Fire Safety Journal 70 (2014) 4660

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Fire Safety Journal

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Outlining the mechanism of ame retardancy in polyamide 66 blended

with melamine-poly(zinc phosphate)
Anil D. Naik a, Galle Fontaine a, Fabienne Samyn a, Xavier Delva b, Jrmie Louisy b,
Sverine Bellayer a, Yann Bourgeois b, Serge Bourbigot a,n
a
ISP/UMETUMR/CNRS 8207, Ecole Nationale Suprieure de Chimie de Lille (ENSCL), Avenue Dimitri MendeleevBt. C7a, BP 90108,
59652 Villeneuve dAscq Cedex, France
b
Floridienne Chimie, 12 Quai des Usines, 7800 Ath, Belgium

art ic l e i nf o a b s t r a c t

Article history: Glass-ber reinforced polyamide 66 is ame retarded with a mixture of melamine-poly(zinc phosphate),
Received 16 May 2014 (Sares400) and diethyl aluminium phosphinate. The performance of this synergistic combination of
Received in revised form additives is multi-modal and a comprehensive investigation is undertaken to elucidate the underlying
27 August 2014
ame retardancy mechanism. The strategy was to characterize the different chemical species responsible
Accepted 31 August 2014
Available online 10 October 2014
for ame retardancy that are generated in gas and condensed phases under different re scenarios.
Following heat release rate (HRR) curve of ame retarded polyamide formulations obtained by mass loss
Keywords: calorimeter, samples in different stages of degradation are collected and investigated. Further ame
Flame retardancy retardants and formulations were degraded in tubular furnace whose temperature protocol relied on
Polyamide-66
thermal degradation prole obtained from thermogravimetric analysis (TGA). In either case, species
Melamine polyphosphate
generated in condensed phase were studied by solid state nuclear magnetic resonance spectroscopy
Aluminum phosphinate
Zinc polyphosphate (magic angle spinning (MAS) NMR; 27Al, 31P and 13C), Fourier transform Infra-red spectroscopy (FTIR),
Sares400 X-ray powder diffraction (XRD), electron probe microanalysis (EPMA), scanning electron microscopy
(SEM), and optical microscopy, whereas TGA coupled FTIR, and pyrolysis gas chromatography mass
spectrometry (Py/GC/MS) were utilised to investigate species released in gas phase. Flame retardancy
mechanism is elaborated based on the identication of the chemical species in both gas and condensed
phases and their specic contributing role.
& 2014 Elsevier Ltd. All rights reserved.

1. Introduction recycling-waste disposal, and theoretical studies involving simulation

Fire risks involving polymers have devastating consequences as
polymer utility ranges from consumer products to high-performance
hardware manufacturing [16]. A panel of ame retardants are
developed to confront these issues and safeguard vulnerable targets
like E&E products, materials used in transport vehicles, building-
construction materials, upholstery etc depending on the type of
plastics and targeted application. The current preventive re safety
trend, aimed at keeping the highest re safety standards, explores
novel additives to insulate polymers from re hazards that are not
only efcient, synergistic, multifunctional, but are tailored to be tagged
with eco-label to comply with stringent regulations [3,7]. Further,
ame retardancy mechanism is multifaceted and an insight into its
mode of action provide valuable information for issues like additive-
polymer compatibility, synergism, re-design strategy for additives,
n
Corresponding author.
E-mail address: serge.bourbigot@ensc-lille.fr (S. Bourbigot).
of re scenario.
Among several inorganic ame retardants (FRs), metal phos-
phates have been an efcient ingredient in the formulation of ame
retardant polymers particularly with cations like Zn2 , Mg2 , Al3 ,
Zr4 , Ti4 [3,4,612]. Midst of them, zinc phosphates (ZnPO) are
found to be multi-faceted in ame retardancy [12]. ZnPOs have rich
structural chemistry mainly due to the coordination exibility of the
zinc ions, which can form polyhedral by coordinating to four, ve or
six donor atoms in the framework. Such zinc polyhedra have the
ability to catenate to chains by face, edge, or vertice-sharing [13].
ZnPO also exhibits a wide glass forming composition ranging from
ultraphosphate region (yZnO/P2O5 o1) to highly cross-linked poly-
phosphate glasses (yZ1) [1418]. The basic structural unit of all
phosphates, crystalline or amorphous, is the PO4 tetrahedron.
Coupling such efcient metal phosphates with tailored organic
molecules is promising strategy to further upgrade phosphates to
attain multi-functionality. In this respect, ame retardancy label of
melamine family was further widened and strengthened by introdu-
cing melamine intercalated metal polyphosphates [8,9,11,19,20].
Sares series is a good example for this that was introduced recently

