Progress in Crystal Growth and Characterization of Materials 64 (2018) 23–61

Contents lists available at ScienceDirect

Progress in Crystal Growth and

Characterization of Materials
journal homepage: www.elsevier.com/locate/pcrysgrow

Review

Solution combustion synthesis, energy and environment: Best parameters for T

better materials
⁎
Francesca Deganelloa, , Avesh Kumar Tyagib
a
Istituto per lo Studio dei Materiali Nanostrutturati (ISMN) – Consiglio Nazionale delle Ricerche (CNR), Via Ugo La Malfa 153, 90146 Palermo, Italy
b
Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400 085, India

A R T I C LE I N FO A B S T R A C T

Keywords: Solution combustion synthesis (SCS) is a worldwide used methodology for the preparation of inorganic ceramic
Solution combustion synthesis and composite materials with controlled properties for a wide number of applications, from catalysis to pho-
Energy and environment tocatalysis and electrocatalysis, from heavy metal removal to sensoristics and electronics. The high versatility
Ecofriendly procedures and efficiency of this technique have led to the introduction of many variants, which allowed important opti-
Materials optimization
mization to the prepared materials. Moreover, its ecofriendly nature encouraged further studies about the use of
Synthesis parameters
sustainable precursors for the preparation of nanomaterials for energy and environment, according to the
Fuel types
Fuel amount concept of circular economy. On the other hand, the large variety of expressions to define SCS and the often-
Waste-derived fuels contradictory definitions of the SCS parameters witnessed a scarce consciousness of the potentiality of this
Mixed fuels methodology. In this review article, the most important findings about SCS and the selection criteria for its main
Reproducibility parameters are critically reviewed, in order to give useful guidelines to those scientists who want to use this
Microstructural templates methodology for preparing materials with improved or new functional properties. This review aims as well (i) to
bring more clarity in the SCS terminology (ii) to increase the awareness of the SCS as a convenient tool for the
synthesis of materials and (iii) to propose a new perspective in the SCS, with special attention to the use of
ecofriendly procedures. Part of the review is also dedicated to precautions and limitations of this powerful
methodology.

1. Introduction ones already mentioned, is “efficiency”, which is highly required for a

In this era, where the words “sustainability”, “green”, “eco-compat-
ibility”, “ecofriendly”, “environmental benefits”, “energy saving”, “renew-
able”, “circular economy” are the most pronounced ones [1–5], the
human kind became aware of the fact that benefit to the environment
and energy-saving start already from the preparation of materials. In
this perspective, environmental and energy issues do not concern only
the applications of materials, but also the synthesis of the material it-
self.
The need for ecofriendly methodologies to prepare inorganic ma-
terials has been gradually emerging, especially when these materials
are used for energy and environmental applications. The general ten-
dency, in accordance with the recent concepts of circular economy
[2,3,5], is to replace the “commercial” raw materials with the natural
and waste-derived ones [6–13]. To this regard, the sentence “Nature
does not make persistent things… and we should not as well” by Paul
Connett [14••] gives solid basis to chemists for a sustainable future.
Another important word, which is strongly associated with the other
successful synthesis procedure. Efficiency is high for a maximum yield,
minimum energy, minimum time and minimum wastes. From another
point of view, efficiency is high if the scientist knows well the process
and its maximum potentialities and possibilities. In this sense, the
knowledge and the experience on a synthesis procedure make the
process “efficient”, because that synthesis is performed with the best
processing parameters, leading to the best possible material properties.
From these considerations, the importance of getting knowledge
from a synthesis procedure becomes obvious. For example, in the case
of a catalytic material, the kind of knowledge that is essential for an
efficient synthesis procedure is related to the connections between
synthesis parameters, structure, texture, microstructure, morphology,
redox behavior, surface and catalytic performance. Given the extreme
complexity of these connections, the knowledge about a synthesis
methodology is only gained from a systematic research study, which
clearly evidences the effect of a single parameter, maintaining the other
important parameters strictly constant. Examples of such systematic
studies are present in the literature [15••–20].

⁎
Corresponding author.
E-mail addresses: francesca.deganello@cnr.it (F. Deganello), aktyagi@barc.gov.in (A.K. Tyagi).

https://doi.org/10.1016/j.pcrysgrow.2018.03.001

0960-8974/ © 2018 Elsevier Ltd. All rights reserved.

F. Deganello, A.K. Tyagi
In terms of efficiency, not all the solution-based preparation meth-
odologies are equipotential. Each soft chemical method, including so-
lution routes such as solution combustion synthesis, sol-gel technique,
Pechini-like process, co-precipitation process and hydrothermal pro-
cess, has its own merits and demerits over the other. Most of these
processes involve costly starting materials and suffer from the problem
of intermediates, which tend to be moisture sensitive. At times there are
scalability issues and efficiency might be different according to the
composition/properties of the material to be prepared. For example, the
sol-gel synthesis from alkoxides precursors is undoubtedly an efficient
synthesis for silica, alumina or titania-based powders with controlled
porosity [21••,22], although it is time-consuming and not very efficient
for multicomponent compositions, where other methodologies are
preferred [23].
In summary, choosing a sustainable synthesis will be helpful for:
- saving energy, time and costs,
- increasing the efficiency,
- adopting ecofriendly precursors,
- minimizing the waste production,
- getting knowledge about the synthesis-properties relationships,
- producing materials with a benefit for energy, environment, society
and economy.
1.1. Description of solution combustion synthesis
Among the soft chemical methods, solution combustion synthesis
(SCS) is an excellent synthesis method in terms of simplicity, cost-ef-
ficiency and powder quality of the product. SCS is based on a fast and
self-sustained redox reaction between a fuel and an oxidant in the
presence of metal cations. Usually oxidants are metal precursors
themselves, like for example metal nitrates, and the fuel is any organic
material, as for example citric acid, urea and glycine, capable of
forming complexes with metal ions of interest. SCS comes from sol-gel
chemistry [21••] and propellant chemistry [24•], although it uses a
faster procedure than sol-gel techniques [25•], and is recommended for
multicomponent oxides [26,27].
Solution combustion synthesis is a time/energy saving methodology
for the preparation of a large variety of inorganic nanopowders with
high reactivity and tailored defects [15••,28•–35].The final products
that are obtained through SCS are of great phase purity and with su-
perior powder characteristics like higher surface area, narrow particle
size distribution, optimum agglomeration and better sintering proper-
ties [26, 36-39]. Another important advantage is that it can be used
with a variety of precursors, both soluble [15••,40••–45] and insoluble
[9,46-49•]. In view of this, the combustion process has been extensively
used to synthesize various oxides in a nanocrystalline form. SCS has
been also recently used to obtain films for applications in electronics
[50–52].
The general procedure is described in the recent reviews on the
subject [[15••, 28•–31••,33••,53]. Basically, solution combustion synth-
esis consists of three main steps such as (1) formation of the combustion
mixture (2) formation of the gel (3) combustion of the gel. According to
Fig. 1.1.1 a schematic description of these three steps is illustrated. The
desired metal precursors (see also Section 3) are mixed in water solu-
tion with an organic fuel. A gel network is formed in the combustion
mixture upon dehydration of the solution. The combustion process
between the fuel and the oxidant (i.e.: the nitrates and eventually an
additional oxidant), intimately connected in the gel network, is in-
itiated by a thermal or electric source. The decomposition of the gel
should be preferably in single step, uniform, rapid and over a narrow
temperature range, to ensure that no undesired products are formed.
After few seconds, a fluffy powder is obtained, whose features are
strictly connected with the chosen synthesis parameters, like the fuel
type (discussed in details in Section 2.1), the reducers-to-oxidizers ratio
(Φ, discussed in details in Section 2.2.1), the fuel-to-metal cations ratio
24
Progress in Crystal Growth and Characterization of Materials 64 (2018) 23–61
(F/M, discussed in details in Section 2.2.2) and many other parameters.
The fuel is usually an organic compound and it has a central role in the
optimization of the materials properties. The fuel has often the triple
function of reducer, complexing agent and microstructural template
[54••]. Both the nature of the fuel and its content in the reaction govern
the reaction exothermicity and in turn guide the process toward at-
taining the desired powder of the product in terms of phase and powder
properties.
When citric acid is used as a fuel, SCS can also be considered a
variant of the Pechini-based preparation methodologies, generally
classified as inorganic sol-gel methods. In the Pechini-based processes,
organic compounds with carboxylate, hydroxyl and amino functional
groups are added as chelating agents to form a gel network with metal
nitrate precursors [21••,23]. Therefore, in principle, all the conditions
required for a combustion process are effectively present in Pechini-
based syntheses. In fact, there are some similarities and some differ-
ences between Pechini-based methodologies and SCS-based ones that it
is worth to mention in this context, in order to clarify the SCS itself.
Usually, the amount of fuel is so high with respect to the metal cations
(which represent as well the oxidizers for the oxidizing effect of their
counter ions) that the reducers-to-oxidizers ratio (Φ, discussed in details
in Section 2.2.1) is outside the combustion range and the combustion
process does not occur even under high temperature treatment [55,56].
Sometimes, the nitrate anions are decomposed under vacuum before
the thermal treatment [23] so that no oxidant is left for combustion. In
some variants of Pechini process, where no EDTA is added and nitrates
are not decomposed before the thermal treatment [23,57] or a com-
bustion aid is added [55], a more or less intense combustion process
might occur.
For similar reasons, some preparation methods involving soft tem-
plates and nitrate metal precursors might be considered as solution
combustion-based methodologies, like for example the preparation of
metallic silver sponges from dextran as framework-generating agent
and silver nitrate as metal precursor [58].
Beside propellant chemistry [24•] and sol-gel chemistry [21••], an-
other important ancestor of solution combustion synthesis is the solid-
state combustion synthesis [59••], as pictorially described in Fig. 1.1.2.
Solid-state combustion often referred as SHS – Self sustained High
temperature Synthesis - [60a••,61,62] or as SP-CS – Solid Phase Com-
bustion Synthesis – [32••], can be considered as the “grand mother” of
SCS, being the first example of application of the propellant chemistry
concepts to the synthesis of materials [63]. According to this metho-
dology, a mixture of powdered elements is usually pressed into cy-
lindrical pellets. The actual chemical reaction between the various
elements is then initiated at room temperature by a quick and intense
heat source, just like in the fireworks. A combustion wave propagates
through the material in a self-sustained manner. This is known as self-
propagation because the process no longer requires the input of energy.
Therefore, energy saving is just one of the many advantages of these
simple reactions. With respect to SHS, which is essentially used for
preparing metals and alloys, SCS is used for metal oxides. Other im-
portant advantages of SCS are that a large amount of gas is produced,
nucleation without growth occurs, a wide variety of fuels can be used
and there is a concrete possibility of scale–up [39,64].
Later on, between 1985 and 1993, Patil and coworkers [25•,65,66a]
connected for the first time propellant chemistry to the synthesis of
nanomaterials in solution, investigating the formation of complexes
between propellants and metal cations. This gave an outstanding im-
pulse to the following research on solution combustion synthesis and
signed the effective birth of solution combustion synthesis for the fast
and efficient synthesis of inorganic oxides [30••]. Since early eighties,
huge amount of research has been published on the role of various
components in solid propellants, in the binders, in the chemical trans-
formations during combustion and in the generation of mono and
polyoxides [24•,25•]. In 2003, Aruna and Rajam discussed the
process optimization including fuels like urea and ammonium acetates
F. Deganello, A.K. Tyagi Progress in Crystal Growth and Characterization of Materials 64 (2018) 23–61

Fig. 1.1.1. Schematic description of

the three main steps in solution com-
bustion synthesis (SCS) [Adapted from
Mater. Tod: Proc., 4, F. Deganello,
Nanomaterials for environmental and
energy applications prepared by solution
combustion based-methodologies: role of
the fuel, Pages 5507–5516, Copyright
(2017), with permission from Elsevier,
license number 4,181,720,702,998].

[60b]. Many research groups investigated the phenomenon of com-
bustion reactions, going into a deep understanding of chemical
thermodynamics to formulate, quantify and provide a detailed
mechanistic insight into the complex process of solution combustion
[59••,60a••,62–65,66a]. Given the contextual importance of this topic,
some researchers have designed and tested various models for assessing
the flammability of combustible materials. In particular, some studies
have designed new additives that would retard/inhibit the flammability
of various materials to help controlled reaction and hence controlled
synthesis, understanding the effect of such additives on the various
properties of materials, primarily by changing the combustion wave,
lowering of the transition temperature and refining the particle size of
the final product [66b].
A very interesting historical perspective has been published in 2008,

Fig. 1.1.2. Groundwork and features of solution combustion synthesis (SCS).

