Materials Science and Engineering R 117 (2017) 1–25

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Materials Science and Engineering R

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

Review

Bio-based flame retardants: When nature meets fire protection

Lucie Costesa,b , Fouad Laoutida,* , Sylvain Brohezb , Philippe Duboisa,c
a
Laboratory of Polymeric & Composite Materials, Materia Nova Research Center, University of Mons UMONS, Place du Parc 23, B-7000 Mons, Belgium
b
Service de Génie des Procédés Chimiques et Biochimiques, Faculté Polytechnique, University of Mons UMONS,Place du Parc 23, B-7000 Mons, Belgium
c
Luxembourg Institute of Science and Technology, Department Materials Research and Technology, Z.A.E. Robert Steichen, 5 rue Bommel, L-4940 Hautcharage,
Luxembourg

A R T I C L E I N F O A B S T R A C T

Article history:
Received 13 December 2016 Fire retardancy of polymeric materials is a subject of major preoccupation due to the need to minimize
Received in revised form 9 March 2017 fire risk and meet fire safety requirements. Numerous efficient conventional flame retardants based on
Accepted 18 April 2017 halogen, mineral, and other compounds have been developed. However, some of these compounds,
Available online 29 April 2017 particularly halogen flame retardants, are harmful to our health and the environment, and their use has
been restricted. In addition, the increasing concern about the reduction of the ecological footprint of
Keywords: materials, has encouraged the development of new plastics and additives made from renewable
Fire retardant resources. As a result, renewed interest is emerging for the development of sustainable solutions for
Bio-based
flame retardants for polymeric materials. This paper focuses on the identification of biomass compounds
Biomass
that have a potential as flame retardants for polymers due to their high availability and inherent
Sustainable
properties. The last section of this paper explores the recent progress in flame retardant systems, based
on the use of renewable products, which constitutes a promising approach to provide materials with
improved fire resistance.
© 2017 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Toward the development of bio-based flame retardants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.1. Saccharide-based products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1.1. Cellulose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1.2. Hemicellulose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.1.3. Starch, cyclodextrin and isosorbide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.1.4. Chitosan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.1.5. Other saccharide-based compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
2.2. Bio-based aromatic products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
2.2.1. Lignin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
2.2.2. Other bio-based aromatic compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.3. DNA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18

Abbreviations: ABS, acrylonitrile butadiene styrene; Al-Phyt, aluminum phytate; APP, ammonium polyphosphate; B.C., before Christ; CH or CS, chitosan; CO, carbon
monoxide; CO2, carbon dioxide; COT, cotton; CP, cellulose propionate; CuSO4, copper sulfate; DMF, dimethylformamide; DNA, deoxyribonucleic acid; Et3N, trimethylamine;
EVA, ethylene vinyl acetate; Fe(NO3)3, iron nitrate; Fe-Phyt, iron phytate; GDP, gross domestic product; GPCS, glycidyl phosphorous chitosan; HCHO, formaldehyde; H2O,
water; HSO3
, hydrogen sulfite ion; IFR, intumescent flame retardant; KCl, potassium chloride; K2CO3, potassium carbonate; La-Phyt, lanthanum phytate; LbL, layer by layer;
LDH, layered double hydroxide; LOI, limit oxygen index; MCC, microcrystalline cellulose; MCC-P, phosphorylated microcrystalline cellulose; MgCl2, magnesium chloride;
MMT, montmorillonite; NaCl, sodium chloride; NaOH, sodium hydroxide; Na-Phyt, sodium phytate; Na2CO3, sodium carbonate; Na2S, sodium sulfide; NCC, nanocrystalline
cellulose; NH4OH, ammonium hydroxide; NiCl2, nickel chloride; PA, phytic acid; PCL, phosphorylated cellulose; PEC, polyelectrolyte; PEI, polyethylenimine; PER,
pentaerythritol; PET, polyethylene terephthalate; pHRR, peak of heat release rate; PLA, polylactide; PNFC, POSS-modified nanofibrillated cellulose; POCl3, phosphoryl
chloride; POSS, polyoligosilsesquioxane; PP, polypropylene; PT, phosphorylated chitin; PU, polyurethane Tg glass transition temperature; TG-DTG, thermogravimetric-
derivative thermogravimetric; THR, total heat released; TNT, titanate nanotubes; ZnCl2, zinc chloride.
* Corresponding author.
E-mail address: [email protected] (F. Laoutid).

http://dx.doi.org/10.1016/j.mser.2017.04.001
0927-796X/© 2017 Elsevier B.V. All rights reserved.
2 L. Costes et al. / Materials Science and Engineering R 117 (2017) 1–25

2.4. Proteins . . . . . . . . . . . .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

2.5. Phytic acid . . . . . . . . . .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
2.6. Vegetable oils . . . . . . .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
3. Conclusions and perspectives ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
References . . . . . . . . . . . . . . .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23

1. Introduction Moreover, the world demand in energy for the transport sector
was approximately 84 million barrels per day in 2010 and it was
Fire hazard is a constant risk in everyday life because of the estimated to increase to about 116 million barrels per day by 2030
massive use of combustible materials, such as fabrics, polymeric [5]. The Intergovernmental Panel on Climate Change has
materials and wood. The Increased use of systems to prevent fires highlighted in a report that this growing demand is leading to a
or to stop them, such as smoke alarms, sprinklers and emergency rapid increase in greenhouse gas emissions [6]. To reduce CO2 gas
exit plans, has enabled a significant reduction in the number of emissions while meeting the increased energy demand, the
deaths by fire since the late 1900s. Even with these improvements, utilization of renewable instead of fossil resources seems to be a
fire is still an important issue, which costs approximately 1% of feasible option. Renewable carbon sources enable industrial
global gross domestic product (GDP) per year, and causes several processes to be nearly CO2 neutral since bio-based products
thousand deaths in Europe alone [1]. Moreover, in the second half release no more CO2 at the end of their life than was originally
of the 20th century, polymeric materials, which are easily metabolized in the biological production of the raw material.
combustible, became the most universally used materials. These During photosynthesis, plants use sunlight to convert water and
multipurpose materials, which are now essential to modern life carbon dioxide from the atmosphere into carbohydrates [7]. While
[2], have been important to the global economy for many years, in the case of fossil-based products, the CO2 released at the end of
and the plastic industry experienced yearly growth of 8.7% their life was geologically sequestered for millennia, which has
between 1950 and 2012. In order to minimize fire risk and meet been demonstrated to have an impact on the environment [8].
fire safety requirements, solutions to prevent the ignition of the For several decades, the biorefinery has appeared to be an
materials, or to lower the heat released during their combustion, efficient approach for the transformation of biomass components
have been developed and they act by interfering with the processes into biofuels, bio-energy (heat and power) and bio-based chemical
involved in polymer combustion using various physical or products and materials, in the same way as a petroleum refinery
chemical strategies. The main categories of compounds for does for fossil based resources. The difference between the
improving fire behavior are mineral, halogenated, phosphorus- petrochemical industry and a biorefinery lies in the highly
containing, nitrogen-containing, silicon-containing, and nano- oxygen-functionalized bio-based feedstock in comparison to the
metric compounds [3]. Mineral flame retardants, such as alumi- hydro-carbon based fossil resources [9]. Biorefineries are facilities
num trihydroxide, are very efficient in decreasing fire hazard and that convert biomass, i.e. biological materials from living or
they are widely used. However, a large amount must be recently living organisms, into bio-based products. A biorefinery
incorporated to achieve the expected improved fire properties can use a wide range of different feedstocks as input and various
and these additives can cause material defects. Halogenated flame process technologies to convert them. The input products of the
retardants, which have been used since the 1930s, represent a cost- first generation of biorefineries are mainly edible biomass
effective technology, acting in the vapor phase by scavenging products, such as sugar-rich, starch-rich and oily plants, whose
reactive free radicals by releasing halogen radicals that inhibit can be controversial because of the need to use these resources for
combustion. However, due to environmental and health concerns, food. However, the second-generation of biorefineries overcome
the use of halogenated flame retardants has been increasingly this problem by treating residual non-food parts of crops and other
avoided and restricted [4]. Some of these products have been non-food sources, such as grasses and algae. The inedible
proven to be linked to cancer, reproductive problems and impaired lignocellulosic materials which are found in plants and composed
fetal brain development. Moreover, during combustion, they of cellulose, lignin and hemicelluloses represent a promising
induce an increase in smoke and corrosive gases, and they are feedstock to convert into useful bio-based products in biorefi-
persistent environment pollutants if they migrate out of the neries. The wide development of these biorefineries made biomass
polymer matrix. Three halogenated products are currently components more and more easily available for many applications.
forbidden: penta- and octa-bromodiphenyl ether and hexabro- Furthermore, the economic viability of biorefineries requires the
mocyclododecane. To address these problems, considerable use of some of their production for high value applications such as
attention must be devoted to the development of halogen-free flame retardant additives [8].
flame retardant additives. Flame retardant systems that promote This paper, which aims to present recent developments in the
the formation of an insulating char layer on the surface of the valorization of biomass as flame retardant additives for polymeric
burning sample are among the most promising environmentally materials, provides a presentation of the main biomass compo-
friendly strategies for replacing halogenated flame retardants. nents able to generate char during their thermal decomposition
They have indeed proven to be efficient in improving the fire and the recent developments of bio-based flame retardant
behavior of many polymer matrices, while reducing the amount of additives.
smoke released as a result of their condensed phase action. Today,
new solutions of such flame retardants, based on renewable 2. Toward the development of bio-based flame retardants
resources, are attracting great interest, due to their availability and
the growing awareness of environmental issues linked to the Fire retardant additives have high-value applications for which
increased use of fossil feedstock. Furthermore, the development of some biomass constituents are predisposed. In nature, certain
flame retardant systems from renewable resources is suitable for lignocellulosic plants have developed defense behaviors against
supporting the increasingly use of bio-based polymers in many fire aggression. This is the case of cork oak that is more fire-
technical fields, maintaining thus their sustainability and preserv- resistant than other trees owing to the slow combustion of cork,
ing their good environmental impact. containing mainly suberin (waxy substance composed of
 L. Costes et al. / Materials Science and Engineering R 117 (2017) 1–25 3