http://dx.doi.org/10.1016/j.resaf.2014.08.019
0379-7112/& 2014 Elsevier Ltd. All rights reserved.
 A.D. Naik et al. / Fire Safety Journal 70 (2014) 4660 47

by Wehner and Dave [8,9]. Sares400 (hereafter referred S400), plastics (St Fons, France), Diethyl aluminium phosphinate with
Melaminepoly(zinc phosphate) is one among them. The molecular trade name of Exolit OP1230 (AlPi) was from Clariant (Knapsack,
structure of S400 is given in Fig. 1a. This molecule can also be Germany). Sares400, Melaminepoly(zinc phosphate), {(MelH)2
considered as a categorized molecular state of melamine which [Zn(P2O7)]}n) was kindly provided by Catena Additives a fully
shares the responsibility of charge balancing, structure directing owned subsidiary of Floridienne Group (Ath, Belgium) and are
moiety besides actively participating in ame retardancy. On a supplied in polycrystalline form (Fig. 1b and c).
molecular level, the cationic chains of melamine are assumed to be
alternated by anionic ZnPO chains with dense secondary interactions 2.2. Formulations, processing and sampling
with the matrix similar to melamine phosphates [21].
S400 is found to have signicant inuence on re performance of 2.2.1. Formulation and processing
glass-bre reinforced polyamide 66, particularly when coupled with Compounding of formulations (Table 1) were performed using
diethyl aluminium phosphinate and passes mandatory tests like UL- HAAKE Rheomix OS PTW 16 twin screw extruder [11a]. All the
94, and glow wire tests. Further there is substantial reduction in peak materials were dried at 80 1C under vacuum for 24 h prior to
of heat release and total heat release evaluated by mass loss extrusion.
calorimeter [8,9,11]. S400 is also found to be a char/intumescence
forming agent. Our investigation has been focussed on the elucida-
2.2.2. Sampling
tion of ame retardancy mechanism of S400 and aluminium
Samples for the study were collected from two sources (Table 1).
phosphinate (1:2 ratio, total 18 wt% of ame retardants) blended
One is from mass loss calorimeter experiment which is based on HRR
glass bre reinforced polyamide-66. There are several comprehensive
curve [11a] wherein exposure to heat ux/aming were stopped
reports on mechanistic aspects of melamine based ame retardants
and extinguished manually at 100, 300, 600 and 1000 s. The intended
in polyamides [2233]. Our study has been supported by parallel
(100 to 1000 s) time selection for sample collection is principally based
investigation on decomposition of neat S400, and single additive
on HRR prole of PA66/GFAlPiS400 formulation which approxi-
(S400) blended glass bre reinforced polyamide-66. Further supple-
mately denotes ascending, peak, descending and end of degradation,
mentary data on neat polymer, aluminium phosphinate, and alumi-
respectively. The same prole is extended for single additive formula-
nium phosphinate blended polymer are also recorded and used as
tions and neat PA66/GF. Most of the results investigated are based on
references. Samples at different stages of degradation were collected
these tests. Pyrolysis experiments were performed in tubular furnace
based on heat release rate (HRR) curve from mass loss calorimeter.
under nitrogen atmosphere. At the selected temperature, the sa-
Samples were also pyrolysed in tubular furnace based on thermal
mple placed in ceramic crucible was introduced into the quartz tube
decomposition pattern obtained from thermogravimetry. The poten-
xed inside the tubular furnace and kept for 3 h. The tempera-
tial chemical species formed during the decomposition pathway of
ture selection is derived from TGA prole of formulations/additives
these formulations in either method were tracked with solid state
which corresponds to temperature of maximum weight loss in each
nuclear magnetic resonance spectroscopy (MAS NMR; 27Al, 31P and
13 step performed at heating rate of 20 1C/min under nitrogen atmo-
C), Fourier transform Infra-red spectroscopy (FTIR), and X-ray
sphere. Additional temperatures mentioned in Table 1 under this
powder diffraction (XRD). The gaseous products released during
section correspond to either a stable plateau at the end of major
the thermal decomposition of these formulations/additives were
degradation step or completion of decomposition. To have an
characterised by thermogravimetric analysis (TGA) coupled FTIR
and pyrolysis gas chromatography mass spectrometry (py/GC/MS).
Morphology of intumescence/char and additives were studied by Table 1
Materials investigated in the present study and conditions of sample collection.
optical microscopy, electron probe microanalysis (EPMA), and scan-
ning electron microscopy (SEM). The results are gathered to establish Materialsa Sample collection timeb T (1C) prolec
the mode of action of ame retardants in the ame retardancy of (in second)
polyamide 66.
PA66/GF AlPi S400 100, 300, 600, 1000 421, 535, 750
PA66/GF S400 100, 300, 600, 1000 374, 468, 578, 750
PA66/GF AlPi 100, 300, 600, 1000 414, 542
PA66/GF (neat) 100, 300, 600 401
2. Experimental
S400 (neat) 376, 554, 750
AlPi (neat) 452, 510
2.1. Materials AlPi S400 (2:1 ratio, 421, 535, 750
manually mixed)
Abbreviations for the materials used are given in bracket and a
AlPi: 12 wt%; S400, 6 wt%.
are followed throughout this work. Polyamide 66 reinforced with b
Based on HRR curve.
30% glass bers (PA66/GF) was supplied by Rhodia engineering c
For tubular furnace experiment.

