POLYMERS FOR ADVANCED TECHNOLOGIES

Polym. Adv. Technol. 2008; 19: 446–453

Published online 28 April 2008 in Wiley InterScience (www.interscience.wiley.com) DOI: 10.1002/pat.1135

Review
Flammability and fire resistance of composites
reinforced by natural fibers
Ryszard Kozłowski y and Maria Władyka-Przybylak*
Institute of Natural Fibres, Poznan, Poland
Received 3 March 2008; Accepted 3 March 2008

Natural fiber-reinforced composites are more and more frequently applied to building industry and
transportation. Therefore, the knowledge of their behavior during fire is of high importance.
Flammability is one of very important parameters that often limits the application of composites
to a given area. It is well-known that addition of lignocellulosic fibers to polymer changes mechanical
properties of the product obtained. However, little information is available on their fire performance.
The purpose of this review was to obtain fire performance data for several types of composites
reinforced by lignocellulosic fibers. Copyright # 2008 John Wiley & Sons, Ltd.

KEYWORDS: flammability; composites; fire retardancy

AUTHORS’ BIOGRAPHIES
Dr Ryszard Michal Kozlowski is the Director of the Institute of Natural Fibres, Poznan, Poland, Coordinator
of the FAO/ESCORENA European Cooperative Research Network on flax and other bast plants, acting within
ESCORENA system of technical science. He has initiated and conducted the innovative scientific research in
the scope of natural fibers as raw material production and utilization of by- and waste products for example,
bio-composites. His main research interests focus on fire retardancy of lignocellulosic materials, polymers,
and nanotechnology.

Dr Maria Władyka-Przybylak works at the Institute of Natural Fibres in Poznan, Poland. Her main focus of
interest is fire retardancy mechanisms and practical application of fire retardants in fire protection for
flammable materials such as wood, lignocellulosic materials, polymers, fabrics, and other textile materials. She
also deals with composites based on natural fibers and nanocomposites. She is the Coordinator of
Inter-departmental Research Team for Composites.

INTRODUCTION them an attractive ecological alternative to glass, carbon and

The interest in natural fiber-reinforced polymer composite
materials is rapidly growing both in terms of their industrial
applications and fundamental research.1–4 They are renew-
able, cheap, completely or partially recyclable, and biode-
gradable. Plants, such as flax, cotton, hemp, jute, sisal, kenaf,
pineapple, ramie, bamboo, banana, etc., as well as wood,
used from time immemorial as a source of lignocellulosic
fibers, are more and more often applied as the reinforcement
of composites. Their availability, renewability, low density,
and price as well as satisfactory mechanical properties make
*Correspondence to: M. Władyka-Przybylak, Department of Com-
posites, Institute of Natural Fibres, ul.Wojska Polskiego 71b, 60-
630, Poznan, Poland.
E-mail: mwladyka@inf.poznan.pl
y
General Director.
man-made fibers used for the manufacturing of composites.4
The natural fiber-containing composites are more environ-
mentally friendly, and are used in transportation (auto-
mobiles, railway coaches, aerospace), military applications,
building and construction industries (ceiling paneling,
partition boards), packaging, consumer products, etc. There-
fore, the flammability characteristics of the composites based
on polymers and natural fibers play an important role.
Flammability is one of the very important parameters,
limiting often the application of a composite to a given area.
It is known that addition of lignocellulosic fibers to polymer
changes mechanical properties of the product obtained,
which results from properties of lignocellulosic material and
those of polymer. Flammability characteristics of the
composite obtained are also different from those of
components.

Copyright # 2008 John Wiley & Sons, Ltd.

 Flammability of natural fiber-reinforced polymer composites 447

Figure 1. Constituents of natural fiber-reinforced polymeric composite materials.1