polyaliphatic and polyaromatic domains interlinked by glycerol),

cellulose and lignin. These bio-based compounds owe their
advantages as flame retardant additives to their molecular
composition and structure providing them inherent ability to
produce thermally stable charred residues when exposed to fire.
The char formation during the burning of wood is well known [10].
When exposed to heat, the temperature of the wood surface
increases, the water adsorbed in the wood starts to be released and
the decomposition of the wood constituents, i.e. lignin, cellulose
and hemicelluloses, begins around 160–180  C. At 350–360  C,
ignition of the wood can occur in the presence of a spark, and the
accelerated degradation leads to the formation of a charred layer
which acts as an insulator for the underlying wood (Fig. 1).
This charring competency is particularly important for devel-
oping effective flame retardant systems. During the combustion,
charring flame retardant systems act by creating an insulating
layer at the surface of the burning material resulting in the Fig. 2. Thermogravimetric analysis of cellulose, xylan and lignin (10  C/min, under
improvement of its fire behavior by reducing both the thermal and N2) (reproduced from [11] with permission).
oxygen diffusion, as well as the volatilization of combustible
products. Therefore, it is of interest to describe and understand the Biomass components are used by industry to produce large
thermal degradation of lignocellulosic biomass compounds ranges of chemicals and biofuels and have the advantage of
allowing for some char formation. Fig. 2 exhibits the weight loss growing rapidly at a reasonable cost. All of these bio-based
curves of the three main components of lignocellulosic biomass compounds are also interesting for flame retardant applications,
during pyrolysis: cellulose, hemicellulose and lignin. Xylan, which since they are able to produce, in some conditions, a char layer
is the most important representative hemicellulose, has the lowest during their thermal decomposition.
thermal stability, while cellulose is the most stable compound with
the highest onset degradation temperature, but without formation 2.1. Saccharide-based products
of any char residue. Indeed, lignin and xylan appear to have better
char-forming ability than cellulose. However, this char-forming 2.1.1. Cellulose
ability can be modified and improved in some conditions, as Cellulose, the most abundant biopolymer in nature, with 1.1010
explained in the following. to 1.1011 tons produced annually [8], accounts for about half of the
Biomass, the largest reservoir of renewable carbon, is consti- atmospheric CO2 fixed through photosynthesis [16]. It is a fibrous
tuted by about 75% saccharide-based products, usually called component principally found in the cell wall of higher plants as
“carbohydrates”. Carbohydrate is now an obsolete and too-general well as in bacteria, fungi and algae. Cellulose is a polymer formed
term derived from the Greek words Carbo (for Carbon) and hydor by chains of glucose units. Its degree of polymerization ranges from
(for water) indicating that carbohydrates are “hydrates” of carbon. 100 to 40,000, and depends on both its botanical origin and the
However, this is not always true since “carbohydrates” don’t have different treatments used for its extraction. Cellulose chains are
the empirical formula Cm(H2O)n. Saccharide-based products is thus arranged in a tridimensional structure that is stabilized by
much more accurate. These products are mainly produced by hydrogen bonds, van der Waals bonds and hydrophobic inter-
plants through photosynthesis. They are located in plant cell walls actions. The organization of cellulose chains results in the
(Fig. 3) where they serve as structural components (e.g. cellulose, formation of microfibrils that are grouped together to form
hemicelluloses) or in storage organs (seeds, tubers, roots) where cellulose fibers (Fig. 4) containing both crystalline and amorphous
they act as a source of energy (e.g. starch). The structures and regions.
properties of saccharide-based compounds have been intensely Many pre-treatments, including chemical, physical, biological,
and widely studied in the literature [12–14]. Biomass is also mechanical, and combinatorial pre-treatments exist for the
constituted, in less extent, by other renewable products such as fractionation of biomass into its different components and enable
proteins, aromatic compounds, or oils for example. the isolation of cellulose [17]. The most common technique for the
extraction of cellulose from lignocellulosic fibers has been
developed for paper production [18]. In the first step, a pulp is
produced by a mechanical or chemical pulping process. During the
second step, the bleaching, cellulose is purified by a chemical
mixture such as hydrogen peroxide. The treatment of cellulose
fibers with a strong acid can result in the formation of cellulose
nanocrystals. The highly cellulose crystalline regions can be
extracted since acids can easily penetrate into the amorphous
regions having a low level of order and hydrolyze them. The control
of the acid strength, the temperature and the time of hydrolysis is
primordial for the production of micro or nano crystalline
cellulose.
During its thermal decomposition, cellulose can produce
charred structures in some conditions. The chemical reactions
involved during cellulose thermal decomposition and the mecha-
nisms leading to the formation of char are very complex, still
ambiguous and controversial [15,20]. The amount of char formed
and its thermal stability are affected by the thermal degradation
Fig. 1. Heat transfer in the charring wood sample. Adapted by author from [10]. conditions as well as by the surrounding components during
4 L. Costes et al. / Materials Science and Engineering R 117 (2017) 1–25

Fig. 3. Schematic representation of the plant cell wall with the location of the main components in biomass. Adapted by author from [15].

Fig. 4. Representation of a cellulose fiber showing its organization. Adapted by author from [19].

cellulose pyrolysis. According to Broido’s research group, the pyrolysis time. Low heating rates and low temperature treatments
decomposition of cellulose can be represented through two favor the dehydration reactions and the rearrangement of the
competing reactions [21] (Fig. 5). The first step, occurring below cellulose structure resulting in increased char production [24]. The
280  C and leading to the formation of anhydrocellulose, is lower the heating rate is, the higher the residual carbonaceous char
enhanced for low temperatures and a slow heating rate. At higher production is (Fig. 7) [25,26], due to the fact that the activation
temperatures, a competitive, more endothermic unzipping reac- energy of the dehydration reactions is lower than that of the
tion is initiated for the remaining cellulose. This unzipping reaction transglycosylation reaction or the C

C bond cleavage [27].
leads to the formation of tar, while anhydrocellulose undergoes an Furthermore, long residence time can also favor secondary
exothermic decomposition resulting in the formation of char and reactions between released volatile gases and char, increasing
gas (third step). the yield of solid structures [15]. On the contrary, higher
However, Broido’s first kinetic model has been re-examined by temperatures, short residence time and fast pyrolysis promote
Broido and Nelson [22] and their results show that the formation of the depolymerization of the cellulose, enhancing the yield of
anhydrocellulose as an intermediate product is undetectable. volatile products and reducing the solid products. In some specific
Recently, some researchers proposed a more complex kinetic conditions, the favored transglycosylation allowed for the produc-
model considering the formation of “active cellulose”, from the tion of up to 60 wt% levoglucosan [28].
scission of the glycosidic bond and without mass loss, as an The specific characteristics of cellulose, such as its crystallinity,
intermediate step during cellulose pyrolysis [23] (Fig. 6). degree of polymerization, and particle size, can also influence its
The thermal degradation pathway of cellulose can be strongly thermal degradation pathway. A higher crystallinity seems to
affected by the modification of both temperature conditions and increase the quantity of levoglucosan formation and hence reduces

Fig. 5. Kinetic model for cellulose pyrolysis proposed by Broido [21].

 L. Costes et al. / Materials Science and Engineering R 117 (2017) 1–25 5

Fig. 6. Kinetic model for cellulose pyrolysis proposed by Wooten et al. [23].

the char production [29] because the activation energy of pyrolysis solutions, phosphorus-based compounds seem to be the most
of highly crystalline cellulose is close to that of the cleavage of the efficient for these kinds of materials. In 1735, Gay-Lussac was the
glycosidic bond. A higher degree of polymerization of cellulose first to propose a flame-retardant system based on ammonium
yields a lower pyrolysis rate. On the contrary, an increase in the phosphate combined with boric acid, alum solution and iron
surface area of cellulose particles accelerates its decomposition sulfate. Today, cellulose is widely used in many applications such
due to the larger interface available [20]. This could result in as textiles, making paper, as a cheap mechanical reinforcing agent
intensification of charring thanks to more interactions and in polymers, and thus there is still an important issue in terms of its
secondary reactions between the volatile products created and fire behavior. Important research has been carried out to fireproof
the char already formed. cellulosic materials by improving their char forming ability by
The presence of other components during the pyrolysis of combining them with other flame retardant agents or chemically
cellulose also influences its degradation pathway. Some inorganic modifying them [33–37]. As a result, more and more researchers
salts, naturally present in the biomass, such as mineral compounds are trying to take advantage of this char forming property of
in the ash, promote the formation of condensed structures through cellulose to develop new flame retardant additives for polymeric
the catalysis of the dehydration reactions of cellulose upstream materials or to enhance the performances of flame retardant
from the depolymerization reactions, enhancing the yield of solid systems.
products. Several studies have demonstrated a significant catalytic Cellulose surface modification has been reported as an efficient
effect inducing a decrease in the first degradation temperature and way to promote char formation during thermal degradation. Fox
an increase in the amount of char obtained by combining cellulose et al. [38] reported a 5-fold increase in char during anaerobic
and some inorganic salts such as CuSO4, NaOH, Na2CO3, NiCl2, NaCl thermal degradation of nanofibrillated cellulose treated with
[30], MgCl2, ZnCl2 [31], K2CO3, and KCl [32] (Fig. 8). glycidyl phenyl polyhedral oligomeric silsesquioxane. Dobele et al.
The pyrolysis behavior of cellulose is also significantly modified [39] showed that the impregnation of cellulose with more than 5%
by the presence of other biomass organic constituents. As far as of phosphoric acid leads to an important reduction of levogluco-
natural fibers are concerned, Dorez et al. [11] reported that the senone production during pyrolysis. It is worth mentioning that
presence of a low content of lignin with a high content of cellulose levoglucosenone, which is a dehydrated cyclic structure, results
leads to charring by modifying the cellulose degradation pathway, from cellulose depolymerization, and its amount depends on the
promoting the dehydration reactions and the char formation at the amount of phosphoric acid impregnated. A high impregnation of
expense of the depolymerization. phosphoric acid (more than 5%) resulted in a decreased yield of
From a historical point of view, cellulose based materials, such levoglucosenone, indicating the promotion of dehydration reac-
as cotton or flax based fabrics and wood, have always been tions leading to the formation of condensed structures.
considered to be materials with a high risk of ignition and fire Cellulose has the advantage of being easily functionalized, since
propagation. Likewise, the first flame retardant additives were it contains a high amount of hydroxyl functions: three reactive
developed to improve the fire properties of these lignocellulosic hydroxyl functions in positions C-2, C-3, and C-6. This structure
materials. One of the first uses of flame retardants dates back to the offers the possibility of modifying cellulose by all the usual
siege of Piraeus (83 B.C.), in which alum solutions were used to reactions existing for primary alcohols (C-6), secondary alcohols
make wooden walls fire resistant. Among all flame-retardant (C-2 and C-3), ether linkages (b-(1–4) bond), and C

