Journal of Cleaner Production 286 (2021) 125429

Contents lists available at ScienceDirect

Journal of Cleaner Production

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

Review

Agro-waste ash based alkali-activated binder: Cleaner production of

zero cement concrete for construction
VS Athira, V Charitha, G Athira, A Bahurudeen*
Department of Civil Engineering, Birla Institute of Technology and Science Pilani, Hyderabad Campus, Hyderabad, India

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

Article history: Alkali-activated binders are sustainable alternatives to carbon-intensive conventional cements. A
Received 11 August 2020 comprehensive review of the potential of different agro-waste ashes and their performance as precursors
Received in revised form in alkali-activated binders are essential to enable their acceptance in the construction sector. Hence, the
19 November 2020
present study focusses on a systematic review of the alkali-activation of bagasse ash, rice husk ash, corn
Accepted 4 December 2020
Available online 11 December 2020
cob ash, palm oil fuel ash, wheat straw ash, and sugarcane straw ash. Moreover, their influence on the
mechanical and durability characteristics of alkali-activated concrete is also presented. Based on the
Handling editor: Prof. Jiri Jaromir Klemes review, it is found that except for rice husk ash, all the other agro-waste ashes have almost similar silica
content as that of fly ash. The morphologies of the different agro-waste ashes are found to be distinct.
Keywords: Incorporation of agro-waste ashes in fly ash-based binders results in better resistance to acid attack than
Alkali activated binder slag-based binders. Addition of agro-waste ashes brought down the drying shrinkage of slag-based
Agro waste binders significantly. Ambient curing is beneficial for bagasse ash-based alkali-activated mortar speci-
Precursor mens. Water absorption is higher for agro-waste ash based alkali-activated binder specimens due to the
Durability
porous cellular structure of agro-waste ashes. Enhanced performance at elevated temperatures is
Concrete
observed for agro-waste ash based alkali-activated binders. Rice husk ash-based binders are remarkably
Biochar
stable at elevated temperatures.
© 2020 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Current status of agro-waste ash utilisation and significance of the current study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3. Methodology adopted for review . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
4. Characteristics of residual ashes from agro-industries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
4.1. Chemical composition of agro-waste ashes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
4.2. Microstructure of agro-waste ashes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
5. Alkali-activated binders: reaction mechanisms and hydration products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
6. Mechanical characteristics of agro-waste ash based AAB . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
6.1. Influence of activator on the compressive strength of agro-waste ash based AAB . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
6.2. Effects of replacement of slag and fly ash with AWA on the compressive strength of AAB specimens . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
6.3. Influence of molarity of activators on the compressive strength of AAB specimens . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
6.4. Influence of curing on compressive strength of agro-waste ash based AAB specimens . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
6.5. Tensile and flexural strength of agro-waste ash based AAB specimens . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
7. Durability of agro-waste ash based AAB specimens . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
7.1. Resistance of agro-waste based AAB specimens against acid attack . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
7.2. Water absorption of agro-waste ash based AAB specimens . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
7.3. Sulphate resistance of agro-waste ash based AAB specimens . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
7.4. Drying shrinkage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13

* Corresponding author. Birla Institute of Technology and Science Pilani, Hyder-

abad Campus, Hyderabad, 500078, India.
E-mail address: bahur@hyderabad.bits-pilani.ac.in (A. Bahurudeen).

https://doi.org/10.1016/j.jclepro.2020.125429
0959-6526/© 2020 Elsevier Ltd. All rights reserved.
V. Athira, V. Charitha, G. Athira et al. Journal of Cleaner Production 286 (2021) 125429

7.5. Resistance to chloride ingression and corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

8. Performance of agro-waste ash based AAB at elevated temperatures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
9. Directions for future research studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
10. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
Declaration of competing interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

