Polymer Degradation and Stability 200 (2022) 109927

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Polymer Degradation and Stability

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

Char Structure and Charring Mechanism of Phosphazene-Based Epoxy

Resin during Combustion
Jinghong Liu, Xiaoqing Zhang∗, Sihui Liu, Caihong Lei
Guangdong Provincial Key Laboratory of Functional Soft Condensed Matter, School of Materials and Energy, Guangdong University of Technology, No.100
Waihuan West Road, Guangzhou 510006, China

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

Article history: The char structure and charring mechanism were important factors in determining the flame retardancy
Received 7 February 2022 of the polymer. However, relevant research on phosphazene-based polymers, which have excellent fire
Revised 29 March 2022
retardancy, was limited. In our previous work, a phosphazene-based epoxy resin (EHEP-D230) was ob-
Accepted 31 March 2022
tained with a honeycomb-like structure char after combustion. Herein, we further investigated gaseous
Available online 8 April 2022
phase degradation products of the resin through TGA-FTIR, while the condensed phase degradation prod-
Keywords: ucts, the char, were studied using a variety of characterization techniques, including EDS mapping, FTIR,
epoxy resin XPS, solid 31 P-NMR and Raman. The study shows that nitrogen products of phosphazene were found in
phosphazene both the gaseous (e.g. NH3 ) and condensed phases (e.g. pyridine, pyrrole, and quaternary-nitrogen struc-
flame retardancy ture), whereas phosphorus products (e.g. phosphoric acid-like structures) were discovered in the con-
phosphorus densed phase with an uneven distribution. This finding was confirmed by the degradation of the other
char
two phosphazene epoxy resins (HGETP-D230 and HGETP-MNA). Additionally, the distance between two
charring mechanism
defects in the EHEP-D230 char (doped carbon structures) might range between 5.6 Å and 17.2 Å, indi-
cating that the char of EHEP-D230 is highly disordered. Subsequently, we compared our research results
with those of previous studies on phosphazene degradation in the field of epoxy, and offered a global
chemical structure of EHEP-D230’s char. Furthermore, a charring mechanism involving the aggregating-
pressing process of phosphorous was proposed.
© 2022 Elsevier Ltd. All rights reserved.

1. Introduction structures have been employed in a variety of polymers, such as

Polymers are intrinsically flammable because of their high hy-
drocarbon content, so fire retardant additives or reactive agents
are added to polymers to reduce flammability. With an alternat-
ing phosphorus and nitrogen atom structure, phosphazenes are
excellent fire retardants [1], and almost all linear phosphazenes
and cyclic phosphazenes can be applied to fire resistance [2].
The cyclic phosphazene was more popular than the linear phos-
phazene. It was because cyclic phosphazene could be directly
derivatized from hexachlorocyclotriphosphazene (HCCP) by means
of a P-Cl substitution reaction. In the case of linear phosphazene,
vacuum and high temperature (∼250°C) conditions were required
to allow ring-opening polymerization of HCCP and the formation of
linear phosphazene [3]. More importantly, cyclic phosphazene ex-
hibited higher rigidity [4] and thermal stability than linear phos-
phazene [5], making it an attractive candidate for fire retardant
in polymers. Up to now, cyclic phosphazene and corresponding
∗ ilar char morphology has ever been observed [12,17–23]. Hence,
Corresponding author: Dr. Xiaoqing Zhang. Guangdong University of Technology,
China.
E-mail address: zhangxq@gdut.edu.cn (X. Zhang).
polyethylene terephthalate [6,7], polylactic acid [8,9], polyurethane
[10], polybenzoxazine [11], polyamide [12] and epoxy resin [3].
Despite the fact that fire retardant cyclic phosphazene poly-
mers have been widely prepared, researchers have proposed var-
ious flame retardant mechanisms for cyclic phosphazene. Levchik
[7] considered that a vaporizable cyclic phosphazene additive is
most likely to work in the gaseous phase, while in other papers,
crosslinked cyclic phosphazene might be a condensed phase fire
retardant [13,14]. Additionally, the synergistic effect of phospho-
rus and nitrogen on spiro-substituting cyclic phosphazene was re-
ported [15]. It was inferred that phosphazene makes a contribution
to both the gaseous and condensed phases. These findings suggest
that cyclic phosphazene’s flame retardant mechanism is based on
the structure of its substituting group.
In particular, in our previous work, a nonflammable eugenol-
substituting cyclic phosphazene epoxy resin was prepared, and
a honeycomb-like structure char was obtained after the cone
calorimetry test [16]. In cyclic phosphazene epoxy resin, no sim-
we deem that the unique char was a comprehensive contribu-
tion of eugenol, cyclic phosphazene, and the curing agent, and we