THE PROPERTIES OF COMPOSITES Fire resistance and smoke generation properties of

Composite is a material that contains at least two different
components, clearly separated one from another and
uniformly filling its volume, produced in order to create
particular properties. Lignocellulosic natural fibers are
suitable raw materials for the production of a wide range
of composites for different applications. The interest in
using natural fibers, originated from different plant fibers,
as reinforcements for polymers increased during last
few years. These fibers are incorporated into a matrix
material such as thermosetting plastics, thermoplastics, or
natural polymers.5 The significant weight savings and the
ease and low cost of the raw constituent materials make these
composites an attractive alternative material to glass and
carbon fibers. The combination of a plastic matrix and
reinforcing fibers give rise to composites having the best
properties of each component. Since the plastics are soft,
flexible, and lightweight compared to fibers, their combi-
nation provides a high strength to weight ratio to the
resulting composite.
composite materials are major issues these days because,
depending on application, they must pass some type of
regulatory fire test in order to ensure public safety. Thus, it is
important to understand how individual components of the
end-products burn and how best to modify materials to make
them flame-resistant without compromising their uniquely
valuable low weight to high mechanical ratios.6
The most commonly used natural fibers and matrices for
composites are shown schematically in Fig. 1.
Properties of natural fibers
Properties of natural fibers result from their structure and
chemical composition. The mechanical properties of natural
fibers, especially flax, hemp, jute and sisal, are very good and
may successfully compete with glass fiber in specific strength
and modulus (Table 1). Natural fibers show higher
elongation to break than glass or carbon fibers, which may
enhance composite performance. Thermal conductivity of

Table 1. Mechanical properties of natural fibers compared to glass fiber7

Density Tensile strength Young’s modulus Specific Elongation to Moisture
Fiber (g/cm3) (MN/m2) (GPa) modulus break (%) absorption (%)

E-Glass 2.55 2400 73 29 3 —

Flax 1.40 800–1500 60–80 26–46 1.2–1.6 7
Hemp 1.48 550–900 70 47 1.6 8
Jute 1.46 400–800 10–30 7–21 1.8 12
Ramie 1.50 500 44 29 2 12–17
Coir 1.25 220 6 5 15–25 10
Sisal 1.33 600–700 38 29 2–3 11
Abacca 1.50 980 — — — —
Cotton 1.51 400 12 8 3–10 8–25

Copyright # 2008 John Wiley & Sons, Ltd. Polym. Adv. Technol. 2008; 19: 446–453
DOI: 10.1002/pat
448 R. Kozłowski and M. Władyka-Przybylak

Table 2. Chemical composition of some common natural fibers1

Type of fiber Chemical component (%)

Cellulose Lignin Hemicellulose (or pentosan) (%) Ash Microfibrilar/spiral angle (Deg.)

Bast fiber
Flax 64–71 2–5 18.6–20.6 5 10.0
Kenaf 44–57 15–19 22–23 2–5 —
Jute 61–72 12–13 13.6–20.4 0.5–2 8.0
Hemp 70.2–77 3.7–5.7 17.9–22.4 0.8 6.2
Ramie 68.6–76.2 0.6–0.7 13.1–16.7 — 7.5
Leaf fiber
Abacca 56–63 7–10 15–17 3 —
Sisal 675–78 8–11 10–24 0.6–1 20.0
Cabuya 68–77 13 4–8 1.5–2 —
Seed fiber —
Cotton 85–90 07–16 1–3 08–2
Fruit fiber
Coir 36–43 41–45 0.15–0.25 41–45
Stalk fiber
Rice 28–48 12–16 23–28 15–20 —
Wheat 29–51 16–21 26–32 45–9 —
Barley 31–45 14–15 24–29 5–7 —
Oat 31–48 16–19 27–38 6–8 —
Rye 33–50 16–19 27–30 2–5 —
Cane fiber
Bagasse 32–48 19–24 27–32 15–5 —
Bamboo 26–43 21–31 15–26 17–5 —
Grass fiber
Esparto 33–38 17–19 27–32 6–8 —
Sabai — 22 24 6 —
Wood fiber
Coniferous 40–45 26–34 7–14 <1 —
Deciduous 38–49 23–30 19–26 <1 —