1. Introduction that provide a direct and detailed relative comparison of the

different types of agro-waste ashes in view of their chemical,
Building and construction are held accountable for 39% of the physical, mechanical, and durability properties when used as pre-
global energy-related carbon emissions (World Green Building cursors for alkali-activation are lacking in the literature. Therefore,
Council, 2017). The emphasis on developing policy frameworks it is necessary to compile the available data on the chemical and
for attaining a carbon-neutral construction practice has never been mineralogical composition of different AWAs and understand how
more pertinent than at present. The transition from conventional it connects with their performance when activated with alkaline
materials to low-carbon and energy-efficient engineered materials solutions. The polymerisation potential of different precursors re-
for construction is recognised to be one of the preferable methods lies on their mineralogical composition and morphology. Since the
to mitigate the CO2 emissions and the climate change crisis. Cement morphology and mineralogy of the different AWAs are widely
production is one of the largest contributors to the construction varying, it is essential to have an in-depth understanding on the
sector carbon footprint, due to its high embodied carbon (7e8% influence of these ashes and what the best strategy is to yield op-
global CO2 emission from only cement plants) (Cadavid-Giraldo timum performance in alkali-activated concrete. To understand the
et al., 2020). Therefore, the replacement of cement with alterna- differences between the properties of AWA based alkali-activated
tive binders with lesser embodied carbon enables cleaner concrete concrete and industrial by-products based alkali activated con-
production. Previous research studies have reported that the use of crete, it is essential to compare them with the currently used pre-
cement substitutes such as fly ash (FA) and slag can bring down the cursors such as slag and fly ash at similar conditions. Therefore, the
embodied carbon associated with cement production by about current study aims to provide a common platform where the
10e20% (Gan et al., 2017). Alkali-activated binders (AAB) have biomass ashes are compared amongst themselves (with data from
gained significant attention in the past decades as high-quality different studies) and also compared with other industrial by-
binders. AAB can be developed without Portland cement and in products in terms of their properties and performance.
turn, can reduce the embodied carbon emissions. Alkali-activated The following sections provide a comprehensive review on
binders are also beneficial in terms of reusing existing waste re- different AWAs such as rice husk ash (RHA), bagasse ash (BA),
sources such as the residual ashes from thermal power plants (FA) wheat straw ash (WSA), corn cob ash (CCA), sugarcane straw ash
and steel plants (slag). AAB systems include two different phases: (SSA) and palm oil fuel ash (POFA), to assess their influence on the
the precursors and the activators. Precursors are aluminosilicate performance of AAB. The effect of types and molarity of activators
materials whereas activators are alkaline solutions which can on strength attainment of AAB is also discussed. In addition, a
activate the precursors into forming a polymerised aluminosilicate critical comparison of the mechanical and durability performance
gel network. FA and slag are found to be suitable precursor mate- of AWA based AAB specimens is presented for different agro-waste
rials for the development of AAB systems. ashes.
When large amounts of cement substitute materials are used,
the carbon emissions from the transportation of these raw mate-
rials can also contribute to the embodied carbon (Gan et al., 2017). 2. Current status of agro-waste ash utilisation and
Therefore, there is also a need to consider the proximity of the significance of the current study
available resources in order to achieve true sustainability in the
construction sector (Athira et al., 2020a,b). While AAB can replace Biomass being a renewable energy resource, the coal-based
cement consumption, there is still the issue of transporting the FA thermal power plants are gradually being replaced by biomass-
or slag for its manufacture. The sources of FA and slag are generally based power plants for energy production, with the long-term
located much farther away from recovery points compared to goal of carbon emission reduction. For instance, biomass provided
locally available agro-waste ashes (AWA). In this regard, AWA from about 5
1015 Btu in the United States. This accounts for about 5%
various agricultural industries can be used as potential precursors of the primary energy use in the US (EIA, 2020). The sustainable
in the development of AAB concrete. development goals put forth by the United Nations aims to increase
Unlike cement concrete systems, there is a wide array of pa- the share of renewable energy mix significantly by the year 2030.
rameters that need to be considered to obtain the optimal perfor- This is set to increase biomass-based energy production further and
mance of alkali-activated binder systems. Besides, there is as yet no consequently the amount of available residual ashes. In this
consensus nor conviction on the alkali-activation of different agro- perspective, the use of the agro-waste ashes in alkali-activated
waste ashes, and their effects on the performance of AWA based binders is sustainable for two reasons: (i) it enables the reuse of
alkali-activated binders. It is also to be noted that there are no the residual ashes instead of disposal as a waste, which causes
specific international standards for the development of agro-waste severe land pollution, and (ii) It is a viable valorisation route which
ash based AAB or for the optimisation of mixes under different can reduce the need for conventional cement and associated carbon
activation conditions. Even though research studies on alkali- footprint. The current status of availability and utilisation of some
activation of industrial by-products such as fly ash and slag are the residual biomass ashes are given below to better understand
available, researchers are still figuring out the possibility of using the relevance of the research on valorisation of biomass ashes.
various agricultural waste ashes as precursors effectively. Studies Palm oil fuel ash (POFA) is obtained by burning the wastes from
the palm oil industries such as palm oil fiber, kernels, and shells in
2
V. Athira, V. Charitha, G. Athira et al.
the power plants to generate energy (Hamada et al., 2018). Palm
trees are equatorial trees and are mainly produced in the south east
Asian countries such as Indonesia, Thailand, Malaysia etc. Palm
kernel shells are highly viable biomass fuels as their preparation
costs are minimal and they have calorific values identical to low-
grade thermal coal (Provident BioFuels, 2020). The forecasts by
FAO indicates that the demand for palm oil will be tripled by 2050
e implying a larger share of biomass fuel resources and corre-
sponding amounts of the residual biomass ashes. Therefore, it can
be seen that we can utilise POFA in cements without causing any
additional pollution. Sugarcane bagasse ash (SCBA) is the residual
ash obtained from the already installed cogeneration power plants
in sugar mills. Bagasse is burned to generate electricity and a huge
amount of bagasse ash is obtained as a by-product. In India, the
largest producing country, 44200 tonnes/day of bagasse ash is
disposed of as waste (Bahurudeen et al., 2015). Therefore, bagasse is
not exclusively burned for the purpose of producing the residual
ash (SCBA); rather, it is a secondary by-product from the sugar
industries. It is also worth mentioning that bagasse cogeneration
contributed a whopping 11,907 MW electricity in Brazil last year, as
reported in an earlier study (Morais, 2020). Similarly, India also has
a number of cogeneration plants which can ensure the availability
of bagasse ash for use as precursors to alkali-activated binders or as
blending material in cement production. Sugarcane straw ash also
will have the same trend of availability as that of bagasse ash, since
both are dependent of sugarcane production. Husk Power Systems
(HPS) and the Decentralised Energy Systems India (DESI) are two
initiatives that effectively popularized rice husk-based electricity
generation and supply in South Asia. HPS uses the rice husk gasi-
fication technology in a controlled burning system and has already
installed 84 plants in an effort to electrify 300 villages in India, and
the residual ash from these processes can be monetized if used as
low-carbon alternatives for cement and alkali-activated binders.
Therefore, there is no need to burn the rice husk for the purpose of
obtaining the residual ash; rather, it is already available as the by-
product from rice husk-based power generation plants, which are
installed as part of a carbon-neutral energy production pathway
against coal-based electricity production (Bhattacharyya, 2014).
Corn is a widely grown crop in the United States of America e with
about 345 million metric tonnes of corn produced in 2019/2020. As
for the corn cob ash (CCA), it is the ash produced when the inner
part of the corn cob (after removing the corn kernels) is burnt as
fuel. Traditionally, corn cob is burnt to generate heat and used as
fuel in regions where corn is grown in large quantities. If
completely dried, it has a thermal power of 18.35 kJ/kg, which is
comparable to that of the other crop residues (Asonja et al., 2017).
There have been many projects that use corn cob combustion to
produce energy (MyClimate, 2020), and the residual ashes from
these can thus be used as supplementary cementitious materials, as
the chemical composition of these ashes is suitable to be used as a
pozzolan (SiO2 þ CaO > 70%). With this evidence for the shift in the
energy matrix, it is imperative that the secondary by-products of
these biomass combustion/gasification/pyrolysis be used effec-
tively. One of the most promising ways of using these ashes in large
scale is their use as pozzolans in concrete or as precursors in alkali-
activated binders.
Fly ash and slag sources are also available in these countries and
can be used as the primary precursor for alkali-activation. However,
if the source of fly ash and slag are too distant to the recovery
points, the logistics cost and the associated carbon emissions will
effectively offset any benefits of using the same in alkali-activated
concrete production. A detailed treatise on the logistics aspect of
raw material procurement has been provided in earlier research
studies (Athira et al., 2020a,b) and it has been concluded that the
use of SCBA in India is far more effective than using fly ash/slag.
3
Journal of Cleaner Production 286 (2021) 125429
However, it goes without saying that there are some regions in the
vicinity of thermal power plants/steel plants where the use of fly
ash and slag is more beneficial. In such cases where both industrial
by-products and agro-waste ashes are available, a ternary blended
cement or alkali-activated binders containing both of these by-
products can also be attempted.
3. Methodology adopted for review
The primary focus of the present review is to comprehend the
potential of various agro-waste ashes in the production of AAB
concrete. In this view, relevant articles on all types of AWA were
identified with the help of the databases from different indexing
platforms such as Scopus, Google Scholar, Science Direct etc.
Different influencing parameters on the performance of agro-waste
ashes based AAB concrete are considered. Besides, mechanical and
durability characteristics of agro-waste ashes based AAB specimens
are compared with widely used FA and slag based AAB specimens.
There were 6974 documents that mention AAB, in which 3444 ar-
ticles were classified into the subject areas “Material science”, and
“Engineering”. The Boolean search string employed to refine the
search was “title-abs-key (alkali and activation) and (limit-to
(subjarea, “mate”) or limit-to (subjarea, “engi"))”. In this regards,
different available AWA were identified in the initial stage. The
results were further refined by considering the keywords of these
3444 research articles and selecting the appropriate articles. Some
of the keywords identified and used for further refinement of the
research articles are alkali activation, compressive strength, fly ash,
silicates, inorganic polymers, geopolymers, sodium hydroxide,
geopolymer, binders, cement, alkaline activation, alkali-activation,
aluminosilicates, alkali-activated slags, potassium hydroxide, so-
dium hydroxide, ground granulated blast furnace slag, alkaline
activators, cementitious materials, sodium silicate solutions, geo-
polymerisation, agro-waste ash, etc. The research articles were
then narrowed down to 840 documents, which mostly spanned
across a period of 1990e2020, as shown in Fig. 1. Only the relevant
and important articles to the present review were considered from
earlier studies. Well-defined research questions were formulated to
identify the most relevant publications in the area of alkali-
activation of AWAs, specifically in the scope of the present study.
The research articles were further cross-checked to understand
whether they can address the framed research questions for
achieving a systematic review of the available literature. The
research questions formulated as the primary focus of the present
review are:
(i) What are the various agro-waste ashes that can be poten-
tially used as precursor materials for alkali-activation?
(ii) Are there residual agro-waste ashes that can partially/
completely replace FA and slag as precursors for alkali-
activation?
(iii) What are the research studies on agro-waste ashes based
AAB concrete from major agriculture-based countries in the
world?
(iv) Is there a definite pattern of performance with respect to the
alkaline activators used for activating the agro-waste ashes?
(v) What are the different parameters which influence the
alkali-activation of agro-waste ashes?
(vi) Are alkali-activated agro-waste ashes positioned as prom-
ising alternatives to conventional cement concrete?
(vii) Can there be a viable benefit by using the agro-waste ashes in
terms of mechanical and durability properties of alkali-
activated binder?
The research articles that can answer these questions were
V. Athira, V. Charitha, G. Athira et al.
Fig. 1. Number of relevant publications on alkali-activation of aluminosilicate materials in different countries (Left) and over the years (Right).
selected and further studied in detail. Based on the earlier research
studies on the alkali activation of agricultural by-products, six
AWAs were carefully chosen. Using the keywords ‘bagasse ash’, ‘rice
husk ash’, ‘corn cob ash’, ‘palm oil fuel ash’, ‘wheat straw ash’, and
‘sugarcane straw ash’, the collected articles were further refined to
240 articles. Material properties of these six AWAs were collected
and compiled. The data collection was divided into three sections:
(i) physical properties and chemical composition of the ashes,
regardless of the type of application it was used for (ii) compressive
strength properties, irrespective of the alkali-activation process,
and (iii) durability properties of the AAB systems. The search was
restricted to only selected materials and specified properties to
avoid irrelevant publications, and narrowed down the research
articles to 135 articles for review. All peer-reviewed research arti-
cles and review articles were included, while non-peer reviewed
sources were avoided except for some of the authentic sources such
as the International Energy Agency (IEA), World Green Building
Council (WGBC) etc. Each of these articles was gone through judi-
ciously, and 84 articles were finalised for the review process.
4. Characteristics of residual ashes from agro-industries
4.1. Chemical composition of agro-waste ashes
AWA can be used as precursors in alkali-activated concrete.
Generally, inorganic geopolymers are developed from the alkali
activation of raw materials which are rich in silica (SiO2) and
alumina (Al2O3). The alkali-activation reaction mechanism can be
divided into three stages.
The first stage involves the breakdown of SieOeSi and AleOeSi
bonds due to the dissolution of Al and Si from the precursors at the
high pH provided by the alkaline solution. The polycondensation
process occurs in the second stage, followed by polymerisation
reactions, generating a condensed structure of ordered alumino-
silicate gels and calcium aluminosilicate hydrate gels (Pacheco-
torgal, 2008) which gives the required strength and binding
properties. As AWAs have a significant amount of silica and
alumina, these can be used as source materials. The composition of
the end products depends on the precursor, types of activator and
curing conditions (Garcia-Lodeiro et al., 2015). Hence it is essential
to understand the chemical composition of the precursors for
alkali-activation to comprehend their performance in concrete. In
general, the precursors of AAB are broadly classified into two: (i)
4
Journal of Cleaner Production 286 (2021) 125429
low calcium precursors, which has a relatively higher concentration
of SiO2 and Al2O3 and (ii) high calcium precursors which have
relatively more calcium content. Fig. 2 depicts the chemical
composition of different AWAs, and the currently used industrial
by-products FA and slag, as reported in various research studies.
From the figure, it is evident that RHA has the highest silica content
(80e90%), followed by BA. Slag has the least silica content, as it is
classified as a high calcium precursor. Alumina content was found
to be comparable across the different AWAs, with RHA having the
smallest amount. However, the alumina content is found to be
higher for FA and slag (13e25%), compared to AWAs. The main
reaction product, in this case, is sodium-alumino-silicate-hydrate
(N-A-S-H) gel which is formed when the precursor comes in con-
tact with the alkaline medium. Slag was found to have the highest
CaO concentration (36e43%) compared to AWAs. The main reaction
product in the presence of CaO was found to be calcium-aluminate-
silicate-hydrate (C-A-S-H) gel (Garcia-Lodeiro et al., 2015). Fe2O3
concentration of AWAs was similar to that of FA and slag. FA and
slag were found to have less concentration of total alkali content,
and WSA has the highest alkali content. The higher alkali content is
attributed to the higher concentration of potassium oxide (K2O) in
AWA. The negative charge in SiO4 and AlO4 groups is balanced by
ions like sodium (Mangat and Lambert, 2016).
Loss on ignition (LOI) is the mass lost from a material when it is
heated until a constant residual weight is attained. It provides an
indirect indication of the amount of unburnt carbon present in the
material. The presence of unburnt carbon in the precursors can
cause adverse effects in the performance of AAB concrete. For that
reason, a low LOI is preferred for precursor materials. The presence
of unburnt fibrous plant particles leads to high LOI in the residual
ashes, and it is crucial when uncontrolled burning is adopted. From
Fig. 2, it can be seen that slag has the lowest LOI (0.2e1.9%),
whereas CCA has the highest LOI (9.3e10.8%).
Specific gravity is a parameter that affects the batching,
proportioning and the consequent workability as well as the per-
formance of alkali-activated binders developed from AWAs. Pre-
cursors with lesser specific gravity contribute to a higher powder
volume in the slag/FA based alkali-activated binders at higher
replacement levels. Along with the inherent water demand con-
cerns of AAB, this could be a highly significant factor in deciding the
workability of the binder mixture. The specific gravity of BA was
found to be the least among all the different AWAs considered in
this study, ranging between 1.85 and 2.2. As shown in Fig. 3, FA and
V. Athira, V. Charitha, G. Athira et al. Journal of Cleaner Production 286 (2021) 125429