https://doi.org/10.1016/j.polymdegradstab.2022.109927
0141-3910/© 2022 Elsevier Ltd. All rights reserved.
J. Liu, X. Zhang, S. Liu et al.
Fig. 1. Chemical structure of involved epoxy compounds and curing agents.
plan to conduct further research on it. Although a few remarkable
works with comprehensive characterizations have been published
in the flame retardant field [24,25], limited characterizations have
generally been employed to identify the condensed and gaseous
phase products in phosphazene fire retardant systems. For exam-
ple, FTIR was the most frequently used method for char charac-
terization, but it was often the only characterization for char in
numerous studies [22,26–29]. The residual char is usually com-
plicated, and distinguishing accurate information from substantial
overlapping signals is a challenging task, so limited characteriza-
tions might give a subjective conclusion. Consequently, some re-
searchers [12,17,19,26,30–34] considered the P=N bond existed in
residual char due to the discovery of a peak at ∼1200 cm−1 in
FTIR, while others [9,27,29,35–37] held the opposite view that the
peak should be attributed to the P=O bond.
Therefore, in this work, we conducted a follow-up investiga-
tion on the char and pyrolysis gases of eugenol-based phosphazene
epoxy resin (EHEP-D230), which were obtained in our previous
work [16]. The gas phase products were analyzed using TGA-FTIR,
while the condensed phase was discussed based on the results
of EDS mapping, FTIR, XPS, solid 31 P-NMR and Raman. Besides,
hexaglycidylether-triphosphazene (HGETP) was synthesized, and its
relevant resins cured with polyether amine (D230) or methyl nadic
anhydride (MNA) (Fig. 1) were employed as supporting evidence
for TGA-FTIR, FTIR, and XPS. According to the results, the phosp-
hazene degradation products during combustion will be studied as
well. Finally, a possible chemical structure of the EHEP-D230’s char
and a reasonable formation process were proposed.
2. Experiment
2.1. Materials
EHEP was synthesized according to ref [16]. Glycidol, sodium
hydride (60 % dispersion in mineral oil), chromium (III) acetylacet-
onate (Cr(acac)3 ) and methyl-5-norbornene-2,3-dicarboxylic anhy-
dride (mixture of isomers, MNA) were purchased from Aladdin
reagent (Shanghai, China). Hexachlorocyclotriphosphazene (HCCP)
was supported by Shandong Zibo Blueprint Chemical Co., Ltd. JEF-
FAMINE®D230 (AHEW = 60 g/eq) was obtained from Huntsman
Advanced Chemical Materials (Guangdong) Co., Ltd. Other solvents
and inorganic reagents were provided by Tianjin Zhiyuan Chemi-
cal Reagent Co., Ltd. Except for distillation of tetrahydrofuran (THF)
2
Polymer Degradation and Stability 200 (2022) 109927
with sodium to remove water and recrystallization of HCCP from
hexane, other reagents were used as received with no further pu-
rification.
2.2. Synthesis of HGETP
38 g of 60% sodium hydride (0.95mol) was put in a three-
necked flask and washed three times with hexane to remove any
remaining mineral oil. And then, with magnetic stirring, anhydrous
THF (200 mL) was added into the flask to transform the mixture
into a gray-turbid liquid. A solution of glycidol (73 g, 0.98 mol) in
anhydrous THF (150 mL) was added dropwise into the flask un-
der an ice bath, and the hydrogen was removed with nitrogen. It
turned from a turbid liquid to white without the gas escaping 3
hours after glycidol was added, indicating that the dehydrogena-
tion reaction was approximately complete. At that point, a solution
of HCCP (38 g, 0.11 mol) in anhydrous THF (250 mL) was added to
the system under a fresh ice bath, and the reaction was stirred
at room temperature for 24 hours. After removing solids from the
system, the filtrate was concentrated on a rotary evaporator to ob-
tain a viscous liquid. It was further dissolved in CHCl2 , washed
once with H2 O, and twice with saturated NaCl solution. After dry-
ing with Na2 SO4 and removing CHCl2 , a colorless oily liquid with
an 80% yield was obtained. 1 H-NMR (600 MHz, Chloroform-d), δ :
4.19 (ddt, 1H), 3.89 (dtd, J 1H), 3.26-3.22 (m, 1H), 2.84-2.80 (m,
1H), 2.66 (dd, 1H). 31 P-NMR (600 MHz, chloroform-d, decoupling)
δ : 17.9.
2.3. Preparation of epoxy resins and their char
The preparation of EHEP-D230 resin was published [16], and
its char was produced using a cone calorimeter. For the HGETP-
D230 resin, HGETP (30 g) was put into a flask, and stoichiomet-
ric D230 (19.5 g) was added under magnetic stirring. Because of
the poor compatibility between HGETP and D230, the mixture was
heated at 60°C for 2-3 min so they would be homogeneous in
the flask. Sequentially, the mixture was poured into a mold, de-
gassed, and cured with a program of 60°C/1 h + 80°C/2 h+ 100°C/2
h + 120°C/2 h. For the HGETP-MNA resin, HGETP (30 g) was placed
in a flask and Cr(acac)3 (1 g) was added as an accelerant. The sys-
tem was then stirred at 100°C until visually homogeneous. Then,
MNA (47.4 g, 1.18 eq of epoxy group) was added into the flask
and mixed well again. Sequentially, this mixture was poured into a
J. Liu, X. Zhang, S. Liu et al.
mold, degassed, and cured with a program of 180°C/2 h + 200°C/6
h. The curing program of the epoxy resins was set according to the
DSC curves shown in Fig. S3. Finally, the char of HGETP-D230 and
HGETP-MNA was obtained from the LOI test.
2.4. Characterization
All the NMR tests (liquid and solid) were performed at room
temperature using a Bruker AVANCE III 600 MHz nuclear magnetic
resonance spectrometer. Liquid NMR uses CDCl3 as a solvent and
TMS as the internal standard. The solid NMR sample was taken
from the inner and outer char after the cone calorimetry test, and
it was uniformly ground with an agate mortar.
The morphology and Energy Dispersive Spectroscopy (EDS)
analysis of the residual char layer were observed using scanning
electron microscopy (SEM) on a Hitachi S-3400N-Ⅱ scanning elec-
tronic microscope (Japan) at a 15 kV accelerating voltage. Samples
were fixed with “PELCO© Colloidal Graphite (isopropanol Base)”
colloidal graphite from TED PELLA company, and the surface was
sprayed with gold.
Differential scanning calorimetry (DSC) measurements were
carried out on Mettler–Toledo DSC 3 with a heating rate
of 10°C/min and a purge rate of 50 mL/min nitrogen. Sam-
ple preparation: EHEP/D230 was mixed with the assistance
of dichloromethane and the solvent was removed in vacuo.
HGETP/D230 was homogeneously mixed at 60°C and then quickly
frozen with ice water. For HGETP/MNA samples, HGETP and
Cr(acac)3 must be mixed uniformly at 120°C, cooled to room tem-
perature, and then MNA was added and mixed uniformly.
Fourier transform infrared spectroscopy (FTIR) was performed
using a Nicolet IS-50 FTIR spectrometer (Thermo Fisher), and all
the samples were prepared using the KBr method to make disks.
TGA-FTIR was performed on TGA/DSC3+ (Mettler-Toledo) and