25
F. Deganello, A.K. Tyagi
about the discovering and evolution of combustion synthesis from SHS
to SCS, highlighting the different scientific contribution of the various
scientists that worked on this intriguing subject [67•].
The high versatility of SCS and its enormous advantages were ap-
preciated very fast, favoring the growing of new SCS variants for ad-
vanced technological solutions. The existing SCS variants, the chemical
mechanisms involved, the effect of some SCS parameters, like type of
flame, generated gases, temperature, reaction atmosphere and
all the most important thermodynamical, thermochemical and
mechanistic aspects of SCS, have been extensively discussed in the
recent books [68], papers [69,70] and reviews on the subject
[15••,28•–32••,60a••,71•].
Looking at the Scopus database at the statistics of the publications
about “combustion synthesis” (in the article title) over the last 20 years,
about 5000 papers have been published only in the last 10 years, cor-
responding to about 200–300 publications per year. According to the
Fig. 1.1.4. XRD patterns of YIn1-xFexO3 (0.0 ≤ x ≤ 1.0) mixed oxides prepared
by solution combustion synthesis after calcination at 600 °C. Evidence of for-
mation of pure metastable C-type fluorite phases throughout the whole com-
position range (a) x = 0, (b) 0.1, (c) 0.3, (d) 0.5, (e) 0.7, (f) 0.9, and (g) 1.0
[Reprinted with permission from R. Shukla, F. N. Sayed, V. Grover, S. K.
Deshpande, A. Guleria, A. K. Tyagi. Quest for lead free relaxors in YIn1-xFexO3
(0.0 ≤ x ≤ 1.0) system: Role of synthesis and structure, Inorg. Chem. 53, pages
10,101–10,111. Copyright 2014 American Chemical Society].
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Progress in Crystal Growth and Characterization of Materials 64 (2018) 23–61
Fig. 1.1.3. Schematic illustration of the solution combustion synth-
esis applied at the Gd2-xCexZr2-xAlxO7 mixed oxide system and phase
evolution varying composition and synthesis conditions [Reprinted
with permission from R. Shukla, F. N. Sayed, S. Phapale, R. Mishra, A.
K. Tyagi, Sequential evolution of different phases in metastable
Gd2−xCexZr2−xAlxO7 (0.0 ≤ x ≤ 2.0) system: crucial role of reaction
conditions, Inorg. Chem. 52, pages 7873 − 7880. Copyright 2013
American Chemical Society].
Web of Science database, the number of citations per year has been
linearly increasing, reaching 4500 citations last year. In particular, in
the last ten years, some interesting articles have been published cov-
ering several aspects of SCS, all related with energy and environmental
applications [15••,28•-31••,33••]. The large number of publications and
citations demonstrates the high interest of the scientific community for
this preparation methodology.
As shown in Fig. 1.1.2, by using SCS, many single phase compounds
can be prepared, which otherwise would be difficult to synthesize by
conventional methods. For example, Sayed et al. tried the synthesis of
PrScO3, a photo-catalyst, via a solid-state route as well as by using a
glycine–nitrate combustion reaction in various oxidant-to-fuel ratios to
obtain the nanopowders: solid-state synthesized sample gave impure
product, whereas stoichiometric gel-combustion synthesized sample
stabilized the pure PrScO3 phase in a single step [72]. Stabilizing some
of the metastable compounds in the phase relation is another aspect
where combustion synthesis excels over conventional methods. For
example, stability of the fluorite structure in the Gd2−xCexZr2−xAlxO7
(0.0 ≤ x ≤ 2.0) system was attributed - beside to the chemical com-
position - to the non-equilibrium nature of the solution combustion
synthesis and to the nanocrystalline nature of the compound [73]
(Fig. 1.1.3). Thus, it can be observed that by employing SCS method it is
possible to enhance the solubility, leading to new metastable solid so-
lutions and compounds. Similarly, fluorite-type phases have been ob-
served for the YIn1-xFexO3 (0.0 ≤ x ≤ 1.0) system [74] (Fig. 1.1.4).
In addition, as combustion synthesized nanopowders are highly
fluffy and have a large number of active sites, they are used as active
catalyst support. For example, 5% palladium supported on combustion
synthesized fluorite CeZrO4-δ has been used for heterogeneous Suzuki
coupling in water, exhibiting 100% conversion of iodobenzene to bi-
phenyl in 1 h [75].
The number of variants in SCS, beside the chemical composition, is
so large that it is hard to find two papers describing the same proce-
dure. Moreover, there is a general confusion about the terminology
related with the type of combustion synthesis and parameters. In
Table 1.1.1 the most used alternative names for solution combustion
synthesis are reported for the sake of information.
Sometimes the limit between combustion and decomposition only
depends on the ratio between the oxidant and the fuel: if excess of fuel
is added, combustion does not occur and a simple decomposition takes
place. For example, Subramania et al. [131] call their synthesis process
with PVA (polyvinyl alcohol) and citric acid (hexamine, urea) a “sol-gel
F. Deganello, A.K. Tyagi
Table 1.1.1
Alternative terminology used in the literature for solution combustion synthesis.
Alternative names of solution combustion synthesis
Gel combustion
Sol-gel combustion
Sol-gel auto-combustion
Combustion
Combustion synthesis
(Aqueous, wet) combustion synthesis
Combustion method
Combustion-based (method, route)
Combustion (process, approach)
Auto-combustion (synthesis, process, method)
Self-sustained combustion (synthesis, route)
Self-combustion
Self-propagating combustion”
Auto ignition synthesis
Combustion agent-mediated flash synthesis
Citrate-nitrate process
Glycine-nitrate precursor (method, process)
Acetate-nitrate combustion
Combustion of citrate and nitrate precursors
Pyrolysis of oxalate precursors
thermolysis”, since the oxidant content is too low for the auto combus-
tion to be initiated [131].
Beside terminology, there is also a bit of confusion in establishing
the true relationships between synthesis parameters and materials
properties. For example, Biswas et al.[116] studied the effect of the
oxidizers-to-fuel ratio (see Section 2.2.1) on the final properties of
fluorite-type nanopowders, by changing the fuel-to-metal nitrates ratio
(see Section 2.2.2). In this case, two important parameters were
changed at the same time: the oxidizers-to fuel ratio and the fuel-to-
metal cations ratio [116]. Another more recent example is a very de-
tailed study about the effect of cellulose content on the properties of a
cobalt oxide prepared by glycine combustion, where the cellulose
content was varied in a wide range with respect to the cobalt nitrate
amount [46]. The overall effect on the final material was a complex
combination of the two varying parameters, the oxidizers-to-fuel ratio
and the fuel-to-metal cations ratio. Other similar examples are found in
the literature [19•,47,132,133]. Another case is the study of the effect
of the fuel-type without fixing the fuel-to-metal nitrates ratio at the
same value for every fuel [70].
All these factors make the selection of the most convenient pro-
cessing parameters a hard choice for those who are not familiar with
this powerful methodology. However, provided that the most important
parameters - such as for example the fuel type/amount (see Sections 2.1
and 2.2) [54••] and the addition of a secondary fuel (see Section 2.2.1 -
classification 4) [20,102,134–136] or of an external hard template (see
Section 6) [83,114•,137•] - are properly selected, SCS becomes an ef-
fective tool for the fine control of the microstructure, morphology,
oxygen defectivity and, in turn, of the catalytic and electrocatalytic
performance of inorganic nanopowders.
In this review, the selection criteria of the main SCS parameters are
critically discussed and useful information and suggestions are given to
those who want to use SCS for preparing materials. In particular, the
most important relationships between synthesis and properties are
evidenced, in order to lay the foundations for a general efficient and
eco-friendly strategy to obtain materials with optimized properties,
giving a broader sight on the potentialities and limits of this widely
used methodology. In particular, the most recent knowledge of the
solution combustion-based procedures for the preparation of nanoma-
terials for energy and environment, including cathodes, anodes and
electrolytes for IT-SOFC (Intermediate-Temperatures Solid Oxide Fuel
Cells), electrodes for metal-air batteries, catalysts and photocatalysts is
reviewed.
27
Progress in Crystal Growth and Characterization of Materials 64 (2018) 23–61
Bibliographic references
[76,77,78]
[79,80,81]
[82,83,84]
[85]
[10,26,32••,37,38,47,48,59••,60••,62,64,65,67•,68,86–98]
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[119,120]
[121]
[122]
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[125]
[9,126,127]
[128]
[129]
[130]
2. Fuels
A fuel can be generally considered as any organic compound that is
able to react with an oxidant, starting a combustion process. During
combustion, the fuel is oxidized by the oxidants to gaseous products,
whereas metal cations take the oxygen from the oxidants and are
converted to oxides. In the SCS, the fuel has other two important
functions, as illustrated in Fig. 2.1: it should be as well chelating agent
and microstructural template.
The chelating ability towards the metal cations is necessary for
granting its interaction with metal precursors, which is a fundamental
requirement for a successful SCS. If the fuel is able to form complexes
with metal cations, during water evaporation (between step 1 and step
2 of Fig. 1.1.1), first a sol and then a gel network is easily formed. The
role of this network is to maintain the metal cations homogenously
fixed in their position during the combustion process and to establish
good connection between the fuel and the oxidant moieties.
SCS is a fast process and this fast kinetics inhibits the particle sin-
tering and maintains certain porosity in the powder. Moreover, a huge
amount of gases is evolved during the process, favoring the production
of porous powders. Depending on the fuel type and amount, the effect
on the microstructure of the final material may change in relation with
the type of gel network formed by the fuel and with the decomposition
characteristics of the fuel molecules [138,140]. Referring to Fig. 2.1,
the other important function of a fuel for SCS is to act as a micro-
structural template. For example, by using citric acid or sucrose as fuels,
different microstructures and texture were observed for Sm-doped ceria
solid oxide fuel cells electrolyte powders with identical chemical
composition, being sucrose a better fuel for producing well densified,
low grain boundary and high oxygen conducting electrolytes [141]. It
has been also observed in the literature that the interaction of citric acid
with metal cations occurs through formation of metal chelates forming
a gel network, where metal cations are uniformly distributed [21••,56].
As suggested by Podbolotov et al. [140] metal particles nucleation is
preferred at the grain growth in the case of citric acid, since the de-
composition process of citric acid is more complex than for hexam-
ethylenetetramine. Ding et al. [57] also observed that the micro-
structuring ability of a fuel mostly depends on the sol-gel chemistry,
being governed by the velocity of nucleation and the velocity of particle
growth. Hadke et al. [103•] compared NiO nanopowders obtained by
SCS from glycine or urea. They found that glycine, being able to interact
very well with metal cations, had a more intense combustion, a bran-
ched cotton wool structure with softer agglomerates and lower residual
F. Deganello, A.K. Tyagi
Fig. 2.1. Pictorial description of the three main functions of the fuel in solution combustion synthesis.
carbon, but also larger crystal size and lower densification ability with
respect to urea [103•]. Sucrose and carbohydrates in general, with their
large and bulky molecules, tend to leave large voids while burning,
favoring high porosity and high surface area powders [45]. In general,
small crystal size is obtained by using sucrose as a fuel [41] and ag-
glomeration is limited for glucose [142], whereas amylose favors larger
grains [142]. A typical effect of sucrose on the microstructure is related
to the consistent amount of residual carbon, left after any combustion
process involving carbohydrates, which acts itself as microstructural
template during combustion and in the subsequent thermal treatment
[113] (see also Section 6.2).
In the case of polymers and surfactants, the fuel molecules usually
entrap metal cations, whose dimension and nature depends on the type
and molecular weight of the polymeric compound [21••,143]. Polymers
are very effective in limiting the crystal growth, especially if they are
used in association with other fuels, like for example sucrose [144].
Another example is explained in Fig. 2.2, where, according to Fathi
et al.[138] a possible scheme of what happens to the powder micro-
structure by using glycine or urea in SCS for the synthesis of Fe3O4
oxide is illustrated. In this case, urea favors the precipitation of metal
cations inside the gel during combustion, causing nucleation of the
particles and extended agglomeration after combustion [138] (Fig. 2.2).
On the contrary, glycine causes a smoldering combustion with a co-
pious gases evolution and high temperature, producing spongy powders
with larger crystal size and porosity than urea [138] (Fig. 2.2). Other
examples of the microstructural effect of different fuels are available in
28
Progress in Crystal Growth and Characterization of Materials 64 (2018) 23–61
the recent literature [42].
Micron-sized spherical bismuth vanadate (BiVO4) samples were
synthesized by solution combustion synthesis and relationships be-
tween the morphologies and fuel (citric acid with urea) (Fig. 2.3)
contents are thoroughly analyzed by Chen et al. [80].
Often the final material shows a hierarchical microstructure
[92,105,145]. Although the preparation of hierarchically porous ma-
terials can be obtained by several methods [146],the formation of a gel
network and the high rapidity of the combustion process help limiting
the growth, or, in the presence of an external template, help replicating
the microstructure of the original template. Therefore,it can be inferred
that the porosity of the final powder strongly depends on the way the
fuel organizes itself around the metal cations.
The amount of fuel with respect to the oxidants and with respect to
the metal cations is also a very important parameter, since it affects the
nature of the combustion process, the phase composition of the
final powder, the microstructure and other materials features
[15••,47,54••,71•,147•], as described in details in Section 2.2.
The fuel is also able to affect the structure in terms of phase com-
position, microstrain, surface properties, oxidation state of metal ca-
tions in the final powder and oxygen vacancies [28•,31••,134,148].
In summary, both the fuel type and the fuel amount have an evident
effect on microstructural, morphological, structural, redox and surface
properties of the final material.
The fuel in the SCS should: (i) act as a reducer and undergo a proper
combustion with the oxidants at low ignition temperature (ii) be able to
Fig. 2.2. Different microstructural evolution during SCS with
urea (up) or glycine (down). [Reprinted from Ceramics
International, 43, H. Fathi, S.M. Masoudpanah, S.
Alamolhoda, H. Parnianfar, Effect of fuel type on the micro-
structure and magnetic properties of solution combusted Fe3O4
powders, pages 7448–7453, Copyright (2017), with permission
from Elsevier, license number 4,181,721,319,341].
F. Deganello, A.K. Tyagi
Fig. 2.3. FE-SEM images of the samples (A) the samples synthesized with different citric acid contents and (B) the samples synthesized with different urea contents
[Reprinted from J. Sol-Gel Sc. & Technol., Effects of citric acid and urea on the structural and morphological characteristics of BiVO4 synthesized by the sol–gel combustion
method, 76 , 2015, 562, L. Chen, J. Wang, D. Meng, Y. Xing, X. Tian, X. Yu,K. Xu, X. Wu, with permission of Springer, license number 4,181,731,429,061].
chelate metal cations in a gel network to maintain the compositional
homogeneity among all the constituents. The fuel, as desired char-
acteristics, should as well: (iii) form a clear transparent gel (iv) be non-
hygroscopic, economic and readily available.
In specific cases, it has been found that a fuel can be also success-
fully used in SCS if not all these four requirements are fulfilled. For
example, it has been found that, if the gel is not transparent, but con-
tains one of the precursors as suspended powder or solid, the homo-
geneity of the final product is not very much adversely affected, as for
example in the case of insoluble fuels like cellulose, cotton or carbon
nanotubes [9,46–48,149,150•]. From these considerations, it can be
inferred that the interaction of the fuel with metal precursors and with
oxidants can be exploited as well through adsorption or chemisorption
of the soluble components onto the insoluble fuel surface. What is im-
portant is that in the combustion mixture, at least one precursor is in
solution and that the formation of a gel network is ensured. In fact, an
homogeneous gel is formed as well when insoluble fuels like cellulose
are mixed with soluble metal precursors [46] or when insoluble carbon
nanotubes are used as fuels in the so called “multiphase combustion
synthesis” [150•].
The relationship of the fuel type/amount with the materials prop-
erties has been discussed in some recent papers and reviews
[15••,28•,30••,33••,54••]. Here, some useful considerations about the
choice of the type and amount of fuel are provided and a new classi-
fication for fuels and fuel mixtures in SCS is proposed in the next sec-
tions.
2.1. Fuel type
A large variety of organic materials can be used as fuels for the
combustion and useful information about the various SCS fuels can be
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Progress in Crystal Growth and Characterization of Materials 64 (2018) 23–61
found in the literature [30••,31••,33••,64,151]. A mere list of the used
fuels would not add anything to the knowledge about SCS and a unique
classification would not fully highlight all the important aspects of each
fuel. On the contrary, a multiple classification, according to some se-
lected features of the fuels, beside the heat of combustion, is much more
useful in this sense and helps in the selection of the best fuel for the
desired material. Therefore, a new multiperspective approach is pro-
posed in this review, as schematically described in Table 2.1.1 and,
more in details, in the next paragraph.
2.1.1. Multiple classification of fuels and fuel mixtures
Classification 1. Main functional groups present in the fuel molecule
This classification of fuels can be especially useful in order to select
the right fuel/fuel mixture for metal cations of different nature and
different ionic potential.
The first aspect to consider is that these four categories have dif-
ferent complexing ability toward metal cations. Carboxylic groups (Cat.
1.1), for example, are able to complex most of metal cations, although
complexes with alkaline earth cations are less favorite [152•]. In the
presence of high amount of these metal cations, hydroxyl groups (Cat.
1.2) are more convenient [152•]. Alternatively, -NR2 containing fuels
(Cat. 1.3) are also a convenient choice.
Another aspect which is associated with the type of functional group
is the intensity of the combustion reaction. As a general rule, the -NR2
containing fuels are more redox active during the combustion reaction,
than –OH, which is more active than –COOH and this increases the
intensity of the combustion process [31••,99]. A brief presentation of
the main SCS fuels belonging to this first classification is given below,
together with specification of the relative category. It is worth to notice
that, although each fuel has its own features, some common features
can be found for all the fuels belonging to the same category.
F. Deganello, A.K. Tyagi
Table 2.1.1
Multiperspective classification of the fuel types that can be used in solution combustion synthesis.
Citric acid (C6H8O7), for example, falls in the first category of this
classification (Cat. 1.1). It is a low cost fuel, which can be combusted
with nitrates at low ignition temperature (200–250 °C) [123•]. It has
three carboxylic and one hydroxyl group for coordinating the metal
ions to maintain the compositional homogeneity through gel formation
[21••,56]. Citric acid is a nitrogen free and high carbon fuel. On com-
bustion, citric acid gel gives evolution of lots of gases making the
powder properties superior.
Ascorbic acid (C6H8O6) [44,82] and tartaric acid (C4H6O6) [153],
which are fuels with high carbon and free from nitrogen atoms, belong
to Cat. 1.1 and are commonly used for sluggish combustion reaction,
have a weak complexation ability toward metal cations and precipita-
tion can occur early with multiple cation oxidants. The combustion
reactions with these acids are sluggish and can be better controlled to
obtain improved powder properties. As it will be discussed later, a
sluggish combustion might be the right choice for safety reasons or to
avoid excessive powder dispersion (Section 9) and scale up is easier for
sluggish combustion (Section 8).
Aspartic acid (C4H7NO4) [76] and glutamic acid (C5H9NO4) [154]
are acidic α-amino acids with two carboxylic (—COOH) and one amino
(—NH2) groups and still belong to Cat. 1.1 due to the predominance of
the carboxylic acid functional groups. The same compounds can be as
well be positioned in a middle zone between Cat.1.1. and Cat. 1.3, since
30
Progress in Crystal Growth and Characterization of Materials 64 (2018) 23–61
the presence of one amino group is worth to be considered, having its
own role in favoring a better coordination of the metal ions and
maintain the compositional homogeneity through gel formation. The
advantages are the low cost of the organic precursors and a low ignition
temperatures (200–250 °C).
Oxalic acid (C2H2O4) is a dicarboxylic acid, belonging to Cat.1.1 and
can also be used as fuel in SCS [81,155]. For example, it has been found
that oxalic acid is able to produce pure MgO powders with smaller
crystal sizes and superior properties in comparison with other fuels,
including citric acid [81].
Carbohydrates such as glucose or dextrose (C6H12O6), sucrose
(C12H22O11) [105], cellulose ((C6H10O5)n) [46,134] and sorbitol
(C6H14O6) [143,156•], belong to Cat. 1.2 due to the prevalent presence
of hydroxyl moieties in their ring-shaped structure.
Ethylene glycol (C2H6O2) belongs to Cat. 1.2, with a predominance
of hydroxyl groups. It is able to form a gel network with metal cations
and interact with them through steric entrapment [57,143,157,158].
Ethylene diamine tetra acetic acid (EDTA) (C10H16N2O8) is a unique
fuel of Cat. 1.1, with 4 carboxylic acid groups and 2 amino groups,
although it would be better positioned in a middle zone between Cat.
1.1 and 1.3. When precipitation of insoluble metal compounds with
other fuels occurs, then EDTA is used to circumvent the problem of
precipitation.
F. Deganello, A.K. Tyagi
Urea (CH4N2O) [80,103•,136] is the most commonly used SCS fuel
and undoubtedly belongs to Cat. 1.3 of this classification, having two
amino groups attached to a ketone group.
Arginine (C6H14N4O2) [77,159•] and tryptophan (C10H10N2O2)
[159•] are α-amino acids, since they contain one amino group at the α-
position to the carboxyl group. They are capable of complex formation
with metal ions giving a homogeneous gel and undergo combustion at
low ignition temperature. Arginine is a strong basic α-amino acid and
tryptophan is a weakly basic one. Arginine contains two amino (—NH2)
groups and one carboxyl (—COOH) group, whereas tryptophan con-
tains one amino group and a heterocyclic moiety containing nitrogen as
the heteroatom. They are both Cat. 1.3 fuels, owing to the prevalence of
the amino groups. A novel fuel, though not an amino acid, dimethyl
urea (C3H8N2O) [159•], is also used as a combustion fuel of Cat. 1.3 in
some of the combustion reactions. It gives a violent combustion with
very high exothermicity.
Hydrazine monohydrate (N2H4.H2O) [87,160] belongs to Cat. 1.3
and is a strong reducing fuel, capable of forming explosive mixtures
with air (when concentration is >4.7% by volume). It was originally
used in fireworks composition and for power generation in propulsion
applications e.g. thrusters for orbiting satellites. It is a convenient fuel
when carbon impurity is highly undesirable in the product and when a
control in the oxidation state is required during the combustion process.
Another amino group containing fuel of Cat. 1.3 is hexamethylene
tetramine ((CH2)6N4) (HMTA) [42,104]. HMTA is an organic hetero-
cyclic compound that readily solubilizes in water forming complexes.
Due to high enthalpy of combustion, the combustion with HMTA is
highly exothermic and explosive. Therefore, HMTA is the base com-
ponent to produce research-developed explosives (RDX).
Some organic molecules contain an equal proportion of different
functional groups and fall in the fourth category of this classification
(Table 2.1.1). Glycine (C2H5NO2), for example, has a carboxylic acid
group at one end and amino group at the other end and falls in Cat. 1.4.
It is one of the cheapest α-amino acids known that acts as a com-
plexing/coordinating agent for a number of metal ions [42,86]. Glycine
molecule has a zwitterionic character that can effectively form com-
plexes with metal ions of varying ionic sizes and charges that help in
preventing the selective precipitation and maintain the compositional
homogeneity among the constituents. Valine (C5H11NO2) [159•] and
phenyl alanine (C9H11NO2) [159•] are well known neutral α-amino
acids with one amino and one carboxyl group each at α-position, thus
belonging to Cat. 1.4 fuels. The combustion occurs similar to the glycine
combustion reaction, but with more evolution of gases.
Some types of carbons, as for examples carbon nanotubes, can also
be SCS fuels, although they are not completely eliminated in the as
burned powders without a further thermal treatment [150•]. These
fuels belong to Cat. 1.4, since their interaction with metal cations is
probably exploited through adsorption onto the defective oxidized
carbon species (primarily hydroxyl, carboxyl, lactonic groups) on the
carbon nanotube's surface [161].
Classification 2. Origin of the fuel
This classification is based on the origin of the fuel and it is very
useful when environment or economy-based choices must be done,
especially for environmental and energy-related applications.
Commercial fuels (Cat. 2.1) can be costly and not always ecofriendly,
whereas naturally occurring-fuels (Cat. 2.2), like cellulose, cotton,
starch, or other bio-templates used for the preparation of biomorphic
materials, are more economic and environmental friendly
[9,10,44,48,111,162]. For example, fruit, seed and pulp extracts of
Citrullus colocynthis (L.) Schrad were recently used as natural fuels for
the synthesis of biomorphic ZnO for biomedical applications [10].
Fig. 2.1.1.1 shows that, for these three typologies of natural extracts,
different microstructures and morphologies were observed in the final
materials (flower shaped, hexagonal, block like), evidencing the strong
influence of the natural fuel on the powder properties.
Looking at the fuel types according to Cat. 2.3 highlights and
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Progress in Crystal Growth and Characterization of Materials 64 (2018) 23–61
encourages the use of waste-derived fuels for the preparation of mate-
rials for energy and environment as a further benefit for the environ-
ment [40••,54••,93]. Several organic waste-derived fuels (Cat. 2.3), can
be successfully used in SCS to obtain ecofriendly nanomaterials, al-
though literature regarding SCS from the fuels belonging to this cate-
gory is still scarce [40••,54••,93]. A certain number of materials were
prepared from waste-derived precursors by using other solution-based
methodologies [8,11–13]. Among these, waste plastic, waste vege-
tables, animal oils, industrial wastes were considered as waste-derived
organic compounds for the synthesis of carbon-based nanomaterials
(Fig. 2.1.1.2). All the waste-derived precursors illustrated in the figure
might be used in principle as fuels for SCS, adding further advantages to
the entire process.
In Fig. 2.1.1.3 a pictorial description of the SCS approach with
waste-derived fuels is described. Only three typologies of organic
wastes are here considered, although, as explained earlier, many other
wastes can be used as fuels. In this approach, the special features of
each waste-derived fuel are fully used in order to get the best value and
produce ecofriendly nanomaterials with peculiar properties. This is
added to the advantage of using a never-ending source of fuel. The use
of waste-derived nanomaterials for the environmental remediation is a
further ecofriendly aspect of this approach. For example, LaFeO3 with
peculiar properties and high activity for the Crystal Violet photo
bleaching could be obtained by a solution combustion synthesis
wherein the combustion fuel was CVT230, a bio-organic soluble sub-
stance extracted from green wastes [40••]. Insoluble natural or waste-
derived fuels, like cellulose [46,149,163] and cotton [145] can also be
used for the preparation of mixed oxides with peculiar properties.
An intrinsic feature of the waste-derived fuels is their variability.
Nevertheless, if a detailed characterization is performed, together with
a preliminary investigation about the effect of the major impurities and
of waste composition variability on the final product, the waste-derived
fuel might become even an advantage for specific applications with
respect to the commercial fuel. This is the case of LaFeO3 prepared from
CVT230 as a waste-derived fuel, which has superior activity in the
Crystal Violet degradation with respect to the photosensitizer prepared
from commercial citric acid, thanks to its peculiar microstructural
properties [40••]. Indeed, according to the statement by Paul Connett “If
you don't know what is in it (the waste) you even don't know how to handle
it” [14••], a variable composition or, worse, an unknown composition of
the waste, might be a drawback if the waste-derived fuel is taken as it is,
without any preliminary study.
Classification 3. Solubility of the fuel in water (the preferred solvent for
SCS)
Fuels, like citric acid, urea, glycine, sucrose, are the most used so-
luble fuels (Cat. 3.1), although insoluble fuels (Cat. 3.2), like cellulose,
cotton and carbon nanotubes, have been also employed in SCS, espe-
cially for their interesting microstructure-directing capability
[46,48,150•]. As a further advantage, most of the waste-derived organic
substances can be introduced in the combustion mixture as insoluble
fuels. Insoluble fuels interact with the other component of the mixture
through chemical adsorption, which fixes metal cations in a specific
position onto the fuel surface and pores. After the burning of the fuel,
the metal cations form the oxides or the metals with a microstructure
that resembles very much that of the original insoluble fuel (micro-
structural templating) [46,48,150•].
Classification 4. Number of fuels in the combustion mixture
Single fuels, belonging to Cat. 4.1, are, for example, citric acid,
glycine, urea, sucrose etc. Mixed fuels, belonging to Cat. 4.2, include,
among others, sucrose-PEG [134], sucrose-PVA [164], sucrose-ethylene
glycol [165], citric acid-PVA [131], citric acid-succinic acid [166],
urea-PVA [131,167], hexamine-PVA [131], acetic acid-starch [168],
urea-starch [120], cellulose-citric acid [134], pluronic acid-citric acid
[169•], glycine-cellulose [46,145,163], glycine-hydrazine [115], gly-
cine-sucrose [170], glycine-glucose [88], glycine-glycerin [135] and
glycine-citric acid [20] mixtures.
F. Deganello, A.K. Tyagi Progress in Crystal Growth and Characterization of Materials 64 (2018) 23–61

