Polymer Degradation and Stability 127 (2016) 32e43

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Polymer Degradation and Stability

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

Phosphorylation of lignin to ame retard acrylonitrile butadiene

styrene (ABS)
B. Prieur a, M. Meub b, M. Wittemann b, R. Klein b, S. Bellayer a, G. Fontaine a,
S. Bourbigot a, *
a
R2Fire Group/UMET e UMR CNRS 8207, Ecole Nationale Sup
erieure de Chimie de Lille (ENSCL), Avenue Dimitri Mendeleev e Ba ^t. C7a, CS 90108, 59652,
Villeneuve dAscq Cedex, France
b
Group for Design of Interfaces, Division Plastics, Fraunhofer Institute for Structural Durability and System Reliability LBF, Darmstadt, Germany

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

Article history: Lignin is an abundant polyphenol biopolymeric material. Due to its aromatic structure it develops a char
Received 28 July 2015 under re conditions. Lignin was used as ame retardant in acrylonitrile-butadiene-styrene (ABS).
Received in revised form Enhancement of ame retardancy was observed, and the lignin was then phosphorylated to achieve
15 January 2016
highest performance. For the rst time, characterization of FR phosphorylated lignin (P-LIG) was un-
Accepted 25 January 2016
Available online 30 January 2016
dertaken in detail. Grafting phosphorus onto lignin signicantly increases the amount of residue from
the polymer blend at high temperature. At 30 wt.%, P-LIG is well dispersed in ABS and leads to a sig-
nicant reduction of the peak of heat release rate. It is shown that P-LIG promotes char formation by
Keywords:
Lignin
reacting with ABS during thermal decomposition. The char is therefore more cohesive and acts as a
ABS protective layer, such that less fuel from ABS degradation is released to the ame. Thus phosphorylated
Lignin modication lignin is as a promising bio-based ame retardant for ABS.
Flame retardancy 2016 Elsevier Ltd. All rights reserved.
Thermal degradation
Phosphorus

1. Introduction to assess its use as a ame retardant (FR) in polymers including PP

For almost a century, plastic materials have gained considerable
interest for numerous applications and the demand is increasing
exponentially. In order to tune their nal properties for particular
applications, additives are used, most of them coming from fossil
resources. Over the past few years, concerns about depletion of
fossil resources and the increasing needs of their derivative prod-
ucts have forced the scientic community to consider sustainable
resources as a real alternative. Specic interest has been devoted to
biomass and green materials. Among them, lignin has been paid
attention mainly because of its huge availability as a feedstock
across the world. A complete review has been recently published
[1]. Lignin is one of the three components along with cellulose and
hemicellulose responsible for the strength and rigidity of plants.
Recently, lignin has been employed as an alternative to antioxi-
dants [2] or surfactants [3] and even as a chemicals source [4].
However, no major application for lignin has yet been found.
In order to valorize the lignin, several studies were undertaken
* Corresponding author.
E-mail address: serge.bourbigot@ensc-lille.fr (S. Bourbigot).
[5,6], polylactide [7,8], polybutylene succinate [9] and epoxy [10].
Lignin belonging to the family of polyphenols (full aromatic
structure) could indeed develop a char under re conditions such
as in the mass loss calorimeter test. Recently the incorporation of
lignin in an Acrylonitrile-Butadiene-Styrene (ABS) has been inves-
tigated [11]. Lignin was uniformly dispersed through the polymeric
matrix which can be due to afnities between aryl groups from
both phases. Flame retardancy was also studied and it was shown
that lignin is a promising ame retardant since it reduced peak of
heat release rate for combustion of the polymers by 30% with
20 wt.% loading. In all cases, lignin was considered to act as an FR,
but with limited performance. However, lignin can be functional-
ized thanks to its several reactive functions, especially the hydroxyl
groups. Modied lignin is beginning to be widely used in different
applications after modications such as hydroxylation, alkylation,
amination, nitration and others [1]. In the eld of ame retardancy,
few papers deal with modied lignin. Most of the time, lignin is
modied directly by phosphorus based molecules [9,12,13]. In the
case of phosphorylation, the characterization is often limited and
reduced to FTIR and XPS analysis which is not sufcient to establish
the chemical structure of the phosphorylated lignin. Since recently