Fig. 2. Oxides and mineralogical composition of the residual ashes.

Akram et al. (2009); Amin (2011); Arif et al. (2016); Bahurudeen and Santhanam (2015); Chi (2012); Chusilp et al. (2009); Cordeiro and Kurtis (2017); De-Soares et al. (2016);
Ganesan et al. (2007a); Modani and Vyawahare (2013); Almeida et al. (2015); Ríos-Parada et al. (2017); Cordeiro et al. (2009); Muthadhi and Kothandaraman (2013); Sensale (2010);
Zain et al. (2011); Zerbino et al. (2011); Cordeiro et al. (2012); Kusbiantoro et al. (2012a); Riahi et al. (2011); Salami et al. (2017); Monita et al. (2015); Karim et al. (2014); Islam et al.
(2014); Nadziri et al. (2018); Farzadnia et al. (2015); Hussin et al. (2010); Salih et al. (2015a); Runyut et al. (2018); Tangchirapat et al. (2009); Adesanya and Raheem (2009); Mujedu
et al. (2014); Oluborode and Olofintuyi (2015); Memon et al. (2019); Tumba et al. (2018); Oyebisi et al. (2018b); Ahmed and Kamau (2017); Binici et al. (2008); Al-akhras and Abu-
alfoul, 2002; Biricik et al. (2000).

Fig. 3. Specific gravity of different residual ashes.

POFA are found to have an almost similar range of specific gravity
values (2.06e2.7). The specific gravity of WSA varied from 1.9 to 2.3
and is similar to that of BA. Slag has the highest specific gravity
(2.7e2.9) compared to all other ashes. Slag is commonly ground to a
similar fineness of cement and commercially used as an alternative
cementitious material. Fig. 3 shows that most of the AWAs have less
relative density compared to cement and slag, and will lead to
higher water demand to attain the same workability in cement
concrete as well as alkali-activated concrete. Further, the presence
of the lightweight unburnt carbon particles also influences the