Fig. 2.1.1.1. Different microstructural and morphological properties of a ZnO powder prepared by SCS from three different typologies bio-fuels extracted from fruit,
seed and pulp extracts of Citrullus colocynthis (L.) Schrad [reprinted from S. Azizi, R. Mohamad, M. Mahdavi Shahri, Green Microwave-Assisted Combustion Synthesis of
Zinc Oxide Nanoparticles with Citrullus colocynthis (L. Schrad: Characterization and Biomedical Applications, Molecules, 22 (2017) 301:13, under the Creative common
license].

Fig. 2.1.1.2. Different natural and waste-derived precursors used for

the synthesis of carbon-based materials than can be also considered as
fuels for SCS [a) Reprinted from Carbon, 96, J. Deng, Y. You, V.
Sahajwalla, R. K. Joshi, Transforming waste into carbon-based nano-
materials, pages 105–115, Copyright (2016), with permission from
Elsevier, license number 4,181,721,196,769. b) Reprinted from
Renewable and Sustainable Energy Reviews, 58 R. Kumar, R. K.
Singh, D. P. Singh, Natural and waste hydrocarbon precursors for the
synthesis of carbon based nanomaterials: Graphene and CNTs, pages
976–1006, Copyright (2016), with permission from Elsevier, license
number 4,181,721,452,641].