http://dx.doi.org/10.1016/j.polymdegradstab.2016.01.015
0141-3910/ 2016 Elsevier Ltd. All rights reserved.
 B. Prieur et al. / Polymer Degradation and Stability 127 (2016) 32e43
advanced characterizations are undertaken, such as 31P NMR [14].
Phosphorus is indeed well known for its FR properties. Depending
on their nature, phosphorus ame retardants can indeed act either
in the gas phase by inhibiting the ame or in the condensed phase
by interacting with the polymeric matrix and promoting char. The
so called phosphorylated lignin has been for example incorporated
in polypropylene [12], polyurethane [13] and polybutylene succi-
nate [9].
In the lab, the functionalization of kraft lignin (LIG) with a
phosphorus reagent (P-LIG) by a simple and industrially feasible
process to make an effective ame retardant for ABS was the focus
of the work reported here. Indeed this terpolymer is widely used in
a many applications (electrical & electronic sector, automotive)
which require ame retardancy performances. For the rst time,
phosphorylated lignin will be fully characterized. The rst part of
the paper is dedicated to the phosphorylation process and an
advanced characterization of P-LIG. The second part is dedicated to
the thermal stability and re performances of ABS/lignin compos-
ites. Finally, a mode of action of P-LIG as FR in ABS is proposed.
2. Experimental
2.1. Materials
ABS was supplied by Aimplas (Spain) under the trade name of
HI-10 Terluran from BASF. Kraft lignin was provided by UPM,
Finland. Due to the high water uptake, neat kraft lignin were dried
at reduced pressure at 60
C for 1 week before use. Both ABS and
lignin were dried at 75
C for at least 24 h before compounding or
analysis.
2.2. Phosphorylation of lignin (P-LIG)
An illustration of the simplied synthetic route leading to
phosphorylated lignin (P-LIG) is shown in Fig. 1. The objective of the
work was the development of a process suitable for industrializa-
tion and therefore the synthetic route was kept as simple as
possible. Lignin (2 kg) was dissolved in 7.5 L of tetrahydrofuran
(THF). When the lignin was fully dissolved, phosphorus pentoxide
(P2O5) was added at room temperature. The solution was heated at
solvent reux for 7e8 h in the course of which the product was
largely precipitated. After the mixture was allowed to cool at room
temperature, water was added in order to transform excess of P2O5
into phosphoric acid. Then THF was evaporated in a rotatory
evaporator at 40
C under reduced pressure. The phosphorylated
lignin was collected by ltration and washed. In order to remove
residual phosphoric acid, P-LIG was exhaustively extracted with
water in soxhlet apparatus. Finally, the product was dried 24 h at
75
C at reduced pressure.
Fig. 1. Illustration of the synthetic route leading to phosphorylated lignin (P-LIG).
33
2.3. ABS composite preparation
The formulations were prepared using a Thermo Scientic
HAAKE Reomex mixer: 200 g-batches of material were mixed at
200
C and with a shear rate of 50 rpm. First the polymer was
molten for 4 min, afterwards the lignin were incorporated and the
resulting formulation was mixed for 6 min, therefore the residence
time was 10 min. Three formulations were prepared and are listed
in Table 1. The materials were pressed to make plates of
100  100  3 mm3 with a Sogema press at 200
C for 2 min at
20 kN and 8 min at 40 kN.
2.4. Characterization
2.4.1. FTIR
FTIR spectra were recorded using powder sample and a Nicolet
iS10 ATR spectrophotometer in the range of 4000e500 cm1. For
each spectrum 32 scans with a resolution of 4 cm1 were recorded.
2.4.2. Nuclear magnetic resonance
Liquid NMR was performed using a Bruker Advance 300 MHz
spectrometer. Lignin was dissolved in DMSO-d6 for 1H and stan-
dard 31P NMR. Standard 31P spectra were obtained with 1024 scans
and a delay of 2s between each pulse with or without proton
decoupling. Chemical shifts were referenced to DMSO-d6.
Quantitative 31P NMR experiments were carried out following a
slightly modied Granata and Argyropoulos method [15]. Lignin
(30 mg) was dissolved in 0.5 mL of a CDCl3/pyridine mixture (1:1.6
vol/vol). The internal standard used for quantication, N-hydroxy-
6-norbornene-2,3-dicarboximide, was then added (100 mL of 0.1 M
solution in 1:1.6 v/v CDCl3/pyridine mixture). Followed by 100 mL of
0.014 M solution of chromium(III) acetylacetonate in the same
CDCl3/pyridine mixture which was used to complete the solution in
order to homogenize and accelerate phosphorus relaxation. Finally,
100 mL of the phosphitylation reagent, 2-chloro-4,4,5,5-
tetramethyl-1,3,2-dioxaphospholane, was incorporated in the so-
lution. A portion (0.6 mL) of this mixture was eventually introduced
into a NMR tube. The spectra were recorded with 2 s relaxation
time and an average number of 1000 scans. Chemical shifts were
relative to the signal of the phospholane hydrolysis product at
132.2 ppm. The integral value of the internal standard was used for
the calculations of the absolute amount of each functional group.
2.4.3. Apparent particle size
Particle's size distribution was investigated with a Malvern
Mastersizer 3000 apparatus. Analysis was performed in water
(concentration < 0.1%) at room temperature.
2.4.4. Elementary analysis
Elementary analyzer CHNeO-Rapid (Elementar-Analy-
sensysteme GmbH) was used for the elemental analysis of carbon
and hydrogen. The amount were determined following the ASTM D
5291-92 standard. Foos-Heraeus elementary analyzer CHNeO-
Rapid was used for the elemental analysis of oxygen. The oxygen
amount was measured after combustion at 1150
C. For phosphorus
elemental analysis, the amount was determined by photometry
Table 1
Composition (wt.%) of the different formulations.
Sample ABS [wt.%] KL [wt.%] P-LIG [wt.%]
Pure ABS 100 0 0
ABS/30LIG 70 30 0
ABS/30P-LIG 70 0 30
34 B. Prieur et al. / Polymer Degradation and Stability 127 (2016) 32e43