C linkages (C-
2-C-3 bond) [40]. Esterification is the most commonly used and
easiest reaction for the functionalization of cellulose. However,

Fig. 7. Non-isothermal thermogravimetric curves for cellulose pyrolysis in inert gas Fig. 8. TG-DTG curves of pure cellulose and impregnated cellulose (reproduced
at different heating rates (reproduced from [26] with permission). from [31] with permission).
6 L. Costes et al. / Materials Science and Engineering R 117 (2017) 1–25

some difficulties remain, particularly the accessibility of the cellulose (MCC-P), using the same phosphorous acid-urea-
reactive functions due to the highly organized supramolecular modification, was incorporated alone or in combination with a
structure of cellulose resulting from the presence of crystalline bio-based phosphorous compound, aluminum phytate salt (Al-
domains, hydrogen bonds, van der Waal bonds, and hydrophobic Phyt), in PLA to improve its fire behavior [49]. The incorporation of
interactions. 20 wt% MCC-P permitted a slight decrease of the pHRR with
The chemical modification of cellulose is an interesting way to respect to neat PLA in a cone calorimeter test, although it led to a
tailor cellulose properties and enhance its fire-retardant behavior. UL 94 V-0 rating. Using MCC-P alone did not enable the rapid
The phosphorylation of cellulose is the most extensively explored formation of a homogenous charred layer. It had to be combined
modification for improving its char-forming ability, and hence its with Al-Phyt, in PLA, prior to reaching a significant pHRR reduction
fire retardant properties [40,41]. Indeed, the presence of phospho- and a UL 94 V-2 classification. The presence of Al-Phyt in
rus-containing compounds proves to be efficient for catalyzing the combination with MCC-P resulted in the fast formation of the
thermal degradation of cellulose and for favoring the formation of charred layer, which had a homogenous and cohesive morphology,
solid products instead of volatile gases. Phosphorylation was first because of the catalytic effect of aluminum, and the high
developed to improve the fire resistance of fabrics [33–36]. phosphorus content, which modified the degradation mechanism
Numerous publications are dedicated to the development of of cellulose towards char formation. Aoki et al. [50] also found that
phosphorylation reactions for cellulose and are well reviewed by reacting cellulose propionate with alkyl chlorophophates leads to
Illy et al. [42]. This review also provides complete information on cellulose ester derivatives, with phosphoryl side chains, which
the phosphorylation of other renewable resources (other poly- prevent weight loss during pyrolysis by promoting dehydration
saccharides, biophenols . . . ) and it highlights that the main and desaturation reactions of cellulose at lower temperatures,
application of phosphorylated bio-based compounds is polymer encouraging the generation of char. The two phosphorylated
flame retardancy. The phosphorylation reactions of cellulose can cellulose propionates differ by the total proponylation (CP1), or not
be realized through hydroxyl group functionalization with (CP2), of the hydroxyl groups at C6. 20% of the C6 hydroxyls were
phosphoric acid or its salts, phosphorous acid, polyphosphorus free and available for phosphorylation only in the case of CP2. The
compounds, phosphorus pentoxide or phosphorus pentasulfide, authors highlight a difference between the thermal degradation of
halogenated derivatives, phosphonic acid anhydride, or through the CP1 and CP2 phosphorylated derivatives, showing a higher
the grafting of phosphorus-containing polymers. The rate of amount of residue for CP2 phosphorylated derivatives, which they
diffusion of polar phosphorylated molecules in cellulose to obtain a explained by the difference in degree of the C6 hydroxyls
high degree of phosphorylation can be increased by using a phosphorylated between them. Indeed, during the thermal
swelling agent [43,44], and by exploiting microwave energy as an degradation, the CP1 and CP2 derivatives were first desaturated
environmentally friendly solvent-free process [45]. Dahiya et al. in preferential positions (C2/C3 or C6) following the dephosphor-
[46] show that the synthesis of cellulose arylphosphonate ylation (Fig. 9). This led to the formation of more carbonyl groups in
compounds can be considered as a flame retardant treatment the case of CP1, which can participate in a variety of fragmentation
for cellulosic materials, since it results in higher char yields during reactions, leading to vigorous volatilization of flammable products,
thermal degradation. Reacting cellulose with phosphorous acid, in whereas the CP2 degradation resulted in a higher yield of
molten urea, is an interesting pathway that results in highly nonflammable char. The incorporation of the phosphorylated
phosphorylated cellulose derivatives. These cellulose derivatives cellulose propionate derivatives into PLA resulted in a UL 94 V-2
also lead to a high amount of char residue after thermal rating.
degradation due to the creation of polymetaphosphoric acid Fox et al. [51] phosphorylated nanofibrillated cellulose with
structures, inhibiting further decomposition of the cellulose. phosphoric acid, aiming to replace APP in the intumescent flame
However, this phosphorylation reaction leads to the formation retardant system for PLA. They prepared cellulose phosphate fibers
of water soluble cellulose [47,48]. Phosphorylated microcrystalline by soaking them in phosphoric acid/urea mixture, followed by

Fig. 9. Pyrolysis routes of two phosphorylated cellulose propionate derivatives (CP1 and CP2) (reproduced from [50] with permission).
 L. Costes et al. / Materials Science and Engineering R 117 (2017) 1–25 7

neutralization, either with NaOH, or NH4OH. The yield of the superior flame retardant effect of nanocellulose has also been
phosphorylation was low (maximum degree of phosphorylation demonstrated by Fox et al. [51], who obtained V-0 classification in
was 0.78). However, the phosphorylation of cellulose resulted in a the UL-94 test, when nanofibrillated cellulose was combined with
modification of the thermal degradation of cellulose fibers: there ammonium polyphosphate (APP) instead of pentaerythritol (PER)
was a 50  C decrease in both the initial and peak degradation because of the increased melt viscosity induced by the presence of
temperatures, and an increase of over 20% in the char yield. The nanofibrillated cellulose with a high aspect ratio. In addition, the
incorporation of 15 wt% phosphorylated fibers into PLA did not replacement of PER by cellulose fibers increased both the storage
enable a UL 94 classification, contrary to the PLA containing 15 wt% modulus and the glass transition temperature of PLA.
cellulose combined with APP. However, some charring behavior
occurred and the flame went out before it reached the holding 2.1.2. Hemicellulose
clamp. To improve the charring ability of nanofibrillated cellulose Hemicelluloses are composed of highly-branched low molecu-
during its thermal degradation, modification with silicon-con- lar weight chains of different sugars, i.e. a variety of 5-carbon
taining compounds has also been explored [52,53]. Nanofibrillated sugars (D-xylose and L-arabinose), 6-carbon sugars (D-glucose, D-
celluloses have first been encapsulated with polyoligosilsesquiox- galactose, D-mannose) and uronic acid. They can be found in plant
ane (POSS) using an ionic liquid and then used in combination with cell walls where they act as cross-linking material between
APP, as the source of carbon, in an intumescent flame retardant cellulose microfibrils. They contribute to strengthening the cell
system for PLA. The incorporation of 15 wt% APP/POSS-modified wall by interacting with cellulose and lignin [19]. Most of the
nanofibrillated cellulose (PNFC) (3:1) into PLA allowed for a similar hemicelluloses can be extracted from the biomass by using
fire retardant effect when using 15 wt% APP/PER, i.e. similar aqueous alkaline solution treatments [12].
reduction of the heat release rate peak (-45%), and of the total heat Due to the low molecular weight of hemicellulose, its thermal
released (-20%). In addition, it enabled a significant reduction of decomposition is rapid and starts around 180  C, with the
PLA degradation induced by APP during melt processing thanks to maximum weight loss rate between 250 and 350  C [54]. During
cross-linking reactions between the silanol groups of PNFC and the the thermal degradation of hemicellulose, the release of adsorbed
phosphate groups of APP. Limiting PLA number-average molecular water is accompanied by the cleavage of weak side branches. The
weight reduction during melt processing is important for maximum weight loss is obtained by dehydration, decarboxyl-
preserving the mechanical properties of the composite, as well ation, and decarbonylation reactions, which lead to the release of
as for reducing the smoke produced during combustion. volatile gases, such as CO2, CO, H2O, acetic acid, and furfural
Using nano-cellulose instead of micro crystalline cellulose to (Fig. 11). During the main thermal degradation step, some random
improve the flame-retardant behavior of bio-based polymers, such repolymerization between the radicals produced occurs and
as polylactide (PLA), is an efficient approach for reaching better results in the formation of a large amount of char [11]. The better
performances. In a recent study [49], we compared the flame char-forming ability of hemicellulose, compared to cellulose, could
retardant effect of 20 wt% nano (NCC) and micro (MCC) crystalline be explained by the formation of unstable radicals, after the
cellulose. The results show the superior flame retardant effect of cleavage of glycosidic linkages, due to the absence of a sixth carbon
the nano cellulose form, since it enabled an important decrease of and oxygen at the C4, inhibiting the formation of a stabilized
pHRR compared to neat PLA, contrary to microcrystalline cellulose, anhydride. This instability leads to subsequent reactions, such as
which was ineffective. The nanoscale dimensions of NCC led to an transglucosylation and dehydration, to form char [55]. The yield in
increase in the charring effect due to the higher interfacial final residue depends on the type of hemicellulose. Indeed, xylan
interaction between the PLA matrix and cellulose nanoparticles has a higher charring ability than mannose, galactose, and
(Fig. 10). arabinose, due to its highly-branched structure resulting in the
This advantage was also highlighted when both cellulose intense production of radicals and repolymerization [56].
particles have been combined with a bio-based phosphorous flame The thermal degradation of hemicellulose is poorly influenced
retardant additive, i.e. aluminum phytate salt (Al-Phyt). Indeed, a by the other biomass constituents, since its decomposition occurs
reduction of about 40% of pHRR was obtained when 10 wt% NCC at lower temperatures. The presence of minerals can favor ring
particles were combined with 10 wt% Al-Phyt, thanks to the scission with the formation of volatile products, dehydration, and
formation of a more cohesive and homogenous charred layer. The the formation of furans [57]. However, hemicellulose has the