32
F. Deganello, A.K. Tyagi
Fig. 2.1.1.3. Pictorial description of a SCS with waste-derived fuels.
According to the Classification 4, a mixture of fuels can be also used.
A secondary fuel can be added to the primary one in order to have a
finer control of the nanomaterials properties, due to a better interaction
of the metal precursors with the reductants mixture or to a synergic
effect between first and second fuel [166,167,169•].
A general scheme of the mixed fuels solution combustion approach
is described in Fig. 2.1.1.4, where it is highlighted the importance of the
good interaction (i) between secondary fuel and primary fuel, (ii) be-
tween fuel mixture and metal cations.
A secondary fuel may help in the case of multicomponent oxides,
where the stability of some metal complexes with a single fuel is not
high enough. For example, Lyagaevaet al. [135] proposed a glycine-
glycerin fuel mixture to obtain doped CaZrO3 high temperature proton
conductors with improved electrochemical properties [135]. The co-
presence of a complexing and a polymerization agent has been found as
the main cause of the improved properties of the CaZrO3-based material
[135]. According to Gu et al. [88], the addition of glucose to glycine can
be used in combination with carbothermal reduction for the efficient
synthesis of metal carbides. By adding a secondary fuel, also the oxygen
defectivity of a perovskite can be successfully tuned [54••,134]. A more
controlled combustion process (Fig. 2.1.1.5) and superior
33
Progress in Crystal Growth and Characterization of Materials 64 (2018) 23–61
Fig. 2.1.1.4. Schematic description of the mixed fuels approach in solution
combustion synthesis (SCS) [Reprinted from Mater. Tod: Proc., 4, F.
Deganello, Nanomaterials for environmental and energy applications prepared by
solution combustion based-methodologies: role of the fuel, Pages 5507–5516,
Copyright (2017), with permission from Elsevier, license number
4,181,720,702,998].
electrochemical performance was achieved by adding sucrose to glycine
[170]. Another example is the addition of starch to urea for the con-
trolled synthesis of zirconia: by adding different amount of starch to
urea, the process is less rapid with the advantage that the phase com-
position of the final powder can be successfully tuned [120]. Ashok
et al. [46] observed that the addition of cellulose to glycine was able to
finely regulate both the microstructural-morphological properties and
the metallic Co content in the final powder. Hydroxyl groups of cellu-
lose interact with both glycine and metal cations forming specific
metal-oxygen bonds [149]. Similarly, low cobalt oxidation states at the
B-site of a Ba0.5Sr0.5Co0.8Fe0.2O3-δ IT-SOFC cathode were stabilized by a
strong interaction of the metal cations with sucrose-PEG combustion
fuel mixtures with high reducing power [134]. In particular, sucrose-
PEG20000 fuel mixtures with a PEG20000-to-sucrose ratio of 2:1 have
been found to decrease the area specific resistance of the cathode ma-
terial by an order of magnitude [134].
Classification 5. Number of units in a fuel molecule
A single molecule fuel is, for example, citric acid, sucrose, glycine or
ethylene glycol. Monomeric fuels belong to Cat. 5.1. Polymeric fuels,
belonging to Cat. 5.2, are, for example, PEG, PVA, cellulose, starch.
Also waste-derived high molecular weight surfactants like CVT230 are
F. Deganello, A.K. Tyagi
essentially polymeric, although their polymeric unit is not an exact
repetition, since each unit differs slightly from the other [40••]. In this
case, a mean polymeric unit is identified and the propellant calculations
are made as for other simple polymers [40••].
Polymers are rarely used alone as unique fuels in a SCS process
[134,156•,162]. More often, they are used as secondary fuels in com-
bination with other primary fuels [46,120,131,134,164,167,169•].
Classification 6. Capacity of auto-organization of the fuel molecules in
water
Citric acid, glycine, urea are normal microstructural templates (Cat.
6.1). Their structuring action, as well as that of Cat. 6.1 fuels, is
exploited through the formation of metal-oxygen bonds with metal
cations present in the combustion mixture [10,31••,80]. Therefore their
organization in solution, in the sol and then in the gel depends on their
functional groups, on the metal cations present in the combustion
mixture and on the stability constants for complexes formation. Con-
versely, ionic liquids and surfactants are an example of special micro-
structural templates (Cat. 6.2), since they are able to reorganize
themselves in specific patterns (micelles, microemulsions, etc.), which
confer specific microstructure, texture and morphology to the final
powder, independently on the presence of metal cations
[31••,104,121,171]. Oleic acid-assisted SCS, for example, favors, under
specific conditions, the formation of LiMn2O4 nanocubes [171].
Regarding fuels of Cat. 6.2., it must be observed that the effect of the
template on the final material considerably depends as well on the
material composition. For example, it is known that simple oxides and,
in particular, aluminum, silicon, titanium-containing metal cations
precursors can be directly templated into mesoporous oxides by Cat. 6.2
fuels [172,173], although no literature works deal specifically with
SCS-based methodologies. In the case of multicomponent metal cations
mixtures, like for example those used for the preparation of perovskites
and spinels, it is much less easy to create directly a rigid template as-
sembly between the Cat. 6.2 fuels and the metal cations [172], although
there is still a sort of mesostructure generation, due to the effect of the
residual carbon left in the as burned powders [169•]. These metal ca-
tions prefer to be hydrolyzed than forming M-OeC linkages with the
microstructuring agent, being the templating effect in this case more
indirect [169•].
Some polymers, such as P123 (pluronic acid), fall as well in this
category as special microstructural templates [169•]. Fiber-like fuels
and most of the bio-templates used for the preparation of biomorphic
materials are also an example of special microstructural template and
might be used for SCS [10,48,174,175].
Classification 7. Reducing power of the fuel molecule (or of the
34
Progress in Crystal Growth and Characterization of Materials 64 (2018) 23–61
Fig. 2.1.1.5. Example of a glycine-sucrose
mixed fuels approach in solution combustion
synthesis of an electrode materials for Li-air
batteries: effect of the secondary fuel on the
combustion process [Reprinted from Advanced
Powder Technology, 26, C.-G. Han, C. Zhu, G.
Saito, T. Akiyama, Glycine/sucrose-based solu-
tion combustion synthesis of high-purity LiMn2O4
with improved yield as cathode materials for li-
thium-ion batteries, Pages 665–671, Copyright
(2015), with permission from Elsevier, license
number 4,181,730,087,294].
polymeric unit) and fuel mixtures.
The reducing power of a fuel is calculated from the valence concepts
of the propellant chemistry [24•]. For single-fuels (Cat. 4.1) and single
molecules (Cat. 5.1), the reducing power is very simple to calculate: for
example; citric acid, with formula C6H8O7, has a reducing power of
+18, which is the sum of 6 times the valence of C (+4) plus eight times
the valence of H (+1) and seven times the valence of O (−2). Ac-
cording to Classification 7, sucrose, with formula C12H22O11, belongs to
cCat. 7.2, since it has much higher reducing power (+48 = 12∙
(+4) + 22∙(+1) + 11∙(−2)) than citric acid, which can be classified as
a low reducing power fuel (Cat. 7.1). As a rule of thumb, fuels be-
longing to Cat. 7.1 have reducing power below +30. Therefore, for
example, hexamethylenetetramine, with a reducing power of +36,
belongs to Cat. 7.2.
If the fuel is a polymeric compound (Cat. 5.2), it is convenient to
treat the polymer as a group of fuel molecular units [40••,156•].
Therefore, for the valence calculations the polymeric unit is considered,
as if it was a molecule with formula unit equal to the polymeric unit
[156•]. However, the molecular weight of the polymer plays as well an
important role on the powder properties, and must be taken into con-
sideration for the interpretation of the results [143]. In the case of
mixed fuels (Cat. 4.2), the reducing power must be weighted for the
relative molar ratio of all the fuels present in the mixture. For example,
in the case of sucrose - PEG mixtures the reducing power (RP) of a fuel
mixture with PEG: Sucrose molar ratio = 2 is: RP Sucrose + 2 ∙ RP PEG
unit = (+48) + 2 ∙ (+10) = + 68.
When all the other variables are fixed, fuels (or fuel mixtures) with
high reducing power affect the intensity of the combustion process and
the oxidation state of the product [70,134] as well as its oxygen va-
cancies content [31••]. As an example, Khort et al. [70] found that the
Ni content could be optimized by tuning the reducing power of the fuel
as described in Fig. 2.1.1.6. Apparently, fuels with high reducing power
like hexamethylenetetramine (HMT) (Cat. 7.2) clearly favor the for-
mation of reduced species in the as-burned powders even under an
oxidizing environment, as found in the literature for Ni and Cu-based
metallic nanopowders [70,140]. From another point of view, the use of
glycine is less recommended with respect to urea if metallic Ni re-
presents the unwanted secondary phase in the production of pure NiO
nanoparticles [103•]. Although belonging to the Cat. 7.1, glycine has
higher reducing power than urea and still favors partial metallic Ni
formation at T < 600 °C [103•].
All these considerations are valid only if the fuel interacts strongly
enough with all the metal cations. If there is a scarce interaction of the
fuel (fuels) with metal cations, the reducing power of the fuel scarcely
F. Deganello, A.K. Tyagi
affects the materials properties, as discussed in Section 2.2.2.
2.1.2. Selection of fuels for SCS
The fuel forms complexes with metal cations, creating a gel network
where oxidant, metal cations and fuels are connected to each other's.
The stability of the complexes, the nature of the gel formed, the pH of
the precursor gel, the auto-ignition temperature, all depend upon the
selection of a proper fuel. Moreover, the formation of desired phase and
powder properties of the material depend a lot on the fuel selection.
Therefore, selection of the fuel is a very important step in a combustion
reaction and quality of final product is to great extent dependent on this
step.
Unfortunately, there is no “the best” fuel than can be always used
successfully, but there is always a best choice for a fuel in relation to the
type of compound that has to be prepared and its specific application
requirements. For this reason, a multiperspective classification of the
fuel types may help considerably for a comprehensive identification of a
fuel or fuel mixture for SCS.
Further important information, which is not included in the classi-
fication table, is connected with the specific application of the material,
the necessity to scale up, the availability of raw materials, the available
budget, the limitation about waste production and disposal, the even-
tual constraints about materials and/or methods, the available time for
the research and other similar aspects.
It is generally desirable that the selected fuel is readily available,
low cost and water-soluble, should form a uniform transparent gel on
heating and should burn with mass combustion, although there is more
than one case when it might be convenient to break some of these
general rules. The next few examples will describe some simple stra-
tegies for the selection of the fuel according to the proposed classifi-
cations (Table 2.1.1), summarizing the most important aspects related
to the fuel type selection.
Example n° 1: Fuels for metal-containing compositions. If a metal-con-
taining powder has to be prepared, looking at the fuel type
Classification 7, about the reducing power of the fuel, might be
useful: high reducing power fuels are more convenient for producing
metal-containing powders in a single step.
Example n° 2: Fuels for highly porous powders. Fuels with higher mi-
crostructural organization (Cat. 6.2) are preferred for porous pow-
ders. If low Ф must be used (see Section 2.2.1), a fuel with lower
reducing power (Cat. 7.1) can be selected in order to avoid too much
additional oxidant. From another point of view, Cat. 5.2 fuels
35
Progress in Crystal Growth and Characterization of Materials 64 (2018) 23–61
Fig. 2.1.1.6. Effect of fuels with different re-
ducing valence on the adiabatic temperatures,
the Ni content and volume of gases evolved
(vgas/vNi). [Reprinted from Journal of Solid
State Chemistry, 253, A. Khort, K. Podbolotov,
R. Serrano-García, Y. K. Gun'ko, One-step solu-
tion combustion synthesis of pure Ni nanopowders
with enhanced coercivity: The fuel effect, pages
270–276, Copyright (2017), with permission
from Elsevier, license number 4,192,870,
582,908.
(polymeric fuels) and Cat. 7.2 fuels (high reducing power fuels) are
also a good choice, since they easily leave from incomplete oxida-
tion a lot or residual carbon, which then acts itself as a micro-
structural template (Section 6.2). Alternatively, as discussed in
Sections 6.1 and 6.2, a combination of a Cat. 1.1 or Cat. 1.4 fuel with
an external microstructural template would be convenient for ob-
taining high surface area and porosity powders.
Example n° 3: Fuels for defective and disordered structures. Sucrose and
carbohydrates in general tend to limit aggregation among crystals
during combustion, producing highly disordered structures [45].
This distinctive feature might be very useful for the preparation of
defective or metastable phases, although it might be a drawback in
other cases, like for example in the production of highly ordered
magnetic NiFe2O4 spinels [45]. In this case, the larger particle size,
higher aggregation and higher degree of cation ordering for the
NiFe2O4 spinels, more favored by nitrogen containing fuels than by
respect to carbohydrates fuels, have a beneficial effect on the
magnetic properties of these class of compounds [45].
Example n° 4: Fuels for the thermodynamic stabilization of the structure.
If there are two existing phases for a compound, a low and a high-
temperature form, and isolation of one of the two phases is required,
then one should select a citric acid-glycine mixture of fuels with
citric acid in a fuel-deficient ratio and glycine in stoichiometric
ratio, respectively. Citric acid provides low heat of combustion and,
in turn, low temperature phase can be easily obtained, whereas
glycine has high heat of combustion and therefore stabilizes high
temperature modification.
Example n° 5: Fuels for the kinetic stabilization of the structure. SCS is a
very convenient methodology for the controlled preparation of
metastable phases [134] or phases that are stable in a narrow range
of environmental conditions [176]. The main reason is that the auto-
combustion process is very fast, favoring kinetically controlled more
than thermodynamically controlled reactions. In this sense, fuels
with faster and more intense combustion processes are preferred for
preparing powders with metastable inorganic phases.
The velocity of a combustion process may depend on various factors
beside the fuel type, like the combustion beaker type and geometry,
the chemical composition of the final product, the pH, the amount of
residual water in the gel. Fuels with faster and more intense com-
bustion are usually those with more NH2 groups (Classification 1),
like urea and glycine, although some fuel mixtures, like for example
sucrose and PEG mixtures, can be highly reactive as well.
Example n° 6: Fuels for a selected chemical composition. As mentioned
F. Deganello, A.K. Tyagi
Fig. 2.2.1.1. Theoretical and the experimental trend of temperature at in-
creasing Φ values.
earlier, the fuel serves the dual purpose of not only providing the
heat of reaction during the redox combustion process, but also
binding the reacting metal ions so as to bring them in close proxi-
mity to one another. The fuel should have better stability as it
should bind all the metal ions. If it does not, then precipitation
would occur leading to inhomogeneity or secondary phases.
However, higher stability results in high temperature of ignition,
hence optimum condition of better stability and low ignition tem-
perature should be selected for the combustion reaction. If a Ba-
containing compound has to be prepared, care must be taken in the
selection of the fuel that should be able to bind even the recalcitrant
Ba2+ cations. OH-containing fuels (Cat. 1.2), fuels containing sev-
eral functions (Cat. 1.4), polymeric fuels (Cat. 5.2) and mixed fuels
(Cat. 4.2), are better choice for this purpose than Cat. 1.1 fuels, since
their complexing action occurs either through entrapment or
through OH groups, which have higher affinity for Ba2+ cations.
Similar considerations may be applied for Sr2+ cations. In this re-
spect, a preliminary knowledge of the metal-to-fuel possible inter-
actions might be very useful.
Based on these premises, a multiperspective classification of the fuel
clearly allows a better and deeper identification of the fuel to be used
for the SCS of a specific material.
2.2. Fuel-amount
When the fuel type has been selected, half of the work is done.
Beside the fuel type, also the fuel amount plays an important role in the
final materials properties. In this respect, it is very important that the
fuel amount is calibrated with respect to both metal cations and oxi-
dants [54••]. The two main parameters that govern the fuel amount are
the reducers-to-oxidizers ratio, generally known as Φ, and the fuel-to-
metal cations ratio, here named as F/M.
2.2.1. The reducers-to-oxidizers ratio
The original definition of the ratio between reducing and oxidizing
species present in the combustion mixture was after Jainet al. [24•]
according to the propellant chemistry concepts. Jain called this ratio
"equivalence ratio", defining it as:
Φe (equivalence ratio) = ∑ (coeff. of the oxidant elements vs va-
lencies)/(−1) ∑ (coeff. of the reducing elements vs valencies)
For a rapid comprehension of this concept, some research groups
[31••,54••,111,134,177••,178] prefer to define this parameter as:
Φ = (−1) ∑ (coeff. of the reducing elements vs valencies) / ∑ (coeff.
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Progress in Crystal Growth and Characterization of Materials 64 (2018) 23–61
of the oxidant elements vsvalencies)
where Φ = 1 corresponds to a stoichiometric ratio with balanced
reducing and oxidizing species, Φ > 1 means a fuel rich mixture,
whereas Φ < 1 means a fuel lean mixture, in analogy with the fuel-to-
oxidant parameter commonly used in the automotive sector. The reader
is referred to the work of Kiminami [179•] for a detailed explanation
about the significance of this parameter.
This important parameter - also known in the literature as equiva-
lence ratio [25•,31••,103•,111,180], ψ [20] or φ [17,27,31••,181] - is
often matter of confusion in the literature. Sometimes Φ is referred
as the fuel-to-oxidant ratio [93,138,139], fuel-to-oxidizer ratio
[27,47,103•,132,147•,182,] or oxidizer-to-fuel ratio [42,45,53,66a],
although its numerical value is still coincident with Φ, as already ob-
served by Specchia et al.[177••]. Other authors used the fuel-to-oxidant
ratio by considering the fuel molar concentration and the nitrate pre-
cursor concentration [15••,124,126,183]. This parameter gives an idea
of the amount of fuel with respect to oxidants, although it has a dif-
ferent value than Φ and is not representative of the combustion mix-
ture, because (i) reducers can be the fuels as well as metal cations and
some counter anions, like for example acetates, acetylacetonates and
oxalates [24•] (Section 3), (ii) in the presence of more than one fuel
(according to classification 4), the fuel-to-oxidant ratio loses its
meaning and only Φ can be used, since it takes into account the com-
bined reducing power of all the fuels in the mixture according to their
amounts [20].
It must be highlighted that Φ is just a very good approximation and
not the real reducers-to-oxidizers content, as observed by Zhang et al.,
since some of the propellant chemistry assumptions about the oxidation
state of the elements in the final powder may not be always correct
[26].
SCS is not a fully adiabatic process and T measured is always lower
than the theoretical one, because of the heat losses, further favored by
huge gas evolution [30••,147•]. Fig. 2.2.1.1 illustrates the theoretical
(for a fully adiabatic process) and the experimental trend of tempera-
ture vs Φ value, although it must be considered that the observation
would be different for different systems depending upon the complex-
ities of the cations and the combustion mixture. In principle, combus-
tion can be performed from fuel-deficient ratio to fuel-excess ratio
[47,71•], although the nature of combustion and, in particular, the
exothermicity of the reaction are strictly dependent by the reducers-to-
oxidizers ratio [78,147•]. Considering the whole combustion range, the
combustion reaction can be classified into the following categories:
(i) Extremely fuel-deficient combustion reaction. Extremely fuel-deficient
combustion reaction gives flameless smoldered combustion reac-
tion resulting in large evolution of gases. This combustion is per-
formed when the thermal stability of the product is low. As this
reaction is bulk/volume combustion, external heating is required
for completion of the reaction. Moreover, most of the gases
evolved are the toxic NOx [90•] and this might be one reason for
not choosing sub-stoichiometric Φ values.
(ii) Fuel deficient combustion. It has been observed that fuel-deficient
combustion gives sluggish combustion, but yields highly porous
powder with soft agglomerates and better powder properties due
to large evolution of gaseous product. Here also external heating is
required for completion of reaction. For example, better densifi-
cation and high ionic conductivity were obtained for SOFC elec-
trolyte materials at stoichiometric Φ ratios [126] or slightly under
stoichiometric Φ values (slightly lean oxidant-to-fuel ratios) [184],
since they produce high surface area powders with soft agglom-
eration and better densification.
(iii) Stoichiometric combustion. Stoichiometric combustion reaction
gives self-propagating auto-ignition process in violent manner. The
reaction occurs with proper flame that exists for 3–5 seconds.
Exothermicity of the reaction is very high and temperature up to
1800 °C can be reached. Hard agglomerates are formed in
F. Deganello, A.K. Tyagi
stoichiometric combustion due to local partial sintering of the
agglomerate powder. In stoichiometric combustion the powder
properties are governed by fuel, fuel content and exothermicity of
the reaction.
(iv) Fuel excess combustion reaction. In this case, the reaction is similar
to the stoichiometric combustion process. Slightly over-stoichio-
metric Ф values are recommended for safety reasons whenever
explosive combustion processes occurs [27].
(v) Extremely fuel-excess combustion reaction. Extreme-fuel excess
combustion reaction undergoes decomposition of gel without
flame and results in charring of the product. The decomposed
products are generally amorphous with high carbon content and
need to be calcined longer in air for getting rid of the carbonaceous
impurity. One reason for not choosing extremely over-stoichio-
metric Φ values is that toxic CO is the major component of most of
the evolved gases [90•,140].
Therefore, the first important effect of the Φ ratio is, directly, on the
combustion process and, indirectly, on the microstructure and mor-
phology of the powder.
For example, an interesting work of Pourgolmohammad et al. [185]
correlates the Φ ratio to the surface area and magnetic properties of
CoFe2O4 spinel nanopowders, comparing the results obtained from
three types of fuels with some thermodynamic calculations. The main
result was that both crystal size and surface area of the powders de-
creased by increasing Φ ratio, at least up to Φ = 1.25, until a plateau
was reached [185]. This was explained through the comparison of the
adiabatic temperature and of the amount of released gases by each fuel
at different Φ ratios [185].
As another example, stoichiometric Φ values have been found op-
timal for preparing high-density Gd doped ceria by SCS from glycine
fuel [178].
Φ ratio affects the structure, phase composition, defectivity and
oxidation state of the multivalent ions, and all the related materials
properties. As discussed before, flame temperature of a combustion
reaction can be varied playing with the Φ ratio and Bedekar et al. [186]
have used this concept for stabilizing YCrO3 and YCrO4 (Fig. 2.2.1.2).
The combustion reaction performed between metal nitrates and glycine
with the stoichiometric Φ ratio (oxidant-to-fuel = 1:1.66) yielded
YCrO3, whereas fuel-deficient Φ (oxidant-to-fuel = 1:0.50) resulted in
the formation of YCrO4 [186]. Thus, altogether different phases could
37
Progress in Crystal Growth and Characterization of Materials 64 (2018) 23–61
be obtained in a facile manner just by altering the Φ ratio. It may be
noted that it is very difficult to prepare YCrO4 by a solid state reaction
due to the presence of Cr(V), which tends to reduce to Cr(III) during the
reaction.
Rutile to anatase percentage in TiO2 powders can be varied through
the optimization of Φ, being the rutile phase more favored at higher Φ
values [187].
Composite nanopowders with prevalence of Fe3O4 can be obtained
by using fuel rich combustion mixtures, whereas Fe2O3 containing na-
nopowders are favored by low Φ (Fig. 2.2.1.3), although some differ-
ences might be present by changing the fuel type [139]. This re-
lationship is very important for production of magnetic iron oxides.
It has also been recently found that, by using under-stoichiometric
Φ values, single phase MCo2O4 (with M = Zn, Ni, Cu, Fe) spinels can be
obtained, whereas at higher fuel contents the respective single oxides
segregate as secondary phases [124]. Indeed, excess of citric acid in the
gel network could keep the Mn+and Co2+ metal cations enough sepa-
rated each other, favoring the formation of single oxides instead of
mixed oxide spinels.
As another example, optimal composition was obtained at Φ = 1 for
Fe3O4 prepared by SCS from glycine [70]. Recently, Wang et al. pro-
posed an airless system for the production of pure Fe3O4 powders by
SCS from glycine at stoichiometric reducers to oxidizers value [188].
Metallic Ni [70,71•,103•] and metallic Cu [140] are easily formed at
fuel rich conditions without any post-reduction treatment. According to
Manukyan et al. [71•], the formation of metallic Ni is triggered by the
reducing action of NH3 and N2O gases produced by glycine decom-
position. Khort et al. [70], found similar results for glycine and other
fuels, suggesting that other in situ formed reducing gases beside NH3
and N2O, like for example CO, might contribute to the metal oxide
reduction.
Defectivity can be also influenced by Φ ratio, according to Pathak
et al.[109]. They found that the highest defectivity, measured by pho-
toluminescence, was displayed by the powder prepared at stoichio-
metric Φ ratio (Fig. 2.2.1.4), in agreement with the results obtained by
XPS [109].
2.2.2. The fuel-to-metal cations ratio
The fuel-to-metal cations ratio (F/M) is a very important parameter
to optimize, although its role is often underestimated. Very few sys-
tematic studies have been published which investigate the F/M effect
Fig. 2.2.1.2. XRD patterns of nanocrystalline Y-Cr oxides prepared by
solution combustion synthesis evidencing YCrO3 formation at the
stoichiometric Φ ratio (a) and YCrO4 formation at fuel-deficient Φ
ratio (b) [Reprinted from V. Bedekar, R. Shukla, A. K. Tyagi,
Nanocrystalline YCrO3 with onion-like structure and unusual magnetic
behaviour, Nanotechnology, 18 (2007) 155,706, 6 pages, with email
permission from IOP PUBLISHING].
F. Deganello, A.K. Tyagi
on the material properties at fixed reducers-to-oxidizers ratio
[15••,57,152•]. Therefore, as explained in Section 1.1, the interpretation
of the role of this important parameter is not always straightforward,
although some general trend can still be observed. The choice of fuel-to-
metal cations ratio, F/M, depends on the fuel type, on the type and
amount of metal cations to chelate and on the pH value of the
solution mixture [15••,54••,56,122,152•]. Lower F/M may cause
incomplete and/or selective complexation of metal cations
[19•,56,57,122,152•,164], and, consequently, occurrence of segrega-
tion phenomena and secondary phase’s formation (Fig. 2.2.2.1). For
example, Ding et al. [57] found that, at pH = 8, F/M = 1.5 was the
optimal choice for the solution combustion synthesis of Mn–Zn ferrites
by using citric acid and ethylene glycol as fuels. They also found that
metal chelation was favored by addition of a secondary fuel/chelating
agent as ethylene glycol [57]. Therefore, mixed fuels (Cat. 4.2) can be
used in order to enhance the fuel-to-metal cations interaction.
If the interaction of the fuel with metal cations is scarce, the re-
ductive power of the fuel cannot be exploited at its maximum and
combustion process as well as product properties are not optimal
[152•].
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Progress in Crystal Growth and Characterization of Materials 64 (2018) 23–61
Fig. 2.2.1.3. XRD patterns of iron oxides prepared by solution com-
bustion synthesis at different Φ ratio. Full squares indicate the Fe2O3
phase, whereas empty squares indicate the Fe3O4 phase [Reprinted
from Ceramics International, 43, H. Fathi, S.M. Masoudpanah, S.
Alamolhoda, H. Parnianfar, Effect of fuel type on the microstructure and
magnetic properties of solution combusted Fe3O4 powders, pages
7448–7453, Copyright (2017), with permission from Elsevier, license
number 4,181,721,319,341].
Fig. 2.2.1.4. Photoluminescence spectra for ZnO nanoparticles pre-
pared by solution combustion synthesis with different fuels (a) and
different F/O (fuel-to-oxidant) ratio using urea (b) [Reproduced from
T. K. Pathak, A. Kumar, C. W. Swart, H. C. Swart, R. E. Kroon, Effect of
fuel content on luminescence and antibacterial properties of zinc oxide
nanocrystalline powders synthesized by the combustion method, RSC Adv.,
6 (2016) 97,770–97,782, with permission of The Royal Society of
Chemistry, License number 4,181,731,175,302, DOI: 10.1039/
C6RA22341A].
Conversely, too high F/M ratios might decrease the crystallinity of
the powder [158] or shift to higher values the temperature for the
crystalline phase formation [15••,123•], as illustrated in Fig. 2.2.2.2 for
a Ce-doped SrFeO3 prepared by SCS from citric acid at two different
citric acid-to-metal cations ratios. Too high F/M values may limit the
desired interaction among metal cations and formation of mixed metal
oxide structures [164]. F/M has also some influence on the powder
microstructure and morphology, influencing the particle growth, ag-
glomeration directions and sintering of the powders [57,117,123•].
Definition of the F/M parameter for mixed fuels (mf) is more
complex, since, for a mixed fuel with a primary fuel F1 and a secondary
fuel F2, a total F/M should be considered. For example, if F1: M = 2
and F2 : F1 = 1 have been chosen as starting parameters, then (F/M)mf
would be simply equal to [F1] + [F2] / [M]. This value would not add
too much information to the one already available about F1:M and F2:
F1 ratios. Being the redox reaction a central part of the SCS, a more
convenient variable, the wF/M (weighted fuel to metal cations) ratio
was introduced, in order to consider the total F/M ratio, weighted for
the respective F1 and F2 reducing powers [54••,134]. This variable
counts the relative amount of fuels with respect to the metal cations
F. Deganello, A.K. Tyagi Progress in Crystal Growth and Characterization of Materials 64 (2018) 23–61

Fig. 2.2.2.1. XRD patterns of hydroxyapatite synthesized by SCS from tartaric acid with different metal-ion-to-fuel ratio: (a) metal-ion-to-fuel ratio of 1 : 1 followed
by calcination at 900 °C, (b) metal-ion-to-fuel ratio of 1 : 2 followed by calcination at 500 °C for 5 h and (c) metal-ion-to-fuel ratio of 1 : 2 followed by calcination at
900 °C for 2 h [Reprinted from S. Sasikumar, R. Vijayaraghavan, Effect of metal-ion-to-fuel ratio on the phase formation of bioceramic phosphates synthesized by self-
propagating combustion, Sci. Technol. Adv. Mater. 9 (2008) 035,003 (5pp), under the Creative Common License].

taking into account their reducing power. wF/M is complementary to
the Ф ratio, which gives information on the reducing power of the fuels
with respect to the oxidizers.
2.3. Fuel-amount selection
general, low amount of fuel with respect to metal cations would be
preferable, in order to limit the addition of oxidants aids, although the
F/M value should be high enough to grant a full complexation of the
metal cations by the fuels. Here below few short examples will describe
simple strategies for the fuel amount selection.

In general, a stoichiometric Ф is preferable to maximize the release
of energy. Stoichiometric Ф have usually the highest T real and the
process does not consume oxygen from the environment. There are
some cases, when under-stoichiometric or over-stoichiometric values
are more convenient. Regarding the fuel-to-metal cations ratio, its value
considerably depends on the fuel type, on the chemical composition of
the system and on the type of application of the target material. In
Example n° 1: Fuel amount for materials with high or low agglomeration.
If one needs a material for catalysis, then it is desirable to prepare
powders with soft agglomerate by using fuel-deficient combustion.
On the contrary, if one needs materials for column chromatographic
application, then stoichiometric ratio is the best one, as it will
provide hard agglomerate powders and additional mechanical
strength, avoiding choking of the column.