Fig. 1. (a) Molecular structure of S400. ((b) and (c)) SEM images on powder sample of S400 showing polycrystalline morphology.
48 A.D. Naik et al. / Fire Safety Journal 70 (2014) 4660

insight into the potential mutual interactions between additives, elemental analysis. The char surface was transferred on a conductive
additive mixture (AlPiS400 in 2:1 ratio as in formulation) were carbon tape and carbon coated with a Bal-Tec SCD005 sputter coater.
also pyrolysed in tubular furnace and the decomposed samples are Elemental mapping (N, Zn, Si, P, Al, Ca) was performed over an area
studied. Degraded samples studied in the present work were surrounding a glass ber. The analyses were carried out at 15 kV, 15 nA
labelled with a name followed by a number. This number indicates for back scattered electrons (BSE) images and at 15 kV, 40 nA for
either the time at which the mass loss calorimeter experiment is silicon (Si), calcium (Ca), phosphorus (P), aluminum (Al) and zinc (Zn)
stopped (100, 300, 600, or 1000 s) or temperature of maximum X-ray mappings. For mappings, a TAP crystal was used to detect the Si
degradation in each step of TGA curves. Results of tubular furnace and Al K X-ray, and a PET crystal to detect the Ca and P K X-ray.
experiments are supplementary and discussed only wherever
necessary in the paper.
2.3.5. TGA-FTIR analysis
2.3. Instrumental Gas phase analysis were carried out in TGA Q5000 (TA instru-
ments) coupled with FTIR Nicolet iS10 spectrometer (Thermo-
2.3.1. Thermal analysis Fischer). Samples (15 mg) were heated in a 100 L alumina crucible
Thermogravimetric analyses (TGA) were performed using SDT from 50 1C to 800 1C with a heating rate of 10 1C/min under nitrogen
Q600 (TA instruments). Samples (approx. 68 mg) were placed in atmosphere. A balance purge ow of 15 mL/min and a sample purge
open alumina pans covered with gold foil to avoid possible reactions ow of 100 mL/min was maintained. A transfer line with an inner
between pan and phosphorus contents of the samples and heated diameter of 1 mm was used to connect TGA and infrared cell. The
under nitrogen atmosphere with a heating rate of 20 1C/min. temperature of transfer line and gas cell was kept at 225 1C. Prior to
this, samples were maintained for 2 h under nitrogen stream. IR
2.3.2. Mass loss calorimeter spectra were collected in 4004000 cm  1 spectral range with a total
The mass loss calorimeter (Fire Testing Technology (FTT)) is of 450 scans.
used for collecting sample for analysis. Plates (100  100  3 mm3
plates) for calorimeter test were made via compression molding
using DARRAGON press apparatus. Plates were wrapped in alumi-
2.3.6. Pyrolysis GC/MS
nium foil leaving the upper surface exposed to the heater and
Samples (  200 g) were analyzed by Pyrolysis GCMS (Shi-
placed in horizontal position on ceramic block encased in a
madzu, GCMS-QP2010 SE). GC separation was carried out with a
metallic container at a distance of 40 mm from cone base. External
fused silica capillary column (SLB 5 ms) of 30 m length and