Nicolet IS-50 (Thermo Fisher) with a heating rate of 10°C /min and
a purge rate of 20 mL/min nitrogen. All samples were cut from LOI
splines and had a blocky appearance.
X-ray photoelectron spectroscopy (XPS) was carried out on Es-
calab 250Xi (Thermo Fisher). The X-ray source’s beam spot was
650 μm (Al Ka). The Avantage software was employed to fit the
peaks, and the charging correction reference peak was the highest
peaks of C1s (graphite carbon) at 285.0 eV. The EHEP-D230 char
was collected similarly to the solid-state NMR. The HGETP-D230
and HGETP-MNA chars were taken from LOI testing. Additionally,
the char samples were finely ground to ensure that the XPS results
reflected the average.
Raman spectroscopy was carried out on a LabRAM HR Evolu-
tion (HORIBA Jobin Yvon) with a 532 nm laser source. Peakfit v4.12
software was used for the fitting. The EHEP-D230 char sample was
prepared in the same way as for solid-state NMR. The char powder
was spread evenly on a glass slide for testing.
3. Results and discussion
3.1. Degradation Products of EHEP-D230
3.1.1. TGA-FTIR
Gaseous products are the fuel that supports polymer burning,
so the quantity and kind of the gases are important factors in in-
fluencing polymer flammability. Herein, TGA-FTIR was employed to
assess the quantity and kind of the gaseous products.
According to the TGA and DTG results in Fig. 2, EHEP-D230
degraded at 265°C (Td5%), and closed values were observed for
HGETP-MNA and HGETP-D230 (269 and 274°C, respectively). Sub-
sequently, a rapid descent appeared in the curve of EHEP-D230 af-
ter the Td5% point (called Step 1), then the descent rate (slope)
got mild over ∼330°C (called Step 2), and finally little mass loss
3
Polymer Degradation and Stability 200 (2022) 109927
was observed above ∼500°C, which had been reported in previ-
ous work [16]. The mass change of the other two phosphazene
epoxy resins was consistent with EHEP-D230. The values of Td5%
and TGA curves suggest the cyclic phosphazene epoxy resins fol-
lowed a similar degradation process, which may be attributed to
the phosphazene structure. The total amount of evolved gas was
64.5wt%, 45.1wt%, and 68.6wt% for EHEP-D230, HGETP-MNA, and
HGETP-D230, respectively. The highest gas mass of HGETP-D230
was attributed to its aliphatic hydrocarbon network, while EHEP-
D230 with the introduction of eugenol caused a higher char yield
and lower gas mass. For the HGETP-MNA, there may be three rea-
sons for its lowest gas yield. Firstly, MNA had an unsaturated endo-
cyclic structure, which aided in the formation of char. Secondly, an
abundant ester might produce carboxylic acid to promote charring.
Thirdly, a large number of MNAs added was another considerable
reason for the low gas yield.
The characteristic absorption bands of release gas products on
FTIR spectra were used to identify the kind of pyrolysis gases from
EHEP-D230 (Fig. 3). During step 1 (from 265 to 330°C), a series
of strong absorption peaks were found, such as 30 0 0-2750 cm−1 ,
1461 cm−1 , 1377 cm−1 for aliphatic hydrocarbons, 1741 cm−1 for
carbonyl, 1624 cm−1 for olefin, and 1117 cm−1 for aliphatic ether
[38]. Meanwhile, significant absorption of ammonia (3332, 962,
and 929 cm−1 ) and a small quantity of water (burr-like peaks
over 3500 cm−1 ) were also observed. These results suggested that
the main pyrolysis gases in step 1were aliphatic oxygenated com-
pounds and ammonia, which were produced from the degrada-
tion of the polyether amine (D230) structure. As the tempera-
ture increased to step 2 (from 330 to 500°C), the carbonyl, olefin,
and aliphatic ether peaks weakened, while some aromatic prod-
uct peaks were still observable in the FTIR. For instance, a series of
peaks between 1600 and 1450 cm−1 were assigned to the aromatic
rings, and the peak at 1266 cm−1 was attributed to the aromatic
ether (Ar-O) compounds. Additionally, as the absorption peak for
methane at 3014 cm−1 increased, the phenolic hydroxyl absorp-
tion peak at 360 0-350 0 cm−1 was split into two peaks, indicating
that eugenol’s ortho-methoxy phenol structure cracked into cate-
chol derivatives and methane [39]. It was noteworthy that ammo-
nia continued to volatilize even up to a maximum temperature of
475°C in step 2, implying that it degraded from another nitrogen
source, cyclic phosphazene. However, no phosphorus-containing
volatiles were detected in the pyrolysis gases, and it was consid-
ered that they remained in the condensed phase.
The TGA-FTIR and its overview of HGETP-MNA and HGETP-
D230 are shown in Fig. S4-S8. The pyrolysis gases of these two
resins were mainly degraded from the curing agent segment dur-
ing step 1, which was similar to EHEP-D230. For example, the
peaks at 1797 cm−1 for anhydride and 1733 cm−1 for carboxylic
acid indicated degradation of the MNA structure in the case of
HGETP-MNA, whereas 1117 cm−1 of the C-O bond and the peaks
of aliphatic hydrocarbons mentioned previously could prove the
gases from the D230 structure in the case of HGETP-D230. For
step 2, alkyl compounds in the resins were cracked into small
molecules such as methane, and the resulting residue was ready
for carbonization. Meanwhile, some conclusions drawn from EHEP-
D230 could be confirmed by the TGA-FTIR results of HGETP-MNA
and HGETP-D230. Firstly, as indicated in the TGA-FTIR results for
the EHEP-D230, ammonia was detected in steps 1 (between 265
and 330°C) and 2 (between 330 and 500°C). This ammonia gas
might come from two different nitrogen sources, D230 and phosp-
hazene. HGETP-D230, which also contains both phosphazene rings
and D230, had similar results to EHEP-D230 (Fig. S4 and S7). How-
ever, ammonia was observed only in step 2 of HGETP-MNA (Fig.
S5 and S8), which comprises just phosphazene rings. As a result of
the above findings, we concluded that the production of ammonia
during step 1 was due to D230, while the production of ammonia
J. Liu, X. Zhang, S. Liu et al.
Fig. 2. TGA (a) and DTG (b) curves of EHEP-D230, HGETP-MNA and HGETP-D230.
Fig. 3. Pyrolysis gases from EHEP-D230 by TGA-FTIR.
in step 2 was due to phosphazene. Secondly, when compared with
EHEP-D230, the methane peak (3014 cm−1 ) in the FTIR spectrum
of HGETEP-D230 was smaller and almost completely covered by
aliphatic hydrocarbon (30 0 0-2750cm−1 ) peaks in step 2, indicating
that the methane generated by EHEP-D230 was principally cracked
from the methoxy of eugenol rather than other alkane structures.
According to the discussion mentioned above, gaseous prod-
ucts of EHEP-D230 were proposed during the heating process, as
illustrated in Fig. 4. In summary, EHEP-D230 exhibited two steps
of thermal degradation. In step 1, the gaseous products were at-
tributed to the degradation of the curing agent D230 and partial
eugenol structure, whereas the released gases were primarily re-