5
V. Athira, V. Charitha, G. Athira et al.
specific gravity of residual ashes. Therefore, reducing the LOI using
the removal of fibrous particles can also increase the specific
gravity values of these ashes. Hence suitable processing methods
are widely suggested for AWAs to attain appropriate fineness and
relative density.
4.2. Microstructure of agro-waste ashes
Although residual AWAs seem identical, they have different
microstructural characteristics. Fresh and hardened properties of
AAB are significantly influenced by the reactivity and morphology
of the ashes. The morphological characterisation in the microscopic
level of AWAs has been conducted by several researchers using
different microscopic techniques such as the optical microscope,
scanning electron microscope (SEM), scanning probe microscope
(SPM) etc., of which SEM microscopy is the most commonly used
tool for microstructural investigations. It is reported that FA parti-
cles have solid and hollow spherical shaped particles of different
sizes, namely cenospheres and plerospheres, respectively, as shown
in Fig. 4. Cenosphere particles are small hollow spheres whereas
plerospheres are also hollow spheres which are large in size and
accommodate the smaller cenospheres inside them. The distinct
spherical shape of FA particles is reported to enhance the work-
ability of FA based AAB concrete and blended cement concrete (Guo
et al., 2010). The SEM micrograph of BA (see Fig. 4-I) shows different
spherical, fibrous, prismatic, dumbbell shaped and silica-rich
irregular particles. Due to the presence of the carbon-rich coarse
fibrous particles in BA, increased water demand and workability
reduction have been reported for BA based binders (Ganesan et al.,
2007b). From the elemental composition analysis of BA, it has been
reported that the spherical particles consist of Si, O and alkalis,
whereas fibrous particles mostly consist of carbon. The prismatic
particles are also found to be composed of silica (Batra et al., 2008).
Another source of silica in BA is the dumbbell-shaped particles
called the phytoliths interspersed in the granular fibrous particles.
Bagasse ash is reported to have two different types of fibrous par-
ticles such as the coarse fibrous particles (10 mm size) and the fine
fibrous particles (1 mm size) with entirely different microstruc-
tures. However, both these particles have more than 75% carbon in
its composition with almost negligible silica content. Hence, the
complete removal of these particles is suggested for its use as a
pozzolan and precursor in AAB (Bahurudeen and Santhanam, 2015;
Deepika et al., 2017). Cordeiro et al., explained the effect of burning
temperature on reactivity, colour and LOI. Beyond 800  C, recrys-
tallisation of the amorphous silica to tridymite and cristobalite is
reported, and more prismatic particles have been observed in the
micrograph of calcined BA samples at high temperatures (Ganesan
et al., 2007b; Sultana and Rahman, 2013).
The cellular structure of the RHA particles can be seen in Fig. 4-
II. SEM micrographs of RHA show that the particles are angular,
cellular, irregular and highly porous. Cellular structure mostly
consists of amorphous silica which is responsible for its reactivity
(Karim et al., 2015; Paya and Monzo, 2000). The porous cellular
RHA has a very high surface area (with micropores and nanopores)
and can result in high water absorption (Hwang and Huynh, 2015).
Grinding of the as-collected raw RHA breaks down its cellular
structure, and therefore reduces the water absorption capacity and
water demand (Zain et al., 2011). Fig. 4-III shows the microstructure
of POFA. It can be seen that POFA has irregular particles with porous
cellular surface and plerospheres similar to that of FA (Karim et al.,
2013). Grinding of POFA was found to increase both the fineness
and specific gravity (Tangchirapat et al., 2007). The microstructure
of CCA (see Fig. 4-IV) shows different shapes of particles such as sea
rock, cellular, irregular and granular. Similar to that of RHA, the
presence of micropores and macropores in CCA leads to high water
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Journal of Cleaner Production 286 (2021) 125429
demand (Memon and Khan, 2018). Fig. 4-V shows the SEM micro-
graph of WSA, which is also found to have spherical, prismatic,
fibrous and irregular shaped particles. Similar to BA, prismatic
particles consist of only Si and O, whereas spherical particles
consist of Si and O along with some other mineral compounds.
On grinding, fibrous particles which contain mostly carbon are
broken down, and more regular particles are formed (Qudoos et al.,
2018). Fig. 4-V shows that SSA has fibrous, irregular particles and
rough surfaces (Fungaro et al., 2014). As reported in several
research studies, the particles of ground granulated blast furnace
slag are found to be in angular, irregular quadrilateral shapes
(Arvaniti et al., 2015).
5. Alkali-activated binders: reaction mechanisms and
hydration products
Unlike the hydration mechanisms of Portland cement systems,
the reactions and hydration products of alkali-activated binders are
complex, since there are many parameters which can significantly
alter the reaction rates. Alkali-activation primarily depends on the
type of precursors and activator, and the phase assemblages are
investigated in the literature by analysing the XRD patterns, calo-
rimetric curves, and SEM analysis of the hydrated products at
different stages of activation. As discussed earlier, the alkali-
activation may be broadly broken down into three reaction
stages: (i) dissolution, (ii) transportation, and (iii) poly-
condensation. However, depending on the activating conditions,
the reactions may occur sequentially or simultaneously (Pacheco-
torgal, 2008). If the activating solution is solely sodium hydrox-
ide, the sequential mode of reactions is favoured whereas the
introduction of sodium silicate can induce a fast polycondensation
process along with transportation. The alkali-activation of the cal-
cium rich slag and aluminosilicate fly ashes are significantly
different in the reaction routes and hydration products e while the
former process produces CeSeH, the latter reactions lead to a 3-
dimensional aluminosilicate gel network.
As for the activation of blast furnace slag, a higher degree of
hydration is resulted from using activators with higher silica
modulus and sodium content (Na2O) (Krizan and Zivanovic, 2002).
The hydration reactions of alkali-activated slags were investigated
by quantifying the heat released at different stages of activation by
calorimetric methods and it was observed that the reactions can
proceed in three ways: (i) with an initial heat release peak in the
first few minutes followed by a flat curve, (ii) with one initial peak
before the induction period and another accelerated peak after-
wards, and (iii) with two peaks before the induction period and one
after the induction period (Shi and Day, 1995). It is also reported
that any alkali compounds that can react with calcium to produce
more stable reaction products than calcium hydroxide can act as
activators for slag (Hooton et al., 1996). The initial heat release
peaks correspond to the dissolution and dissociation of silica and
the later peaks correspond to the accelerated hydrations. The flat-
tened curve indicates that further hydration reactions are diffusion
controlled. Microstructural investigations using the secondary
electron (SE) mode and back scattered electron mode (BSE) on
alkali-activated slag mortars revealed that there is a considerable
amount of unhydrated slag particles in the binder matrix (Aydin
and Baradan, 2012). The micrographs in the same study showed
that the autoclaved mortar specimens had a much better packing
and better degree of hydration than that of steam cured specimens.
Higher activator modulus was found to result in the production of
CeSeH with lesser Ca/Si ratio in both cases. The SEM-EDS analysis
showed needle like formations in the spherical pores in the auto-
claved slag specimens with Ca/Si ratio 1.08e1.46. The mercury
intrusion porosimetry (MIP) studies also supported the data from
V. Athira, V. Charitha, G. Athira et al. Journal of Cleaner Production 286 (2021) 125429

Fig. 4. SEM micrographs showing the morphologies of agro-waste ashes, fly ash, and slag.

7
V. Athira, V. Charitha, G. Athira et al.
the SEM analysis, with autoclaved specimens having a denser and
finer pore structure compared to the steam cured specimens (Aydin
and Baradan, 2012).
The XRD analysis of alkali-activated fly ash pastes showed the
presence of quartz, mullite, and magnetite crystalline phases which
were also present in the ash and remained unaltered under acti-
vation (Criado et al., 2005). In the same study, Hydroxysodalite and
Herschelite phases were also found to be present in the activated
fly ash pastes along with alkaline bicarbonates. In another study,
the XRD analyses showed that after 24 h of curing at 20  C and 95%
relative humidity, thenardite and siliceous hydrogarnet phases are
formed (Winnefeld et al., 2010). From the Fourier Transform
Infrared (FT-IR) spectra, a significant shift in the AleO and SieO
bands were observed, indicative of the changes in the Si/Al ratio
of the reaction product. Alkali-activated fly ash generally shows a
lesser heat of hydration than Portland cement systems; however,
this has no bearing on strength attainment. For instance, Winnefeld
et al. (2010) showed that the activated low calcium fly ash had the
lowest heat of hydration and the highest compressive strength of
all the different types of fly ash used in the study. The thermogra-
vimetric (TGA) studies on the activated fly ash pastes show a mass
loss in the range of 80e250  C, indicative of the decomposition of
sodium aluminosilicate hydrates (N-A-S-H). In line with the infor-
mation obtained from XRD analysis, the mass loss at this range was
found to be the highest for low calcium fly ash pastes, implying
higher amounts of N-A-S-H and correspondingly higher strength.
From the SEM images of the activated pastes in the same study, it
was found that the smaller spheres of fly ash were mostly fully
dissolved whereas the larger spheres with dimeters >10 mm were
unaffected by dissolution reactions. Moreover, the low calcium fly
ashes have a denser microstructure with needle like phases
compared to the poorly connected matrix of activated high calcium
fly ashes.
Salih et al. (2015b) investigated the properties of alkali-activated
palm oil fuel ashes blended with slag at various levels of replace-
ment. The amorphous halo in the XRD patterns of raw POFA shifted
to higher angles after activation, suggestive of new amorphous
phases. Replacing a portion of POFA with slag showed significant
differences in the XRD patterns wherein the reaction products
started becoming more crystalline with respect to the level of
replacement. It is seen that while the slag activation products are
mostly crystalline, POFA activation products are predominantly
amorphous. Therefore, for having reasonable strength, it is better to
use a POFA-slag blend rather than pure POFA. FT-IR spectra showed
that the SieO band is right-shifted after POFA was activated,
whereas for slag inclusion, the SieO band shifted left. This shows
the differences in the nature of the reaction products formed in
both cases. The shift of the SieO band to a lower wavenumber is
attributed to the inclusion of Al4þ atoms into the original SieOeSi
structure. This is possible as slag has a higher alumina content than
that of POFA (see Fig. 2), and under the alkaline conditions the
alumina ions dissolve and modify the SieOeSi structure into
SieOeAl structure, lowering the wave number of the T-O band
 
