhar, and V. S. Arunachalam. 2004. “Pyroly-
sis of rice husk.” Curr. Sci. 87 (7): 981–986.
Binod, P., R. Sindhu, R. R. Singhania, S. Vikram, L. Devi, S. Nagalakshmi,
30% RSA. The chloride permeability, as measured by RCPT of N. Kurien, R. K. Sukumaran, and A. Pandey. 2010. “Bioethanol pro-
RSA blended concrete at different replacement levels, followed duction from rice straw: An overview.” Bioresour. Technol. 101 (13):
the same trend as that of the water permeability. Therefore, at 4767–4774. https://doi.org/10.1016/j.biortech.2009.10.079.
10% level of replacement, RSA blended cement can produce better BIS (Bureau of Indian Standards). 2004. Method of tests for strength of
concrete than control in terms of compressive strength and concrete. IS 516-1959 (Reaffirmed 2004). Berlin: BIS.
durability. Bryś, A., J. Bryś, E. Ostrowska-Ligęza, A. Kaleta, K. Górnicki, S.
Głowacki, and P. Koczoń. 2016. “Wood biomass characterization by
DSC or FT-IR spectroscopy.” J. Therm. Anal. Calorim. 126 (1):
Conclusions 27–35. https://doi.org/10.1007/s10973-016-5713-2.
Cao, Y., and H. Tan. 2004. “Structural characterization of cellulose with
The suitability of the rice straw from the thermochemical conver- enzymatic treatment.” J. Mol. Struct. 705 (1–3): 189–193. https://doi
sion of rice straw as a pozzolanic material has been described in this .org/10.1016/j.molstruc.2004.07.010.
paper. The investigations into the mineralogical and morphological Chen, H., W. Zhao, and N. Liu. 2011. “Thermal analysis and decomposi-
tion kinetics of Chinese forest peat under nitrogen and air atmospheres.”
profiles of raw rice-straw samples proved its amorphous nature and
In Energy and fuels, 797–803. Washington, DC: American Chemical
the presence of distinct dumbbell-shaped phytoliths in the rice-
Society.
straw matrix. The RSA obtained from various pyrolytic tempera- Coats, A. W., and J. P. Redfern. 1964. “Kinetic parameters from thermog-
tures was silica rich and amorphous. Concrete specimens blended ravimetric data.” Nature 201 (4914): 68–69. https://doi.org/10.1038
with RSA showed about a 6.3% increase in compressive strength /201068a0.
compared to control concrete at a level of replacement of 10%. The Dhyani, V., and T. Bhaskar. 2018. “A comprehensive review on the pyroly-
resistance of concrete against water penetration and chloride in- sis of lignocellulosic biomass.” Renewable Energy 129 (Dec): 695–716.
gression was found to be significantly enhanced upon the addition https://doi.org/10.1016/j.renene.2017.04.035.
of RSA up to a level of replacement of 20%. However, the maxi- DIN (Deutsches Institut für Normung). 1991. German standard for deter-
mum reduction in water penetration (20.9%) and chloride penetra- mination of permeability of concrete. DIN 1048. Berlin: DIN.
tion (29.6%) compared to control was observed for specimens at Doyle, C. D. 1961. “Kinetic analysis of thermogravimetric data.”
10% level of cement replacement. J. Appl. Polym. Sci. 5 (15): 285–292. https://doi.org/10.1002/app
.1961.070051506.
Gopinath, A., A. Bahurudeen, S. Appari, and P. Nanthagopalan. 2018. “A
circular framework for the valorisation of sugar industry wastes: Review
Data Availability Statement on the industrial symbiosis between sugar, construction and energy in-
dustries.” J. Cleaner Prod. 203 (12): 89–108. https://doi.org/10.1016/j
Some or all data, models, or code that support the findings of this .jclepro.2018.08.252.
study are available from the corresponding author upon reasonable Jenkins, B., L. Baxter, T. Miles, and T. Miles. 1998. “Combustion proper-
request. ties of biomass.” Fuel Process. Technol. 54 (1–3): 17–46. https://doi
.org/10.1016/S0378-3820(97)00059-3.
Jindo, K., H. Mizumoto, Y. Sawada, M. A. Sanchez-Monedero, and T.
References Sonoki. 2014. “Physical and chemical characterization of biochars de-
rived from different agricultural residues.” Biogeosciences 11 (23):
Abou-Sekkina, M. M., R. M. Issa, A. E. D. M. Bastawisy, and W. A. 6613–6621. https://doi.org/10.5194/bg-11-6613-2014.
El-Helece. 2010. “Characterization and evaluation of thermodynamic Ma, Z., J. Wang, Y. Yang, Y. Zhang, C. Zhao, Y. Yu, and S. Wang. 2018.
parameters for Egyptian heap fired rice straw ash (RSA).” Int. J. Chem. “Comparison of the thermal degradation behaviors and kinetics of palm
2 (1): 81–88. https://doi.org/10.5539/ijc.v2n1p81. oil waste under nitrogen and air atmosphere in TGA-FTIR with a com-
Anala, R., and P. Nambisan. 2015. “Study of morphology and chemical plementary use of model-free and model-fitting approaches.” J. Anal.
composition of phytoliths on the surface of paddy straw.” Paddy Water Appl. Pyrolysis 134 (Sep): 12–24. https://doi.org/10.1016/j.jaap.2018
Environ. 13 (4): 521–527. https://doi.org/10.1007/s10333-014-0468-5. .04.002.
Appari, S., V. M. Janardhanan, R. Bauri, and S. Jayanti. 2014. “Deactiva- Nelson, M. L., and R. T. O’Connor. 1964. “Relation of certain infrared
tion and regeneration of Ni catalyst during steam reforming of model bands to cellulose crystallinity and crystal lattice type. Part II. A