Fig. 10. HRR curves of PLA, PLA/cellulose (MCC or NCC) and PLA/Al-Phyt/cellulose composites (reproduced from [49] with permission).
8 L. Costes et al. / Materials Science and Engineering R 117 (2017) 1–25

Fig. 11. Proposed reaction scheme for xylan pyrolysis (reproduced from [55] with permission).

disadvantage of a lower initial thermal decomposition tempera- of acetylated starch increased with increasing degree of substitu-
ture, which limits its use as filler in polymeric matrices. tion (DS), owing to the low amount of remaining hydroxyl groups
in starch molecules after acetylation. In fact, the substitution of
2.1.3. Starch, cyclodextrin and isosorbide hydroxyl groups by acetyl groups reduced the dehydration reaction
Starch is a polysaccharide composed of amylose, a linear occurring via inter- or intra-molecular reactions. The increase of
polymer made of glucose units, and amylopectin, a highly starch decomposition temperature is very interesting since it
branched polymer containing short glucose segments linked to enables its use in technical polymers, which are processed at high
the main glucose chain [58]. Amylose and amylopectin are temperature.
organized in semi-crystalline structures called starch granules Starch has been mainly used as a carbon source in intumescent
[59]. flame retardant systems [68–71]. Intumescent systems can protect
Starch is separated from proteins and other components by a materials during combustion through the formation of an
chemical treatment using an aqueous solution of sulfur dioxide, expanded carbonized layer. The creation of intumescent systems
sodium hydroxide, protease, sodium carbonate or ammonium usually requires three components: an acid source, a carbonization
hydroxide after the mechanical reduction of the plant material source, and a blowing agent. One of the most common intumescent
(seed, tuber or root) [60]. systems for thermoplastics contains a combination of ammonium
Whatever the nature of native starch, its thermal degradation polyphosphate (APP) and pentaerythritol (PER). The APP acts as the
occurs in three stages. The first step corresponds to a physical acid source, with the release of phosphoric acid, and simulta-
dehydration related to the release of absorbed water. The second neously as the blowing agent, with the release of ammonia. The
stage, which starts at around 300  C, concerns chemical dehydra- PER acts as the carbonization agent. With the increasing
tion and thermal decomposition, with thermal condensation temperature, the degradation of the thermoplastic and the carbon
between hydroxyl groups, leading to the formation of ether source starts, and is catalyzed by the released phosphoric acid,
segments and water liberation. Dehydration of neighboring leading to the formation of radical compounds. The presence of the
hydroxyl groups in the glucose ring also occurs, resulting in the carbonization agent results in the trapping of some degradation
formation of C¼C bonds or ring scission. Aromatic rings, such as products in the solid phase, leading to the creation of P

O

C
interconnected benzene and furan structures are formed at higher links and polyaromatic structures, which are expanded by the gas
temperature. The last stage takes place above 500  C, with released. During the combustion, starch interacts with the other
carbonization reactions and the formation of large conjugated constituents of the intumescent system, such as APP or halogen-
aromatic structures [61–66]. free flame retardants, including nitrogen and phosphorus, and
The thermal decomposition and stability of starch depend leads to the formation of expanded char at the surface of the
mainly on its composition and structure. It has been found that the burning sample, limiting oxygen diffusion and heat transfer. Reti
thermal stability of corn starches decreases with increasing et al. [68] developed a PLA composite containing 12 wt% APP and
amylose content [63]. The chemical modification of starch by 28 wt% starch, with a 32% LOI value. Wang et al. [70] obtained a
grafting new functional groups has also been evidenced to affect its fire-proofed PLA containing 10 wt% starch and 20 wt% intumescent
thermal behavior [64,67]. The thermal decomposition temperature flame retardant (IFR) composed of microencapsulated APP and
 L. Costes et al. / Materials Science and Engineering R 117 (2017) 1–25 9

melamine (2:1), classified UL 94 V-0, and with a 41% LOI value, Antiblaze RD-1, into poly(ethylene terephthalate) films, imparted
thanks to a high charring effect (Fig. 12). Excellent flame retardant substantial flame retardancy to the material [75]. Alongi et al. also
behavior was also obtained with a poly(vinyl alcohol) composite used this kind of embedding method by preparing cyclodextrin
filled with starch and microencapsulated APP [69]. nanosponges, characterized by a network containing internal and
It has been shown that the combination of starch with a content external cavities, where the phosphorous compounds can be
of 1–5 wt% with a phosphorus- and nitrogen-containing flame entrapped. The presence of phosphorous compounds into the
retardant in PLA further improves its flame retardant properties, cavities of the nanosponges led to the formation of a thermally
mainly by inhibiting the dripping behavior [71]. The presence of stable complex and enabled the in situ generation of phosphoric
starch led to a synergistic effect with the flame retardant, resulting acid at high temperatures. This process induced the dehydration of
in an increased char yield. When the flame retardant and starch cyclodextrin in the presence of this acid source, giving rise to
were incorporated into PLA foam composites, the improvement of enhanced char formation. The incorporation of cyclodextrin
the fire properties was however less important due to the nanosponge-phosphorous compounds into an ethylene vinyl
formation of channels and enlarged surface defects during the acetate copolymer [76], polypropylene, linear low density poly-
foaming process, resulting in enhanced oxygen diffusion and heat ethylene or polyamide 6 [77] improved their fire behavior.
transfer. Isosorbide is a sucrose-derived diol which has attracted interest
Oxidized starch has also been proven to have a high flame as a bisphenol-A substitute. Isosorbide has also been used to
retardant ability [72]. Starch is a polysaccharide easily oxidized to improve the fire behavior of PLA [78]. Polyphosphonates, synthe-
form salts of polyoxyacids, by oxygen in the presence of copper sized by direct polycondensation of isosorbide and phenyl-
salts and alkali. The fire-retardant efficiency of oxidized starch is phosphonic dichloride, provide PLA with flame-extinguishing
due to its thermal decomposition mechanism leading to the behavior at UL-94. This flammability reduction has been explained
formation of foam coke around 150–280  C. The formation of such by the release of phosphorus-based radicals in the gas phase.
a foam coke at the early stages of decomposition is due to the Howell et al. [79] also prepared phosphorus esters, from isosorbide
reduction of starch viscosity, and the reactions of intermolecular and castor oil derivatives, which they incorporated in epoxy
dehydration and decarboxylation that promote char formation. polymer to obtain 1 to 2 wt% phosphorus content. They obtained
This foam coke possesses excellent heat-shielding barrier proper- materials with greatly reduced pHRR and enhanced LOI values
ties that significantly improves wood fire behavior when an compared to pristine epoxy polymer.
aqueous solution of oxidized starch was used to treat it.
Cyclodextrins, which are starch derivative compounds, are 2.1.4. Chitosan
made up of sugar bound together in a ring (Fig. 13) produced by Chitin, that is the second most abundant natural polysaccha-
enzymatic conversion. b-cyclodextrin was first evaluated as part of ride, is the major constituent of some living organisms. It is found
an intumescent flame retardant system for low density polyethyl- in the cell wall of fungi and yeasts, in the shell of crustaceans, and
ene formulations [73]. Compared to other polyol carbon sources, in the exoskeleton of arthropods. Chitosan, the fully or partially
i.e. PER, xylitol, or sorbitol, the action of b-cyclodextrin as a carbon deacetylated form of chitin, is one of the very few natural polymers
source, in combination with ammonium pyrophosphate, was which has a primary amino group along its backbone. A number of
lower, although its thermal degradation leads to the formation of research studies focus on the application of chitosan as a surfactant
high amounts of carbonaceous residue. However, in more recent or in clinics and drug delivery systems, due to its non-toxicity and
studies, b-cyclodextrin proved to be as effective as a PER substitute high biocompatibility. In addition, chitosan may present some
in an intumescent flame retardant system for PLA [74], or as an interest for flame retardant applications, thanks to its carbohy-
embedding agent for phosphorous compounds [75–77]. The PLA drate structure containing hydroxyl groups, which can be used as
composite containing 20 wt% b-cyclodextrin/APP/melamine char forming agents in flame retardant systems for polymers. Hu
(1:2:1) showed a LOI value of 34.5 and passed UL 94 V-0 rating, et al. [80] chemically modified chitosan and studied it as a flame
thanks to the formation of a great amount of char [74]. The retardant in epoxy acrylate resin. They performed a two-step
incorporation of embedding cyclodextrin-inclusion compounds, chemical modification of chitosan. They grafted phosphorus by
containing a phosphorus nitrogen commercial flame retardant, i.e. using phosphorous pentoxide followed by grafting glycidyl

Fig. 12. Pictures of char residues of samples after combustion (a) PLA, (b) PLA/30 IFR, (c) PLA/25 IFR/5 starch, (d) PLA/20 IFR/10 starch (reproduced from [70] with permission).
10 L. Costes et al. / Materials Science and Engineering R 117 (2017) 1–25