(T ¼ Al/Si) in the process (Skv ara et al., 2009). Therefore, inclusion
of slag resulted in the development of SieOeAl linkages and the
substitution of Al into the CeSeH chains, forming C-A-S-H gels
which results in a higher degree of polymerisation and cross-link
formation (Provis, 2014). Rice husk ash can act as a silica source
for the development of alkali-activated binders. The inclusion of
rice husk ash in slag based AAB has had significant differences in
the microstructural properties of the reaction products, as
described by (Mehta and Siddique, 2018). Incorporation of RHA is
found to produce a denser microstructure compared to activated
slag pastes, due to the co-existence of CeSeH, C-A-S-H, and N-A-S-
H. The presence of these phases was confirmed based on SEM-EDS
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Journal of Cleaner Production 286 (2021) 125429
analysis and XRD analysis in the study. However, after an optimum
level of replacement (15%), the silica content in RHA rendered
further polymerisation impossible, resulting in the formation of
porous unhydrated matrix and subsequent reduction in strength.
This was also confirmed by another study where fly ash was
replaced by rice husk ash, and at higher levels of replacement fly
ash was left unreacted (Detphan and Chindaprasirt, 2009).
6. Mechanical characteristics of agro-waste ash based AAB
6.1. Influence of activator on the compressive strength of agro-
waste ash based AAB
Understanding the effect of activators in the alkali activation
process is crucial as they play a vital part in the polymerisation
reaction. Some of the alkaline solutions that are used as activators
are sodium hydroxide (NH), sodium silicate (SS), a combination of
sodium hydroxide and sodium silicate (NH þ SS), potassium hy-
droxide (KOH), sodium carbonate (Na2CO3), sodium sulphate
(Na2SO4) etc. However, the most commonly used activators for the
production of alkali-activated binders are NH, SS, and NH þ SS.
Among all the alkaline solutions used for slag-activation, Na2SiO3 is
found to result in the highest compressive strength (See Fig. 5). This
higher compressive strength upon using Na2SiO3 as an activator can
be attributed to the homogeneity in the microstructure of paste at
early ages, compared to NaOH (Wang et al., 1994). Apart from slag,
100% POFA based alkali-activated binder also exhibited an
improved compressive strength when activated by sodium silicate
solution. Slag activated using 2M Na2SiO3 showed a compressive
strength of 85 MPa after 28 days, which is significantly higher
compared to other binders, as shown in Fig. 5b. Higher compressive
strength of slag based AAB with sodium carbonate (2M) as an
activator was reported compared to the strength of AAB with NH
(4M) as the activator in a study. This can be due to the effect of its
anion CO23 (Wang et al., 1994).
The compressive strength of FA based AAB specimens is re-
ported to be lesser than slag based AAB specimens for each acti-
vator type. However, a combination of NH (9M) þSS resulted in the
highest compressive strength for FA based AAB specimens. It is also
interesting to note that the observed compressive strength of FA
based AAB specimens with NH (9M)þSS activator combination is
greater than slag based AAB specimens with Na2SO4 (2M) as well as
NH (4M) as shown in Fig. 5b after 28 days. Similar performance was
witnessed for BA, and SSA based AAB specimens when 25%
replacement of slag with BA and SSA was adopted. In another study,
in which NH (10M)þSS was used as an activator for 100% slag, very
high early age and later age (28 days) compressive strength of
70.5 MPa and 100 MPa were reported correspondingly (Deepika
et al., 2017). Therefore, it can be decided that a combination of
NH þ SS is the most effective activator, in terms of compressive
strength for the production of agro-waste ashes based AAB con-
crete. This is valid whether the primary precursor is slag or FA or
even if it is 100% AWA. Maximum compressive strength was re-
ported at 7-day for the AAB mortar (with 75% slag and 25% BA using
KOH activator). In contrast, the minimum compressive strength
was also reported for NH (8M) þSS for the same curing duration.
The compressive strength of BA using NH (8M)þSS is reported as
the highest for the slag and BA combination while minimum
strength was observed for specimens with NH (8M) as an activator
after 28 days. The higher initial strength for KOH based activator for
BA was attributed to the presence of higher potassium content in
BA. The higher the size of the alkali-metal cation; the greater is the
number of AleOeSi bonds in aluminosilicate solutions and gels.
The increase in cation size will influence the redistribution of Si and
silicate reactants, and larger amounts of silicate reactants are
V. Athira, V. Charitha, G. Athira et al.
Fig. 5. Influence of activator on (a) 7-day and (b) 28-day compressive strength of AAB.
formed (McCormick et al., 1989). Since potassium is a larger cation
than sodium, it could have helped in a higher rate of dissolution of
Si, which supports in geopolymerisation and early age strength
gain of the AAB specimens. Hence, the higher compressive strength
is reported for KOH based AAB systems than NaOH based AAB in the
early stages of curing (Xu and Van Deventer, 2000). The maximum
strength for SSA 25% at all ages of curing was observed for speci-
mens activated by NH þ SS with a modulus ratio (Ms ¼ SiO2/Na2O)
of 0.5. Even though the activator is accountable for higher amounts
of silicate anions with Ms ¼ 0.75, it showed inferior strength than
that of other specimens activated by other alkaline solutions.
However, at 90 days, the maximum compressive strength was re-
ported for Ms ¼ 0.75 based specimens compared to other activators
(Moraes et al., 2016). It is interesting to note that the activation of
POFA was the most fruitful when an individual water glass solution
at a relatively lesser concentration (3M) was used, rather than using
NH at higher molarity of 12M or NH (12M)þSS. The same trend in
the compressive strength was observed at an early age and after 28
days.
6.2. Effects of replacement of slag and fly ash with AWA on the
compressive strength of AAB specimens
Fig. 6 shows the effect of replacement of FA and slag with
different agro-waste ashes on the compressive strength of AAB
specimens with NH þ SS activator. Partial substitution of slag with
15% and 25% BA results in a marginally higher compressive strength
than control AAB specimens (100% slag) at 7 days of curing. How-
ever, the later age strength gain of BA blended AAB specimens is
lesser than that of control, as is evident from the lesser normalised
compressive strength (See Fig. 6b). Generally, the observed reduc-
tion in the strength gain after the initial curing duration could be
due to the lack of hydration of slag when ambient curing is adopted
instead of the water curing. 25% replacement of slag with SSA
exhibited better compressive strength than other replacement
levels, and it is higher than control AAB specimens. The early age
compressive strength of SSA-slag binder is reported to be lesser at 7
days as the silicate ions from the solution did not participate in the
polycondensation process (Moraes et al., 2016). When the
replacement level of slag with CCA is increased, a corresponding
reduction in the strength is witnessed. This may be attributed to the
dilution effect, where the slag content is also decreased. Further,
the observed reduction in the compressive strength could also have
been the result of the retarded dissolution of the aluminosilicate
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Journal of Cleaner Production 286 (2021) 125429
species from CCA (Oyebisi et al., 2018a). From Fig. 6, it can be seen
that the replacement of FA with RHA increases the compressive
strength. All replacement levels of FA with RHA showed higher
strength than control specimens and 35% slag replacement with
RHA had the highest compressive strength compared to other
replacement levels. Although RHA blended AAB specimens
exhibited higher strength than control specimens, replacement
levels beyond 35% exhibited an apparent reduction in the
compressive strength, as shown in Fig. 6a. It is interesting to note
that a similar pattern is also observed at 28 days. The strength
reduction for the level of replacement beyond 35% may be due to
the relatively large RHA particles which remain unreacted in the
binder matrix (Hwang and Huynh, 2015).
In the same way, for slag replaced with POFA, beyond 30% level
of replacement, the coarser particles remain unreacted and led to a
drop in the compressive strength of AAB specimens. At 28 days, 30%
replacement of slag with POFA led to a higher strength than control
specimen; however, the gradual reduction was clearly witnessed
with further increase in the level of replacements as shown in Fig. 6
(Islam et al., 2014).
6.3. Influence of molarity of activators on the compressive strength
of AAB specimens
Molarity of the alkaline activator solution has a significant in-
fluence on the strength of agro-waste based AAB specimens. Usage
of low molarity activators in AAB results in lesser compressive
strength compared to activators with a higher concentration
(Chindaprasirt et al., 2009). From Fig. 7, it can be seen that at 28
days with an increase in the concentration (in terms of molarity),
the compressive strength is also found to be increased for slag, FA,