(Spectrophotometer CADAS 100) after dissolution of the sample in rate of 10
C/min was applied from 50 to 800
C. Each sample was
acid mixture and further reaction with ammonium molybdate. tested two times to ensure repeatability of the obtained results.
Difference weight loss curves were calculated (Equation (1)) in
2.4.5. Dispersion order to determine a potential increase or decrease in the thermal
Scanning electron microscopy (SEM) images were taken at stability of the formulations, due to the incorporation of lignin into
various levels of magnication using a Hitachi S4700 eld emission ABS. These represent the difference between the experimental TGA
gun SEM at 6 kV. All samples were ultra microtomed with a dia- curve for the mixture (wexp(T)) and the linear combination of TGA
mond knife using a Leica UltraCut microtome at room temperature curves (wthe(T)) for the neat components (Equation (2)).
to obtain smooth surfaces. Electron Probe Micro Analysis (EPMA)
(Cameca SX 100) was used to characterize the dispersion of P-LIG in DwT wexp T  wtheo T (1)
ABS. X-ray mappings were carried out at 15 kV, 40 nA and a PET
crystal was used to detect the P Ka X-ray. Back-scattered electron wtheo T 0; 7  wABS T  0; 3  wLIG T (2)
pictures of the samples were taken at 15 kV, 15 nA.
Where wABS(T) and wLIG(T) are the experimental TGA curves of ABS
2.4.6. Fire testing and LIG respectively.
A Fire Testing Technology (FTT) Mass Loss Calorimeter was used
to perform measurements on samples following the procedure
3. Results and discussion
dened in ASTM E 906. The equipment used is identical to that used
in oxygen consumption cone calorimetry (ISO 5660), except that a
3.1. Phosphorylation of the lignin (P-LIG)
thermopile in the chimney is used to obtain heat release rate (HRR)
rather than by employing the oxygen consumption principle. The
The phosphorylation consists in grafting phosphorus moieties
procedure involved exposing plates (100  100  3 mm3) in hori-
onto lignin by interaction of free hydroxyl groups of lignin with
zontal orientation. Samples were wrapped in aluminum foil leaving
P2O5. The formation of phosphate groups is expected (see Fig. 1).
the upper surface exposed to the heater (external heat ux of
For the rst time, the phosphorylated lignin has been fully char-
35 kW/m2) and placed on a ceramic backing board at a distance of
acterized. In order to set the reaction conditions, pure lignin was
35 mm from the cone base. The mass loss calorimeter was used to
characterized using the Argyropoulos 31P NMR method [15]. This
determine the following principal re properties: time to ignition
technique is widely used in the lignin eld since it is very precise
(TTI), heat release rate (HRR) as a function of time, peak of heat
and reproducible [16e19]. It consists in the derivatization of the
release rate (pHRR) and total heat release (THR). All values were
lignin with a phospholane agent. This agent reacts with the lignin
calculated from the thermopile voltages recorded with a Graphtech
free hydroxyl groups. The phosphylated groups are then quantied.
GL220 data logger. When measured at 35 kW/m2, HRR, THR and TTI
The level of phosphitylation is directly related to the concentration
values are reproducible to within 10%. Tests were performed three
of hydroxyl groups. The results are presented in Table 2. More than
times to ensure reproducibility.
hydroxyl concentration, this spectroscopic method gives precious
To investigate the gases released during the MLC experiment,
information about the monomers (h e p-hydroxyphenyl; g e
the MLC unit was connected to a Fourier transform infrared spec-
guaiacyl; s e syringyl) ratios and therefore about the lignin's
trometer (MLC e FTIR). Using this device, released gases were
structure (Fig. 2). This analysis was performed only for LIG because
analyzed online quantitatively and qualitatively. Gas picking pistol
the P-LIG was unfortunately only partially soluble in the solvent
and transfer line were provided by M&C Tech Group; FTIR, Anta-
mixture. LIG is a g-type lignin, conrming that LIG is originated
ris Industrial Gas System was provided by ThermoFisher. The
from softwood species as mentioned from the producer. The con-
transfer line between the MLC and FTIR is 2 m long and was heated
centration of free hydroxyl groups concentration is 6.3 mmol/g,
up to 185
C. To assure constant temperature of the transfer line,
divided into three types: 67% of phenolic, 27% of aliphatic and 6% of
two temperature controllers were installed. Before analyzing the
carboxylic acid.
gases by FTIR, soot particles were removed by two different heated
After phosphorylation, LIG and P-LIG were characterized using
lters (2 and 0.1 mm). The temperature of the FTIR gas cell was set
spectroscopic methods. IR-ATR spectroscopy was undertaken to
at 180
C and the pressure at 650 Torr. The optical pathway is 2 m
compare the structures. Spectra are presented in Fig. 3. The curves
long and the chamber of the spectrometer is lled with dry air. FTIR
were baseline-corrected and normalized at the maximum intensity
spectra obtained using MLC-FTIR were treated using OMNIC soft-
of absorption at 1510 cm1 (aromatic skeleton stretch) [23]. The
ware. Using MLC-FTIR the following gases were quantied: water,
spectrum of the neat lignin (LIG) exhibits bands typically reported
carbon monoxide, carbon dioxide, water, nitrogen dioxide and
[21,22], such as aromatic ring vibrations due to the phenylpropane
hydrogen cyanide. Quantication is repeatable within 10%.
monomers observed at 1595, 1510 and 1425 cm1. The OeH from
Pyrolysis combustion ow calorimetry (PCFC) (Fire Testing
both aliphatic and aromatic chains are responsible of the wide
Technology e FAA Micro Calorimeter) was used to assess the
absorption band centered at 3400 cm1. It is overlaid by possible
ammability of the formulations. Tests were performed according
residual water, which cannot be avoided during FTIR measure-
to ASTM D-7309 at a heating rate of 1
C/s, a maximum pyrolysis
ments. The CeH vibrations of CH2 and CH3 groups are detected at
temperature of 750
C and a combustion temperature of 900
C.
2935, 2840 and 1460 cm1. It is interesting to notice the presence of
The ow was a mixture of O2/N2 20/80 cm3 min1 and the sample
only specic bands attributed to g moieties (1265, 1125, 855 and
weight was 7.5 0.3 mg. All experiments were made in triplicate
and HRR values are reproducible to within 5%.
Table 2
2.4.7. Thermogravimetric analysis Quantication of the reactive hydroxyl groups of LIG.
Thermogravimetric analysis was carried out using a Setaram 92 Sample OH content [mmol/g] Monomers ratio
unit. Samples were contained in silica crucibles robed with gold [%]
sheet to prevent reactions between phosphorus and silica. Samples Phenolic Aliphatic Carboxylic S g h
were ground into powder using a cryo-grinder (500 mm lter). After
LIG 4.2 1.7 0.4 13 84 3
an isotherm of 20 min at 50
C for thermal homogeneity, a heating
 B. Prieur et al. / Polymer Degradation and Stability 127 (2016) 32e43 35

0.32 ppm) clearly shows that there is no phosphoric acid in the

lignin. Regarding H3PO4 spectrum, no coupling 31Pe1H is observed
as there is only one relatively wide peak. This could be explained by
the high lability of the acid protons and so the coupling intensity is
very low. Chemical shifts of the P-LIG peaks and phosphoric acid are
very close, thus indicating that the environment of the phosphorus
nuclei is comparable with H3PO4, as expected (see Fig. 1). This could
reasonably suggests that the substitution of one PeOeH bond by a
Fig. 2. Chemical structure of the lignin's monomers [20].

Fig. 3. FT-IR of neat lignin (LIG) and phosphorylated lignin (P-LIG).

815 cm1) while only traces of h types and s bands are
observed. These observations are consistent with the above 31P
NMR analysis. After phosphorylation, the intensity of OeH band at
3400 cm1 was reduced while an additional band appeared at
1000 cm1 which was attributed to stretching vibration of P-OR
(-R LIG in this case). These changes indicate that phosphorus
groups were probably grafted onto the lignin molecules.
Liquid 31P NMR was done to complete the IR-ATR study and to
elucidate in detail the P-LIG structure. Spectra are presented in
Fig. 4.
Without decoupling, three main peaks are observed
at 1.11, 1.17 and 1.22 ppm. The comparison with H3PO4 (-
PeOeR (R LIG) makes the multiplet shift towards higher eld.
Experiment with 1H decoupling was also undertaken. It could be
assumed that there are two different types of phosphorus since two
peaks are observed. The middle peak increases signicantly (ar-
rows) while the smallest peak disappears. By looking closer, a
triplet can be distinguished without 1H decoupling, the third peak
being overlapped by the highest peak. A little shoulder is indeed
observed, and the highest peak decreases slightly when using 1H
decoupling. A coupling constant of 7.5 Hz was measured in the
triplet. Therefore, it can be supposed that the phosphorus is
coupled with two protons (J3PeH 7.5 Hz), which are part of a CH2
group of the lignin. The highest peak can be attributed to a PeO-R0