© ASCE 04021123-13 J. Mater. Civ. Eng.

J. Mater. Civ. Eng., 2021, 33(6): 04021123

 new infrared ratio for estimation of crystallinity in celluloses I and II.” Procedia 16 (Jan): 758–762. https://doi.org/10.1016/j.egypro.2012
J. Appl. Polym. Sci. 8 (3): 1325–1341. https://doi.org/10.1002/app.1964 .01.122.
.070080323. Traoré, M., J. Kaal, and A. Martínez Cortizas. 2016. “Application of FTIR
Nybacka, L. 2016. Fourier transform infrared spectroscopy of glucose. spectroscopy to the characterization of archeological wood.” Spectro-
Uppsala, Sweden: Fourier Transform Infrared Spectroscopy. chim. Acta, Part A 153 (Jan): 63–70. https://doi.org/10.1016/j.saa.2015
Ounas, A., A. Aboulkas, K. El harfi, A. Bacaoui, and A. Yaacoubi. 2011. .07.108.
“Pyrolysis of olive residue and sugar cane bagasse: Non-isothermal USDA. 2020. World agricultural production. Washington, DC:
thermogravimetric kinetic analysis.” Bioresour. Technol. 102 (24): USDA.
11234–11238. https://doi.org/10.1016/j.biortech.2011.09.010. Varma, A. K., and P. Mondal. 2016. “Physicochemical characterization and
Piperno, D. R. 2006. Phytoliths: A comprehensive guide for archaeologists
pyrolysis kinetic study of sugarcane bagasse using thermogravimetric
and paleoecologists. Lanham, MD: Rowman Altamira.
analysis.” J. Energy Resour. Technol. 138 (5): 052205. https://doi.org
Ramasamy, V. 2012. “Compressive strength and durability properties of
/10.1115/1.4032729.
rice husk ash concrete.” J. Civ. Eng. 16 (1): 93–102. https://doi.org/10
.1007/s12205-012-0779-2. Yadav, R. S. 2019. “Stubble burning: A problem for the environment, agri-
Roselló, J., L. Soriano, M. P. Santamarina, J. L. Akasaki, J. Monzó, and J. culture and humans.” Down To Earth. Accessed June 4, 2019. https://
Downloaded from ascelibrary.org by CASA Institution Identity on 07/17/21. Copyright ASCE. For personal use only; all rights reserved.

Payá. 2017. “Rice straw ash: A potential pozzolanic supplementary www.downtoearth.org.in/blog/agriculture/stubble-burning-a-problem-for

material for cementing systems.” Ind. Crops Prod. 103 (Sep): -the-environment-agriculture-and-humans-64912.
39–50. https://doi.org/10.1016/j.indcrop.2017.03.030. Yang, H., R. Yan, H. Chen, D. H. Lee, and C. Zheng. 2007. “Characteristics
Shi, J., D. Xing, and J. Li. 2012. “FTIR studies of the changes in wood of hemicellulose, cellulose and lignin pyrolysis.” Fuel 86 (12–13):
chemistry from wood forming tissue under inclined treatment.” Energy 1781–1788. https://doi.org/10.1016/j.fuel.2006.12.013.

© ASCE 04021123-14 J. Mater. Civ. Eng.

J. Mater. Civ. Eng., 2021, 33(6): 04021123