BA and RHA based AAB specimens. With the rise in molarity, the
hydroxyl ion concentration increases, facilitating the dissolution of
silicates and aluminates from the precursors, leading to increased
polymerisation and subsequent higher strength (Deepika et al.,
2017).
In the case of POFA blended AAB specimens, the rise in the 28-
day compressive strength with increase in molarity is not signifi-
cant. Moreover, beyond the molarity of 8M, reduction in the
strength is also detected at 7 days. Efflorescence is also reported
with an increase in the molarity (Salih et al., 2013). For CCA based
AAB specimens, a marginal increase in the compressive strength
was stated from 12M to 14M at 7days, however further increase in
the molarity to 16M led to a reduction in the compressive strength.
V. Athira, V. Charitha, G. Athira et al.
Fig. 6. Effect of replacement of precursor on (a) 7-day and (b) 28-day strength of AAB.
Fig. 7. Influence of activator molarity on strength attainment of AAB.
Similar behaviour was also reported for the compressive strength of
CCA based AAB specimens at 28 days. Efflorescence was also
spotted in CCA based AAB specimens when high molarity activator
was used. Influence of molarity for slag-CCA based AAB (replace-
ment of slag (40%) with CCA) is also similar to that of 100% CCA
based AAB specimens. Nevertheless, the reduction in the
compressive strength from 14M to 16M is found to be lesser for
CCA-slag blended AAB compared to 100% CCA based AAB speci-
mens (Oyebisi et al., 2018b).
6.4. Influence of curing on compressive strength of agro-waste ash
based AAB specimens
The effect of curing on strength gain is shown in Fig. 8. For Slag-
BA based AAB specimens, (20% BA and 80% slag), ambient cured
specimens had enhanced compressive strength compared to ther-
mally cured specimens with same mix proportion and curing
duration. This is due to the loss of water when the specimens were
cured at 65  C, which decreases the hydration of slag (Deepika et al.,
2017).
In contrast, POFA as well as FA based AAB specimens exhibited
10
Journal of Cleaner Production 286 (2021) 125429
better strength for heat-cured specimens (without slag) at 3 days,
and a similar trend is also reported for 28 days. The compressive
strength is increased due to the heat curing. Hence, the geo-
polymerisation process speeds up, and reaction products are
formed faster than in the ambient curing (Kim et al., 2014). It is
clear from the above trend that the hydration of slag is influenced
by heat curing and subsequent changes in the compressive strength
were witnessed for slag-agro waste ash based AAB specimens.
6.5. Tensile and flexural strength of agro-waste ash based AAB
specimens
All agro-waste ashes based AAB specimens shown in Fig. 9 were
activated by sodium-based activator solution (NH þ SS). When FA is
replaced with 20% POFA, tensile and flexural strengths are found to
be increased by 13.6% and 5% respectively compared to FA (100%)
based AAB specimens. However, for the replacement of FA with
POFA beyond 20%, the tensile strength of AAB specimens is reduced
compared to control specimens as well as 20% AAB specimens.
Moreover, a similar trend is also observed in flexural strength.
For 40% replacement of FA with POFA, the tensile and flexural
V. Athira, V. Charitha, G. Athira et al.
Fig. 8. Effect of curing on the (a) early age and (b) 28-day strength of alkali-activated binders.
Fig. 9. Flexural strength (left) and tensile strength (right) of agro-waste ash based AAB specimens with different level of replacements.
strengths of AAB specimens were found to be decreased by 23% and
12% respectively. Tensile and flexural strengths are increased with
increase in the curing duration, which tracked a similar trend as
that of compressive strength. By replacing 10% of slag with RHA, a
marginal increase in the tensile strength (2.6%) is reported
compared to 100% slag based AAB specimens. The increase in
tensile and flexural strengths for AAB specimens with 10% RHA can
be attributed to the smaller particle size of the RHA used in that
study compared to slag and the consequent filler effect (Venkatesan
and Pazhani, 2016a). When 20% of slag is replaced with RHA, the
tensile and flexural strengths reduced by 36% and 32% compared to
100% slag based AAB specimens. The reduction in the strength upon
addition of RHA beyond 10% may be attributed to the differences in
solubility between slag and RHA in AAB, and also the suppression of
geopolymerisation process because of the increased SiO2/Na2O ra-
tio. The solubility of silicates from RHA is reported to be signifi-
cantly lesser than that of slag (Kusbiantoro et al., 2012b), leading to
a reduction in the geopolymerisation reaction and compressive
strength. As RHA is predominantly siliceous in nature (see Fig. 2), it
can also contribute to an increased SiO2 concentration in the pore
solution, which is reported to inhibit the polycondensation process
of the precursors. Similarly, it is stated that at replacement levels
25% and 40% of slag with BA, the tensile strength of AAB specimens
is improved by 11% and 6% correspondingly. For 20% and 40% re-
placements of slag with CCA, tensile strength is marginally
11
Journal of Cleaner Production 286 (2021) 125429
decreased by 2.5% and 6.7% in that order compared to reference
AAB specimens. However, in the case of 40% blended CCA speci-
mens, the flexural strength is found to decrease by 4.2% (Lee and
Van Deventer, 2004).
7. Durability of agro-waste ash based AAB specimens
Cement concrete and alkali-activated concrete structures are
prone to deterioration over the course of time due to the action of
aggressive external agents. Some of the most common reasons for
concrete deterioration are (i) water penetration, (ii) drying
shrinkage, (iii) acid attack, (iv) sulphate attack, (v) chloride
ingression which induces corrosion, (vi) exposure to fire etc. This
section details the performance of agro-waste ash based AAB
specimens against the above-mentioned external aggressive
agents.
7.1. Resistance of agro-waste based AAB specimens against acid
attack
AAB concrete is susceptible to acid attack when the concrete
surfaces are exposed to aggressive acidic environments such as in
sewer linings, sewer pipes, industrial constructions etc.
(Bahurudeen et al., 2015). The acid attack leads to dissolution and
leaching of constituents from the concrete matrix. Exposure to
V. Athira, V. Charitha, G. Athira et al.
various acids such as hydrochloric acid (HCl), sulfuric acid (H2SO4),
acetic acid (CH3COOH) and nitric acid (HNO3) has been reported to
cause more damages than high molecular weight acids such as
stearic, palmitic and oleic acids.
The acid attack generates even more damages in the case of
reinforced concrete structures, as the ingressed Hþ ions will create
a chemical inequilibrium, leading to the depassivation of rebars and
corrosion of the concrete structures. The damage is typically
measured in terms of residual compressive strength, mass loss and
corroded depth. Fig. 10 and Fig. 11 show the residual compressive
strength (%) and mass loss (%) of different agro-waste based AAB
specimens in comparison to cement concrete and fly ash/slag based
AAB specimens. These specimens were immersed in acidic solu-
tions (HCl and 5% H2SO4) for different durations. Residual
compressive strength is measured as the compressive strength
retained by the specimen after acidic exposure. It can be seen from
Fig. 10 that 100% slag based AAB specimens have lesser residual
compressive strength (31.4%), and a high mass loss when immersed
in HCl solution for 200 days. However, the residual compressive
strength of cement concrete was significantly lesser than slag based
AAB specimens and comparable to that of 25% BA blended AAB
specimens. It is imperative to note that specimens with 50% WSA,
25% metakaolin and 25% FA (WSA50/FM50) exhibited the highest
resistance against acid attack, with a minimal loss of compressive
strength (18.16%) compared to other AAB specimens after 28 days
of immersion in H2SO4 solution. When the duration of immersion
was increased from 7 to 28 days, there was a significant loss (16%) in
the compressive strength (Matalkah et al., 2016). 10% POFA blended
FA based AAB specimens showed a remarkable resistance even
after immersing in an acidic peat solution for 120 days (Satya et al.,
2016).
AAB specimens exhibited reasonable resistance against acid
even after immersion in H2SO4 for 180 days. From Figs. 10 and 11, it
can be seen that the mass loss values corresponding to the reduc-
tion in the compressive strength for different AAB specimens.
Various studies, as shown in the figures, have reported enhanced
acid resistance for AAB concrete than cement concrete (Chi et al.,
2015). The relatively low acid resistance of OPC paste specimens
can be due to the higher Ca/Si ratio, which leads to the formation of
a pervious layer on the surface of the specimens. In contrast,
Fig. 10. Strength loss of specimens after exposure to acids.
12
Journal of Cleaner Production 286 (2021) 125429
inorganic geopolymers form dense Si gel layer on the surface,
which inhibits further acid ingression into the alkali-activated
concrete specimens.
7.2. Water absorption of agro-waste ash based AAB specimens
Water absorption of different alkali-activated mortar after 24 h
of immersion in water is shown in Fig. 12. It can be seen that slag