Fig. 13. Chemical structure of b-cyclodextrin nanosponges (reproduced from [77] with permission).

methacrylate groups (Fig. 14). This two-step modification resulted padding [81]. In this study, authors took advantage of the
in the improvement of both the charring effect and the oppositely charged chitosan and montmorillonite clay to construct
compatibility with epoxy acrylate resin. The fire behavior of epoxy a multilayered film on the surface of the PLA or PU substrate
acrylate/GPCS were gradually improved with the increasing (Fig. 15). The flammability of the PU foams was tested by the
loading of GPCS in the matrix, because of the modification of application for 10 s of a flame from a butane torch. The uncoated PU
the thermal degradation mechanism of the composite, promoting ignited immediately and was completely consumed, whereas the
the char formation and preventing the release of combustible coated PU extinguished after about 30 s, and showed a preserved
volatile products. foam structure under the charred layer in the case of the thickest
Chitosan has also been used in combination with clay, to act as a nanocoating applied. During the combustion, a charred layer was
protective coating on PLA and PU, for applications such as high- created, which was made mainly of clay platelet aggregates. The
performance packaging or for building insulation and furniture improvement of the fire behavior of PU coated with clay-chitosan
 L. Costes et al. / Materials Science and Engineering R 117 (2017) 1–25 11

Fig. 14. Synthesis of phosphorylated chitosan (reproduced from [80] with permission).

was confirmed in a cone calorimeter test at 35 kW/m2, which deposited on cotton fabrics in combination with chitosan, the PT
revealed a 52% reduction of the pHRR compared to uncoated PU. played a role similar to that of phosphorylated cellulose in their
The layer by layer technique is increasingly used for flame previous work [82]. The same group also improved the fire
retardant applications, particularly for textiles. Pan et al. [82] behavior of cotton fabrics by depositing a layer by layer chitosan/
deposited polyelectrolyte multilayer films of cationic chitosan (CH) titanate nanotubes (TNT) coating on their surface [84]. The
and anionic phosphorylated cellulose (PCL). The CH/PCL-coated improved fire behavior was related to the highly protective
cotton fabrics exhibited lower initial degradation temperature and morphology of the network formed by the TNT during the
higher residual weight than neat cotton fabrics, owing to the combustion. It acted as an efficient physical barrier, due to the high
earlier degradation of PCL. The PCL acted as an acid source to surface area of the TNT and its excellent adsorption property,
produce phosphoric acid in situ, catalyzing the dehydration and decreasing the amount of organic volatile gases. This research
condensation of the cellulosic material. This resulted in better fire group also developed a fully bio-based coating containing chitosan
behavior of the CH/PCL-coated cotton fabrics (reduced pHRR and and lignosulfonate that significantly improved the fire resistance of
THR), thanks to the promotion of the formation of a protective a flexible polyurethane foam, in addition to enhancing its tensile
charred layer, with the combined effects of PCL, char-forming and strength [85]. The association of cationic chitosan and anionic
blowing abilities of CH. The sample coated with 20 bilayers at a ammonium polyphosphate has also been investigated in a layer by
higher PCL concentration was self-extinguishable in the vertical layer assembly technique on cellulose [86], to produce an
flame test. Along the same lines, Pan et al. [83] deposited intumescent flame retardant system, with chitosan as the carbon
polyelectrolyte multilayer films of cationic chitosan (CH) and source and blowing agent, and APP as the acid donor. The efficiency
anionic phosphorylated chitin (PT) on cotton fabrics. When of this system increases in function of the P content in the coating.

Fig. 15. Representation of layer by layer (LbL) assembly with chitosan (CH) and montmorillonite clay (MMT) (reproduced from [81] with permission).
12 L. Costes et al. / Materials Science and Engineering R 117 (2017) 1–25

2.1.5. Other saccharide-based compounds different bonds. Many researchers have focused their studies on
Tea saponin is a natural carbohydrate, containing saccharide the structure of lignin, but it is still unclear due to its complexity
moieties combined with a triterpene derivative, that can be and variability [90–94]. Fig. 19 represents a model of a lignin
extracted from the nutshell of camellia. It has been used as a structure to show these different links and functional groups.
blowing agent and carbon source in an intumescent flame The extraction of lignin from the other constituents of biomass
retardant system containing APP and PER, for alkyd varnish is possible by using the same pre-treatments used for cellulose
[87]. The presence of the carbon rich tea saponin (Fig. 16) enabled isolation and developed for the paper-making industry and
cooperation with PER to strengthen the charred layer created. biorefineries. The most efficient and commercially available
Howell et al. [88] showed that tartaric acid, a sugar acid that is a processes leading to isolated lignin from wood are described in
by-product of wine production, obtained during the conversion of Fig. 20. These processes are divided into two categories: sulfur and
grape stock to wine by fermentation, is an excellent starting point sulfur-free processes. Kraft and lignosulfonate lignins are obtained
for the development of organophosphorus flame retardants from the kraft and the sulfite processes, which were developed for
through its conversion to the corresponding diethyl ester, prior pulp and paper industries. Sulfur treatments result in the
to its treatment with phosphorous compounds (Fig. 17). During its production of some black liquor which is acidified to recover
thermal degradation, the phosphorus modified tartaric acid is lignin. Kraft lignin generally contains a low amount of sulfur,
likely to liberate diphenylphosphinic acid, promoting the forma- whereas lignosulfonate lignin has a high content of sulfur, in the
tion of char. form of sulfonate groups. Kraft lignin typically has a number
average molar mass between 1000 and 3000 g/mol. It also contains
2.2. Bio-based aromatic products a high amount of condensed structures and a large number of
phenolic hydroxyl groups because of the b-aryl bond cleavage
2.2.1. Lignin which occurs during the cooking process. These structural
Lignin is the second most abundant biopolymer of high characteristics result in an alkali soluble lignin with a Tg around
molecular weight. It constitutes 15–25% of the dry weight of 140–150  C. Lignosulfonate lignin has a higher number average
woody plants [19]. Lignin is deposited in the plant cell wall as part molar mass than kraft lignin (15000–50000 g/mol). However, its
of the process of cell maturation after cell elongation, through high content in sulfonate groups makes it water soluble. Sulfur-
which it provides mechanical support and prevents the penetra- free lignins such as organosolv lignin and soda lignin are recovered
tion of destructive enzymes in order to limit plant degradation. by precipitation after solvent pulping or after alkaline pulping.
Lignin has a complex structure composed of a cross-linked 3D Sulfur-free lignins have a low molecular weight (500–5000 g/mol)
network whose base unit is phenylpropanoid. Phenylalanine and a lower Tg than kraft lignin, particularly organosolv lignin,
ammonia lyase, tyrosine ammonia lyase and other enzymes lead which has a Tg around 90–110  C. Soda lignin is soluble in an alkali
to the synthesis of lignin monomers from phenylpropanoid: p- solution, while organosolv lignin is not water soluble but is soluble
coumaryl, synapyl and coniferyl alcohols, which differ from each in a wide range of organic solvents. All these details are given to
other by the degree of methoxylation in their aromatic ring highlight that, in addition to the effect of the botanical origin of
(Fig. 18). These monolignols are subjected to radical oxidation, lignin, its structure and properties are also affected by the
allowing the radical monomers to create covalent links between extraction process.
each other and to polymerize. After the polymerization, the The thermal degradation of lignin begins between 150  C and
different monolignols result in p-hydroxyphenyl, guaiacyl and 275  C and continues up to 700  C with the formation of stable
syringyl units. The composition of the different units of lignin is charred residues, of 30 to 50 wt% under inert atmosphere [97,98].
mainly linked to the plant species [89]. Guaiacyl lignin is generally Its main steps correspond to a first mass loss, below 180  C,
found in softwoods (gymnosperm) and guaiacyl-syringyl lignin is resulting from water release and condensation reactions, and to a
more present in hardwoods (angiosperm). second mass loss in a broad temperature range, from 150  C to
Lignin contains a wide variety of functional groups (methoxyl, 800  C, resulting from lignin structure decomposition and leading
phenolic hydroxyl, aldehyde, and carboxylic acid groups) and many to the formation of highly stable carbonaceous structures [99].

Fig. 16. Molecular structure of tea saponin.

 L. Costes et al. / Materials Science and Engineering R 117 (2017) 1–25 13

Fig. 17. Synthesis of diethyl-2,3-diphosphinato-1,4-butanedioate from diethyl ester tartaric acid (reproduced from [88] with permission).

Fig. 18. Monolignols involved in lignin biosynthesis.