39
F. Deganello, A.K. Tyagi
Example n° 2: Fuel amount for metal-containing powders. As discussed
before in this paragraph, by using SCS, it is possible to prepare
metal-containing powders directly in the metallic state, without any
further reducing post-treatment. Fuel rich conditions with high Ф
values (usually around 2) should be selected for this purpose.
Example n° 3: Fuel amount in the case of waste–derived fuels. If waste-
derived fuels are used, it is convenient to use the maximum amount
of waste in order to maximize the recycle of wastes. Therefore, high
F/M values would be a good choice, although an important aspect to
be considered is that waste-derived fuels have usually high com-
bustion heat and their combustion is often sluggish, slow and mul-
tistep. In those cases, beside high F/M values, stoichiometric Ф
values - reached by adding an oxidant aid - would be a better choice,
although the final composition of the system might limit the F/M
and Ф values to a specific range, in order to get single-phase pro-
ducts, especially in the case of multicomponent mixed oxides.
Example n° 4: Fuel amount for metastable or defective powders. As
pointed out before, the high velocity of the SCS process favors the
production of powders with metastable and defective phase com-
position. In order to stabilize metastable and defective composi-
tions, stoichiometric Ф values are recommended, since the max-
imum velocity is attained. If an oxygen defectivity is desired, higher
Ф values might be a better choice, since higher amount of fuel
means higher amount of reductant and lower oxidizers content.
Example n° 5: Fuel amount for a sustainable choice. It is very important
to highlight that a sustainable choice of Ф and F/M is always pos-
sible when a material has to be prepared by SCS. A reduced amount
of fuel is preferable for a sustainable synthesis, avoiding un-
necessary use of resources, but - as pointed out in the introduction
section - sustainability means as well efficiency. Therefore, if a
higher fuel amount with respect to metal cations and oxidizers re-
sults in more efficient products, this would be the best choice even
for a sustainable synthesis. For similar reasons, high pH (from am-
monia addition) (Section 4), and addition of excessive amounts of
additional oxidants, like for example ammonium nitrate,
(Section 3.2), are to be avoided, since they would increase the
production of noxious NOx gases in the combustion fumes.
3. Metal cations precursors, oxidants and additional oxidants
A metal precursor is a substance that contains a specific metal cation
and it is used to introduce that specific element in the combustion
mixture, providing the metallic elements to the final material. In
combustion and redox reactions, an oxidant is defined as a moiety that
provides oxygen for the fuel (reducer). Metal precursors often contain
themselves the oxidizing moieties as counter anions. The most used
metal precursors are commercial nitrates, since they are water-soluble
40
Progress in Crystal Growth and Characterization of Materials 64 (2018) 23–61
Fig. 2.2.2.2. XRD patterns of Ce-doped SrFeO3 powders prepared by
SCS from citric acid at citric acid-to-metal cations ratio (C/M) of 2 or
4 after calcination at 600 °C for 5 h [Reprinted from J. European
Ceram. Soc., 29, F. Deganello, G. Marcì, G. Deganello, Citrate-nitrate
auto-combustion synthesis of perovskite-type nanopowders: a systematic
approach, pages 439–450, Copyright (2009), with permission from
Elsevier, License number 4,192,870,371,948].
and have low cost [15••,101,134,189,190]. Other used metal precursors
are oxy-nitrates [191], chlorides [189,192•,193] and oxychlorides
[116]. The use of chlorides is not recommended, since they might ad-
sorb or get incorporated onto the powder and contaminate it [193],
although chlorides might be eventually dissolved in concentrated nitric
acid, followed by a heating treatment to eliminate the chlorine gener-
ated from the treatment [116]. Oxalates [115,130,194], acetates
[128,195], hydroxides [165], acetylacetonates [148] or alkoxides
[49•,157,77] are also used as metal precursors for SCS. However, in
these cases, an additional oxidant is needed, since the net valence of the
counter anion is positive, thus becoming a reducer and not an oxidizer
like in the case of the other metal precursors. The use of metal pre-
cursors different from the conventional nitrates, might have some ad-
vantages, as pointed out by Kaur et al. [165]. They managed to prepare
ferrite at lower temperature, starting from iron hydroxides [165]. They
claimed that Fe-O bond in iron hydroxides is more polar and easy to
break than in nitrate precursors, favoring the ferrite formation at lower
temperatures [165]. Metal sulphates and phosphates are stable at
higher temperature and do not provide enough oxygen for combustion.
Therefore, they are generally not considered as precursors for com-
bustion reaction, but with some exceptions, like in the case of titanyl
sulphate, which was successfully used as oxidizing metal precursor by
Rajeshwar et al. [34••]. Metal oxides suspensions have been also used as
metal precursors by Burgos-Montes et al.[49•], who prepared mullite
powders by SCS starting from silica colloidal suspension. Nitrates and
oxynitrates can be also generated in situ from other metal precursors, as
described by Zhou et al.[147•]. They used a titanium oxynitrate as Ti
source, which was generated from tetrabutyl titanate with the help of
HNO3 [147•].
Natural or waste-derived inorganic metal precursors have been also
used as precursors for SCS [190,196]. Gabal et al., for example, ex-
tracted a mixture of Zn and Mn metal precursors from battery wastes
and used them for the synthesis of Mn-Zn-Fe spinels nanoparticles de-
posited onto carbon nanotubes [190]. Choudary et al. extracted Ca
metal precursor from chicken eggshell wastes to prepare calcium
magnesium silicates by SCS with citric acid as a fuel [196]. It is worth to
notice that other natural and waste-derived precursors, already used as
inorganic source for other type of preparation methodologies after ex-
traction, in principle might be used directly with SCS, avoiding most of
the preliminary treatment of the original metal source. For example,
Sawant et al. [7] successfully used sea salt as Mg source in the presence
of sucrose as carbon source, for the solution-based synthesis of MgO/C
catalysts. Rice husk was also used as silicon precursor for preparing
SiO2 and SiC-containing powders by using solid-state methodologies
like self-propagating high temperature synthesis [197] or solution-
based methodologies different from SCS [198]. Glass from automotive
wastes was also used as Si precursor through a solid-state synthesis by
F. Deganello, A.K. Tyagi
Table 3.1.1
Multiperspective classification of the metal precursor's types that can be used in solution combustion synthesis.
ball milling combined with in situ thermal reduction treatment with
Bakelite [199]. Extracts from oily cold rolling mill sludge [200] or from
exhausted batteries [190] have been also used as metal cation source
for the sustainable preparation of mixed oxides by wet methods.
The choice of the metal cation obviously affects the chemical
composition of the final product and the metal cation acts itself as re-
ducer (positive charge), whereas the counter anion (i.e. NO3−) acts as
oxidizer [24•,151]. The type of metal precursor – the substance that
contains the metal and is used to introduce the metal in the combustion
mixture - may have an effect on the combustion process itself [201a],
on the phase composition [34••,115,192•] and even on the micro-
structural/morphological properties [34••] of the final powder. For
example, Colussi et al. [192•] showed that the metal support interaction
in Pd/ceria catalysts is different depending on the type of metal pre-
cursor used, as demonstrated by TPO (Temperature Programmed Oxi-
dation) experiments. They also found that Pd-Ce solid solution with
ordered supercell structure was obtained starting from nitrate pre-
cursors, whereas a disordered structure was obtained for chlorides and
acetate precursors [192•]. Other interesting examples are discussed by
Rajeshwar et al. [34••]. In a recent literature paper, Kang et al. highlight
the effect of the metal precursor in relation to its interaction with the
fuel, by comparing cerium nitrate and cerium ammonium nitrate in the
presence of fuels like glycine and hydrazine [201b].
3.1. Multiple classification of metal cations precursors
In order to help in the identification and in the choice of the metal
cation precursors for SCS, it is here proposed a multiple classification,
which is illustrated in Table 3.1.1.
Classification A. Role of the metal cations’ counter anion
Classification A follows the most common classification of metal
precursors, based on the metal cations’ counter anions, although the
different categories point out as well to the role of the counter anion in
the combustion process. Cat. A.1 (i.e.: Classification A, Category n° 1) is
the most used one, since metal nitrates and oxy-nitrates belong to this
category. Nitrate anions are oxidants and participate actively to the
redox reactions occurring during the combustion process. Chromates,
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Progress in Crystal Growth and Characterization of Materials 64 (2018) 23–61
phosphates and vanadates also belong to this category: in these parti-
cular cases, the positive cation of the metal precursor is ammonium,
whereas the metal-containing part is the counter anion itself
[80,122,155,166]. Oxalates, acetates, acetylacetonates and alkoxides
precursors can be placed into Cat. A.2 and they must be taken into
account in the propellant chemistry calculations as reducers. Oxides,
chlorides, sulphates and phosphates, whose anions do not participate to
the combustion process, are positioned in Cat. A.3.
Classification B. Origin of the metal precursor
Classification B comes from the same considerations exposed for the
Classification 2 of the fuel types (Table 2.1.1). Commercial metal pre-
cursors are the most commonly used. Cat. B.2 and Cat. B.3 take into
consideration more ecofriendly and less expensive solutions. For ex-
ample, sea-salt as Mg precursor [7] belong to Cat. B.2 . Oily cold rolling
mill sludge as Fe precursor [200], glass wastes as Si precursor [199],
egg shells as Ca precursor [196], rice husk ash as Si or C precursor
[197,198] or extracts of mixed metal precursors from exhausted bat-
teries as Zn and Mn precursors [190] are placed into Cat. B.3
Classification C. Solubility of the metal precursor in water
Classification C introduces another important aspect, which is the
solubility of the metal precursors. The solubility degree and modality
determine the way the metal precursor interacts with the other com-
ponents of the combustion mixture. To Cat. C.1 belong, for example,
metal nitrates, metal acetates, acetylacetonates, chlorides, extracts from
exhaust batteries, sea-salt. Cat. C.2 embraces all the insoluble metal
precursors like, for example, silica colloidal suspensions [49•], or alu-
mina powder [101] or carbon [150•].
Classification D. Microstructural templating ability of the metal pre-
cursor
Similar to the Classification 6 of the fuel types (Table 2.1.1), Clas-
sification D points out to the possibility to control the final micro-
structure of a material by a proper selection of the metal precursor.
Metal precursors belonging to Cat. D.1 are able to organize around
themselves the other components of the combustion mixture, affecting
the final microstructure. For example, alumina nanofibers are a con-
venient microstructural template for the CuO/alumina nanocomposites
[101]. Another interesting example is discussed by Fraigi et al. [193],
F. Deganello, A.K. Tyagi
who used hydrolyzed metallic tin and tin chloride precursors for the
synthesis of SnO2. They found that surface area and crystal size of the
SnO2 powders were enhanced by using the hydrolyzed metallic tin
solution [193]. Even porous insoluble powders, like for example silica,
alumina or carbon, can act as inorganic microstructural templates
(Section 6). Cat. D.2 contains metal precursors, like, for example, all the
metal nitrates, chlorides and others, which, although capable to orga-
nize themselves in a gel network with the fuel-chelating agent, do not
affect specifically the final microstructure of the powder. In these cases,
the templating effect of the fuel (or of an external template) plays a
major role in the final microstructure of the material.
Classification E. Oxidation state of metal cations in the metal precursor
It has been found that the oxidation state of the metal cations in the
metal precursor, although not preventing the product formation, might
influence the final material in terms of structure and microstructure
[202] and Classification E takes into account this aspect. For example,
by using cerium (III) nitrate for the preparation of CeO2 nanoparticles,
the oxidation state of cerium needs to change from III (in the metal
precursor) to IV (in the final material). If, on the contrary, ceric am-
monium nitrate is used, the oxidation state is the same than in the final
material and this makes the process easier [202] and could be of help in
the selection of the most convenient metal precursors.
3.2. Additional oxidants
Oxidants are usually the counter anions from metal precursors like
for example nitrates [15••,27] and dichromates [38], but not phos-
phates, which are simply a source of elements for the final compound
[122,166]. Additional oxidants - called as well oxidant aids or com-
bustion aids - are often needed, in order to regulate the combustion
process and the reducers-to-oxidizers ratio [15••,20,27,49•,55,128,
151,127,114•]. An additional oxidant is necessary to compensate the
excess of fuel, in order to maintain the Φ ratio at its stoichiometric
value (i) when metal cations require - for the complete metal com-
plexation [2] or for the optimization of the final microstructure [203] -
a complexant/fuel amount higher than the amount required by the
combustion equation, (ii) when counter anions are reducers and in-
crease too much the reducers amount [27,128,130], (iii) when chloride
or oxide precursors are used, which do not have any oxidizing power
[189], or (iv) in the case of mixed fuel mixtures [20,55].
As already observed in the Introduction section (see Section 1.1),
most of the research studies about the effect of the fuel content on the
materials properties were performed without adding any additional
oxidants [19•,46,47,70,116,132,133]. This means that both the fuel
amount with respect to the metal cations and the fuel amount with
respect to the oxidants were varying, causing some confusion in the
interpretation of the experimental results. Other authors added a
combustion aid to a fuel-metal cations mixture, highlighting the posi-
tive role played by the additional oxidant, without mentioning its effect
on the Φ ratio, and the experimental trends were very complicate to
understand [43,55,128].
Overall, what is generally recognized regarding the effect of adding
an additional oxidant is that the intensity of the combustion process,
the reaction temperature and the amount of gases evolved increase. It
has been observed that the crystal size decreases and the surface area
increases. The effect of the additional oxidant is more evident in the
cases of high starting reducers-to-oxidizers ratios - even outside the
combustion range [55] - or in the case of reducers-to-oxidizers values
close to stoichiometric ones [43,115,127]. This is because an increase
of the additional oxidant means a decrease of the reducers-to-oxidizers
ratio. Since the combustion process is not fully adiabatic, the fuel is not
completely oxidized in the as-burned powders and additional oxidant
supplies the lost energy.
NH4NO3 or HNO3 are the most commonly used additional oxidants
[15••,27,49•,55,114•,127,128,151,195,203]. Other additional oxidants
include ammonium perchlorate, which is also used as solid oxidizer in
42
Progress in Crystal Growth and Characterization of Materials 64 (2018) 23–61
rockets and missiles [204]. The use of HNO3 is convenient since it helps
in the dissolution of some insoluble metal compounds [147•], although
it strongly affects the pH of the combustion mixture and is less efficient
than NH4NO3 [49•].
Recently, the ambiguous role of ammonium nitrate has been eluci-
dated, pointing out to a careful use of extra oxidants in the balance of
an oxidizing reducing mixture [205]. De Sloovereet al. [205] found that
ammonium nitrate might as well be decomposed endothermically, thus
inhibiting the combustion process.
3.3. Selection of metal precursors
The ideal requirements for the metal precursors are:
- Good solubility in water and dilute acid,
- Inhibition capability of other cations precipitation,
- Oxygen provision for the combustion reaction,
- Formation of only gaseous by-products of oxidation to obtain at the
end only the desired material.
The first two requirements are not so strict (see Section 2) since
several insoluble components have been successfully used in SCS.
Moreover, a silica suspension was already used in the literature as Si
precursor for the solution combustion synthesis of mullite nanopowders
[49•]. Therefore, the possibility to use waste-derived insoluble metal
precursors might be also evaluated. In addition, even in the presence of
a precipitate, homogeneous powders would be produced, if the pre-
cipitate is in the form of a suspension and inglobated/incorporated in
the gel [15••].
Based on these premises and on the proposed multiple classification
(Table 3.1.1) some useful indications for a sustainable choice of metal
precursors are given in the following examples.
Example n° 1: Metal precursors for porous powders. In order to improve
the porosity of a powder and maximize its interaction with gases or
solutions, the first approach to try is using Cat. D.1 metal precursors,
with some microstructuring ability. It could be also convenient, for
example, to use one of the metal precursors in the form of highly
porous solids (Cat. C.2), in order to take advantage of its micro-
structural templating ability. Alternatively, for simple oxides, the
same sol-gel knowledge about hydrolysis and polycondensation can
be applied to some metal alkoxides (Cat. A.2) – especially Si, Ti and
Al –, in order to construct a proper gel network and get a higher
porosity in the final material. This is especially useful, if we want to
prepare, for example, a TiO2 powder as a support of metal catalysts.
Example n° 2: Metal precursors for sustainable synthesis. Although Ti
alkoxides might be the best choice for the preparation of titania
catalysts supports, an insoluble Ti precursor (Classification C), a
natural or a waste-derived Ti precursor (Classification B) would
lower the price and decrease the complexity of the procedure,
making it more scalable.
4. Effect of pH
pH has a primary role in determining the dissociation degree of the
organic fuels with acid/basic moieties and thus their chelation ability to
the metal cations [15••,19•,56,152•,206]. Its effect is strictly associated
with the chemical composition of the system and with the fuel-to-metal
cations ratio [152•]. High F/M values are not effective in term of
complexation ability of the fuel, if the fuel molecules are not fully
dissociated [15••,19•,152•]. For example, Pourgolmohammad et al.
[19•] found that the best combination of pH and fuel-to-metal cations
ratio for an optimized CoFe2O4 spinel nanopowders was high pH and
high F/M (1.25) (Fig. 4.1). Junliang et al. [152•] observed that pH ≥ 7
and F/M ≥ 1.5 are necessary to obtain single-phase barium hexaferrite
powders through SCS from citric acid.
F. Deganello, A.K. Tyagi
pH can affect microstructure and morphology [15••,19•,84,207•],
intensity of the combustion process [15••,19•,108,152•,206,208] and
structure [19•,209,152•] and even introduce slight distortion in the
structure, especially at higher pH values [84]. Ammonia has a primary
role in the formation of the combustion gel network as demonstrated in
the literature [108,152•,208,209]. Kim et al. [209] found that addition
of ammonia altered consistently the sol, increasing its gelation and
polymerization. Komova et al.[108] found that addition of ammonia to
the glycine-metal nitrates system increased the combustion intensity
and affects positively the powder properties. They evidenced by FT-IR
measurements and by chemical analysis of the combustion mass (even
after vacuum drying), that ammonia was fixed in the gel network as
NH4NO3, which was not present as a crystalline phase, but had strong
interaction with the other components [108].
Another role of pH was highlighted by Lwin et al.[207•]. They evi-
denced that higher pH values favor the formation of metal hydrates,
which can be more easily transformed into crystals [207•]. This faster
rate of solidification affects microstructure and morphology, by de-
creasing the grain size [207•], as illustrated by the trend in Fig. 4.2.
Conversely, the particle size from TEM results increases (Fig. 4.2), due
to the crystals agglomeration caused by strong magnetic interaction
between the ferrite crystallites [144].
As a general rule, pH level of the solution must be maintained in the
slight acidic range in order to prevent any precipitation of metal hy-
droxides or other salts, since precipitate formation of any form is
43
Progress in Crystal Growth and Characterization of Materials 64 (2018) 23–61
Fig. 4.1. Effect of pH and of fuel-to-metal ca-
tions ratio on the formation of complexes for
the synthesis of CoFe2O4 spinels nanopowders
by glycine combustion synthesis [Reprinted
from Ceramics International, 43, B.
Pourgolmohammad, S.M. Masoudpanah, M.R.
Aboutalebi, Effects of the fuel type and fuel
content on the specific surface area and magnetic
properties of solution combusted CoFe2O4 nano-
particles, pages 8262–8268, Copyright (2017),
with permission from Elsevier, License number
4,181,730,171,887].
considered detrimental to the combustion process, which is a redox
reaction step. Fuels with amino acids, due to the presence of basic and
acidic groups in the same molecule, are capable of forming zwitter ions
or dual-natured ions in aqueous solutions with a basic part, ammonium
ion (NH4+) and an acidic part, carboxyl anion (COO−).
All these considerations are applicable in solution, since pH is a
parameter defined for acidic/neutral/basic solutions. It may happen
that a fuel is in the solid form and metal cations are in solution or vice
versa, since redox reactions in the combustion process occur as well
between a component in a solid form and a component in solution
[46,49•,134]. Even in these cases, the acidity of the solution has a
central role, since the acid/basic moieties on the surface of the insoluble
compound are influenced by the pH in the solution with whom they are
in contact.
5. Initiation mode and type
Two main initiation modes exist in SCS, volume combustion mode
and self-propagating combustion mode [30••,62,63,71•,114•,210,211],
although the first one is much more commonly used. Often these
combustion modes are used as well for describing the nature of the
combustion process [53,62,147•].
In volume combustion mode the entire combustion mass is uni-
formly heated until ignition occurs [63,71•,212••]. In the self-propa-
gating combustion mode, initiation is usually started at one end of the
Fig. 4.2. Effect of pH on the particle size and grain size
of Mg-Mn ferrite spinels prepared by SCS from citric
acid in the presence of ammonia [Reprinted from
Materials Characterization, 110, N. Lwin, R. Othman,
A. F. M. Noor, S. Sreekantan, R. Singh, C.-C. Tin, T. C.
Yong, Influence of pH on the physical and electromagnetic
properties of Mg–Mn ferrite synthesized by a solution
combustion method, pages 109–115, Copyright (2015),
with permission from Elsevier, License number
4,192,870,698,392].
F. Deganello, A.K. Tyagi
pelletized precursors [108,114•,212••]. Alternatively, the combustion
can be locally initiated on the dried gels by using a resistively heated
tungsten wire [71•] or a nichrome wire connected to a voltage slider
[211]. A similar initiation modality was applied in the impregnate ac-
tive layer combustion (IALC), where the solution is impregnated into a
cellulose active layer, which acts as a complexant, fuel and micro-
structural template, assisting the combustion process [85].
Komova et al.[108] found that enhanced crystallinity and higher
phase purity could be obtained by conducting the combustion reaction
in the self-propagating mode (Fig. 5.1). It has been further observed by
Manukyan et al. [71•] that this combustion mode is more controllable
and favors a more homogenous microstructure in the as-burned pow-
ders.
The most used initiation type is the muffle furnace [25•,42,109].
The big advantage of this initiation type is that uniform heating is ap-
plied to the combustion mass. The main disadvantage is that the process
cannot be observed (unless special IR camera are mounted or an optical
pyrometer is used [25•,71•]). Combustion in muffle furnace is usually
very violent, lot of powder is lost and the furnace become easily dirty,
although there are some convenient set-ups that can be used for this
purpose [42] (Fig. 5.2).
A large number of literature works about SCS makes use of the hot
plate under fume hood [15••,27,40••,137•,213]. Sometimes, the com-
bustion process is initiated by a thermal heating in the muffle furnace
directly from the solution, like in the work by Chen et al. [213]. In the
Fig. 5.2. A convenient experimental set-up for VCS initiation in muffle furnace [Reprinted from Boletín de la Sociedad Española de Cerámica y Vidrio , J. Gilabert, M.
D. Palacios V. Sanz, S. Mestre, Fuel effect on solution combustion synthesis of Co(Cr,Al)2O4 pigments, Copyright (2017) in press, by Email permission from Elsevier Spain].
44
Progress in Crystal Growth and Characterization of Materials 64 (2018) 23–61
Fig. 5.1. Enhanced crystallinity and phase purity in the as burned
powders for SHS initiation mode than for the VCS one [Reprinted
from Advanced Powder Technology, 27, O.V. Komova, V.I. Simagina,
S.A. Mukha, O.V. Netskina, G.V. Odegova, O.A. Bulavchenko, A.V.
Ishchenko, A.A. Pochtar, A modified glycine–nitrate combustion method
for one-step synthesis of LaFeO3, 496–503, Copyright (2016), with
permission from Elsevier, License number 4,233,651,045,142].
same work, the authors introduced ultrasonic irradiation during
heating in the muffle furnace, in order to decrease particle agglom-
eration during combustion. Ultrasounds favored a homogeneous hon-
eycomb structure originated from the cavitation bubbles [213]
(Fig. 5.3).
Another emerging and promising initiation type is the microwave
oven [43,57,91,107,111,143,214]. Better microstructural and textural
properties (surface area, crystal size, grain size) and lower area inter-
face resistance were observed for cathode powders prepared by SCS
with microwave initiation type [107,158]. In Fig. 5.4 the SEM pictures
of two La-Sr-Co-Fe-O (LSCF) powders prepared by conventional initia-
tion in the oven and microwave initiation is confronted [107]. Reduced
agglomeration and more uniform size distribution were obtained by
microwave heating [107] (Fig. 5.4). Microwave initiation has as well
some limitations, like the high cost of the equipment, the low size limit
of the combustion reactor and the impossibility to monitor the particle
growth mechanism during the combustion process [111].
6. External microstructural template
In the classical SCS procedure, the fuel itself acts as microstructural
template, although some examples in the literature exist where an ex-
ternal microstructural template (EMT) is further added to the com-
bustion mixture [27,83,137•,215,216,217•]. The most used EMT are
silica, colloidal silica, alumina, inorganic salts and carbon. The EMT
F. Deganello, A.K. Tyagi Progress in Crystal Growth and Characterization of Materials 64 (2018) 23–61