and FA based AAB specimens exhibit improved resistance against
water absorption than cement concrete. Moreover, slag based AAB
mortar specimens exhibited lesser water absorption than FA based
AAB specimens.
This could be due to (i) the formation of C-(A)-S-H gel with
significant bound water content and (ii) owing to the finer particle
size which can fill the pores resulting in reduced water absorption
(Chi et al., 2015). However, the ternary blended alkali-activated
specimens with POFA, RHA, and slag as precursors exhibited a
relatively higher water absorption. In the same way, another
ternary blended AAB specimens with RHA, FA, and slag also
exhibited higher water absorption than that of OPC concrete and
FA/slag based binary AAB specimens. This may be attributed to the
fact that sodium hydroxide was used as the sole activator solution
for the other mixes, while a combination of both sodium hydroxide
and water glass was used for FA and slag AAB mixes. As discussed
earlier, a combination of NH and SS is more beneficial for the
development of a denser microstructure and consequent
enhancement in the compressive strength. It can also be seen that
even though only sodium hydroxide is used as the sole activator in
the case of 25% BA blended alkali-activated slag concrete, and it
exhibits an improved resistance against water penetration than the
ternary mixtures. This could be due to the higher molarity of NaOH
(8M) used for activating BA25/Slag75 than that used for the ternary
blends (2.5M). The enhanced performance of AAB specimens at
higher molarity of NaOH has already been discussed in section 6.3.
The absorption of the water content due to the presence of porous
cellular structured fibrous particles in unprocessed AWAs can result
in unreacted particles in AAB. This could also have been a factor in
increasing the water absorption of unprocessed agro-waste ashes
blended AAB specimens.
V. Athira, V. Charitha, G. Athira et al.
Fig. 11. Mass loss of the AAB specimens for different durations of acid immersion.
Fig. 12. Water absorption of different agro-waste ash based AAB specimens.
7.3. Sulphate resistance of agro-waste ash based AAB specimens
Sulphate attack leads to expansion, cracking, disintegration and
strength loss of concrete. The different sources of sulphate ions are
soil, seawater or the bacterial action in sewers. Some of the com-
mon sulphate solutions which can deteriorate concrete are mag-
nesium sulphate (MgSO4), solutions of sodium and potassium
sulphates (Na2SO4, K2SO4) or seawater.
Sulphate resistance can be measured by determining the loss in
the strength, loss in weight of specimens and mainly percentage of
expansion. Fig. 13 depicts the residual compressive strength of AAB
immersed in sulphate solution for various duration. Exposure of
slag based AAB specimens to MgSO4 solution led to the loss in the
compressive strength similar to that of OPC specimens. In contrast,
exposure to Na2SO4 solution led to the lesser loss in the compres-
sive strength of the exposed specimens. Addition of BA to alkali-
activated slag specimens did not improve the strength, as shown
in Fig. 13 (Pereira et al., 2015). The inclusion of RHA and POFA to
alkali-activated slag specimens performed well in case of sulphate
resistance. POFA based AAB specimens with 2% polyvinyl alcohol
fibres showed better performance in the sulphate environment.
13
Journal of Cleaner Production 286 (2021) 125429
Reduction in the strength was higher at 60e90 days of immersion.
X-ray diffraction (XRD) analysis exhibited that the peaks repre-
senting crystallinity were reduced because of the effect of sulphate
solution, which can be the reason for reduced compressive strength
(Salami et al., 2017). Alkali activated specimens with slag and FA
provided better resistance against sulphate (Na2SO4) environment.
In the initial days of exposure (up to 28 day), there was no signif-
icant change in the strength implying that Na2SO4 did not interfere
in the polymerisation due to higher Si/Al ratio. In contrast, as the
duration is increased, Si/Al ratio is decreased, leading to a reduction
in the compressive strength (D zunuzovi c et al., 2017).
7.4. Drying shrinkage
Drying shrinkage plays a vital role in the longevity of the
structure. Shrinkage is caused due to the loss of water and forms
cracks in the concrete surface. During the initial days, shrinkage
stresses are formed upon drying, which causes strain in the con-
crete. Fig. 14 shows the drying shrinkage of different agro-waste
based AAB specimens at different curing durations. It can be seen
that the highest shrinkage is observed for slag based AAB speci-
mens. However, the drying shrinkage for slag and RHA blended AAB
specimens was found to be significantly less. It was reported that
compared to OPC concrete, AAB specimens developed using slag
and RHA had lesser drying shrinkage as the excess water in the
matrix was minimal in AAB specimens. This also led to a reduction
in the porosity of the AAB specimens, and hence better perfor-
mance is attained (Zabihi et al., 2018). Shrinkage of the matrix
significantly depends on the loss of water from mesopores. It is
reported that the distribution of mesopores was higher (74e81.3%)
in slag based AAB specimens than that of OPC specimens
(36.4e24.7%). Besides, the distribution of macropores is reported to
be higher in OPC specimens. The higher distribution of mesopores
could also have resulted in the higher drying shrinkage of slag
based AAB specimens (Collins and Sanjayan, 2000).
The incorporation of 50% FA was also found to reduce the drying
shrinkage of slag based alkali-activated binders to a greater extent,
as shown in Fig. 14. POFA based AAB specimens also exhibited
enhanced performance against drying shrinkage compared to 100%
slag based AAB specimens (Huseien et al., 2018).
V. Athira, V. Charitha, G. Athira et al.
Fig. 13. Residual compressive strength of specimens immersed in a sulphate solution.
Fig. 14. Drying shrinkage of agro-waste ash based AAB specimens.
7.5. Resistance to chloride ingression and corrosion
Alkali-activated binders generally have a higher resistance to
chloride permeability due to their denser microstructures and low
permeability compared to Portland cement concrete systems (Lee
et al., 2019). Fly ash/slag based geopolymer concrete specimens
are found to have lesser “charge passed” values compared with
similar grade of ordinary concrete at all curing ages as per rapid
chloride permeability test, indicating greater resistance against
chloride ingress. It was also observed that fly ash based AAB has
better resistance than slag based AAB against chloride ion pene-
tration (Tennakoon et al., 2017). The incorporation of rice husk ash
up to 10% enhanced the microstructure of slag based AAB, and
subsequently the total charge passed values of activated slag con-
crete with 10% RHA is found to be ~12% lesser than that of 100% slag
based AAB (Venkatesan and Pazhani, 2016b). However, for further
replacement percentages, the total charge passed values increased.
This is in confirmation with the studies on the hydration reaction
14
Journal of Cleaner Production 286 (2021) 125429
kinetics of RHA based alkali-activated binders as reported by
Detphan and Chindaprasirt (2009). The chloride penetration
resistance of the other agro waste ash based AABs are not yet
explored in detail. The permeability of agro-waste ash based AAB
concrete is considerably less, and hence it is a viable option for
corrosion resistant concrete structures.
8. Performance of agro-waste ash based AAB at elevated
temperatures
Concrete surfaces are often exposed to high temperatures when
used in indoor flumes, foundry floors, industrial chimneys, etc. The
poor performance of cement concrete under elevated temperatures
have led researchers to focus on the development of fire-resistant
cementitious systems. Fire resistance of AAB developed from
different industrial and agricultural by-products are presented in
Fig. 15, in terms of loss in the compressive strength when exposed
to elevated temperatures. Irrespective of the cementitious systems,
V. Athira, V. Charitha, G. Athira et al.
Fig. 15. Performance of agro-waste ashes based AAB specimens exposed to elevated temperatures.
the loss in compressive strength was found to increase with respect
to increasing temperatures. The compressive strength loss was
significant in case of OPC concrete beyond 400  C, as the portlandite
(Ca(OH)2) in the hydrated cementitious matrix is dehydrated in the
temperature range of 410e470  C (Gabrovsek et al., 2006). A
consistent loss in the compressive strength was observed for RHA
based AAB specimens with an increase in the temperature. The
strength loss was found to be relatively low at lesser temperatures.
The initial strength loss may be attributed to the evaporation of the
moisture content. At higher temperatures, the presence of silicates
in RHA based AAB causes a swelling effect due to thermal expan-
sion, which creates pressure inside the hardened binder resulting
in the development of micro-cracks. For that reason, a higher
reduction in strength is observed (Kim et al., 2014).
Interestingly, 100% FA based AAB specimens and the ternary
blend of WSA, FA, and metakaolin showed an increment in the
compressive strength at temperatures lesser than 600  C. An in-
crease of 4.2% in the compressive strength was observed in ternary