natural fibers is low, (0.29–032 W/m K) therefore they make a
good thermal barrier.
The chemical composition of selected natural fibers is
shown in Table 2. The components of natural fibers include
cellulose, hemicellulose, lignin, hemicellulose, and
extraneous materials. Plant fibers are characterized by
cellular structure. Each cell contains crystalline (i.e. ordered)
cellulose regions (microfibrils) which are interconnected via
lignin and hemicellulose fragments.8 A cell has one external
wall and three thick side walls. The more parallel to fiber axis
microfibrils are arranged, the higher is the fiber strength.
Most of natural fibers have porous structure (seen in
cross-section) which can be a factor facilitating their
saturation with resins.
The thermal stability of natural fibers can be studied,
among others, by thermogravimetric analysis (TGA). The
measurements were carried out on a Setaram instrument in
helium flow using heating ramp of 58C/min.
Curves of TGA of bast fibers (flax, hemp) and leaf fibers
(cabuya, abacca) are shown in Fig. 2, where TGA represents
changes in weight in relation to change in temperature and
DTGA is the first derivative of the former curve.
As can be seen from the Fig. 2, the natural fibers start
degrading at about 2308C. The thermal degradation of bast
fibers (hemp, flax) is a one-stage process, but that of leaf
fibers (cabuya, abacca) proceeds in two stages, where the first
of them falls in the temperature range of 230–2808C and the
other in the range of 280–3008C. The low temperature
degradation process is associated with the degradation of
Copyright # 2008 John Wiley & Sons, Ltd.
hemicelluloses, whereas the high-temperature one with that
of lignin degradation. The apparent activation energies for
the two processes are about 117 and 146 kJ/mol, which
correspond to the degradation of hemicelluloses and lignin,
respectively. Thermal decomposition kinetics of natural
fibers has been reviewed in detail by Yao Fet et al. for
activation energy with dynamic TGA.9
The thermal degradation of natural fibers is crucial for the
development of natural fiber composites and thus it has a
bearing on the curing temperature in the case of thermoset
and extrusion temperature in the case of thermoplastic
composites.10
Flammability of fibers has been investigated by the cone
calorimetry technique. In Fig. 3, heat release rate (HRR) and
mass loss rate (MLR) of bast fibers (flax, hemp) and leaf fibers
(abacca, cabuya) are shown. It results from Fig. 3 that HRR
from bast fibers is considerably lower than that from leaf
fibers.
The lower heat release rates of hemp and flax fibers could
be put down to their lower lignin content (Table 2). During
thermal decomposition of lignin, relatively weak bonds
break at lower temperature, whereas the cleavage of stronger
bonds in the aromatic rings takes place at higher tempera-
ture.11 Thus, with a lower lignin content, the degradation
begins at a higher temperature, but the fibers do not have the
oxidation resistance given by the aromatic rings in the
lignin.12,13
In order to improve thermal stability, attempts have been
made at coating and/or grafting the fibers with monomers.10
Polym. Adv. Technol. 2008; 19: 446–453
DOI: 10.1002/pat
 Flammability of natural fiber-reinforced polymer composites
Figure 2. a and b: Curves of thermogravimetric analysis
(TGA) and their first derivatives (DTGA) for bast and leaf
fibers.
Of a considerable importance to the flammability of fibers,
cellulosic ones in particular, appear to be crystallinity and
orientation. An increase in the crystallinity of lignocellulosic
fibers brings about an increase in the levoglucosan (LG)
formation during pyrolysis. LG is considered to be the
cellulose monomer, and it is usually evolved in the form of an
extremely flammable fluid tar.14 The activation energy of
cellulose pyrolysis increases with increasing crystallinity. An
obvious way to decrease the flammability of cellulosic fibers
would therefore be to decrease the crystallinity of the fibers
before or during pyrolysis and combustion. It might also be
possible to treat the fibers with an effective swelling agent
simultaneously with a fire retardant additive.15
Properties of matrix polymers
The most common matrix materials for composites are
thermoset or thermoplastic polymers and biopolymers. The
major types of thermoplastic materials are polyolefins,
including polyethylene (PE) and polypropylene (PP); poly-
vinyl plastics, including polyvinyl chloride (PVC), poly-
styrene (PS), acrylonitrile-butadiene-styrene (ABS); cellulose
derivatives, including cellulose nitrate, acetate, butyrate, and
propionate; and aromatic compounds, including polycarbo-
nate (PC), phenoxy resins, polysulfone, and polyimide.16
The major types of thermosetting materials are epoxy
resins and unsaturated polyesters (UP); phenolic resins
(including phenol-formaldehyde ones); amino resins (e.g.
melamine-formaldehyde and urea-formaldehyde ones),
polyurethane.
Copyright # 2008 John Wiley & Sons, Ltd.
449
The examples of biopolymers based on renewable resources
are: cellulosic plastics, polylactides (PLA), starch plastics, and
soy-based plastics and microbial synthesized biopolymers,
i.e. polyhydroxy alkanoates (PHAs). The behavior of some
polymers during fire was characterized in Table 3. The most
widely used laboratory tests are the limiting oxygen index
(LOI) and cone calorimeter. Table 3 presents limiting oxygen
indices (LOI) and peak HRR (the latter being determined on
the ground of cone calorimetric measurements).
According to Horrocks and Kandola,6 the ranking of fire
resistance of thermoset resin composite components can be
presented as follows:
Phenolic > Polyimide > Bismaleimide > Epoxy >
Polyester and vinyl ester.
The manufacture of composites
Natural fiber-containing composites can be manufactured
by almost all production techniques. Thermosets are
processed by simple processing techniques such as hand
lay up and spraying, compression, transfer, resin transfer,
injection, compression injection, and pressure bag molding
operations. The use of a few other methods, such as cold
press molding, filament winding, pultrusion, reinforced
reaction injection molding, and vacuum forming, is hardly
reported in the case of composites.10 The processing of
natural fiber thermoplastic composites involves extrusion
of the ingredients at melt temperatures followed by shaping
operations such as injection molding and thermoforming.
Fiber–fiber interaction as well as fiber–matrix interaction
play a crucial role in determining the properties of such
composites.10
FLAMMABILITY OF COMPOSITES
The natural fiber composites, when exposed to fire or any
other high-intensity heat source, are subject to thermal
decomposition and combustion depending on conditions.
The intensity of heat stimulus, oxygen concentration, and
circulation of gas in the area where combustion can occur
influences the time to ignition of composites as does the
intensity of combustion process. Relevant factors include the
rate of flame spread, HRR, mass loss, and carbonization
rates. Combustibility of a composite depends on a number of
factors such as the nature of composite and the kind of raw
materials used for its manufacture (both natural fibers and
polymers), its density, structure, thermal conductivity,
humidity, etc.
There are two methods for increasing fire retardancy of
composites:20