31
Fig. 4. P NMR of Phosphoric acid and P-LIG (left) and P-LIG with and without 1H decoupling (right).
36 B. Prieur et al. / Polymer Degradation and Stability 127 (2016) 32e43
where R0 is an aryl group of the lignin since there is no coupling
with proton (J4PeH is too low to be observed). By comparing areas
peaks, it appears that there is more reaction between P2O5 with
phenol groups than with aliphatic hydroxyl groups (peak
ratio 2:1). In conclusion, both ATR-IR and liquid 31P NMR con-
rms that kraft lignin was successfully phosphorylated and that
phosphate groups are linked to phenolic and aliphatic groups.
Several analyze were then performed in order to characterize P-
LIG in a quantitative and qualitative way. First, elementary analysis
was undertaken in order to quantify phosphorus in the lignin.
Average particles size were also measured. The results are listed in
Table 3. As expected, phosphorus is detected with the elementary
analysis and was quantied at 4.1% in the lignin. Percentages of
other atoms are comparable and conrm that no signicant change
occurred in the lignin structure. Concerning the apparent particle
size, P-LIG appears to be more than 4 times higher than LIG. It is
known that the particle size is a function of different process pa-
rameters, such as reaction temperature, concentration of reagents
and purication methods. Moreover afnity between the phos-
phate groups can promote agglomerate formation of the P-LIG
particles. All these parameters lead to precipitation of the product
during the reaction. P-LIG particles are a result from the above
described procedure and have a roughly fourfold diameter of the
original lignin particles. In conclusion, phosphorylated lignin were
characterized in detail and it was shown that the phosphorylation
was successful. The next step consists in incorporating LIG and P-
LIG into ABS and assessment of the re performances of the
composites.
3.2. Dispersion of the lignin in the ABS matrix
Since the nal properties of a composite, such as the FR per-
formance, strongly depends on the quality of dispersion of the
llers in the polymeric matrix [11], dispersion of LIG and P-LIG in
ABS was investigated by SEM. As expected from the particle size
analysis, the composite with P-LIG exhibited much bigger ag-
glomerates than LIG. The compounding process, therefore, did not
break these agglomerates. In order to reduce the size of P-LIG ag-
glomerates, further work could be focused on optimizing either the
phosphorylation parameters, the grinding of P-LIG or the process
parameters such as shear stress and residence time in the extruder.
It is not commented further because it is not the purpose of this
paper. Putting aside their sizes, lignin particles were well dispersed
in the ABS to form a homogeneous composite. The interface ABS/
LIG or P-LIG was observed at higher magnication and the imaging
are shown in Fig. 5. In both formulations, no cracks or defects were
noticed (except streaks due to ultramicrotome cut) indicating a
good interfacial compatibility between the ABS and the lignin, even
if this one was phosphorylated.
In the case of ABS/30P-LIG, additional back-scattering electron
(BSE) imaging and EPMA phosphorus mapping presented in Fig. 6
were conducted to evaluate the phosphorus distribution in the
composite. On such mapping, the warmer the color (warm red)
the higher the probability of nding the phosphorus element. The
imaging shows that phosphorus remains on the lignin particles and
so is consistent with the characterization done on P-LIG. Moreover,
Table 3
Phosphorus quantication and apparent particle size of LIG and P-LIG.
Samples Apparent particles size [mm] Elementary analysis
%C %H %O
LIG 79 63.3 5.8 26.7
P-LIG 367 60.6 5.6 24.7
phosphorus is found everywhere in the particle, which means that
phosphorylation occurred not only on lignin surface but also
deeper in the structure.
3.3. Thermal stability
Thermogravimetric analysis (TGA) was used on one hand to
determine the degradation steps of LIG and the inuence of the
phosphorylation on its decomposition behavior (Fig. 7), and on the
other hand to evaluate the thermal stability of the ABS/30LIG or e
P-LIG composites (Fig. 8).
Fig. 7 presents thermo-oxidative and pyrolytic decomposition of
LIG and P-LIG. Data are summarized in Table 4. As has already been
reported in the literature, no clear separate decomposition step can
be observed [2,6,12]. The complexity of the lignin structure indeed
promotes many decomposition steps, several of them overlapping
with each other. The lignin starts to degrade (5 wt.% loss) at 250
C
under air and 260
C under inert atmosphere, and maxima of mass
loss rate (MLR) are reached at 471 and 389
C respectively (Table 2).
The amount of residue remaining at 800
C is about 1 wt.% under air
conditions and 39 wt.% under nitrogen conditions. The lignin is
therefore a charring material under pyrolytic conditions. Char for-
mation is due rst to the dehydration in the structure, thus leading
to ester formation, then rearrangements and nally formation of
condensed aromatic structures [24]. The presence of aryl groups in
the initial lignin structure also promotes char formation.
After phosphorylation, P-LIG starts to decompose at lower
temperature (215
C) in comparison to LIG. This information is very
important for choosing the right processing temperature and
therefore the polymer in which the P-LIG could be incorporated.
Then above this temperature the MLR decreases in comparison to
that for LIG leading to a stabilization. The maximum MLR values is
reduced from 1.2 to 0.4 wt.%/
C and from 0.3 to 0.1 wt.%/
C under
thermo-oxidative and pyrolytic conditions respectively. At high
temperature, the residue amount increases from 39 wt.% for LIG to
55 wt.% for P-LIG.
It appears clearly that the phosphorylation induces a slight
thermal destabilization below 400
C. Dehydration in P-LIG may
occur at lower temperature because it may be activated activated
and catalyzed by P-species. Indeed it is known that phosphoric
acid-based molecules, such phosphates as in the P-LIG structure,
catalyzes dehydration of bio-based products of low thermal sta-
bility including starch [25]. Even if the LIG chemical structure dif-
fers from starch, especially regarding aromatic sites of LIG, some
analogy can be established considering hydroxyl and ester groups
with respect to dehydration potential.
Above 400
C a signicant thermal stabilization as a conse-
quence of the phosphorylation occurs. First, a higher MLR reduction
in the presence of oxygen may be attributed to the phosphorus
which is known for preventing oxidation of the char [26]. More-
over, the stabilization observed in inert conditions also demon-
strates that the presence of phosphorus increases the char
formation due to condensed phase interactions. Therefore, the
phosphorylation enhances the thermal stability of LIG at high
temperature, involving several condensed phase process. This sig-
nicant improvement is obtained with only 4.1% of phosphorus in
the lignin structure.
Plots for the pyrolytic and thermo-oxidative decomposition of
ABS/30LIG or ABS/30P-LIG composites are presented in Fig. 8 and
the data in Table 5. In the case of neat ABS, the pyrolytic decom-
position is a one-step process [27], [28]. The polymer degrades
completely from 365
C to 500
C with a maximum weight loss
%P
observed at 420
C. The incorporation of 30 wt.% of LIG induces a
0.0 thermal destabilization since the composite starts to decompose at
4.1
335
C, 30
C lower than pure ABS. This is attributed to the lower
 B. Prieur et al. / Polymer Degradation and Stability 127 (2016) 32e43 37

Fig. 5. SEM imaging of ABS/30LIG (left) and ABS/30P-LIG (right).