heat ux of 50 kW/m2 was used for all the experiments.
0.25 m thickness. Analyses were carried out in direct pyrolysis
mode. The temperature selection is based TGA pattern of con-
2.3.3. Spectral and XRD analysis cerned sample. The furnace is set for the nal temperature and
FT-IR spectra were recorded on Nicolet Impact 400 D spectro- sample is pyrolysed for 0.5 min. Helium was used as a carrier gas
meter in Attenuated Total Reection (ATR) mode in the range at pressure of 120 kPa with a split ratio of 50. The transfer line was
5004000 cm  1 at room temperature. To minimize the signal to maintained at 275 1C. Column temperature is programmed in the
noise ratio, the spectra are acquired as a result of 32 scans with a following way. The initial column temperature was held at 35 1C
resolution of 4 cm  1. for 1 min followed by a temperature ramp at 10 1C/min to a nal
X-ray powder diffraction (XRD) spectra were recorded using a temperature of 300 1C and isotherm for 20 min. The MS was
Bruker AXS D8 diffractometer in the 51601 range at RT. (Cu K operated under Electron Ionization EI mode. An online computer
1.5418 , 40 keV, 25 mA) in conguration 2-theta/theta. The acq- using GCMS real time analysis and PY-2020i software controlled
uisition parameters were as follows: a step of 0.021, a step time of 2 s. GC/MS system. The eluted components were identied by library
31
P NMR measurements have been performed on a Bruker search and only signicant peaks observed in the total ion
Avance II 400 at 40.5 MHz using a 3.2 mm probe, with/without chromatograms were studied and compared to a mass spectral
cross polarization (CP, 1H31P), with dipolar decoupling (DD) and database (GCMS postrun analysis, and NIST).
magic angle spinning (MAS) at a spinning speed of 20 kHz. The
delay time between two pulses was xed at 120 s without CP
and 5 s with CP. The spectra were acquired with 32 scans. The
reference used was 85% H3PO4 in aqueous solution.
27
Al NMR measurements have been performed on a Bruker
Avance II 400 at 104 MHz using a 3.2 mm probe, with MAS of
20 kHz. The delay time between two pulses was xed at 1 s. The
spectra were acquired with 1024 scans. The reference used is 1 M
solution of aluminum nitrate.
13
C NMR measurements have been performed on a Bruker
Avance II 400 at 100.4 MHz using 3.2 mm probes, with CP 1H13C,
dipolar decoupling (DD) and MAS of 10 kHz. For all samples, a
delay time between two impulsions of 5 s and a contact time of
1 ms were used. The spectra were acquired with 1024 scans. TMS
is used as reference for the chemical shift.

2.3.4. Microscopy
Morphology of samples was studied using scanning electron
microscope (SEM), (Field emission gun (FEG) Hitachi S4700). VHX
digital optical microscope (Keyence, VH-Z 100R) was used to investi-
gate texture of samples. An electron probe microanalyser (EPMA) Fig. 2. TG curves for formulations and additives (20 1C/min heating rate, under
using wavelength dispersive X-ray spectrometers was used to perform nitrogen atmosphere).
 A.D. Naik et al. / Fire Safety Journal 70 (2014) 4660 49