Fig. 5.3. Effect of the ultrasonic irradiation on the powder morphology and porosity. TEM images of the as-combusted powders prepared by a) conventional SCS b)
pre-ultrasound SCS c) ultrasonic –assisted SCS [Reprinted from Q. Chen, Q. Liu, X. Chu, Y. Zhang, Y. Yan, L. Xue, W. Zhang, Ultrasonic-assisted solution combustion
synthesis of porous Na3V2(PO4)/C: formation mechanism and sodium storage performance, J. Nanopart. Res. 19 (2017) 146 (10 pages), with permission from Springer,
License number 4,192,880,068,440].

Fig. 5.4. Effect of the microwave in-

itiation type onto the powder mor-
phology and porosity. FESEM images
and EDS spectrum of LSCF powders
synthesized by using a, c) conventional
(hot plate-preheated oven) initiation or
b, d) microwave initiation [Reprinted
from Ceramics International, 43, S.A.
M. Ali, M. Anwar, M. R. Somalu, A.
Muchtar, Enhancement of the interfacial
polarization resistance of La0.6Sr0.4Co0.2
Fe0.8O3-δ cathode by microwave-assisted
combustion method, pages 4647–4654,
Copyright (2017), with permission
from Elsevier, License number
4,192,870,802,349].

does not fully participate to the redox reaction during the combustion
process, although it might act as an obstacle to the combustion wave
propagation (as in the case of EMT with low thermal conductivity) or it
might influence the oxidation states of the mixed valence metal cations
in the as-burned powder (as in the case of carbon-based EMT, which
create a reducing environment). The EMT might be either eliminated
after its templating action [27,83,114•137•,215] or it can be kept in the
final product as a metal oxide/EMT or metal/EMT composite
[112,216,217•]. All the hard templates used in the hard templating
synthesis [218,219,220] can be in principle conveniently used as ex-
ternal templates for SCS. There is also the possibility to create a metal
oxide highly dispersed onto a high surface area support, by preparing
the nanocomposite through an in situ SCS process [189]. In this case,
alumina support does not enter in the combustion mixture as formed
oxide powder, but it is introduced as aluminum nitrate precursor and is
then transformed in the oxide form concomitantly to the metal pre-
cursor [189].
Therefore, in order to prepare by SCS porous powders for catalytic
and electrocatalytic applications, two main approaches might be con-
sidered: playing with the fuel type and amount, using the micro-
structural templating ability of the fuel or adding an external hard
template, in order to get high surface area supported oxides (without
etching) or highly porous oxides (after etching of the hard template).
The most common types of external microstructural template are
discussed below, evidencing the relationships between the EMT and the
properties of the produced material.
6.1. Silica
All the fuels described in Section 2 are soft templates, since they
participate actively to the combustion reaction, leaving their micro-
structural trace even after their decomposition. In this SCS variant,
called “soft-hard templating approach” (SHT) or “template-assisted com-
bustion process”, a concept independently introduced for the first time in
2014 by Deganello et al. [137•] and by Manukyan et al.[114•], a hard
EMT like silica is introduced in the combustion mixture with the role of