Fig. 6. SEM imaging (left) and EPMA mapping (right) of P-LIG dispersed in ABS.

Fig. 7. TGA curves for LIG and P-LIG under thermos-oxidative and inert atmospheres at 10
C/min.

thermal stability of LIG. A nal residue of about 14 wt.% is left at
800
C. This value was expected from the linear combination of
Equation (2). Regarding ABS/30P-LIG, no destabilization is observed
while an interesting increase of 17 wt.% of the residue amount at
800
C is noticed. Again, this amount was expected from the linear
combination of Equation (2). So no synergistic effect on the nal
residue was noticed.
The thermo-oxidative decomposition is more complex since it
involves an apparent two-step process. The rst step ranges from
325 to 420
C with a weight loss of 70 wt.% for neat ABS. The second
step, formation of the transient char commonly observed in styr-
enics [29], occurs from 460 to 590
C which then decomposes
entirely (30 wt.%) such that no residue is left. The start of the
decomposition occurs 15
C lower when 30 wt.% LIG is incorporated
in ABS. Then LIG enhances the thermal stability of ABS for the rst
step of decomposition by reducing the MLR from 1.8 to 1.2 wt.%/
C
and by limiting the weight loss to 50 wt.% instead of 70 wt.%. At
higher temperatures, LIG destabilizes the transient char by
increasing MLR from 0.4 to 1.3 wt.%/
C and reducing the step's
temperatures range (445e530
C). Considering P-LIG, putting aside
38 B. Prieur et al. / Polymer Degradation and Stability 127 (2016) 32e43

Fig. 8. TGA Curves of ABS, ABS_30LIG and ABS_30P-LIG composites under air (left) and nitrogen (right) atmospheres.

Table 4
Thermogravimetric data of LIG and P-LIG.

Thermo-oxidative atmosphere Inert atmosphere

T5% [ C] TMAX [ C] MLR [%/ C] Res [%] T5% [
C] TMAX [
C] MLR [%/
C] Res [%]

LIG 250 471 1.2 1 259 389 0.3 39

P-LIG 214 489 0.4 6 216 400 0.1 55

Table 5
Thermogravimetric data for ABS/lignin composites.

Thermo-oxidative atmosphere Inert atmosphere

T5% [
C] TMAX [
C] MLR [wt.%/
C] Res [wt.%] T5% [
C] TMAX [
C] MLR [wt.%/
C] Res [wt.%]

ABS 325 405a 1.3 1.6 366 422 1.8 1.4

ABS 30LIG 311 505b 1.3 1.5 335 410 1.2 14.2
ABS 30 P-LIG 306 355a 0.7 3.3 358 425 1.4 17.1
a
MLRMAX reached during the 1st step of decomposition.
b
MLRMAX reached during the 2nd step of decomposition.

the decrease of T5% by 20
C due to earlier degradation of the lignin,
it appears that ABS is more thermally stable. The MLR is indeed
reduced to 0.7 wt.%/
C for the rst step while the transient char
amount is increased up to 52.2 wt.%. For the second step, even if the
MLR increases slightly to 0.5%/
C in comparison to that of neat ABS,
the composite remains more stable than ABS.
In conclusion, incorporation of LIG does not clearly improve
thermal stability of ABS. But after phosphorylation, the ABS/P-LIG
composite exhibits a signicant enhancement of thermal stability
compared to that of ABS alone. Differential TGA under air is shown
in Fig. 9 and was undertaken to point out the difference of thermal
decomposition behavior of ABS/lignin composites whether LIG or
P-LIG were used. LIG stabilizes ABS below 500
C and then signif-
icantly destabilizes the transient char. The destabilization involved
during the rst step produces a less thermally stable transient char.
On the contrary, P-LIG leads to a destabilization followed by a
stabilization of the transient char. In this case, interactions in the
rst step lead to a more stable transient char. In any case, this
analysis shows that LIG or P-LIG interacts with the ABS matrix
during thermal degradation of the composite in the presence of
oxygen, which might have an inuence on the performance under
re conditions.
3.4. Fire performances of the composites
3.4.1. Mass loss calorimeter results (MLC)
The heat release rate (HRR) is considered to be one of the most
important parameters in re testing. For example a high HRR
causes fast ignition and potential ame spread. In this context,
mass loss calorimeter (MLC) testing was undertaken with a heat
ux of 35 kW/m2 in order to simulate a mild re scenario. The
curves are presented in Fig. 10, the pictures of the residues in Fig. 11
and the results in Table 6.
Virgin ABS exhibits a strong combustion starting after 80 s
exposure to the heating cone element. The combustion peak rea-
ches 480 kW/m2, the total heat released is about 70 MJ/m2 and only
few ashes as residue remained (5 wt.%). Addition of 30 wt.% LIG
leads to a faster ignition since the TTI is only 50 compared to 80 s,
but the pHRR is decreased by 43%, so is the THR but only by 13%.
Ash residue of 12 wt.% remains. When LIG is substituted by P-LIG,
no further decrease of TTI is noticed while pHRR is interestingly
reduced by 58% and THR by 20% in comparison to the corre-
sponding values for neat ABS. Again, a bimodal curve is recorded.
Moreover, the residue is increased by 17 wt.% and seems more
cohesive than that obtained with LIG composite. Incorporation of
LIG or P-LIG induces a faster ignition. Several assumptions might
explain this observation. First, the thermal stability study indicated
that lignin was a destabilizing additive for the ABS and thus pro-
moted earlier release of decomposition products. Then, it was
shown that incorporation of lignin in ABS causes change in the
sample color from light camel (neat ABS) to dark brown (ABS/30LIG
or P-LIG) leading to an increase of the heat absorption. This sug-
gests emissivity changes of the colored samples. Therefore an in-
crease of the temperature in the sample could occur due to
radiative heat from the cone. This emissivity change can be
responsible for a stronger heating of the decomposition gases, thus
 B. Prieur et al. / Polymer Degradation and Stability 127 (2016) 32e43 39

Fig. 9. TG Diff analysis for ABS/lignin composites under thermos-oxidative atmosphere.