Below 250  C, lignin hydroxyl groups catalyze the cleavage of acidic the same way, lignins obtained by the same extraction process, but
functions and the formation of water and CO2. The maximum originating from different vegetables, displayed different thermal
decomposition rate of lignin occurs between 200  C and 500  C and degradation profiles [97,99].
corresponds to depolymerization reactions leading to the forma- As reported in the case of cellulose, the presence of mineral
tion of various volatile products, whose nature and amount are compounds generally leads to more char formation, due to
directly related to lignin composition. For example, a lignin catalysis of the thermal degradation at lower temperatures and
containing more guaiacyl units releases more coniferyl alcohol, repolymerization reactions [57].
coniferyl aldehyde, isoeugenol, and vanillin [99]. In addition, some Using lignin in high value applications is a growing field of
monomeric radicals are created during thermal degradation and research. Lignin was first frequently used as a low-cost reinforcing
induce repolymerization reactions which result in the formation of agent for mechanical and thermal properties in thermoplastic
thermally stable aromatic networks (Fig. 21). The nature of the polymers, in thermoset polymers, in rubber composites, and in
radicals formed depends on the temperature at which the bonds foam-based composites [104]. Lignin must be surface-modified in
are cleaved. At low temperatures, the weak linkages, such as b-O-4 most cases to enhance its mechanical reinforcement effect. Lignin
ether bonds, are cleaved first and phenolic radicals are produced, has also demonstrated some compatibilizing properties in
which can be further fragmented to form other smaller compounds polymers, such as between thermosetting resin and flax fibers
or radicals, or be involved in repolymerization by free radical [105]. Many other promising technical applications have already
reactions. At higher temperatures, stronger bonds, such as C

C been reported in the literature. It can be used to control the release
linkages, start to be cleaved, and then most of the functional groups of fertilizers and herbicides in agriculture, as a dispersant,
are eliminated, while the aromatic rings remaining in char adsorbent (UV-adsorbent), ion exchanger [106], for the saccharifi-
carbonize to form a condensed ring network. cation of lignocelluloses in the production of biofuels, in electro-
The thermal degradation of lignin, and hence the amount of chemical applications, and for the synthesis of carbon fibers [107].
char formed is a complex mechanism, which can be influenced by Furthermore, modifications and transformations of lignin have
many parameters, such as the thermal conditions, the presence of been developed to produce fine chemicals [9,108]. Another widely
other components, the botanical origin of lignin, and its extraction investigated high value application for lignin concerns its
process. application to improve the flame retardant behavior of polymeric
The amount of the three monolignols strongly affects lignin materials.
thermal degradation [101]. Results highlighted that methoxyl The incorporation of 15 to 20 wt% lignin into polypropylene (PP)
groups are necessary as well as o-quinone methide, which seems [109,110] has proven to be effective in improving its fire behavior.
to be a key-intermediate for the formation of the char during The pHRR, THR, and mass loss rate of the composite generally
pyrolysis. decrease with the increasing lignin loading. The important amount
The extraction mode of lignin is also an important parameter, of char formed during the combustion acts as an insulating layer at
that was shown to be responsible for the modification of the the surface of the burning material, which prohibits the diffusion
thermal behavior of lignin, as seen for kraft and organosolv lignins, of oxygen and heat, and the volatilization of degradation products.
that do not have exactly the same thermal behavior [102,103]. In However, the presence of lignin has been reported to be
14 L. Costes et al. / Materials Science and Engineering R 117 (2017) 1–25

Fig. 19. Main linkages in a softwood lignin (reproduced from [95] with permission).

Fig. 20. Extraction processes to separate lignin from lignocellulosic biomass and the corresponding lignins produced (reproduced from [96] with permission).

responsible for a slight decrease of both material thermal stability Increasing the dispersion state of lignin in the matrix, as well as
and time to ignition, due to its lower degradation temperature. In the interfacial adhesion, also leads to better fire properties of the
the case of polypropylene, authors claimed that an interaction composite. As far as acrylonitrile butadiene styrene (ABS)
between lignin and the hydrocarbon radicals, coming from copolymer/lignin composite is concerned, the addition of a
polypropylene thermal degradation, could lead to the formation compatibilizer agent, i.e. styrene ethylene-co-butadiene stryr-
of a more efficient shield. Furthermore, the addition of lignin up to ene-grafted-maleic anhydride, enabled further enhancement of
15 wt%, affected neither the mechanical properties of polypropyl- the flame retardant behavior [111]. This improvement was due to
ene, nor the release of CO during combustion. It is worth the formation of an intact and almost whole charred layer, with
mentioning that CO release during combustion is the main cause compact microscopic morphology, at the surface of the burning
of death during a fire. sample.
 L. Costes et al. / Materials Science and Engineering R 117 (2017) 1–25 15

Fig. 21. Proposed mechanism for lignin decomposition and char formation (reproduced from [100] with permission).

The effectiveness of lignin as a flame-retardant agent is strongly

dependent on its structure and its specific chemical composition,
as we can see in its own behavior against fire. In fact, the
combustion of two lignins, obtained from different extraction
processes, i.e. kraft lignin and organosolv lignin, has been reported
to be different [102,103]. Results highlight that both the pHRR and
the effective heat of combustion, obtained in cone calorimeter and
microcalorimeter tests, were much lower for kraft lignin than
those obtained with organosolv lignin (Fig. 22). The low heat
release observed with kraft lignin was attributed to the formation
of sulfur dioxide, generated from sulfur present in this lignin.
However, the incorporation of 20 wt% each of these lignins into
PLA, resulted in different behavior, since pHRR reduction was more
important when organosolv lignin was used, although it displayed
a higher pHRR during its combustion (Fig. 23). This result seems
controversial, but it was attributed to the in situ formation of ester
bonds between the carboxylic acid and hydroxyl functions at the
extremities of PLA chains and the numerous reactive groups of
organosolv lignin, which limited the volatilization of low molecu- Fig. 22. HRR curves obtained from microcalorimeter test of kraft lignin (Lig Alk) and
organosolv lignin (Lig Org) (reproduced from [102] with permission).
lar weight fragments.
The fire retardant effect of lignin can be further increased by its
combination with other flame retardant additives [110], such as
metallic hydroxides and phosphorus-based compounds. These
combinations increase the amount of char thanks to the formation
of inorganic thermally stable compounds, in addition to the
catalyzed organic char. This phenomenon results in a further
reduction of the heat release rate.
The use of lignin as the carbonization agent instead of PER, in
intumescent systems, is a suitable solution for enhancing the
amount of bio-based materials, while maintaining fire retardant
performances in PLA [68,112–114]. Flame retardant performance
can be further improved by adding a small amount of organo-
modified montmorillonite. The incorporation of nanoparticles
allows for the reduction of the amount of flame retardants, while
preserving their effectiveness. Reducing the total amount of
additives incorporated is expected to affect positively mechanical
properties, as well as thermal degradation during melt processing
[113].
Fig. 23. HRR curves of neat PLA and PLA/20 wt% kraft or organosolv lignin
The incorporation of phosphorous compounds, such as (reproduced from [103] with permission).
orthophosphoric acid, also enhances the amount of char formed
[98] by catalyzing lignin dehydration. Similar results have also The complex structure of lignin, which contains a wide range of
been reported by Li et al. [115], highlighting the effect of functional groups, offers many possibilities for chemical mod-
phosphorus-containing inorganic compounds, such as ammonium ifications [96]. The chemical treatments of lignin can be organized
polyphosphate and ammonium dihydrogen phosphate, on the into three groups: lignin fragmentation or depolymerization,
thermal degradation and charring process of lignin. These synthesis of new functional groups on lignin, and the function-
compounds promoted the cleavage of the C

O linkage in the alization of hydroxyl groups. Pyrolysis or oxidation are two
lignin structure resulting in the formation of a highly conjugated techniques by which lignin can be depolymerized. The main
and cross-linked system. reactions used for the synthesis of new chemical active sites on
16 L. Costes et al. / Materials Science and Engineering R 117 (2017) 1–25

lignin are halogenation, sulfomethylation, amination, hydroxyal- of the product. Char forming ability is directly related to the
kylation, alkylation/dealkylation, and nitration. The modification amount of phosphorous grafted. In order to enhance the final
of hydroxyl groups has been studied the most, since lignins contain phosphorus content, Yu et al. [124] first increased the amount of
a lot of highly reactive phenolic hydroxyl groups and aliphatic hydroxyl groups, by using formaldehyde, prior to grafting
hydroxyl groups. The principal reactions for the functionalization phosphorous/nitrogen compounds. They prepared the phospho-
of lignin hydroxyl groups are esterification, etherification, reaction rus-nitrogen intermediate by reacting imidazole with POCl3, and
with isocyanates, sylilation, phenolation, and oxidation/reduction. then reacted lignin-OH with the phosphorus-nitrogen intermedi-
Lignin modification aims to produce high value chemicals (vanillin, ate (Fig. 24). They obtained a PN-lignin, containing 8.1 wt%
simple and hydroxylated aromatics, quinines . . . ), or to increase phosphorus and 7.2 wt% nitrogen, and incorporated it in polypro-
the range of their applications, by enhancing their reactivity, pylene. Compared to untreated lignin, PN-lignin induced better
solubility in organic solvents, and ease of processing. The thermal and fire behavior, thanks to the formation of a continuous
phosphorylation of lignin is being increasingly studied [42], and very compact charred residue. The incorporation of 20 wt% PN-
generally in order to improve its flame retardant properties. lignin within polypropylene resulted in a decrease of pHRR and
Phosphorylated lignin, which has both a thermally stable aromatic THR of 72% and 15%, respectively, in respect to neat polypropylene.
structure and phosphorous groups, usually exhibits a much higher This reduction is even more than the reduction obtained with the
char forming potential [116], which can be attributed to the polypropylene filled with 30 wt% of unmodified lignin.
dehydration effect of the phosphoric acid compounds generated Increasing the amount of hydroxyl groups present in lignin has
during thermal degradation. The phosphorus-containing com- also been done in a patent [125], where hydroxymethylated lignin
pounds catalyze the degradation of hydrocarbon molecules into was treated with POCl3 and used as a flame retardant for image
char during combustion. This char, when the phosphorous output equipment, such as printers. Xing et al. [126] also prepared
compound is incorporated into a polymer material, coats the hydroxypropyl lignin prior to its phosphorylation, by using POCl3
un-burnt material and cuts the fuel supply to the flame, inhibiting and ethylene glycol, as shown in Fig. 25. This phosphorylated lignin
further propagation of the flame. It is worth mentioning that in (lignin-POH) has been incorporated into polyurethane foams in
some cases, using modified lignin does not allow for the combination with APP. This blend revealed better thermal stability
enhancement of the amount of charred structures. This was for and fire behavior than polyurethane foams containing only
example observed in the case of PBS containing alkali lignin encapsulated APP, thanks to an interaction between encapsulated
modified with different phosphorus-based compounds (dihydro- APP and lignin-POH allowing for the formation of a charred layer,
gen ammonium phosphate, a homopolymer of (methacryloyloxy) which retained more degradation products in the residue.
methyl phosphonic acid, a copolymer of (methacryloyloxy)methyl Furthermore, the authors demonstrated that polyurethane foams
phosphonic acid and methyl methacrylate) [102]. It would appear containing APP and lignin-POH had a more uniform morphology,
that the flammability parameters of PBS/modified lignin compo- with smaller average cell size, and that the mechanical properties
sites are only slightly further improved due to no increase of the (compressive strength, storage modulus) were enhanced com-
amount of the char, although it enabled for the formation of pared to neat polyurethane foam, owing to the high degree of
charred structures with strengthened microscopic morphology crosslinking when lignin was present.
and better cohesion. Increasing the amount of hydroxyl groups prior to lignin
Several phosphorylation reactions exist for the preparation of phosphorylation, as well as grafting phosphorus- and nitrogen-
phosphorylated lignin: by reacting chloro-phosphorus com- containing compounds seem to be the most relevant strategies for
pounds, such as phosphane chlorides [117], phosphorus oxy- ensuring better flame retardant properties. In a recent study,
chloride [118], thiophosphorus oxychloride [119], and Costes et al. [103] prepared ammonium phosphate modified lignin,
chlorophosphazene [120], through Williamson reaction. Phospho- containing 7 wt% nitrogen and 9 wt% phosphorus, by using POCl3
ric acid has also been used for this aim [121,122], as well as and ammonium hydroxide. Using 20 wt% phosphorus-nitrogen-
phosphonate [123]. The phosphorus-containing lignin, obtained modified kraft lignin in PLA enabled UL 94 V-0 classification to be
by phosphorylation with chloro-phosphorus compounds, is more attained, and a of 40% decrease in pHRR, without any reduction of
stable and less soluble, due to the increased cross-linked structure the time to ignition compared to neat PLA (Fig. 26). It is worth