lated to the eugenol structure degradation in step 2. As the tem-
perature continually increased, the methoxy groups and the phos-
phazene ring thermally cracked into methane and ammonia, re-
spectively. It was also worth noting that the production of wa-
ter and ammonia during the degradation would help to prevent
the other fuel gases, such as ethers and methane, from burning
fiercely. Finally, about 35.5% by weight of non-volatile substances
are retained in the condensed phase as residual char.
4
Polymer Degradation and Stability 200 (2022) 109927
3.1.2. EDS Mapping
The honeycomb-like structure char of EHEP-D230 attracted our
interest most, because a char with a similar appearance had never
been reported in other phosphazene epoxy papers. Additionally,
the char exhibited a heterogeneous morphology in SEM, suggest-
ing that they might have a different chemical composition. Hence,
EDS mapping was performed to gain a better understanding of the
element distribution in the EHEP-D230’s char.
EDS Mapping of carbon, nitrogen, and oxygen elements exhib-
ited a similar pattern to SEM images (Fig. 5), implying the three
elements were evenly distributed in the carbon layer. In the case
of phosphorus, the light field was found in a gap between vesi-
cles, which was quite different from the distribution of C, N, and
O, indicating that phosphorus elements had gathered in the gap.
However, because no information about the chemical structure of
the char was obtained, we have no idea why this aggregation oc-
curred. To clearly answer this question, we intend to conduct fur-
ther research on the char of EHEP-D230.
3.1.3. FTIR
The infrared spectrum is a frequently utilized method for study-
ing the char component. It can give us approximate information
about the infrared active compounds in the char. As shown in
Fig. 6, the characteristic phosphorus compound peaks were iden-
tified, such as a broad peak between 3200 and 2500 cm−1 for PO-
H, peaks in the range of 1604 cm−1 for the O=P-O structure, and
a peak at 490 cm−1 for P=O [40].It indicated that phosphoric acid
(O=P-OH) existed in the condensed phase after cyclic phosphazene
epoxy combustion. The presence of a strong peak at 970 cm−1
for the P-OC bond implied that phosphoric acid was connected to
the carbon layer rather than dissociating in char. Besides, the lo-
cation of the P-OC bonds at 970 cm−1 suggested that the oxygen
atom was linked to the aromatic rather than the aliphatic part of
char, because the absorption of P-O (C aliphatic) is located at a
higher wavenumber (usually more than 10 0 0 cm−1 ) than that of
P-O (C aromatic) [40]. These results showed that phosphoric acid-
like structures (O=P-OH) were the main phosphorus compounds
in char, which were linked to the aromatic part of the carbon layer
through the P-OC bond.
Nitrogen compounds were also detected. For example, the peak
at 3419 cm−1 is attributed to a secondary amine, and this peak
is in the high wavenumber region of the secondary amine (3450-
3250 cm−1 ), which implies that this secondary amine was a cyclic
secondary amine [38]. Meanwhile, there remained debate on the
peak’s assignment at 1400 cm−1 [41]. We considered that it should
be attributed to the semi-circular ring stretching vibrations of a ni-
trogenous heterocycle [38], such as the melamine structure, which
J. Liu, X. Zhang, S. Liu et al.
Fig. 4. Gaseous products of EHEP-D230.
Fig. 5. Element mapping of EHEP-D230 char.
agrees with the view of Wei Mingzhu et al. [41]. In particular, the
same nitrogen-containing absorption was observed in HGETP-MNA,
which had a single nitrogen source from phosphazene (Fig. S10),
demonstrating that some nitrogen of the phosphazene remained
in the condensed phase in the form of the heterocyclic structures,
while the others escaped into the gaseous phase. However, based
on the FTIR results, we were unable to identify the existence of
the entire phosphozene ring that existed in the char. The typical
vibration absorption of N=P-N in the phosphozene ring was often
detected between 1170 and 1438 cm−1 [42], but this range was
part of a fingerprint region with complex and overlapping peaks.
For example, aromatic C-OP would form one or more peaks at
∼1200 cm−1 [40], P=O vibrations would show a wide range of
1097-1314 cm−1 [43], and aromatic C-OC absorption would cover
the region 1200-1250 cm−1 [38]. Hence, additional studies should
be performed to gain a greater understanding of the char’s chemi-
cal composition.
3.1.4. XPS
The chemical composition of char was further investigated us-
ing XPS. The C, O, N, and P element contents of the EHEP-D230
char were 70.8 %, 22.0 %, 3.6 %, and 3.6 % (Table S1), respectively.
The TGA-FTIR and FTIR results above show the nitrogen products
of phosphazene were detected in both the gaseous and condensed
phases, whereas phosphorus products were discovered in the con-
densed phases. That means the phosphorus content in the char
should be higher than that of the nitrogen one, which was con-
5
Polymer Degradation and Stability 200 (2022) 109927
firmed by the element contents of the HGETP-MNA char (Table S1).
However, the same phosphorus and nitrogen content were found
for EHEP-D230 char. It also indicated that a section of the N ele-
ment in the D230 segment would remain in the condensed phase.
The high-resolution XPS result of the EHEP-D230 char is exhib-
ited in Fig. 7. In the C1s spectrum, the curve was resolved into
three peaks (285.0, 286.2, and 289.2eV). The peak at 285.0 eV was
attributed to the C-C bond in graphite, the peak at 286.2 eV was
assigned to the C-O bond in aromatic oxide, and another peak at
289.2 eV corresponded to the carbonyl groups of quinones [44].
These are consistent with the FTIR results (Fig. 6, the character-
istic absorption of quinones was between 1550 and 1680 cm−1 ,
lower than carbonyl [45]). As for the peaks at 286.2 eV, the bind-
ing energy of C=N also peaks here [46], but the C-O bond was
still the main cause of this peak due to the oxygen content almost
six times that of nitrogen in the EHEP-D230 char. In addition, the
N1s spectrum was fitted by three peaks located at 398.7, 400.0,
and 401.4 eV, respectively. The peak at 398.7 eV was attributed
to the pyridine structure, the peak at 400.0 eV was assigned to
the pyrrole in accordance with its FTIR absorption of 3419 cm−1 ,
and the peak at 401.4 eV corresponded to the quaternary-nitrogen
structure (graphitic nitrogen structure) [47–49]. These results indi-
cated that the nitrogen element was doped with a heteroaromatic
structure in char. The phosphazene structure (-P=N-) that is usu-
ally claimed in char was also considered in this study. According
to references [50,51], the -P=N- binding energy (398∼400 eV) was
found to be related to the phosphorus substituents, the higher the
J. Liu, X. Zhang, S. Liu et al. Polymer Degradation and Stability 200 (2022) 109927