Fig. 10. MLC curves of neat ABS, ABS 30LIG and ABS 30P-LIG.

Fig. 11. MLC residues of ABS (left), ABS 30LIG (center) and ABS 30P-LIG (right).

promoting the ignition. An increase of the thermal conductivity heat diffusion through the sample, and so better heat evacuation
may also be expected by the incorporation of aromatic full struc- from the surface. Because the TTI is decreased, it seems that the
tures induced by lignin. Higher thermal conductivity means high change in heat absorption at the surface of the sample is more
40 B. Prieur et al. / Polymer Degradation and Stability 127 (2016) 32e43
Table 6
MLC data for ABS, ABS 30LIG and ABS 30P-LIG.
TTI [s] pHRR [kW/m2]
ABS 80 482
ABS 30LIG 49 275
ABS 30P-LIG 49 202
signicant than that of thermal conductivity. Change in heat ab-
sorption coupled with earlier release of combustible products can
explain the reduction of TTI. Apart from a shorter TTI, signicant
pHRR reductions of pHRR are observed, especially with P-LIG.
However, THR reductions are less impressive. This is due to an
enlarged combustion peak which could be explained by the second
peak around 180 s. Indeed, during the combustion, the char starts
to crack and the collapse, thus allowing further heat release, and so
is responsible for the second peak of the bimodal curve [30].
From these results it seems clear that the presence of phos-
phorus in the lignin structure enhances the FR properties of the ABS
composite. It has to be taken into consideration that only 1%
phosphorus is part of the composite. As was seen above, 4.1% of
phosphorus is indeed found in the lignin and the loading of P-LIG in
the composite is set at 30 wt.%. Even with low phosphorus content,
a positive effect on FR performances is achieved. So phosphoryla-
tion of lignin seems to be very promising in terms of ame
retardancy.
In the next step, attention will be devoted to understand the
mode of action of P-LIG. First, the thermal stability analysis showed
that interactions occurred during the composite decomposition
between ABS and the lignin. An increase of the char residue amount
was recorded, also during MLC testing. The study done on the
condensed phase is not sufcient for a general understanding of the
P-LIG mode of action. Therefore, gas phase analysis was under-
taken. Decomposition gases were identied and quantied by
infrared spectroscopy and combustion was then further investi-
gated by micro-calorimetry.
3.4.2. Gas phase analysis
Gases released during the MLC test were identied and
Fig. 12. FTIR gas analysis of neat ABS, ABS 30LIG and ABS 30P-LIG.
DpHRR/ABS [%] THR [MJ/m2] DTHR/ABS [%] Residue [wt.%]
0 72 0 5%
43 63 13 12%
58 58 20 17%
quantied using an Antaris FTIR. There is no report of the analysis of
gases released during re testing of neat ABS. However, evolution of
gases during thermal decomposition in TGA of ABS under pyrolytic
conditions has previously been investigated [27,28,31]. Neat ABS
starts to release butadiene monomer around 340
C, then aromatics
such as styrene are evolved from 350 to 360
C. Acrylonitrile
evolves in the range 400e450
C.
The MLC coupled FTIR is entirely different from the TGA coupled
FTIR since there is a ame and the mass transfer cannot be
compared regarding the sizing of the samples. In order to evaluate
the combustion, water, CO and CO2 were quantied. HCN and NO
(only a small amount of NO2 was detected) were also observed as
typical ABS degradation gases. Gases evolution curves of ABS, ABS/
30LIG and ABS/30P-LIG are presented in Fig. 12 and data in Table 7.
First, combustion gases of the three formulations are compared.
For both composite formulations, all gases start to evolve 20 s
earlier than for neat ABS. In the case of ABS 30LIG, the same amount
of water is released while 8% diminution of CO2 evolution is
observed. Both NO and HCN releases are decreased by 17%. In the
case of ABS 30P-LIG, the release at a similar amount of water is
released. Carbon dioxide evolution is further reduced by 23%, as is
NO by 29%. On the contrary, an increase of 17% in the cyanuric acid
release is observed.
As expected, the shape of the curves mimics the bimodal MLC
HRR curves. For ABS/30LIG, as the pHRR's were reduced in MLC,
similar reductions in the release of water, CO2, CO and NO are
observed. Reduction of water evolution is less signicant since
lignin combustion produces mainly water and CO2 (see PCFC study
below). Peaks due to the release of water and CO2 CO decreases
more for ABS 30P-LIG, meaning that less combustibles were burnt.
The total amount detected of CO2 is particularly reduced. On the
 B. Prieur et al. / Polymer Degradation and Stability 127 (2016) 32e43
Table 7
FTIR data e Quantication of gases releases.
Peak of gases release [vppm]
H2O CO2 CO NO
ABS 35249 68746 2233 615
ABS 30LIG 23685 (23%) 44477 (35%) 1642 (26%) 388 (37%)
ABS 30P-LIG 20818 (41%) 36260 (47%) 1565 (30%) 324 (47%)
Italic signies reduction (in percentage) of evolving gases in comparison to pure ABS.
contrary, CO evolution is not further decreased, so the CO/CO2 ratio
is increased for ABS/30P-LIG. This means that the combustion is
more incomplete. Inhibition process in the ame or change in the
composition of decomposition gases may be the cause of this
observation. In addition, NO release is also further reduced to 29%.
Being directly related to ABS decomposition, this suggests that
some ABS degradation process in the condensed phase may have
changed thus resulting in a reduction of ABS decomposition
products. Interactions of P-LIG with ABS matrix are indeed sup-
ported by differential TGA. Changes in the decomposition pathways
or reactions between degradation products and FR may be
considered. Regarding HCN, an increase in gas evolution is
measured. Less HCN was burnt (since it is detected at the top of the