45
F. Deganello, A.K. Tyagi
Fig. 6.1.1. General scheme of the soft-hard templating approach (SHT), with silica as hard template.
additional microstructural template, as described in Figs. 6.1.1 and
6.1.2.
A combination of soft and hard template strategies is very useful to
obtain high surface area highly porous oxides or perovskite-type ma-
terials for catalytic purposes. Silica, for example is a well-known hard
template. By combining soft and hard templates, powders with con-
trolled porosity can be obtained. In this case, the main role of the soft
template is to act as a reducer and to organize a gel network around the
hard template and the metal cations (metal chelator), whereas the
function of the hard template is only to act as a metal cation absorber
(metal chelator/adsorber) and as a microstructural template for the
final powder.
For example, by using the SHT approach with porous silica hard
templates, perovskite materials with controlled porosity and surface
area values up to 160 m2/g can be obtained [137•]. The textural
properties of the final material depend very much on the original hard
template used [137•] as described in Fig. 6.1.3. Although in the SHT
approach, two microstructural templates are effectively present, the
fuel and the external hard template, the hard templating effect dom-
inates [137•]. Compared with the classical hard templating methodol-
ogies [218,219,220], this approach has higher simplicity, efficacy and
reproducibility [137•]. Among the two silica-templated procedures
described in the literature [114•,137•], the SHT procedure is less time
consuming and simpler, because it avoids repeated impregnation under
vacuum.
Similar to the classical hard templating methodologies, an etching
procedure is necessary for eliminating the silica before the final thermal
treatment, followed by filtering, washing and drying [137•]. Never-
theless, not all the silicon is eliminated after the etching procedure,
since during the combustion process, a strong interaction between silica
and metal precursors occurs and a considerable amount of amorphous
metal silicates is concomitantly formed [137•]. This might be appar-
ently a drawback for all the electrochemical-related applications, al-
though it must be noticed that these silicates are the main responsible
Dong, S. Roslyakov, A. S. Mukasyan, Ultrasmall α‑Fe2O3 Superparamagnetic Nanoparticles with High Magnetization Prepared by Template-Assisted Combustion Process, J.
Phys. Chem. C., 118 (2014) 16,264 − 16,271. Copyright (2014) American Chemical Society].
46
Progress in Crystal Growth and Characterization of Materials 64 (2018) 23–61
for the high porosity of the final material, transmitting most of the
porous framework from the original silica template to the final powder
[137•]. For this reason, the SHT approach from silica hard templates
can be considered a valuable procedure for the synthesis of powders
with high surface area and porosity, especially for catalytic/electro-
catalytic applications [27,137•]. A further feature of the SHT approach
is the possibility to obtain mesoporous powders using templates with
ordered mesoporosity [137•], although for calcination temperature of
the powder higher than 700 °C, the mesoporosity is usually lost. For
similar reasons, at calcination temperature of around 800 °C, amor-
phous silicates becomes crystalline and loose most of their porous fra-
mework, affecting the textural properties of the final material [137•].
Therefore, it must be known that all these features might limit the
chemical composition of the perovskites prepared using this metho-
dology.
Colloidal silica can also be used instead of solid silica in order to
prepare by SCS metal oxides with very regular porosity [215]. The
colloidal status forces the combustion to occur in confined nanospaces
[215].
Alternatively, silica might be also used as EMT to obtain metals,
metal oxides or perovskites particles finely dispersed onto an inert
support for catalytic applications [217•]. In these cases, silica is not
eliminated by etching, but acts as a microstructural template for a fast
and effective control of the active phase crystal dimensions in a one-pot
synthesis.
6.2. Carbon
Carbon-based materials have been extensively used as micro-
structural templates for the synthesis of a variety of nanomaterials,
thanks to their high porosity [221]. Due to their electric, catalytic and
textural properties, they have been often included in composites for-
mulations for a variety of applications, such for example in electrodes
for metal-air batteries, in supercapacitors, and electrochemical sensors
Fig. 6.1.2. Silica-templated SCS for the
preparation of high surface area oxides.
A) Initial template B) Template im-
pregnated by reactive solution C)
Initiation of reaction with self-propa-
gation D) Nanoparticles are formed in-
side channels of the template E)
Template has been leached and iron
oxide nanoparticles are obtained
[Reprinted with permission from K. V.
Manukyan, X. Liu, J. K. Furdyna, Y.-S.
Chen, A. Orlov, S. Rouvimov, G. H.
Bernstein, P. Li, X. Li, W. Porod, S.
F. Deganello, A.K. Tyagi
[222,223]. Carbons can be considered as ecofriendly templates, since
they are easily obtained from natural or waste-derived organic com-
pounds by SCS [93] or by other methods [11,12].
SCS in the presence of carbon can be considered as a modification of
the SHT approach, where silica is replaced by carbon as external hard
template. Even though carbon template is not oxidized during the
combustion process, it is oxidized at higher temperatures, during the
final thermal treatment. Therefore, in this case, no etching procedure is
necessary, because the carbon can be eliminated during a suitable
oxidative thermal treatment. On the contrary, if metal/carbon or metal
oxide/carbon nanocomposites are desired, a thermal treatment under
inert atmosphere can be chosen, avoiding carbon oxidation [31••]. In
some specific cases, carbon may even act as a fuel, as for example when
carbon nanotubes are used [150•].
Contrary to silica, during the combustion process, carbon does not
act as heat insulator, partially blocking the combustion wave, although
carbon does not interact easily with metal cations. Indeed, it must be
noticed that the presence of carbon favors a reducing environment for
metal cations [224], even if the interaction with metal cations is low.
Carbon might act as a microstructural template as well if it is in-
troduced in the combustion mixture as a carbon precursor. In this case,
fuels with hydroxyl functional groups (according to Classification 1),
polymeric (according to Classification 5), with high structuring ability
(according to Classification 6), like for example sucrose and glucose, are
particularly convenient for preparing metal oxides with good porosity
[113] or metal/carbon and metal oxide/carbon nanocomposites
[112,224]. A mixed fuel of pluronic acid and citric acid (according to
Classification 4) is also convenient for preparing mesostructured oxides,
as observed by Lertpanyapornchai et al.for SrTiO3 [169•].
Recently, also metal/carbon nanocomposites and perovskite/carbon
nanocomposites were obtained by SCS, as described in Figs. 6.2.1 and
6.2.2. In Fig. 6.2.1 a reducing thermal treatment under hydrogen re-
duced the metal oxide to metallic particles, preserving the carbon
produced in the as-burned powders [112]. In Fig. 6.2.2, a very mild
thermal treatment under air (350 °C for 30 min) was chosen for the
synthesis of a LaMnO3/Vulcan nanocomposite electrode, which showed
superior electrochemical performance with respect to the mechanical
mixtures [225]. Apparently, the carbon was under strong contact with
the perovskite phase and this greatly enhanced the ORR [118,225].
Another important effect of carbon is to decrease the crystal size and
agglomeration degree of the perovskite [118].
Under optimized conditions, carbon-based inorganic nanocompo-
sites can be also prepared starting from any organic fuel with no further
treatment [92] or with a post thermal treatment of the as-burned
powders under inert atmosphere [224]. This particular SCS procedure,
as already pointed out, takes advantage of the fact that the combustion
process is not completely adiabatic, due to heat dispersion in an open
beaker and voluminous evolution of hot gases. This leaves after
47
Progress in Crystal Growth and Characterization of Materials 64 (2018) 23–61
Fig. 6.1.3. Correlation between the specific surface area (large empty
rhombs) and the cumulative pore volume (small full rhombs) of LaFeO3-based
nanopowders with the cumulative pore volume of the original silica template
[Reprinted from F. Deganello, M. L. Testa, V. La Parola, A. Longo, A. C.
Tavares, LaFeO3-based nanopowders prepared by a soft-hard templating ap-
proach: the effect of silica texture, J. Mater. Chem. A 2 (2014) 8438–8447, with
Permission from Royal Society of Chemistry].
combustion a certain amount of carbon as result of an incomplete
combustion [78,79,103•, 147•169•], unless non-carbonaceous fuels are
used [87]. Alternatively, Han et al. [48] performed the combustion
directly in a tubular resistance furnace under inert atmosphere
Fig. 6.2.3. In this case, the structure directing effect is due to the ori-
ginal fuel, although the presence of the carbon during the thermal
treatment under inert atmosphere plays an important role in the mi-
crostructure of the final material, similarly to what has been observed
for materials prepared by using other synthesis methodologies
[7,222,223,226].
6.3. Other inorganic templates
In the powders prepared by combustion-based processes, agglom-
eration, both hard and soft type, is very common [103•,159•,
178,180,227]. One possible cause is the intrinsic nanostructured nature
of the SCS prepared powders [159•]. In some cases, hard agglomeration
can affect adversely the powder properties [159•,178,180]. If a soft
agglomeration occurs, a ball milling post treatment might be useful to
eliminate the soft-agglomerates [159•].
As mentioned in the previous paragraph, carbon, for example, is
able to decrease the agglomeration degree [118]. Alternatively, by
adding an inorganic salt to the combustion mixture, like for example
NaCl or KCl, it is possible to protect the crystals from intense agglom-
eration [68,96,110,228,229,230]. Like in the SHT approach, the in-
organic salt must be washed away in order to get the desired compo-
sition. It is believed that the main role of the inorganic salt is to form a
crust and keep the nanocrystal separated during the combustion and the
thermal treatment [228]. Apparently, the inorganic salts adsorb most of
the heat released during the combustion process, keeping it unavailable
for the particle crystallization [103•].
Tong et al. [110], prepared MnCr2O4 spinel nanocrystals by LiCl-
assisted SCS. The powders produced in the presence of the salt had
cubic shape and uniform dispersion, as showed in Fig. 6.3.1. Similarly,
in the work by Manukyan et al. [96], the molten salt-assisted SHS
method was used by adding NaCl as inert diluent in a dry combustion
process for the synthesis of MoS2 with particles below 1 micrometer.
Indeed, the templating action of NaCl was also manifested in a so-
lution-based methodology that, apparently, did not involve any auto
combustion process [231]. In the same work, an inorganic salt (NaCl)
was used, in combination with glucose, as sacrificial template for the
synthesis of two-dimensional LaxFeO3/C nanocomposites for micro-
wave dielectric applications, as described in Fig. 6.3.2.
Recently, Zhao et al. [232] proposed a new synthesis of graphene
sheets by using a barium ferrite assisted-intercalation into expanded
graphite. The barium ferrite sols were able to reach the expanded
graphite spaces that, after the combustion process, were filled with the
BaFe12O19 powders, which caused a further expansion of the graphite
F. Deganello, A.K. Tyagi
layers until graphene sheets formation. The barium ferrite powders
were then etched by hydrochloric acid [232].
6.4. In situ procedures
An important advantage of SCS is the possibility to produce metal
catalysts supported onto monoliths or foams [33••,177••] as illustrated
in Fig. 6.4.1. In this approach, the EMT is a monolith or a foam and is
dipped into a solution containing the SCS precursors.
For example, alumina pellets were used as supports/microstructural
templates for the direct combustion synthesis of metal supported cat-
alysts by Cross et al. [233•]. They found that highly diluted impregna-
tion sols could be easily impregnated on a compacted porous alumina
pellet, producing uniformly dispersed Ni particles onto alumina sup-
port, after self-propagating ignition [233•]. Similarly, monolithic alu-
mina fibers have been also used as support for copper oxide by Aghayan
et al. in a single-step wet-combustion method [101], forming core-shell
microstructures of mesoporous alumina and highly oriented copper
oxide nanoparticles.
In situ SCS procedures have been also successfully used for the
preparation of oxide films in situ deposited onto temperature-sensitive
substrates for optoelectronic applications [51], oxide transistors [52] or
p-type substrates for applications in oxide electronics [32••,50,
234,235]. Furthermore, according to Tang et al. [236], high oxygen
storage capacity mesoporous doped-ceria nanotubes were fabricated by
SCS owing to the templating action of anodic alumina oxide monoliths.
7. Selection of other “minor” parameters
In order to obtain the desired powder quality one should also op-
timize the amount of water, the gelation time, the size of the batch, the
flame temperature, the number of moles of gases evolved and the re-
action kinetic of the combustion reaction. Although they may seem
“minor” parameters, an accurate control of them ensures a better
quality of the product and higher reproducibility of the final materials
properties.
48
Progress in Crystal Growth and Characterization of Materials 64 (2018) 23–61
Fig. 6.2.1. Example of a synthesis by SCS of a metal-carbon nano-
composite in two simple steps [Reprinted from Journal of Alloys and
Compounds, 695, M. Huang, M. Qin, D. Zhang, Y. Wang, Q. Wan, B.
Jia, X. Qu, Q. He, Facile synthesis of sheet-like Fe/C nanocomposites by a
combustion-based method, pages 1870–1877. Copyright (2017), with
permission from Elsevier, License number 4,181,730,344,958].
7.1. Water content
Water is the most commonly used solvent for the combustion mix-
ture, although some authors prefer acetone, ethylic alcohol or ethylene
glycol [50,79,106,157,206], which might be a better choice if metal-
organic compounds are used as metal precursors [79,106,142] or when
SCS is used for film deposition [50,52,234]. Voskanyan et al. [237•]
used furfuryl alcohol both as a solvent and as a fuel for the preparation
of CuOeCeO2 catalysts. In particular, they found that the ignition
temperature was lower than in the SCS from glycine [237•]. It has been
also found that organic solvents-although they usually do not partici-
pate directly in the combustion process-influence the combustion re-
action when present in the coordination sphere of metal cations in the
gel network, affecting the materials performance [206].
An important parameter that is often neglected is the initial amount
of water used for the dissolution of the precursors. It may be also noted
that the thermal dehydration process is an important step, because any
excess water left behind would lead to a sluggish combustion, dete-
riorating the phase purity and powder quality [38].
Only a few papers in the literature discussed the effect of water
content in the SCS [210,238]. In particular, Xanthopoulou et al. [210]
elucidated the effect of water content on the materials properties. In
particular, they observed that the structure and properties of the metal
hydrates in solution and their decomposition characteristics were
strictly related to the initial concentration of the metal precursor (i.e.
the initial amount of water) [210]. More recently, Gilabert et al. ob-
served a clear trend of the structural and morphological properties of a
(Co, Ni) Cr2O4 pigments powder with the initial concentration of the
metal precursors [238]. These authors found that secondary phase
formation increased (Fig. 7.1.1) and grain growth was favored with
high initial concentration values [238].
Other authors, tried to avoid the use of water in the SCS, using a
methodology closer to the solid-state combustion synthesis
[94,120,202]. In the work of Hwang et al.[97,202], a dry route was
used to prepare CeO2 nanopowders from urea as a fuel and ceric am-
monium nitrate as a convenient cerium precursor and oxidant. Ring-
uedè et al. [94] also used a dry combustion synthesis for the preparation
F. Deganello, A.K. Tyagi
Fig. 6.2.2. Superior electrochemical performance of a perovskite/carbon na-
nocomposite over simple mechanical mixtures. A) CVs in 1 M NaOH under N2
B) negative RDE scans in O2-saturated 1 M NaOH at 900 rpm after background
subtraction C) kinetic currents at 0.85 V vs. RHE. In the insert of B, Levich-
Koutecky plots at 0.5 V vs. RHE. The black lines and bars corresponds to the
nanocomposite [Reprinted from Electrochemistry Communications, 50, G.
Kéranguéven, S. Royer, E. Savinova, Synthesis of efficient Vulcan–LaMnO per-
ovskite nanocomposite for the oxygen reduction reaction, pages 28–31. Copyright
(2015), with permission from Elsevier, License number 4,181,730,459,176].
of Ni cermet materials. They took the advantage of the fact that nitrates
are hygroscopic and can melt at low temperature, favoring the mixing
of the components. Therefore, even in the “absence” of water, a gel or a
sort of melt is always formed before the auto ignition. Another example
in the literature where molten precursors are used is the work by Chen
et al. [95]. These authors used Li and Mn acetates precursors, which
melted at 100 °C, for the synthesis of LiMn2O4 [95].
49
Progress in Crystal Growth and Characterization of Materials 64 (2018) 23–61
It must be reminded that dissolution of all the precursors is not al-
ways strictly necessary in SCS [46,49•,134]. The use of insoluble fuels
like cellulose and cotton has been already established [46,134]. It has
also been found that some carbons, like carbon nanotubes, can be
successfully used as insoluble fuels in the so called “multiphase com-
bustion synthesis” [150•]. Other insoluble metal precursors have been
also proposed [49•]. In this case, the interactions among the con-
stituents of the combustion mixture obviously change in the presence of
insoluble components: adsorption onto the insoluble component surface
and mixing modality of the mixture become determining steps of the
synthesis.
7.2. Gelation conditions
The gel formation is a central step of the SCS, which is indeed a gel
combustion process. In principle, any phase separation during the
thermal dehydration process of the sol should be avoided. The gel thus
formed maintains an intimate blending between fuel and oxidant,
which is necessary for the combustion process. Regarding the gelation
conditions, all the considerations that are applicable to sol-gel pre-
paration methodologies can be directly transferred to SCS [12]. In this
respect, some general rules are recalled as follows:
(i) Initial pH. The initial pH of the combustion mixture strongly affects
the gelation ability of the mixture, especially if the pH value is too
low to grant the formation of complexes between fuel and metal
cations [19•,239]. Kim et al.[209] found that 24 h of sol aging and
3.5 vol% ammonia addition were necessary to reach a proper
viscosity of the sol in order to form the desired apatite crystals.
(ii) Gelation time (sol aging). Gelation and pH variation are strongly
related phenomena. It has been found that the course of gelation
can be monitored by measuring pH during the solvent evaporation
and that pH of the solution decreases during the gelation process
[79,240] (Fig. 7.2.1). This is due to the progressive formation of
bonds between metal cations and the oxygen moieties of other
hydrolyzed precursors, which release H+ ions, increasing the
acidity of the solution [79,209,240]. This also explains why ad-
dition of ammonia accelerates gelation [209]. Gelation time (aging
of the precursor solution until gel formation) has been found to
influence some of the powder properties. Liu et al.[240], for ex-
ample, found that prolonged thermal aging of the sol hindered
pure apatite formation.
(iii) Gelation temperature. Gelation is an endothermic process.
Therefore, by increasing the temperature, gelation is faster
[79,240]. Manukyan et al. [71•] subjected the gel to thermal aging
for 24 h at different temperatures, from 30 °C to 120 °C. They
found that by increasing the aging temperature, the maximum
combustion temperature increases [71•].
(iv) Gel aging. The effect of gel aging (the time that the gel is left aging
after it was formed) on the combustion process and powder
properties has been rarely mentioned in the SCS related studies
[79,156•]. From these few studies [79,156•] and from the general
knowledge about sol-gel processes [12], it can be argued that gel
aging might have some influence on the organization of the pre-
cursors in the gel network and therefore on the final material.
Esmaeili et al. [156•] found that after 20 minutes of gel aging at
room temperature, a decrease in surface area of the final powder
occurs. Wang et al.[79] observed that long gel aging times increase
the ignition temperature for combustion. Therefore, it is re-
commended to use the same gel aging time when two materials
prepared by SCS are compared or when reproducibility of the
batches is needed.
7.3. Chemical composition
Chemical composition strongly affects the combustion process and
F. Deganello, A.K. Tyagi
the choice of the other SCS parameters [125]. For example, it has been
found that transition metal cations ignite at lower temperatures and
favor a more intense combustion than alkaline and alkaline earth ca-
tions (Fig. 7.3.1) [38]. Even among the transition metal elements there
are evident differences, as it has been found by Striker et al.[100] by
comparing the combustion process and the materials properties of
LaFeO3 and LaMnO3 prepared by SCS from two different fuels. Appar-
ently, a difference in the combustion temperature of the metal pre-
cursors with the fuel in multicomponent mixtures changes the effective
reducers-to-oxidizers ratio, influencing the combustion process [100].
Another example, depicted in Fig. 7.3.2, shows the case of the Cu-Cr-O
spinels prepared by SCS from urea at different copper nitrate con-
centrations [241]. Beside the fuel type/amount, the combustion process
intensity was affected by the chemical composition [241]. The ignition
temperature is also affected by the chemical composition of the mixture
[38,237•]. A possible reason could be a stronger bond between transi-
tion metal oxides and the fuel [38]: depending on the chemical com-
position, stronger or weaker metal-to-fuel interactions are present in
the combustion mixture, leading to a stronger or weaker redox reaction
between the fuel and the oxidant [38]. Alternatively, it might be that a
catalytic effect by some specific cations occurs during polymerization
and combustion, as observed by Voskanyan et al.in the case of furfuryl
alcohol as a fuel [237•]. Other authors found some important differ-
ences in the combustion process features for the preparation of per-
ovskite type powders with different B-site metal cations, ascribing them
to the different redox activity of the metal cations involved [15••].
Therefore, it might happen that the combustion procedure must be
adapted according to the chemical composition of the product and to
the concentration of the constituents, in order to avoid a too high ig-
nition temperature and a too intense/slow combustion.
7.4. Laboratory equipment
A suitable choice of laboratory equipment might be important to
50
Progress in Crystal Growth and Characterization of Materials 64 (2018) 23–61
Fig. 6.2.3. Schematic illustration for
preparing Fe3O4/C composites by SCS
using cotton as a natural fuel
[Reprinted from Materials Today
Energy, 5, C.-G. Han, N. Sheng, C. Zhu,
T. Akiyama, Cotton-assisted combustion
synthesis of Fe3O4/C composites as ex-
cellent anode materials for lithium-ion
batteries, pages 187–195. Copyright
(2017), with permission from Elsevier,
License number 4,181,730,580,558].
increase the efficiency of a synthesis as well as for safety and en-
vironmental issues [15••,25•,33••,42,97,98,115,188,214,242,243•]. For
example, an excessive intensity of the process may be harmful for the
experimenter and, at the same time, it may cause too much dispersion
of the powdered product in the surroundings, with environmental
consequences and yield reduction (see Section 9). In this regard, the
choice of the combustion beaker is very important, since the nature of
the beaker affects the combustion intensity [15••]. It must be also taken
into account that the beaker geometry may even inhibit the combustion
process [25•].
The basic setup is usually very simple, comprising of an evapora-
tion/combustion vial (usually a glass or porcelain beaker), a stirrer
(usually magnetic), a heating system (usually a hot plate with tem-
perature control) and an initiation system (usually an hot-plate or a
muffle furnace). Nevertheless, setup may vary a lot depending on type
of product to be prepared and on the type of in situ control of the
combustion process [97,98,214,243•]. For example, thermocouples
might be also used for the monitoring of the combustion process and
register the temperature-time profiles [97,98]. Sometimes, a system for
the gas collection and analysis is considered [214,243•]. A special setup
has been also proposed for a combinatorial solution combustion
synthesis [242]. Sometimes the combustion vial might be half-closed if
an airless atmosphere is needed for obtaining powders with metal ca-
tions in a reduced oxidation state [115,188,243•]. For in situSCS pro-
cedures (see Section 6.4) a different setup is required, since a dip-
coating apparatus for the impregnation of the monolith with the solu-
tion of precursors is also necessary [33••,177••]. Scale up and industrial
SCS processes might require a special setup for continuous production
[85] (see also Fig. 8.2).
Stainless steel beaker are generally preferred, for their mechanical
resistance (Fig. 7.4.1) [15••], although porcelain crucibles [97,98], glass
beakers/flasks or quartz beakers are also used [42,214] (Fig. 5.2). Glass
is cheap, can be easily shaped in the desired form, is transparent and
makes it possible to monitor the combustion process. The main
Fig. 6.3.1. TEM images of MnCr2O4 spinel nanoparticles prepared by
SCS after calcination at 700 °C/3 h with (left) or without (right) ad-
dition of LiCl as a microstructural template [Reproduced from Y.
Tong, J. Ma, S. Zhao, H. Huo, H. Zhang, A Salt-Assisted Combustion
Method to Prepare Well-DispersedOctahedral MnCr2O4 Spinel
Nanocrystals, Journal of Nanomaterials 2015 (2015) Article ID
214,978, 5 pages (http://dx.doi.org/10.1155/2015/214978), under
the Creative Commons Attribution License].
F. Deganello, A.K. Tyagi
drawbacks of the glassy combustion synthesis reactors are that they can
be easily broken by thermal shock and Si impurities might be released
from the glass at the high temperatures reached by the combustion
process. Ceramic beakers are not convenient for intense processes, but
they might be the right choice in the case of a less intense combustion
[15••]. The beaker dimension is dictated by the final amount of product
to be obtained in a single batch and increases with the increasing of the
combustion intensity. Generally speaking, a 3 L beaker might be used
for producing 2–5 g of product, depending on the type and intensity of
combustion process.
Some of the issues related to scale-up and some of the safety and
environmental issues will be further discussed in Sections 8 and 9.
8. Reproducibility and scale-up procedures
Reproducibility of a preparation methodology is often required and
is a critical aspect of any synthesis procedure, especially for high
amount of powder. SCS is a reproducible and scalable methodology,
only if all the important parameters and their effect on the materials
properties are properly identified and controlled.
As an example, one of the most important parameters to be con-
trolled is the proportion of the combustion mass to the combustion
beaker size, which should be maintained constant from a batch to an-
other, in order to grant the reproducibility of the combustion process. In
Fig. 6.4.1. Schematic illustration of in situ SCS for the preparation of industrial catalysts [Reprinted from S. Specchia, G. Ercolino, S. Karimi, C. Italiano, A.Vita,
Solution combustion synthesis for the preparation of structured catalysts: a mini-review on process intensification for energy applications and pollution control, International
Journal of Self-Propagating High-Temperature Synthesis 26 (2017) 166–186, with email permission from Allerton Press].
51
Progress in Crystal Growth and Characterization of Materials 64 (2018) 23–61
Fig. 6.3.2. Schematic illustration of the NaCl-templated synthesis of
LaxFeO3/carbon 2D nanocomposites [Reprinted with permission from X. Liu,
L.-S. Wang, Y. Ma, H. Zheng, L. Lin, Q. Zhang, Y. Chen,Y. Qiu, D.-L. Peng,
Enhanced Microwave Absorption Properties by Tuning Cation Deficiency of
Perovskite Oxides of Two-Dimensional LaFeO3/C Composite in X‑Band, ACS
Appl. Mater. Interfaces, 9 (2017) 7601 − 7610. Copyright (2017) American
Chemical Society].
fact, the combustion process is quasi-adiabatic, in the sense that it tends
to be adiabatic as much as the combustion reaction is fast enough with
respect to the heat dispersion (or dissipation) with the surroundings
(beaker, air) [30••,147•]. Moreover, many hot gases are evolved during
combustion, facilitating the heat exchange with the environment
[30••,147•]. Therefore, the combustion process comes far from being
adiabatic if either the reaction is too slow or the heat dispersion (dis-
sipation) is too fast and voluminous. With these premises, in order to
have a complete combustion, the combustion mass should not be too
small with respect to the size of the combustion beaker, otherwise the
adiabatic nature of the process is far from being attained and too much
heat dispersion causes a delay or even a block in the combustion.
Unfortunately, only few literature works deal with experiments
about reproducibility of the SCS [98,244•,245,246], although re-
producibility is a fundamental issue for any industrial application. In
particular, Gilbert et al. observed for spinel pigments that reproduci-
bility was generally good, although pigments crystallinity clearly varied
with the batch replica in a specific composition range (Fig. 8.1). The
authors ascribed any variability in the pigments crystallinity to the fast
reaction kinetics associated with the combustion process which prevent
the spinels to reach their equilibrium structure [244•]. The authors
hypothesized that maybe some of the relevant parameters were not
strictly maintained constant from batch to batch [244•]. Literature re-
sults have shown that as long as accurate control of all the synthesis
F. Deganello, A.K. Tyagi
Fig. 7.1.1. Mass percentage of secondary eskolaite phase versus chemical
composition Ψ of Co1-ΨNiΨCr2O4 (0 ≤ Ψ ≤ 1) pigments prepared by SCS from
Urea and effect of the initial metal precursor's concentration in water solution
[Reprinted from Ceramics International, 42, J. Gilabert, M. D. Palacios, V. Sanz,
S. Mestre, Characteristics reproducibility of (Fe, Co)(Cr, Al)2O4 pigments obtained
by solution combustion synthesis, pages 12,880–12,887. Copyright (2016), with
permission from Elsevier, License number 4,192,870,903,532].
Fig. 7.2.1. pH variation of a hydroxyapatite sol with 5 vol % NH4OH with
gelation time [Adapted from J Mater Sci: Mater Med, Synthesis of high purity
hydroxyapatite nanopowders via sol–gel combustion process, 20 (2009) 1223, J.
Wang, L. L. Shaw. With permission of Springer, License number
4,181,740,020,676].
parameters is performed, SCS reproducibility is ensured. In the parti-
cular case of waste-derived fuels (Classification 2 of fuel type) and
waste-derived metal precursors (Classification B of metal precursor
type), the reproducibility of the materials properties is strictly con-
nected to the reproducibility of the original waste and this might re-
present a limit, unless each batch of waste-derived precursors is care-
fully characterized.
Reproducibility is often connected with scalability, since industrial
production of high amount of powder requires reproducibility tests in
order to grant high-level production [245,246].
The medium amount of powder that can be prepared by SCS in a 1L-
3 L beaker varies from 1 to 5 grams per batch [46,47,123•,170], al-
though the maximum amount per batch strongly depends on the choice
of other synthesis parameters which affect the intensity of the com-
bustion process, like the chemical composition, the fuel type, the fuel
52
Progress in Crystal Growth and Characterization of Materials 64 (2018) 23–61
Fig. 7.3.1. Autoignition temperatures for stoichiometric mixtures of single
metal nitrates and glycine. Certain transition metals such as chromium form a
strong charge transfer complexes in solution with glycine, displacing water
from the coordination sphere. Strontium ions are not well complexed by gly-
cine, particularly in acidic solutions [Reprinted from Mater. Lett., 18, J. J.
Kingsley, L. R. Pederson, Combustion synthesis of perovskite LnCrO3 powders using
ammonium dichromate, pages 89–96. Copyright (1993), with permission from
Elsevier, License number 4,192,871,277,798].
amount, the type/dimensions of combustion beaker. For higher
amounts of powder, some SCS parameters and procedures have to be
revised. Larger combustion beakers and/or special scale-up procedures
have been adopted for the preparation of 20–500 g of powders per
batch [60a••,215,89,247•,202,98,245,246,183]. For example, a special
apparatus was invented by Mukasyan et al. [60a••,89,247•] for the
continuous production of high surface area nanopowders by im-
pregnated active layer combustion (Fig. 8.2). Hwang et al. [98,183,202]
proposed a dry combustion route for the preparation of 25–100 g of
powder per batch. Gaggero et al. [119] proposed a combustion-based
scale up process in continuous-feeding configuration for the transfor-
mation of hundred grams of asbestos-containing wastes to inert abra-
sive/refractory materials.
9. Precautions and limitations
Combustion process is simple and efficient, although a few pre-
cautionary measures are necessary while performing the process, either
for safety reasons or for intrinsic limitations of this methodology.
(i) Knowledge of parameters. Complete information about the fuel and
its behavior should be compiled. Initially, small batch reactions are
useful to understand the behavior of the fuel, the oxidants and the
other synthesis parameters, in order to establish synthesis-struc-
ture-properties relationships, which are essential for preparing
reproducible and high performance materials. A special care
should be taken in understanding the mechanisms of the com-
bustion process, through a deep characterization of the gas output
and of the combustion mass transformations during the synthesis
through complementary techniques, as suggested by Nersisyan
et al. [32••]. This could be very useful as well for safety reasons (see
also point (ii)).
(ii) Safety issues. The combustion process is spontaneous and vigorous
and safety issues must be carefully considered [63]. A large
amount of heat (exothermicity) is released in a very short duration.
F. Deganello, A.K. Tyagi
(iii) Reactivity and sensitivity of the powder. Combustion-synthesized
(iv) Yield. A main drawback of SCS is that some powder is lost due to
Fig. 7.4.1. Set-up for the SCS with a 1 L stainless steel beaker.
There must be an arrangement for safe ventilation of the gaseous
products to avoid any kind of damage to the experimenter. Com-
bustion process should be carried out in a wide mouthed appa-
ratus, with large volumes. In general, narrow opening containers
may lead to an explosion during the evolution of large volume of
gaseous products. Nevertheless, Wang et al. recently proposed an
airless system for the preparation of Fe3O4 by SCS in a beaker with
a perforated rubber plug and they succeeded in the synthesis [188]
(Fig. 9.1). Another half-closed system has been proposed by
Deshpande et al. [115] (Fig. 9.2), which allows performing ex-
periments under air, argon or oxygen. Other closed and half-closed
set-ups have been described in the literature [87,243•]. The
53
Progress in Crystal Growth and Characterization of Materials 64 (2018) 23–61
Fig. 7.3.2. Variation of the maximum, combustion tempera-
ture at increasing copper nitrate concentration in the initial
solution, used for the preparation of Cu-Cr-O spinels by SCS.
The blu line corresponds to the first peak and the red line
corresponds to the second peak in the temperature/times
profiles [Reprinted from Ceramics International, 43, V.
Novikov, G. Xanthopoulou, Yu. Knysh, A.P. Amosov, Solution
Combustion Synthesis of nanoscale Cu-Cr-O spinels: Mechanism,
properties and catalytic activity in CO oxidation, pages
11,733–11,742. Copyright (2017), with permission from
Elsevier, License number 4,192,870,485,503].
vigorous SCS process can be also contained in a microreactor array
system for combinatorial synthesis [242].
Another drawback is the possible production of hazardous gases,
like NOx and CO, derived from an incomplete combustion
[32••,33••,60a••,90•,177••]. Therefore, in the choice of the fuel
type/amount, safety and environmental issues have to be carefully
considered. Stoichiometric Φ values and fuels that favor a rapid
and complete combustion are generally recommended. If the
combustion process is too much violent at stoichiometric Φ values,
the use of mixed fuels might be a good choice, when the secondary
fuel helps in controlling the intensity of the combustion process
[170]. In the case of industrial scale-up combustion processes, NOx
abatement reactors are recommended [33••,177••].
Overall, the high degree of control of the process through the se-
lection of the fuel-related parameters allows taking all the required
safety measurements even in scale up and mass combustion reac-
tions. In fact, a self-sustained smoldering combustion process - si-
milar to the combustion process occurring in SCS - has been ap-
plied as safe and efficient alternative to the incineration of the
solid or liquid wastes, by embedding the wastes in a porous matrix,
to promote high surface area for heat and mass transfer [248].
powders are very reactive due to their high surface area. The right
conditions of calcinations and their proper storage in desiccators
are recommended to avoid any attack from atmospheric gases (e.g.
formation of carbonates due to attack of atmospheric carbon di-
oxide) and moisture.
the evolution of gases in the combustion process or due to the
formation of a “soufflé” of powder coming out of the combustion
beaker, as for example it occurs often when sucrose is use as a fuel
[41] (Fig. 9.3).
Up to about 20 wt. % of the calculated amount is often lost during
combustion due to the large amount of gas evolved in few seconds,
although the amount of lost powder depends on the intensity of the
process and in turn on the chemical composition of the final
powder, the fuel type/amount, the proportion of the combustion
mass to the combustion beaker, the beaker type, the ignition
mode/type [15••,123•]. This inconvenience can be partially over-
come by using special combustion reactors [49•] or fixing a pro-
tective grid over the combustion beaker [27,103•,191], although,
these solutions are not applicable in the case of violent gas evo-
lution. Alternatively, a semi-closed system can be used (see also
F. Deganello, A.K. Tyagi
Fig. 8.1. Reproducibility of the crystal size (a) and cell parameters (b) evolu-
tion for (Fe, Co)(Cr, Al)2O4 pigments prepared by SCS over the chemical
composition for Fe1-ΨCoΨCr2-2ΨAl2ΨO4 (0 ≤ Ψ ≤ 1), where Ψ = 0 corresponds
to FeCr2O4 and Ψ = 1 to CoAl2O4 spinels [Reprinted from Ceramics
International, 42, J. Gilabert, M. D. Palacios, V. Sanz, S. Mestre, Characteristics
reproducibility of (Fe, Co)(Cr, Al)2O4 pigments obtained by solution combustion
synthesis, pages 12,880–12,887. Copyright (2016), with permission from
Elsevier, License number 4,192,870,903,532].
point (ii)), with the double advantage of the powder loosing pre-
vention and possibility to collect and examine the evolved gases
(Fig. 9.2).
(v) Importance of controlling parameters. The high versatility of SCS is
mainly due to the high number of parameters that can be changed
in order to produce a material with the required properties. If some
of these parameters can not be controlled (because of a lacking of
knowledge or because of other circumstances), reproducibility is
not fully ensured in SCS (see Section 8). Therefore, it must be taken
into consideration that SCS is a powerful methodology only when
all the relevant synthesis parameters are controlled and their effect
on the materials properties is well known.
(vi) Presence of carbon residues (see also Section 6.2). A varying per-
centage of residual carbon is often present in the as-burned pow-
ders prepared by SCS [78,79,103•,147•], unless fuels that do not
contains carbon atoms are used, like for example hydrazine [87].
The amount of residual carbon essentially depends on the fuel type
and amount, although it may be as well connected with other
54
Progress in Crystal Growth and Characterization of Materials 64 (2018) 23–61
Fig. 8.2. General scheme (a) and actual view (b) of the apparatus for con-
tinuous combustion synthesis of nanopowders by using the impregnated active
layer (IALC) method [a) Reprinted from Current Opinion in Solid State and
Materials Science, 12, S.T. Aruna, A. S. Mukasyan, Combustion synthesis and
nanomaterials, pages 44–50. Copyright (2008), with permission of Elsevier,
License number 4,192,871,133,212; b) Reprinted from A. S. Mukasyan, P.
Dinka, Novel Approaches to Solution–Combustion Synthesis of Nanomaterials,
INTERNATIONAL JOURNAL OF SELF-PROPAGATING HIGH-TEMPERATURE
SYNTHESIS, 16 (2007) 23–35, with email permission of Allerton Press].
factors, as for example the geometry/type of beaker, the amount of
powder produced and the presence of external templates. The
presence of carbonate or carbonate-like residues in LaFeO3 per-
ovskites has been detected as well in the calcined powders, when
citric acid was used as a fuel [129,249] or, in higher proportion,
when a waste-derived complex polymer was used as a fuel [40••]. It
has been found that the presence of residual carbonates in LaFeO3
has an evident effect on its dielectric and resistance behavior
[129]. It has also been reported that these carbonate residues
might be responsible to alter the surface charge of the perovskite,
favoring interaction with some specific wastewater organic sub-
strates [40••].
If metal-carbon and metal oxide/carbon nanocomposites have to be
prepared (see Section 6.2), the presence of residual carbon is not a
problem.
It is evident from the literature that the type and amount of such
residual carbonates depends on the type of fuel and on the calcination
temperature [40••,129,249]. If residual carbon represents a problem,
the calcined powder can be partially or totally cleaned by an ultrasonic
treatment followed by drying [40••].
10. Conclusions and perspectives
Solution combustion synthesis is an old concept, although it has
F. Deganello, A.K. Tyagi
Fig. 9.2. An example of a closed experimental setup for SCS for the direct
synthesis of magnetite nanopowders [Reprinted with permission from K.
Deshpande, A. Mukasyan, A.Varma, Direct Synthesis of Iron Oxide Nanopowders
by the Combustion Approach: Reaction Mechanism and Properties, Chem. Mater.,
16 (2004) 4896–4904. Copyright (2004) American Chemical Society].
been capable of evolving over time, becoming a methodology of choice
in all the environment and energy-related issues. Its distinctive features
can be summarized in Fig. 10.2 and discussed in the following.
A minimum amount of water is necessary for the formation of a gel
network, essential requirement for the homogeneous disposition of the
metal cation network, although the presence of some insoluble com-
ponents is also acceptable in SCS. The insoluble precursors interact with
the other soluble components through surface adsorption. The con-
sciousness about this aspect easily extends the applicability of SCS to
other natural and waste-derived organic and inorganic precursors.
The SCS procedures proposed in the literature are a consistent
number, only limited by the number of different materials that can be
prepared by this methodology, from nanostructured simple oxides to
complex nanocomposites. Special scale-up procedures have been as
well developed, for the industrial production of SCS products, high-
lighting the high degree of control that this methodology is capable on
the final material.
The choice of the SCS parameters depends on various factors: fuel
type, fuel amount, metal precursors type, chemical composition, etc.,
all affecting the final properties of the powder. Moreover, in the se-
lection of the synthesis parameters, a sustainable choice is also possible
and should be always considered. New multiple classifications were
55
Progress in Crystal Growth and Characterization of Materials 64 (2018) 23–61
Fig. 9.1. An example of half-closed and
airless system for the solution com-
bustion synthesis of Fe3O4 powders
from glycine as a fuel and ferric nitrate
as metal precursor [Reprinted from
Journal of Alloys and Compounds, 719,
X. Wang, M. Qin, F. Fang, B. Jia, H. Wu,
A. A. Volinsky, X.Qu, Effect of glycine on
one-step solution combustion synthesis of
magnetite nanoparticles, pages 288–295.
Copyright (2017), with permission
from Elsevier, License number
4,192,870,250,685].
proposed both for the fuels and for the metal cations, helping to select
properly the type of fuel and of the metal cation precursors and to fix a
sort of identikit of the fuel or fuel mixture. From this review it clearly
emerges that the choice of SCS parameters is not a simple choice, but a
multiperspective choice, according to the multiple aspects to consider
and to the multiple possibilities offered to the chemist, in particular,
and to the materials scientist, in general. It should be specifically re-
minded that the fuel plays a pivotal role in the powder properties,
which are strictly connected with the fuel features and amount.
Chemical composition of the final material should also be taken into
consideration in the choice of the SCS parameters, especially con-
cerning the formation temperature of the desired phase, the presence of
mixed valence cations and the extent of interaction of specific metal
cations with the fuel mixture.
A detailed knowledge of the main SCS parameters and their careful
control are of paramount importance, ensuring a better quality of the
products. Especially regarding energy and environmental applications,
the most important SCS parameters to be controlled in the synthesis are
fuel type, fuel amount (Φ and fuels-to-metal cations ratio), pH, type of
metal precursors, external template. As described in Fig. 10.2, the
materials properties that can be controlled by these SCS main para-
meters are phase composition, metastable phases formation, micro-
structure, morphology, texture, redox properties, defectivity, surface
etc.. According to the figure, the fuel and fuel-related parameters affect
all the materials properties and must be controlled with high accuracy
(Fig. 10.2, grey parameters). Another interesting observation is that
almost all parameters are able to affect the microstructural-morpholo-
gical-textural properties (Fig. 10.1, orange connections), allowing a
wider range of optimization for these very important properties.
Without a careful and detailed knowledge of the SCS parameters af-
fecting the products properties, the number of SCS parameters and their
effect on the final materials properties might be an obstacle to the re-
producibility of the synthesis.
This review also draws attention to all the sustainable and eco-
friendly aspects of solution combustion synthesis as a valuable tool for
the preparation of inorganic nanomaterials for energy and environ-
mental applications. The possibility to use soluble as well as insoluble
precursors further widens the horizons of this versatile methodology,
opening the way to the flexible use of natural and waste-derived pre-
cursors for the eco-sustainable synthesis of nanomaterials.
In summary, SCS can be used successfully for the preparation of
materials for energy and environmental purposes, enabling a sustain-
able synthesis that can be applied to a variety of precursors to prepare a
variety of materials. This preparation methodology has been capable of
growing with technology and development and it is expected that it will
continue growing in the future, with new approaches and strategies for
the materials preparation. As a further advantage, this methodology
concerns the materials chemistry of the future, which is already - and is
going to become more and more – a sustainable transformation of
F. Deganello, A.K. Tyagi Progress in Crystal Growth and Characterization of Materials 64 (2018) 23–61