application of different types of fire retardants during the
manufacturing process,

application of fire retardants, especially intumescent coat-
ings, at the stage of finishing.

Fire resistant natural fiber-containing composites can be
obtained by the following methods:

impregnation of natural fibers or lignocellulosic particles
with fire retardants before the manufacturing process,

implementation of fire retardants in liquid or solid form
during the manufacture of composites,
Polym. Adv. Technol. 2008; 19: 446–453
DOI: 10.1002/pat
450 R. Kozłowski and M. Władyka-Przybylak

Figure 3. Heat release rate (HRR) (a) and mass loss rate (MLR) (b) determined by using a cone calorimeter for natural fibers.

application of non-flammable binders, resins, polymers, aimed at covering and separating natural fibers or ligno-

insulation of composites to prevent from penetration of cellulosic particles and this is accompanied by migration of
heat flux (intumescent coatings and fire barriers), fire retardants into the interior of flammable materials, thus

application of nanoparticles to lignocellulosic composites. resulting in fire protection of the latter. The most commonly
used fire retardant additives are the following chemical
These methods can be used alternatively or jointly. In compounds: boric acid; ammonium phosphates and borates;
general, the addition of non-combustible components is ammonium sulfate and chloride; zinc chloride and borate;
phosphoric acid; dicyanodiamide; sodium borate; and
Table 3. Limiting oxygen indices (LOI) of some polymers18 antimony oxide.21,22 They are added usually in the form of
and some heat release rates obtained by cone calorimeter19 powder and their amount ranges from 5 to 10% in relation to
dry mass (8% on average). Particle size of fire retardant
HRR [kW/m2] (Heat
Polymer LOI flux 40 kW/m2) strongly influences its efficiency and the amount to be added,
particularly when used for fire retardation of polymers.
Polypropylene 18 1509 Organic fire retardants, based mainly on organobromine
Polyethylene 18 1408
compounds, are also used. Their application is, however,
Poly(vinyl chloride) 42 175
Polystyrene 18 1101 limited by high toxicity of products of thermal decompo-
Poly(methyl methacrylate) 18 665 sition and combustion of materials containing such com-
Poly(butylene terephthalate) 25 1313 pounds.23,24
ABS 19 944 A considerable attention was paid recently to the
Polycarbonate 27 429
application of inorganic clays to the modification of
Polyimide 43 —
polymers. The most common inorganic materials used as
Copyright # 2008 John Wiley & Sons, Ltd. Polym. Adv. Technol. 2008; 19: 446–453
DOI: 10.1002/pat
 Flammability of natural fiber-reinforced polymer composites
Figure 4. Heat release rate (HRR) from composites based on PP and natural fibers compared to PP.
mineral fillers are montmorillonite, alummino-silicates,
vermiculite, and perlite. Chemical modification of clays
with or without flame retardant additives may also yield
interesting results.25 Nanocomposites constitute a new
development in the area of flame retardancy and offer
significant advantages over conventional formulation where
high loadings are often required.26
It is worth mentioning that PP composites reinforced with
lignocellulosic fibers and their flammability are widely
studied.27–30 Results of measurements of HRR during
combustion of a composite obtained by compressing PP
and natural fibers are shown in Fig. 4. The amount of natural
fibers added to PP was 30% and the thickness of the samples
studied was 5 mm. It can be concluded from the mentioned
figure that all type of fibers investigated bring about a
decrease in HRR.
On the ground of the HRR curves, a conclusion can be
drawn that both thermal decomposition and combustion of
PP-cellulose fiber composites occur in a way different from
that observed for PP alone. When fiber content exceeds 30%,
HRR curves of the composites resemble those of lignocellu-
losic materials, where two characteristic peaks can be
seen.29,30 Although the presence of flax fibers brings about
an earlier ignition of PP composite, the process of combus-
tion proceeds at significantly lower HRR and MLR.29,30
Other studies have been focused on the flammability of
variety of cellulosic materials modified by additives used as
flame retardants.31–35 Le Bras et al. have studied the effect
resulting from the combination of pentaerythritol with flax
fibers in an intumescent PP/fiber/ammonium polypho-