chimney), so the oxidative power of the ame was probably
decreased. Moreover, the pHRR and THR of the composites were
lowered. It can therefore be assumed that some interactions in the
gas phase are responsible of this phenomena. PCFC was undertaken
to support this assumption.
Combustion of the pyrolysis degradation gases was investigated
by PCFC [32]. It is important to note that the sample size is very
different that for MLC (few mg for PCFC, > 30 g for MLC) and that
the conditions in PCFC are strictly pyrolytic. However, precious
information can be obtained such as gas phase action [33] or a
change in the nature of the released gases [34]. Fig. 13 and Table 8
presents PCFC curves and summarizes PCFC data respectively.
Combustion of LIG starts around 238
C. The total heat released
is 9.8 kJ/g and the pHRR reaches 151.5 W/g. At the end of the test,
39 wt.% of the initial sample mass remains residue remains in the
pan. P-LIG values are hard to take into account since the evolved
Fig. 13. PCFC curves of LIG, P-LIG and formulations of ABS and lignin.
41
Quantication of gases [vppm]
HCN H2O CO2 CO NO HCN
101 346032 713528 26412 6310 1107
64 (37%) 344293 (1%) 657549 (8%) 23181(12%) 5216 (17%) 920 (17%)
74 (27%) 334239 (1%) 550762 (23%) 26644 (0%) 4450 (29%) 1297 (17%)
decomposition products only slightly burn and therefore mea-
surements are done at the detection limit of the apparatus. The nal
residue is about 59 wt.%. In the case of the neat ABS, the combustion
ranges from 340 to 500
C and reaches a pHRR of 600 W/g and THR
of 40 kJ/g. Addition of 30 wt.% of LIG induces a pHRR reduction of
about 30% and THR reduction of 23%. Moreover, the onset tem-
perature is lowered by 20
C leading to a shift of the combustion
peak towards lower temperature. ABS/30P-LIG combustion exhibits
the same pHRR reduction as LIG (30%), but the THR reduction is
more signicant and reached 28%.
Combustion of LIG does not release much combustible material
according to the results. Indeed more than 60 wt.% of LIG degraded
to gases, with water and CO2 probably the main products released.
The char yields are consistent with those obtained from TGA.
Regarding ABS/30P-LIG, 40 wt.% of the P-LIG decomposed in gases,
but only a very low combustion occurred. Inhibition or change in
the ABS decomposition process may be the cause of this observa-
tion. Then, pHRR reductions of both composites are related to
loading, 30%. As LIG and P-LIG do not participate (or not signi-
cantly) to the combustion, the pHRR is reduced only because
30 wt.% of ABS is replaced by non-combustible loading. The
absence of further decrease seems to indicate that no inhibition
occurs in the gas phase. However, ABS/30P-LIG exhibits a better
THR reduction. Indeed the combustion begins later and stops as
about the same time as for LIG, inducing a narrower peak. As it was
shown in the MLC-FTIR studies, both composites ignite at the same
time (earlier than for neat ABS). In MLC testing, equal TTI means
that the required concentration of combustibles gases is reached at
the same time. Therefore, only an inhibition process can explain the
42 B. Prieur et al. / Polymer Degradation and Stability 127 (2016) 32e43
Table 8
PCFC data for ABS, ABS 30LIG and ABS 30P-LIG.
Tonset [
C] pHRR [W/g] DpHRR/ABS [%]
LIG 238 151.5 e 9.8
P-LIG 125 12.9 e 1.9
ABS 340 602.6 0 37.7
ABS 30LIG 320 411.7 31.7
ABS 30P-LIG 340 411.0 31.8
PCFC peak shift of ABS/30P-LIG towards higher temperature
(20
C) in comparison to that for ABS/30LIG. This assumption is
supported by the difference in combustion between LIG and P-LIG.
This inhibition can be induced by the release of phosphorus radi-
cals, which can scavenge radicals from the ame.
4. Conclusions
The re retardancy performance of ABS polymer containing
lignin and phosphorylated lignin has been investigated. Phos-
phorylated lignin has been fully characterized using several tech-
niques (IR-ATR, liquid NMR, EPMA, and TGA). The results show that
4.1% of phosphorus is contained in the lignin structure. The thermal
stability of P-LIG was signicantly enhanced in comparison to that
for LIG. ABS/LIG and ABS/30P-LIG composites with 30 wt.% loading
were then examined. SEM and EPMA images showed that loadings
were well dispersed in the polymeric matrix, thus illustrating a
good compatibility in the system. ABS 30P-LIG exhibited very
promising FR performance since pHRR and THR are reduced by 58
and 20% respectively (MLC). However, TTI was slightly decreased.
MLC/FTIR and PCFC techniques showed that P-LIG was acting
mainly in the condensed phase by interacting with ABS during the
decomposition of the composite. These interactions induce less
release of combustibles to the ame while a charring protective
barrier is formed at the composite surface, which becomes less
efcient after a certain combustion time. A slight inhibition effect in
the ame was observed as well, probably caused by release of
phosphorus species into the gas phase.
Acknowledgments
This work has received funding from the European Union's
Seventh Framework Programme (310187) for research, technolog-
ical development and demonstration. Therefore the authors want
to acknowledge all the partners from the FRP 7 Phoenix Project. The
authors want also thanks M. Vandewalle and M. Bria for having
contributed to this work.
References
[1] S. Laurichesse, L. Ave
rous, Chemical modications of lignins : towards bio-
based polymers, Prog. Polym. Sci. 39 (2014) 1266e2120.
[2] C. Pouteau, P. Dole, B. Cathala, L. Averous, N. Boquillon, Antioxidant properties
of lignin in pp, Polym. Degrad. Stab. 81 (2003) 9e18.
m, Modication of industrial softwood kraft lignin
[3] X. Du, J. Li, M.E. Lindstro
using Mannich reaction with and without phenolation pretreatment, Ind.
Crops Prod. 52 (Jan. 2014) 729e735.
[4] C. Amen-chen, H. Pakdel, C. Roy, Production of monomeric phenols by ther-