Fig. 6. FTIR sepctum of EHEP-D230 char.

Fig. 7. High resolution XPS of EHEP-D230 char.

electronegativity of the substituents, the higher the binding en-
ergy. Given the char’s chemical environment, we assumed that the
most likely substituent was aryloxy, whose binding energy of phos-
phazene compounds was reported at 398.0±0.3 eV [51,52]. How-
ever, the phosphazene structure does not appear to be present in
the char because the peak at 398.0 eV cannot be obtained by split-
peak fitting in the N1s spectrum.
Besides, the curve of O1s was divided into two peaks at 533.4
and 531.9eV. The former was attributed to the ether band (-O-)
of aromatic ether and phosphate, while the latter was assigned to
the carbonyl (C=O) of quinones and the phosphoryl (P=O) of phos-
phate [44,53,54]. These results were consistent with the FTIR and
C1s spectrum conclusions. As for the P2P spectrum, two peaks at
135.0 and 134.2 eV were used to fit the curve. The peak at 135.0 eV
was attributed to phosphorus in multiunit phosphoric acid, such as
pyrophosphoric acid or polyphosphoric acid, which was reported at
135.3 eV in the NIST Database [52], indicating that the phosphoric
acid structure was dehydrated to produce polyphosphoric acid or

6
J. Liu, X. Zhang, S. Liu et al.
31
Fig. 8. Solid state P-NMR of EHEP-D230 char.
pyrophosphoric acid structure. The peak at 134.2eV was assigned
to the phosphoric acid-like structure (one phosphoric acid struc-
ture) linked to the carbon layer through P-O-C bonds [55]. Accord-
ing to their area under the fitting curve, phosphoric acid-like struc-
tures were the main component of P-containing structures in the
EHEP-D230’s char. HGETP-D230 and HGETP-MNA both had similar
peaks and attributions for C, O, N, and P (Fig. S11), except ∼289
eV for carbonyl in HGETP-D230 and ester in HGETP-MNA.
3.1.5. Solid-state 31 P-NMR
To confirm that no phosphazene structure or P-N bond struc-
ture exists in the char of EHEP-D230, solid-state 31 P-NMR was per-
formed. As shown in Fig. 8, there was only one visible peak that
was located at 0.3 ppm and covered the range -5 to +5 ppm.
This signal was attributed to phosphoric acid-like structures, such
as O=P-(OAr)2 OH and O=P-(OAr)(OH)2 [55]. This indicated that
most of the phosphorus elements in EHEP-D230 char existed in
the form of O=P-(O)3 , which was consistent with the results ob-
tained by FTIR and XPS. Additionally, the other three peaks at
50.0, 32.1, and -49.8 ppm were found in the enlarged graphs of
Fig. 8. The peaks at 50.0 and -49.8 ppm were assigned to spin-
ning sidebands of the main peak at 0.3 ppm due to their sym-
metrical distribution on both sides of the main peak [54,56]. The
peak at 32.1 ppm could be caused by the O=P(Ar)3 structure which
was reported at 33.1 ppm [55], or by the O=P-(OAr)2 (Ar) struc-
ture which was reported at 30.4 ppm [57]. These structures with
P-C bonds might be produced through two possible processes. One
process involved the removal of CO or H2 O molecules from phos-
phoric acid-like structures (O=P-O-C or O=P-OH) to produce phos-
phoryl radicals (O=P•), which could react with aromatic radicals
(Ar•) on the graphite to generate O=P-Ar at high temperatures
[55]. The other possible process was that phosphazenium cation
(N=P+ − OAr1), an ionization form of the phosphazene structure
(N=P-OAr1), reacted with the aromatic ring (Ar2) on other phos-
phazenes at a temperature higher than 400°C [58]. It would result
in the formation of an N=P-Ar2 structure with a P-C bond, which
would further degrade during combustion into O=P-(OAr)2 (Ar) or
O=P(Ar)3 structures and remain in the char. Both processes pro-
duced O=P-(OAr)2 (Ar) or O=P(Ar)3 structures, suggesting that the
original resin structure of EHEP-D230 was completely carbonized
and the phosphazene structure was most likely destroyed. What’s
more, no other peaks were found to prove the existence of the
phosphazene structure according to phosphazene 31 P-NMR [59].
In summary, FTIR, XPS, and 31 P-NMR analyses revealed that the
structures of quinones (C=O), aromatic oxides (C-O), and nitrogen
7
Polymer Degradation and Stability 200 (2022) 109927
Fig. 9. Raman of EHEP-D230 char.
heterocyclics (N1s ) in EHEP-D230 char. Phosphorus was predom-
inantly found in a phosphoric acid-like structure, and little P-C
bond structure observed. Additionally, it definitely demonstrated
that no phosphazene ring structure existed in the char that was
degraded during combustion.
3.1.6. Raman
The Raman spectroscopy technique is widely used to character-
ize carbonaceous materials. Typically, the Raman curve is fitted us-
ing two peaks (D1 and G peak). The vibration peaks of disordered
carbon (D1 peak) and sp2 -hybridized carbon or graphitic carbon