Fig. 24. Functionalization mechanism of lignin with phosphorus and nitrogen compounds (reproduced from [124] with permission).
 L. Costes et al. / Materials Science and Engineering R 117 (2017) 1–25 17

mentioning that the presence of ammonium groups strongly

reduces the thermal degradation effect of lignin during melt
processing and fire testing, delaying the release of volatile gases
since time to ignition remains similar to that of pristine PLA.
Furthermore, the derivatization of lignin reduced its flammability
since no ignition occurred in contrast with unmodified lignin
during cone calorimeter test.
Urea and orthophosphoric acid have also been used to produce
modified lignin with phosphorus and nitrogen contents up to 8.6%
and 13.9%, respectively [122]. This modified lignin was used to
improve flame retardant properties of epoxy resin. A bio-based
flame retardant based on a modified industrial lignin containing
phosphorus, nitrogen, and copper elements improved the thermal
stability and flame retardancy of polypropylene/wood composites
compared to the unmodified lignin [127].
Phosphorylated lignin flame retardants act mainly in the
condensed phase, but some gas phase effects have been detected
Fig. 26. HRR curves of neat PLA and PLA/20 wt% unmodified or modified lignin
by Prieur et al. [116] in acrylonitrile butadiene styrene (ABS) composites (reproduced from [103] with permission).
containing a phosphate grafted lignin (4.1% of phosphorus), obtained
by a chemical modification with P2O5. Acrylonitrile butadiene 2.2.2. Other bio-based aromatic compounds
styrene (ABS) containing 30 wt% modified lignin showed a pHRR Phloroglucinol, a bio-based phenolic compound, has been used
reduction of 58% and a THR reduction of 20% compared to neat ABS after its phosphorylation as a flame retardant for epoxy thermosets
(Fig. 27). The improved flame retardant effect with P-lignin was [131]. Different chlorophosphates, i.e. dimethyl chlorophosphate,
mainly explained by an action in the condensed phase, with the diethyl chlorophosphate and diphenyl chlorophosphate, were
better interaction of the P-lignin with ABS, inducing the formation of grafted onto phloroglucinol hydroxyl groups by means of a
an insulating charred barrier at the surface of the burning composite. Williamson reaction. It was highlighted that the R groups used
This barrier limited the release of combustible products to the flame. on phosphate, and the phosphorus content, impact the thermal
However, authors also highlighted, in the same study, a slight effect behavior of the modified phenolic compound, as shown in Fig. 28.
in the gas phase by the release of phosphorus radicals that scavenge However, when these different compounds were introduced, in
radicals from the flame. order to obtain the same amount of phosphorus in the resin
The functionalization of lignin with nitrogen-containing com- formulations, the same improved fire behavior was achieved. The
pounds is another method that has been investigated to improve its same research group used phloroglucinol to synthesize two
fire retardant properties [128,129]. The nitrogen-containing lignin phosphorus-and-sulfur-containing flame retardants that differ
could be used advantageously in association with phosphorous by the presence of reactive epoxy functions [132]. The two flame
compounds and acts as an intumescent flame retardant system in retardants led to improved fire behavior when incorporated into
polymeric materials: the phosphorous compound is the acid source, epoxy thermoset, thanks to a condensed phase action. However,
while lignin is the carbon source allowing for char formation, and the the reactive approach seems to be more promising than the
nitrogen compound grafted to lignin leads to a release of non- additive one because of the higher charring effect related to
combustible gases to expand the char. A nitrogen-containing lignin covalent bonding between the flame retardant and the matrix.
has been obtained through Mannich reaction between lignin and Levulinic acid, a bio-based chemical derived from sugar
urea [129], resulting in the covalent grafting of nitrogen (14.45 wt% extraction from a biomass platform, can be used to produce
nitrogen). PLA containing 23 wt% APP/urea modified-lignin (4:1) diphenolic acid [133]. Such a diphenolic acid has been utilized to
displayed a LOI value as high as 34.5, UL 94 V-0 classification, and it synthesize a phosphorus- and nitrogen-containing phenolic flame
had the best fire behavior in the cone calorimeter test, with the retardant (Fig. 29). When incorporated into acrylonitrile-butadi-
highest amount of stable carbonaceous char. The urea modified- ene-styrene, it acts as a charring agent to increase the char yield of
lignin is a better charring agent when combined with APP than the blend and to improve its flame retardancy.
unmodified lignin thanks to the intumescent effect. The same Cardanol, a bio-based product derived from cashew nutshells,
behavior was also observed when lignin-silica hybrids, prepared was used in a bio-based flame retardant system to improve the fire
using the sol-gel method, was combined with APP as a PLA flame behavior of epoxy resin [134]. Cardanol was first reacted with
retardant system [130]. It seems that the presence of more nitrogen butane sulfone to synthesize a surfactant. The cardanol surfactant
or silicon in the sample led to the formation of higher quality, was then used to modify a layered double hydroxide nanofiller (m-
compact and denser charred residues, richer in oxygen and LDH). The addition of m-LDH proved to be efficient for improving
phosphorus, which were able to slow down heat and mass transfer the fire behavior of epoxy resins compared to pristine LDH, thanks
between the gas and condensed phases.

Fig. 25. Chemical modification of lignin with POCl3 and ethylene glycol (reproduced from [126] with permission).
18 L. Costes et al. / Materials Science and Engineering R 117 (2017) 1–25

Fig. 27. HRR curves of neat ABS, ABS/30 wt% lignin, ABS/30 wt% P-lignin (reproduced from [116] with permission).

to a uniform dispersion state leading to the formation of a compact fluxes, except at 75 kW/m2. The elevated heat fluxes limit the
and continuous charred layer during combustion. expansion of the residue due to the quick explosion of the
bubbles, generated during the thermal decomposition, and the
2.3. DNA lack of compactness of the char.
Cotton fabrics coated with DNA showed improved fire behavior
Deoxyribonucleic acid (DNA) is a molecule found in all living thanks to better charring ability [137–139] (Fig. 32). During the
organisms. It carries the genetic information and it is considered to combustion, both the thermal degradation of DNA and that of
define the identity of each subject. It is a long polymer made of cellulose contributed to the char formation, because of the
repeating nucleotide units, arranged in a double helix. Each phosphoric acid generated, which catalyzes their dehydration
nucleotide is composed of a nitrogen-containing nucleobase, i.e. and auto-crosslinking. At least 10 wt% DNA must be coated on the
cytosine, guanine, adenine, and thymine, a five-carbon sugar, i.e. surface of cotton to reach flame out, under the application of a
deoxyribose, and a phosphate group (Fig. 30). methane flame. The addition of 19 wt% DNA on the cotton blocked
DNA represents a potential as a bio-based flame retardant its ignition, under a heat flux of 35 kW/m2, thanks to the formation
acting as an all-in-one intumescent flame retardant system for of an intumescent layer and the absorption of heat from the
polymeric materials [135]. Indeed, it contains the three typical surrounding zone, responsible for the decrease of the temperature
components of these systems and it is able to form an during the combustion [137]. The cotton self-extinguished when
intumescent char when exposed to heat [136]. Under the action DNA was coupled with chitosan, in a layer by layer assembly [140].
of temperature, the phosphate groups produce phosphoric acid, DNA, in bulk or used as a coating, is also a suitable flame
which constitutes the acid source; the deoxyribose units act as retardant for ethylene vinyl acetate (EVA) copolymer (containing
the carbonization agent by decomposing with auto-crosslinking 18 wt% vinyl acetate). DNA coating was more effective than its bulk
process, giving rise to the formation of aromatic structures, and addition, in EVA, thanks to its exceptional thermal shielding
the nitrogen-containing bases act as the blowing agent by properties, which limited the increase of the surface temperature
releasing ammonia. Fig. 31 shows the residues of DNA samples during fire tests, and which forced EVA to undergo pyrolysis
after a cone calorimeter test, at different heat fluxes. An expanded instead of burning. EVA coated with DNA exhibited greatly
char is created during the combustion under the different heat postponed combustion and highly reduced pHRR (Fig. 33), and

Fig. 28. TG curves of the phosphorylated phloroglucinols (10  C/min, under N2) (reproduced from [131] with permission).
 L. Costes et al. / Materials Science and Engineering R 117 (2017) 1–25 19

Fig. 29. Synthesis of (a) methyl diphenolate (MDP) from diphenolic acid, (b) poly(MDP-phenyl dichlorophosphate), (c) poly(MDP-phenyl dichlorophosphate-melamine)
(reproduced from [133] with permission).