mochemical conversion of biomass : a review, Biores. Technol. 79 (2001)
277e299.
[5] G. Gallina, E. Bravin, C. Badalucco, G. Audisio, M. Armanini, A. De Chirico,
F. Provasoli, Application of Cone Calorimeter for the Assessment of Class of
Flame Retardants for Polypropylene, vol. 22, 1998, pp. 18e21 no. July 1995.
[6] A. De Chirico, M. Armanini, P. Chini, G. Cioccolo, F. Provasoli, G. Audisio, Flame
retardants for polypropylene based on lignin, Polym. Degrad. Stab. 79 (1) (Jan.
2003) 139e145.
[7] C. Reti, M. Casetta, S. Duquesne, R. Delobel, J. Soulestin, S. Bourbigot, Intu-
mescent Biobased-polylactide Films to Flame Retard Nonwovens, vol. 4, no. 2,
THR [kJ/g] DTHR/ABS [%] Residue [wt.%]
e 39
e 54
0 0%
29.2 22.5 13%
27.2 27.9 23%
2009, pp. 33e39.
[8] R. Zhang, X. Xiao, Q. Tai, H. Huang, Y. Hu, Modication of lignin and its
application as char agent in intumescent ame-retardant poly(lactic acid),
Polym. Eng. Sci. (2012) 2620e2626.
[9] L. Ferry, G. Dorez, A. Taguet, B. Otazaghine, Chemical modication of lignin by
phosphorus molecules to improve the re behavior of polybutylene succi-
nate, Polym. Degrad. Stab. (2015).
[10] A.A. Alalykin, R.L. Vesnin, D.A. Kozulin, Preparation of modied hydrolysis
lignin and its use for lling epoxy polymers and enhancing their ame
resistance, Russ. J. Appl. Chem. 84 (9) (Oct. 2011) 1616e1622.
[11] P. Song, Z. Cao, S. Fu, Z. Fang, Q. Wu, J. Ye, Thermochimica acta thermal
degradation and ame retardancy properties of ABS/lignin : effects of lignin
content and reactive compatibilization, Thermochim. Acta 518 (1e2) (2011)
59e65.
[12] Y. Yu, S. Fu, P. Song, X. Luo, Y. Jin, F. Lu, Q. Wu, J. Ye, Functionalized lignin by
grafting phosphorus-nitrogen improves the thermal stability and ame
retardancy of polypropylene, Polym. Degrad. Stab. 97 (4) (Apr. 2012)
541e546.
[13] W. Xing, H. Yuan, P. Zhang, H. Yang, L. Song, Y. Hu, Functionalized lignin for
halogen-free ame retardant rigid polyurethane foam: preparation, thermal
stability, re performance and mechanical properties, J. Polym. Res. 20 (9)
(Aug. 2013) 234.
[14] G. Dorez, B. Otazaghine, a. Taguet, L. Ferry, J.M. Lopez-Cuesta, Use of Py-GC/MS
and PCFC to characterize the surface modication of ax bres, J. Anal. Appl.
Pyrolysis 105 (Jan. 2014) 122e130.
[15] A. Granata, D.S. Argyropoulos, a Reagent for the Accurate Determination of the
Uncondensed and Condensed Phenolic Moieties in Lignins, J. Agric. Food
Chem. 43 (1995) 1538e1544.
[16] S. Tohmura, D.S. Argyropoulos, Determination of arylglycerol-b-aryl Ethers
and other linkages in lignins using DFRC/31P NMR, J. Agric. Food Chem. 49
(2001) 536e542.
[17] A. Fradet, Structural Analysis of Alfa Grass ( Stipa tenacissima L.) Lignin Ob-
tained by Acetic Acid/Formic Acid Delignication, Biomacromolecules (2011).
[18] J.-Y. Kim, S. Oh, H. Hwang, U.-J. Kim, J.W. Choi, Structural features and thermal
degradation properties of various lignin macromolecules obtained from
poplar wood (Populus albaglandulosa), Polym. Degrad. Stab. 98 (9) (Sep.
2013) 1671e1678.
[19] C. Crestini, D.S. Argyropoulos, Structural analysis of wheat straw lignin by
quantitative 31 P and 2D NMR spectroscopy. The occurrence of ester bonds
and r -O-4 substructures, J. Agric. Food Chem. (1997) 1212e1219.
[20] D.W. Rutherford, R.L. Wershaw, L.G. Cox, Changes in Composition and
Porosity Occurring during the Thermal Degradation of Wood and Wood
Components, 2004.
[21] F. Monteil-Rivera, M. Phuong, M. Ye, A. Halasz, J. Hawari, Isolation and char-
acterization of herbaceous lignins for applications in biomaterials, Ind. Crops
Prod. 41 (Jan. 2013) 356e364.
~ a, J. Labidi, J.M. Echeverria, I. Mondragon, Physico-chemical
[22] a Tejado, C. Pen
characterization of lignins from different sources for use in phenol-
formaldehyde resin synthesis, Bioresour. Technol. 98 (8) (May 2007)
1655e1663.
[23] D. Schorr, P.N. Diouf, T. Stevanovic, Evaluation of industrial lignins for bio-
composites production, Ind. Crops Prod. 52 (Jan. 2014) 65e73.
[24] S. Duquesne, S. Bourbigot, Char Formation and Characterization, in:
C.A. Wilkie, A.B. Morgan (Eds.), Fire Retardancy of Polymeric Materials, Second
Edition, second ed., CRC Press, 2009, pp. 239e259.
[25] R. Dupretz, G. Fontaine, S. Bourbigot, Fire retardancy of a new polypropylene-
grafted starch: Part II: investigation of mechanisms, J. Fire Sci. 32 (3) (Nov.
2013) 210e229.
[26] F. Trotta, M. Zanetti, G. Camino, Thermal degradation of Cyclodextrins, vol. 69,
2000, pp. 373e379.
[27] M. Suzuki, C.A. Wilkie, The thermal degradation of acrylonitrile-butadiene-
styrene terpolymer as studied by TGA/FTIR, Polym. Degrad. Stab. 47 (1995)
217e221.
[28] L. Di Cortemiglia, G. Camino, L. Costa, M. Gualta, Thermal degradation of ABS,
Thermochimica 93 (1985) 187e190.
[29] S. Bourbigot, J.W. Gilman, C. a. Wilkie, Kinetic analysis of the thermal degra-
dation of polystyreneemontmorillonite nanocomposite, Polym. Degrad. Stab.
84 (3) (Jun. 2004) 483e492.
[30] B. Schartel, T.R. Hull, Development of re-retarded materials d Interpretation
of cone calorimeter data, Fire Mater. 31 (2007) 327e354.
[31] C.A. Wilkie, The Thermal Degradation of Acrylonitrile- Butadiene-styrene
 B. Prieur et al. / Polymer Degradation and Stability 127 (2016) 32e43 43

Terploymer Grafted with Methacrylic Acid, vol. 47, 1995, pp. 223e228.
[32] R.E. Lyon, R.N. Walters, Pyrolysis combustion ow calorimetry, J. Anal. Appl.
Pyrolysis 71 (1) (Mar. 2004) 27e46.
[33] M.-C. Despinasse, B. Schartel, Inuence of the structure of aryl phosphates on
the ame retardancy of polycarbonate/acrylonitrileebutadieneestyrene,
Polym. Degrad. Stab. 97 (12) (Dec. 2012) 2571e2580.
[34] M. Coquelle, S. Duquesne, M. Casetta, J. Sun, S. Zhang, S. Bourbigot, Investi-
gation of the decomposition pathway of polyamide 6/ammonium sulfamate
bers, Polym. Degrad. Stab. (Feb. 2014) 6e13.