(G-peak) are located at approximately 1365 and 1600 cm−1 , re-
spectively. The degree of graphitization of carbon materials is cal-
culated by the area ratio (AD1 /AG ) or intensity ratio (ID1 /IG ) of the
D1 and G peaks. The two-peak fitting method seems to be suit-
able for ordered carbon materials, such as graphene and graphene-
based nanoforms, where the D1 and G peaks are distinct and sepa-
rate [60]. For highly disordered carbon materials, such as char and
soot, their Raman spectra are more complex, so it is necessary to
introduce three additional peaks (D2, D3, D4) for spectral fitting
[61]. Each of the five peaks (D1, D2, D3, D4, G) has its own physical
meaning [61]. However, many studies in the field of flame retar-
dancy use the two-peak method to fit the Raman spectra of char,
which may result in a low ID1 /IG (AD1 /AG ) ratio because the large
peak composed of D3, D2 and G peaks is often regarded as the
“G peak”. Here, we adopt the more convincing five-peak method
to fit the Raman spectrum curve, as shown in Fig. 9. The Raman
spectrum of EHEP-D230 char was resolved into five peaks (D1, D2,
D3, D4, and G), the fitting parameters for which are described in
Table S2, and the corresponding attributions are detailed in refer-
ence. The fitting results showed that the intensity ratio of ID1 /IG
was 1.836, and AD1 /AG was 4.274. Then, the distance between two
defects, LD , was calculated using Eq. (1) for undoped amorphous
carbons (LD < 3 nm) [62,63]:
    I ( D1 )
LD 2 nm2 = 5.4∗10−2 ∗EL 4 eV4 ∗ (1)
I (G )
where EL (eV) is the excitation energy of the 532 nm laser source,
which is 2.3367 eV. It should be noted that Eq. (1) is only valid for
samples without charged impurities and intercalants, as charged
impurities and intercalants are not Raman active (do not cause D
peaks) [63]. However, it was still used to calculate the defect dis-
tance of the char of EHEP-D230 because there was no more con-
venient way to estimate the LD of doped carbon than with this
equation [64,65]. As a result, the calculated LD value of 1.72 nm
(17.2 Å) was obtained. EHEP-D230’s char was doped with phospho-
rus and nitrogen, which were defects but might not have caused
J. Liu, X. Zhang, S. Liu et al. Polymer Degradation and Stability 200 (2022) 109927

• NH3 . However, characterizations were never found in

some different views about products from phosphazene:

• phosphazene, polyphosphoric acids and phosphorus

Gases mainly came from the organic part, but there are

• polyphosphoric acid, phosphorocarbonaceous and

• ambiguous “phosphorus compound”.[34,36,72,73]

=2.04[18], 2.71-2.89[66], 3.30[30], 2.41-2.67[68],

• little N element became gas phase species.[29]

• Structures with N=O,N-H,C-N,N-P bonds. [35]

• Two-peak fitting method, Area ratio AD1 /AG

phosphorooxidative.[27-29,35,66,67,69-71]
• chemicals containing P-O-C(Ar).[66]
• NH3 and phosphoramidic acid.[35]

• phosphazene.[14,17,21,22,26]
the works.[17,36,66,67]

1.13-1.16[36], 1.19[71].
• C-N compound[29, 66]
oxides.[18,19,30,68]
Views in other works

• No Fitting.[70]
• phosphazene.
Fig. 10. A possible minimum unit of EHEP-D230 char (C19.6 NO6 P)x .

the D peak, so the calculated LD value of 1.72 nm was the maxi-

• heterocyclic structure, such as pyrrole-, pyridine- and

• Five-peaks fitting method, ID1 /IG =1.84, AD1 /AG =4.27

mum distance for the defects. It implies that the length of the or-
dered carbon structure was 1.72 nm, approximately equal to six

• poly phosphoric acid-like structure with a little

aromatic rings in length. On the other hand, based on the atomic
ratio determined by XPS (3.1.4), the chemical formula of the EHEP-
D230’s char was (C19.6 NO6 P)x , suggesting that approximately 19-20
• most pyrolysis gases from the organic part (non-phosphazene part).

carbon atoms were doped with one phosphoric acid-like structure

(O=PO3 ), one nitrogen heterocycle, and one ether bond or carbonyl

quaternary-nitrogen structure
O=P(Ar)3 and O=P(Ar) (OAr)2
group. As illustrated in Fig. 10, we constructed a possible penta-
aromatic ring structure for C19 NO6 P. It was a minimum unit for
(C19.6 NO6 P) x , because the number of P and N atoms might be a
• the phosphazene also degraded and released NH3

minimum integer at this proportion. The LD of this structure could

• Phosphorus and some nitrogen remain in char.

be approximately regarded as LDmin , the minimum value for the

char’s LD . Hence, we could get the LDmin value of 5.6 Å by simple
Results in this work

geometric calculation.
In summary, the following range of values for LD was deter-
mined:
LDmin = 5.6 Å < LD < 17.2 Å = LDmax
Comparison this work to others works on phosphazene degradation.