sphate/pentaerythritol/melamine system.35 These studies
have shown that char-forming fibers need an intumescent
composite structure that maintains coherence of the
protective shield and thermal barrier properties to result
in a high level of flame resistance of the material. By using an
intumescent model additive, they have shown that combi-
nation of charring cellulosic material and intumescent
system allowed us to obtain an optimized flame retardant
formulation.
Copyright # 2008 John Wiley & Sons, Ltd.
451
There are little reports on the flammability of composites
consisting of thermoset resins reinforced with natural
fibers.36,37 Thermal degradation and flame resistance of
composites made of different natural fibers, UP, and
modified acrylic resins (Modar) were studied by Manfredi
et al.37 Their study was aimed at evaluating thermal
degradation, smoke evolution, and flame resistance of
different natural fiber-containing composites and glass
fiber-containing composites with the same matrix. The
percentage of fibers was 30% by volume. By comparing
results obtained with different matrices, they have concluded
that fire risk was similar when using composites with
unsaturated polyester and Modar matrices (Fig. 5). However,
ignition time was longer for Modar-based composites than
for polyester-based ones. The smoke hazard during fire was
clearly lower for the Modar matrix composites due to the
char forming property of this resin. Among the composites
with Modar matrix, the one reinforced with sisal fiber has
shown the highest fire risk and, in global terms, the worst fire
resistance. Jute fiber-containing composites were character-
ized by quick growing but short-lasting fire and, conversely,
flax fiber-containing composite developed long duration but
slow growing fire.
Figure 5. Fire risk of natural fiber-containing composites.
(&) based on Modar matrix and (&) based on polyester
matrix. This figure is available in color online at www.
interscience.wiley.com/journal/pat
Polym. Adv. Technol. 2008; 19: 446–453
DOI: 10.1002/pat
452 R. Kozłowski and M. Władyka-Przybylak
Fast development of biodegradable polymers in the last
few years has resulted in increasing interest in the research
on the so-called green composites that are reinforced with
natural fibers, that is, on biocomposites. Efficient use of green
composites can contribute, to a certain extent, to the solution
of waste accumulation problem. Due to the fact that the
above composites undergo complete biodegradation, they
can be effectively utilized by composting. In the study by
Matko et al., who investigated flame retardancy of biode-
gradable polymers and biocomposites,38 various cellulose-
and starch-containing biocomposites were compared in the
flame-retarded form. The efficiency of flame retardants was
determined in PP, polyurethane, and starch-based biocom-
posites. It was found that plasticized starch thermoplastic,
fully degradable biopolymer can be flame retarded effi-
ciently by the introduction of as low as 10% of ammonium
polyphosphate and LOI value of 60 can be achieved with 30%
of flame-retardant additive. They concluded that although
bio-based polymers seem to be more expensive than the
traditional mass polymers, their flame retardancy can be
achieved in relatively simple and inexpensive ways.
SUMMARY
Although in ancient Egypt, many centuries BC, clay mixed
with straw and dried in the sun, was used as a composite
construction material, it was not until early 20th century that
it was noticed that raw materials produced each year by the
nature can be applied to the manufacture of composites as
reinforcing materials. Low price and easy availability of
natural fibers are their advantages from the point of view of
the application as a reinforcement to polymeric composites.
Wide possibilities of the application of such composites to the
building industry and transportation require, however,
applying flame retardancy in their case. The choice of
appropriate flame retardants enables to make composites
(that are usually flammable) hard-to-ignite materials, thus
extending the range of their applications. As a result of the
introduction of flame retardants to composites, time to
sustainable ignition can be extended, flame phase of
combustion can be limited or eliminated, HRR and surface
flame spread can be reduced, and hazardous condensation
eliminated.
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