blended AAB specimens exposed to 300 C. Further increase in the
temperature beyond 600  C has led to a drop in the compressive
strength of about 28.6% (Matalkah et al., 2016). In contrast, gain in
the compressive strength was observed as 27% and 11% for tem-
peratures 400 and 600  C respectively for FA based AAB specimens.
Microstructural analysis showed that after exposure to elevated
temperatures below 600  C, the microstructure has transformed
into a more reacted matrix with crystalline products which can be
the reason for the gain in compressive strength of AAB specimens
with fly ash in the stated temperature range (Rashad and Zeedan,
2011). It was also reported that the XRD patterns of FA based AAB
specimens showed the presence of mullite at room temperature as
well as at elevated temperatures. Mullite is the only stable crys-
talline phase in the matrix which has high-temperature stability
with oxidation resistance and low thermal expansion (Ranjbar
et al., 2014). Even though the presence of mullite is reported in
alkali-activated slag concrete, more amount of calcium-based
products (CeN-A-S-H) were detected which decomposes at
elevated temperatures, thus creating pores in the matrix (Shaikh,
2018). This can be the cause for higher loss in the compressive
strength of alkali-activated slag concrete. It is evident from Fig. 15
that agro-waste ashes based AAB specimens perform better at
elevated temperatures when compared to slag based AAB speci-
mens and OPC concrete specimens. Compared to RHA based AAB
specimens, the loss in the compressive strength of slag based AAB
specimens and OPC specimens was higher by 43% and 47%
15
Journal of Cleaner Production 286 (2021) 125429
respectively at 700  C. The ternary blend of POFA, RHA and slag
surpassed 100% RHA based AAB specimens, showing a lesser
reduction in the compressive strength. The strength loss of OPC and
slag based AAB specimens was found to be 67 and 70% higher than
the ternary blend at 700  C. The least strength loss at 700  C was
found for the ternary blend of WSA, FA and metakaolin (18.1%)
when compared to all other AAB specimens. In general, portlandite
is the dominant element in the deterioration of cement concrete at
elevated temperatures (Rashad et al., 2016). Hence, compared to
inorganic geopolymers, conventional cement concrete performs
below par at elevated temperatures. As a result, agro-waste based
AAB specimens can be used as a sustainable binder with better
resistance against elevated temperatures.
9. Directions for future research studies
Based on the comprehensive review, the performance of agro-
waste ash based alkali-activated binders is found to be compara-
ble with slag/fly ash based alkali-activated binders. However, agro-
waste ashes are not widely utilised in the development of AABs. The
foremost barrier for the delay in translating the research outputs of
agro-waste ashes based AAB concrete into industrial-scale practice
is the lack of a detailed performance evaluation. Therefore, there is
a need for further investigations to understand the influence of
different agro-waste ashes in the performance of AAB concrete. The
following studies are suggested for further research to enable
better utilisation of agro-waste ash based AAB concrete.
 The primary barrier in AAB concrete applications is the high cost
of alkaline activators. It is essential to focus on the development
of low-cost activators. Extraction of alkaline activators from RHA
has been previously reported. Studies on similar approaches are
essential to extract low-cost alkaline activators from silica-rich
agro-waste sources. Thus, studies on the development of low-
cost activators are suggested.
 Based on the review, influence of characteristics of activators is
found to be significant on the performance of AAB. Hence a
detailed study on the selection of the suitable alkaline activator,
its dosage, and other associated parameters for each agro-waste
ash needs to be studied.
 Studies on ternary alkali-activated concrete particularly with
agro-waste ashes are found to be highly limited. Therefore, in-
vestigations on the performance of ternary blended alkali-
activated concrete are recommended.
V. Athira, V. Charitha, G. Athira et al.
 Using AWAs in conjunction with fly ash can be especially helpful
since the fly ash can supply the alumina content required for
developing cross-linking and denser microstructure.
 Research studies on the microstructural characteristics and re-
action mechanisms of fly ash and slag based AAB specimens are
widely reported. Similar investigations need to be conducted for
different agro-waste ashes based AAB to understand their re-
action kinetics.
 There are minimal studies on the corrosion resistance of agro-
waste ash based AAB concrete. Therefore, corrosion resistance
of agro-waste ash based AAB needs to be investigated.
 Identification of the locally available agro-waste resources for
alkali-activation and standardisation of the mixture proportions
for that specific material is key in adopting their industrial-scale
practice. For instance, India and Brazil are the largest sugar
producers and have sugarcane bagasse ash in abundance. Hence
a detailed characterisation, performance evaluation, develop-
ment of specific codal provision for the use of BA based AAB will
enable its acceptance. In a similar manner, major rice-producing
nations could benefit from using RSA and RHA as precursors.
 Large scale infrastructural projects and government-funded
construction projects are mandated to follow the national
standards and regulations. Therefore, the official inclusion of
agro-waste based AAB concretes in international standards
needs to be attempted, based on round-robin tests.
 Studies on the quantification of availability and accessibility of
all agro-waste ashes in the major agriculture-based countries is
needed for their efficient recycling in AAB.
 Further research studies on source variability of agro-waste
ashes are vital to understand their consistent performance in
AAB concrete.
 Studies on the performance of agro-waste based AAB concrete in
constructed facilities such as buildings, bridges etc. are highly
limited. Field studies on building facilities are needed to un-
derstand its performance in real structures and it also helps to
correlate the laboratory observations with their field
performance.
10. Conclusions
Use of six agro-waste ashes as source material in the alkali-
activated binder and their influence on the performance of con-
crete are systematically reviewed. Specific conclusions drawn from
the review are given below:
 RHA has the highest silica content and all other agro-waste
ashes have almost similar amounts of silica (above 45%). Corn
cob ash is found to have the highest alumina content compared
to other agro-waste ashes.
 Agro-waste ashes have higher loss on ignition due to the pres-
ence of unburnt fibrous particles. However, suitable processing
methods like simple sieving process helps to reduce the LOI.
 Variation in the specific gravity between different agro-waste
ashes is found to be significant. Bagasse ash has the least spe-
cific gravity compared to the other AWAs, whereas the specific
gravity of POFA varies from 2.1 to 2.7, similar to that of fly ash.
 Each AWAs has dissimilar microstructure. However, spherical,
fibrous, and irregular particles are observed in the micrograph of
BA, WSA and SSA. The porous cellular structure of RHA causes
higher water absorption. Grinding of RHA collapses its cellular
structure and reduces the water absorption.
 NH þ SS activator is the most efficient activator for AWA-based
alkali-activated binders. A similar trend is reported for fly ash
and slag-based alkali-activated binders.
16
Journal of Cleaner Production 286 (2021) 125429
 Compressive strength is increased with the increase in the
molarity for BA, RHA, fly ash and slag. Reduction in the
compressive strength is noticed beyond 8M and 14M for POFA
and CCA based AAB respectively. Efflorescence is reported for
higher molarity in CCA based specimens.
 Hydration of slag is hindered in heat curing and caused lesser
strength compared to ambient curing and water curing.
Ambient curing is better for BA based AAB specimens, whereas
heat curing is beneficial for POFA and slag based AAB specimens.
 With increase in the immersion period in acid and sulphate
solutions, all agro-waste ash based AAB specimens exhibited
higher loss in compressive strength compared to control
specimens.
 Agro-waste ashes based AAB specimens showed enhanced
performance at elevated temperatures compared to slag based
AAB. Nevertheless, at higher temperatures beyond 600  C, the
presence of silicates in RHA based AAB specimens causes a
swelling effect due to thermal expansion, and reduces the
strength.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
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