Phosphorus-containing structure

For reference, the LD values for methane soot, ethylene soot,

Nitrogen- containing structure

and benzene soot were 11.7 Å, 12.2 Å, and 13.0 Å [62], respectively.
They are commonly recognized as disordered char with an amor-
phous carbon structure. Thus, the EHEP-D230’s char was classified
as highly disordered with a low degree of graphitization. Through
the scattering of electrons and phonons, this disordered char could
Graphite layer

achieve lower thermal conductivity, protecting the underlying resin

from high temperatures.

3.2. Comprehensive analysis and comparison of products during

EHEP-D230 degradation
Product in different phase

As stated in the introduction, there are numerous arguments

concerning phosphazene degradation. From 20 0 0 to 2021, 22
pieces of literature [14,17–19,21,22,26–30,34–36,66–73] on the
Condensed

themes of “epoxy” and “phosphazene” were collected, and their

Gas phase

views on phosphazene degradation were sorted out in Table 1.

phase
Table 1

Only a small proportion (7/22) of the literature was devoted to

research on pyrolysis gas. This literature supported our conclu-
sion that gases were primarily composed of small molecules that
had cracked from their organic components (namely, the non-
phosphazene part). More than half of the literature (5/7) reported
that phosphazene would degrade to NH3 , but characterizations
were never found in these works except in Liang [35]. Based on

8
J. Liu, X. Zhang, S. Liu et al.
TGA-MS results, however, Xu [29] holds a contrary view that little
N elements become gaseous phase species. This statement may be
somewhat arbitrary because it was difficult to detect NH3 with MS
[35]. Additionally, only small amounts of P-O-C compounds were
found in the gas phase in the work of Liang [35] and Shi [66],
and no significant phosphorus-containing gas was observed using
TGA-FTIR in this work. At the same time, EHEP-D230 exhibited a
dense char surface and excellent smoke suppression performance
[16], which implied the EHEP-D230 char has good barrier proper-
ties. Hence, we believe that the flame retardant effect of phosp-
hazene acts mainly in the condensed phase. This flame retardant
effect was provided by the physical barrier of the char.
However, the chemical composition of the phosphazene char
has caused heated discussions among scholars. Four factions hold
different views on the phosphorus-containing structure in the con-
densed phase. Faction 1 (5/22) considered that the phosphazene-
like structure still remained in the char, while faction 2 (9/22)
believed that the phosphoric acid-like and phosphoric ester-like
structures were present in char rather than phosphazene. Further-
more, faction 3 (4/22) supported a compromise in which all of
these structures existed in char. Faction 4 (4/22) observed the
presence of phosphorus-containing structures but did not attribute
them. In the literature claiming the presence of a phosphazene-like
structure (the faction 2,3) in char, FTIR was the only characteriza-
tion method used to confirm this structure, and its characteristic
P=N peaks were quite different, such as 1150 cm−1 [68], 1180/1145
cm−1 [18], 1196 cm−1 [17], 1208 cm−1 [30], 1220 cm−1 [21], 1240
cm−1 [14], 1258 cm−1 [22], and a broad peak between 1200 and
1271 cm−1 [26]. The one-sided FTIR characterization, the wide
peaking range of the P=N bond, and the fingerprint-region location
make the existence of the phosphazene-like structure hard to con-
vince. Meanwhile, faction 2 thought the phosphazene-like struc-
ture still existed but never conducted a study in the gas phase,
suggesting faction 2 is unaware of phosphazene degradation. 4/7
of the literature that supported the neutral faction 3 conducted
a study in gas, and they only employed FTIR to characterize the
char, implying they lacked evidence to deny the existence of phos-
phazene. In this study, since the degradation of phosphazene has
been confirmed in TGA-FTIR and the existence of phosphazene has
not been confirmed by XPS and NMR, we are more inclined to fa-
vor faction 2. Apart from phosphazene, there were also a few dif-
ferent opinions on the nitrogen-containing structure. For example,
the majority of the literature discussing nitrogen-containing struc-
tures in char approved the presence of the C-N structure, but Liang
[35] considered that both N=O and P-N structures could be found
in char due to their banding energies of 401.3eV and 398.3 eV in
XPS, respectively. As is well known, the N=O of nitro groups was
at 406.1 eV, suggesting that nitro groups were unsuitable for at-
tribution, and the N=O of nitroso groups was at 400.1eV, close to
the results of 401.3eV, but nitroso groups have not been specifi-
cally reported for coals or chars [48], and it was easy to react with
unsaturated bonds [74], which were abundant in char. As a result,
we believe the 401.3eV peak was caused by quaternary nitrogen
rather than N=O. Additionally, we hold a conservative attitude to-
wards the P-N bond, because it might lead to various attributions,
such as P-NC’s (1110-930cm−1 [75]) location in a similar region as
P-OC and PO-C, and its XPS peak (398.3 eV) overlapping with the
pyridine-like structure at 389.9 eV [48].
All of the Raman char analyses used a two-peak fitting method
to evaluate the graphitization degree of char, except that Seraji
[70] didn’t fit the Raman curves. Although some of them [30,68,71]
claimed that they used the intensity ratio, i.e., the peak-to-height
ratio, as a parameter to evaluate the degree of graphitization, it
is clear from the fitting results that they are actually using the
area ratio (AD1 /AG ). Therefore, AD1 /AG will be used as a parame-
ter to compare Raman data between different literatures. The area
9
Polymer Degradation and Stability 200 (2022) 109927
ratio (AD1 /AG ) of 4.27 obtained by the five-peak fitting method
in this work was significantly higher than that obtained by the
two-peak fitting method in other works (AD1 /AG = 1.13-3.30). It
indicated that the two-peak fitting method resulted in a higher
graphitization degree and that it might be oversimplified to use
the two-peak fitting method to determine the graphitization de-
gree of doped char, which was usually mixed with oxygen, nitro-
gen, and phosphorus. Meanwhile, compared with the control group
(the pure resin), some studies indicated that phosphazene pro-
motes graphitization [36,66,68,70,71], while others [18,30] discov-
ered that phosphazene leads the char to become more disordered.
The former considered that ordered char was more stable when
exposed to fire, whereas the latter thought that a small carbona-
ceous microstructure could protect the substrate from fire. How-
ever, as far as we know, there are no specific studies or direct evi-
dence relating graphitization degree to fire retardancy, and Raman
inactive defects in char would make the result inaccurate. There-
fore, we believe that employing Raman with simple fitting curves
to measure the graphitization degree of doped char from combus-
tion might yield misleading results. More research on the relation-
ship between graphitization degree and fire retardancy is neces-
sary.
3.3. Chemical structure of EHEP-D230 char
After a comprehensive analysis and comparison of EHEP-D230
degradation, we attempted to make a graphic representation of its
chemical structure. As discussed in 3.1.6, the size of the ordered
carbon structure (LD ) in EHEP-D230’s char was between 5.6 Å and
17.2 Å, indicating that the ordered carbon structure had more than
two aromatic rings but less than six aromatic rings. Hence, we
chose the medium value of them, four aromatic rings, as the typ-
ical structure for the EHEP-D230’s char. Additionally, our charac-
terization results confirmed that the phosphorus in the char was
mainly in the form of a phosphoric acid-like structure. Because this
structure is more polar and may form hydrogen bonds, we specu-
late that it is the primary cause of the phosphorus element ag-
gregation in the gap. All of the speculative structures described
above were confirmed by combining FITR (cm−1 ), XPS (eV), 31 P-
NMR (ppm) and Raman spectroscopy (LD ) results. Finally, the pro-
posed structure of EHEP-D230’s char was illustrated in Fig. 11.
3.4. Charring mechanism of the unique EHEP-D230’s char
Based on the gas phase and condensed phase results, we pro-
posed a possible charring mechanism for the unique char of EHEP-
D230 in Fig. 12 (a)-(e). In the beginning, when the resin was ex-
posed to the heat flow (a), its network near the surface cracked,
producing tar composed of various oligomers (b). As the oligomer
was heated further, it degraded into smaller molecules and even
gases such as NH3 , H2 O, and other organic gases, leading to the
formation of tiny bubbles in the tar (c). At the same time, phosp-
hazene also decomposed into a phosphoric acid-like structure, and
a small amount of aggregation might occur for three possible rea-
sons. Firstly, the similarity compatibility principle prevented the
polar phosphoric acid-like structure from dissolving in the low-
polar tar. Secondly, hydroxyl in a phosphoric acid-like structure
might act as an attractor for another phosphoric acid-like struc-
ture through hydrogen bond (O•••H-O) coordination or polarity ef-
fect. Thirdly, the phosphoric acid-like structure was expelled from
the tar because the aromatic rings-rich tar tends to produce a
more stable graphite structure with π -π stack. As time went by,
the bubbles and the phosphorous aggregation grew gradually. And
the tar swelled as well because of the growing bubbles, as shown
in (d). When the bubbles grew large enough, they would touch
J. Liu, X. Zhang, S. Liu et al. Polymer Degradation and Stability 200 (2022) 109927