Fig. 9.3. Self-propagated combustion processes by using a) citric acid b) tartaric acid c) sucrose and d) lactic acid as fuels [Reprinted from J. Supercond Nov Magn,
Effect of Fuel on the Synthesis, Structural, and Magnetic Properties of M-Type Hexagonal SrFe12O19 Nanoparticles, 28 (2015) 1589, S. K. Chawla, Prabhjyot Kaur, R. K.
Mudsainiyan, S. S. Meena, S. M. Yusuf, with permission of Springer, License number 4,192,880,238,845].

Fig. 10.1. Distinctive properties of Solution Combustion Synthesis (SCS).

56
F. Deganello, A.K. Tyagi
Fig. 10.2. The six most important SCS parameters affecting the relevant properties of materials for energy and environmental applications.
waste-derived and natural precursors into valuable products.
This paper highlights that traditional solution-based synthesis
methods, like precipitation, co-precipitation and sol-gel techniques, are
just a part of SCS, which, in facts, represents a complex methodology
that connects very well many different aspects of the materials synth-
esis, including those pertaining the traditional preparation methods. In
addition, SCS means the opportunity to connect research to industry,
research to technological development, research to sustainable society.
Finally, coming back to the beginning of the story, SCS embraces all
together the words mentioned in the Introduction Section, like “sus-
tainability”, “green”, “eco-compatibility”, “ecofriendly”, “environmental
benefits”, “energy saving”, “renewable”, “circular economy”, “efficiency”,
and, apparently, its versatility and potentiality is only limited by the
creativity of the scientists that use it.
Recommended reading
Papers of particular interest, published within the period of review,
have been highlighted as:
• Paper of special interest.
•• Paper of outstanding interest.
Acknowledgments
Prof. N.B. Singh (UMBC Baltimore, USA) is greatly acknowledged
for his encouragement in writing this review. The authors thank all the
coauthors from reference papers n° 15, 54, 134, 40, 137, 141, 249, 72,
73, 75, 123, 128, 151, 159, 176, 186 for their valuable contribute to the
research about SCS during the last 15 years.
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