Fig. 30. DNA molecular structure.

yields of CO and CO2 in the smoke. However, the important cysteine-rich proteins, contain both sulfur and nitrogen atoms
volumetric expansion observed in the case of the combustion of and are produced by filamentous fungi. The presence of such
pure DNA did not occur, which was attributed to the intimate protein-based coatings on cotton fabrics induces a premature
interactions between DNA and EVA. cellulose thermal decomposition, thus favoring the char forming
DNA has also been used in flame retardant thin films for pathway, instead of the depolymerization with further production
polyethylene terephthalate (PET) foams [142]. The films were of volatiles, thanks to the release of acidic species, such as
deposited in a layer by layer assembly of negatively charged poly phosphoric or sulfuric acid. A similar char forming effect has also
(acrylic acid), APP or DNA, and of positively charged poly been reported on polyester or polyester-cotton blends coated with
(diallydimethylammonium chloride). The layer by layer coatings caseins [143]. When cotton fabrics are coated with caseins or
containing APP displayed fire retardant performance that was hydrophobins, their fire behavior improves, as depicted in Fig. 34,
superior to the DNA-based ones, due to the greater thickness of the with a significant increase in the total burning time and a strong
coating. reduction in the total burning rate, thanks to the formation of a
charred layer.
Whey proteins were first studied for the production of edible
2.4. Proteins and biodegradable films for food packaging. However, their use as a
flame retardant coating has been justified by their good oxygen
Proteins, such as casein, hydrophobins, or whey protein, have barrier properties and great water vapor adsorption [145]. The
been shown to present some interest as flame retardants, mainly cellulosic substrates coated with whey protein shows a reduced
for cotton fabrics [143–145], thanks to their chemical structures. In burning rate and an increased total burning time, thanks to the
fact, casein, the major protein in milk, and which could be obtained combined effects as an oxygen barrier, hindering its diffusion, the
as a co-product of skim milk production, is a phosphorus- high moisture content, resulting in heat absorption, and the
containing molecule, while hydrophobins, a large family of improved char-forming ability.
20 L. Costes et al. / Materials Science and Engineering R 117 (2017) 1–25

Fig. 31. DNA residues after cone calorimeter tests under different heat fluxes (reproduced from [136] with permission).

could result in interferences with the intestinal absorption of

cations or with the action of some enzymes, leading to minerals
and protein deficiencies, which is why the presence of phytic acid
in food products has long been considered controversial [147].
However, phytic acid, or its salts, has since proved to be effective
in various applications: as an antioxidant, anticancer agent, and
for corrosion inhibition as phytate coating on metals [148]. Its use
as a flame retardant has also attracted research, owing to its
renewability and its high phosphorus content (28 wt%). It was
first used in combination with chitosan as part of a coating
deposited via a layer by layer assembly on cotton fabric [149].
Results show that the fabrics protected by the coating, containing
a high amount of phytic acid, are self-extinguishable and present
better fire performance than those coated with material with a
high chitosan content. Such a polyelectrolyte complex, containing
chitosan and phytic acid (Fig. 35), has also been incorporated into
an ethylene-vinyl acetate copolymer inducing improved fire
behavior, thanks to the formation of highly expanded and stable
charred structures, attributed to the simultaneous presence of
phosphorus, nitrogen, and carbon [150].
Phytic acid has also been used in combination with other
Fig. 32. TG curves of neat and treated cotton fabrics in isothermal conditions
nitrogen-based compounds as polyelectrolyte systems, such as
(350  C) in air (reproduced from [137] with permission).
polyethylenimine (PEI) [151], or melamine [152], for polypropyl-
ene, or as an electrically-conductive and flame retardant system
2.5. Phytic acid
with polyaniline for paper [153]. The combination of both
phosphorus and nitrogen in these systems led to greater
Phytic acid is the major storage form of phosphorus in plant
improvement of the thermo-oxidative stability and flame retard-
seeds. It can constitute up to 6% of dry weight of cereals and
ancy of these materials, thanks to the formation of an intumescent
oilseeds [146]. Its structure contains six phosphate groups,
char as shown in Fig. 36.
providing it with a strong chelating potential. This property
 L. Costes et al. / Materials Science and Engineering R 117 (2017) 1–25 21

Fig. 33. HRR (A) and THR (B) curves of neat EVA and EVA_DNA in bulk and on surface (reproduced from [141] with permission).

The combination of phytic acid with both nitrogen- and silicon-

based compounds has been advantageously used by Wang et al.
[154] to improve the fire retardant properties of cotton fabrics. The
authors deposited a coating containing a nitrogen-modified silane
hybrid and phytic acid on cotton fabric through a layer-by-layer
assembly. The intumescent coating significantly increased the fire
resistance of the cotton fabric by catalyzing the dehydration of
cellulose and the formation of an expanded charred layer, through
the action of phosphorus and nitrogen species, while the presence
of the silicon-containing compound led to the formation of silica,
thermally stabilizing the charred residues.
Using phytate salts is another way to employ phytic acid as a
flame retardant agent for polymeric materials. In fact, using the salt
form limits the migration that occurs when phytic acid is
incorporated alone into PLA. In this study, the authors evaluated
different metallic phytate salts, i.e. sodium, aluminum, iron and
lanthanum phytate salts, as individual flame retardants in PLA
Fig. 34. HRR curves of neat cotton and cotton coated with caseins or hydrophobins [155]. Aluminum phytate exhibited the greatest flame retardant
(reproduced from [144] with permission). properties thanks to the fastest formation of the homogenous
charred layer at the surface of the burning sample, as shown in the

Fig. 35. Schematic illustration of the preparation of polyelectrolyte from chitosan (CS) and phytic acid (PA) (reproduced from [150] with permission).
22 L. Costes et al. / Materials Science and Engineering R 117 (2017) 1–25

Fig. 36. LOI values (a) and char residues after LOI tests (b) of PP, PP/PEC system, PP/20 PEI and PP/20 PA (reproduced from [151] with permission).

Fig. 37. Images of (a) PLA/20% Na-Phyt, (b) PLA/20% Al-Phyt, (c) PLA/20% Fe-Phyt, and (d) PLA/20% La-Phyt after 250 s of combustion (reproduced from [155] with permission).

Fig. 38. The chemical reaction between epoxidized glycerolysis castor oil and diethyl phosphate (reproduced from [161] with permission).
 L. Costes et al. / Materials Science and Engineering R 117 (2017) 1–25 23

pictures of the different samples taken at half-combustion time various bio-based compounds, i.e. saccharide-based products, bio-
(250 s) (Fig. 37). However, the incorporation of aluminum phytate based aromatic compounds, DNA, proteins, phytic acid and
into PLA resulted in a sharp decrease in the molecular weight of vegetable oils, can be used as efficient green flame retardant
PLA, due to the catalysis of the hydrolysis of PLA chain ester bonds additives owing to their outstanding char-forming ability. During
during melt processing. The substitution of some aluminum the combustion of a material, the production at its surface of such
phytate by sodium phytate appears to be an efficient approach for thermally stable charred structures improves its fire behavior by
addressing this problem, while maintaining the improved fire reducing the diffusion of oxygen and heat, and inhibiting further
properties. volatilization of combustible products. The char layer acts as an
Ferric phytate was used as part of a flame retardant system, also insulating barrier protecting the underlying material.
containing graphene, to improve the fire behavior of PLA [156]. In The association of these bio-based compounds with other
fact, phytic acid acted as an electrolyte and modifier to prepare components, particularly phosphorus and nitrogen containing
functionalized exfoliated graphene. Ferric phytate was obtained by products, has proven to be effective in improving their flame-
mixing the functionalized graphene with Fe(NO3)3. The incorpo- retardant action. Furthermore, this association usually enables the
ration of 3 wt% ferric phytate functionalized graphene in PLA efficiency of flame retardant systems to be enhanced when the
greatly limited the fire hazards: a significant reduction of pHRR, partners are chemically modified/linked.
low CO yield, and the formation of a highly protective charred To further improve flame retardant systems based on renew-
layer. The presence of the phosphate groups of phytic acid able resources, investigations must be conducted to find out
facilitates the electrochemical exfoliation of graphene, and also chemical treatments allowing higher grafting yields, to enhance
imparts higher flame retardant ability. the compatibility with the polymer matrix, as well as to limit
Phytic acid has also been used as an individual flame retardant polymer thermal degradation effects during melt processing. In
agent for wool fabric, on which it was combined by means of fact, papers generally focus on the study of the fire and thermal
electrostatic interaction between the positively charged amino behaviors of the composites and the effects of the flame-retardant
groups contained in wool and the negatively charged phosphate additives on the other material properties (mechanical, processing,
groups of phytic acid [157]. The treated wool fabrics displayed compatibility, . . . ) are often less investigated.
improved fire behavior thanks to the action of phytic acid in the Special attention must also be paid to the botanical origin and
condensed phase. PLA nonwoven fabric treated by immersion in a the extraction processes of these bio-based compounds, and their
phytic acid solution, followed by a drying and a curing step, impact on the flame-retardant behavior. This point presents a
presented better fire behavior in the vertical burning test and major issue that requires more studies before hoping for an
microscale combustion calorimetry analysis, compared to untreat- industrial application. Indeed, the effects of the wide variability of
ed PLA fabric [158]. structure and composition of these bio-based compounds, such as
in the case of lignin for example, need to be more deeply
2.6. Vegetable oils understood and controlled to overcome their limitations.
Another drawback that could limit the use of these bio-based
Vegetable oils are annually renewable natural resources found compounds as flame retardant additives for polymeric materials
in oilseeds, that are mostly composed of triglycerides, a glycerol concerns their thermal stability. For example, hemicellulose has
molecule esterified by fatty acids. They present increasing interest low thermal stability that restricts its use in some technical
for the formation of polymeric materials [159], but also for flame polymers, even if its thermal degradation enables the production
retardant applications. In fact, through their hydroxyl groups, of more char than cellulose.
triglycerides can react with isocyanates to produce polyurethane
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