Fig. 11. Chemical structure of the EHEP-D230 char.

Fig. 12. A possible mechanism of forming EHEP-D230 char.

each other and press on the phosphorous aggregation, which re-
sulted in the phosphorous aggregation moving to the triangle area
among the three bubbles because of the minimum stress affect-
ing the phosphorous aggregation in this area. Meanwhile, as the
bubbles continued to grow, the phosphorous aggregation distorted
and became the vesica gap. Finally, the tar completely decomposed
into char and frozen the final appearance (e), as observed in the
SEM. Thus, we considered the aggregation-pressing of phosphorous
products during combustion as a possible mechanism for the for-
mation of honeycomb-like EHEP-D230 char.
4. Conclusion
In this work, the gaseous products and chemical structures
of EHEP-D230 char were thoroughly investigated. It showed that
a portion of the phosphazene ring and tertiary amine of the

10
J. Liu, X. Zhang, S. Liu et al.
D230 structure decomposed to produce NH3 , but no significant
phosphorous compounds were detected in the gaseous phase by
TGA-FTIR. The condensed phase retained a significant amount
of phosphorus and a minor amount of nitrogen derived from
phosphazene and D230. These results were supported by two
other phosphazene-containing samples, HGETP-D230 and HGETP-
NMA. It was found that the majority of nitrogen-containing and
phosphorus-containing structures in the char were aromatic N-
heterocyclic structures and phosphoric acid-like structures, respec-
tively. In addition, some of the phosphoric acid-like structures
might dehydrate to form polyphosphoric acid or pyrophospho-
ric acid. Furthermore, the char of EHEP-D230 was highly disor-
dered, with LD values greater than 5.6 Å but less than 17.2 Å.
The aggregation-pressing of phosphorous products during combus-
tion may be a mechanism for the formation of the honeycomb-like
EHEP-D230 char. Through our work, we expect that researchers
will pay more attention to the degradation of phosphazene-based
polymers and conduct a more comprehensive analysis of their
burned char.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared to
influence the work reported in this paper.
CRediT authorship contribution statement
Jinghong Liu: Conceptualization, Investigation, Writing – orig-
inal draft. Xiaoqing Zhang: Writing – review & editing, Funding
acquisition, Data curation. Sihui Liu: Writing – review & editing.
Caihong Lei: Resources.
Acknowledgements
This work was financially supported by the National Nature
Science Foundation of China (No. 52073065) and the Guangzhou
Emerging Industry Development Fund Project of the Guangzhou
Development and Reform Commission.
Supplementary materials
Supplementary material associated with this article can be
found, in the online version, at doi:10.1016/j.polymdegradstab.
2022.109927.
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