3. Results measured based on HRR curve (Fig. 3a) with associated parameters
[11]. As seen from HRR curve, neat PA66/GF burns easily with a
3.1. Thermal decomposition behaviour and mass loss calorimetry high peak of heat release rate (pHRR) value of 354 kW/m2 and
results totally decomposed leaving behind only glass ber residue. Addi-
tion of single component FR, like AlPi (pHRR, 149 kW/m2) or S400
Thermal decomposition prole of additives and formulations (106 kW/m2) alone in PA66/GF reduces the pHRR by 58 and 70%
are displayed in Fig. 2 and thermal parameters are summarized in respectively and results in small amount of char (Fig. 3b). The
Table 2. S400 additive exhibits two unequal decomposition steps optical microscope image on the residue of PA66/GFS400 shows
yielding to signicant amount of residue. The second step is very that surface is not continuous but full of voids and is mainly formed
gradual and weight loss continues until 770 1C. The FRs modify the with a mesh of glass bre sparsely holding char (Fig. 3d and e). The
initial thermal stability of PA66/GF and its thermal degradation synergy between the two additives is clearly evidenced in HRR
pattern. Single additive formulation PA66/GFS400 undergo decom- curve of PA66/GFAlPiS400 with signicant reduction in pHRR
position in three steps but a short plateau is found only between 500 (62 kW/m2;  82% reduction). The value of total heat release (THR)
and 580 1C. PA66/GF AlPiS400 decompose in a single major step for PA66/GF is 77 MJ/m2 and is reduced to 43 MJ/m2 in PA66/
also exhibiting a plateau in the same region with a signicant residue GFAlPi and nearly same for PA66/GFS400 (36 MJ/m2) and two
weight. A stable species is formed in this temperature range which additive formulation (31 MJ/m2). Another important parameter is
gradually decomposes compared to PA66/GF S400 (Table 2). While time to ignition (TTI) which is 72 s for PA66/GF, slightly less for
neat PA66/GF decomposes completely, its two additive counterpart PA66/GFAlPi (43 s) and PA66/GF S400 (66 s). On the other hand,
yields signicant amount of char. PA66/GFAlPiS400 has been efcient in resisting the heat ux by
The response and performance of formulations to a simulated prolonging TTI to 111 s. It is to be noted that degradation is
re scenario is evaluated by mass loss calorimeter and they are extended over a period of time with a secondary HRR peak and
there is contribution to char/intumescence.
During the mass loss calorimeter experiment it is observed that
Table 2
Thermal parameters for additives and formulations (20 1C/min heating rate, under under the high heat ux, the upper surface of polymer plate
nitrogen atmosphere). undergoes bubbling until it starts to swell. The bubbles shrink into
irregular but continuous coarse structure that forms a glassy
Compound Steps T (1C) range Weight Residue intumescence (Fig. 3c). This shiny envelope is pushed upwards
(major) loss (%) weight (%)
by the pressure of released gases produced by the burning
PA66/ 1 309502 55.1 34.6 materials underneath forming a dome shaped intumescent struc-
30GF AlPi S400a ture. This is crack-free, hollow and supported with densely inter-
PA66/GF S400 3 278430 37.0 32.2 woven glass-bres (Fig. 3g) making a strong protective barrier
430518 19.5
between un-degraded polymer and heat ux. Optical microscope
518699 09.4
PA66/GF AlPi1 1 341504 53.1 35.7 study on intumescence surface reveals presence of numerous
S400 2 325402 14.2 44.4 protrusions resembling cells (Fig. 3f).
402780 39.5 The ammable and non-ammable gases released before and
AlPi 2 420466 40.2 42.3 after intumescence play a key role in controlling the parameters of
474541 17.0
PA66/GF 1 337504 68.8 31.2
the HRR curve. Types of volatiles can be conveniently traced
and their evolution is mapped by in situ TGA-FTIR and further
a
There is gradual weight loss until 800 1C after the rst stage of decomposition. conrmed by pyrolysis GCMS. These are described in the

Fig. 3. (a) Mass loss calorimeter response of formulations. (b) Residue in PA66/GF S400 formulation. (c) Intumescence in PA66/GF AlPi S400 formulation. ((d) and (e))
Optical microscopic images on PA66/GF S400 residue. (f) Intumescence surface in PA66/GF AlPi S400. (g) Undersurface of intumescence in PA66/GF AlPi S400.
50 A.D. Naik et al. / Fire Safety Journal 70 (2014) 4660

Fig. 4. TGA-FTIR under nitrogen atmosphere of (a) PA66/GF (b) PA66/GF AlPi S400.

following sections. Chemical species responsible for ame retar-

dancy embedded in the intumescence/char are discussed under
condensed phase analysis.

3.2. Gas phase analysis

3.2.1. FTIR-TGA studies

The evolved gas analysis carried out for PA66/GFAlPiS400 is
displayed in Fig. 4 and compared with PA66/GF. Identication of
gases in the FTIR spectra is based on earlier reports and relating
to characteristic bands [26,29,31,3436]. Neat PA66/GF shows no
signicant evolution of volatiles until 30 min (300 1C). There-
after simultaneous but gradual evolution of hydrocarbon (3000
2800 cm  1), CO2 (2368, 667 cm  1), cyclopentanone or its derivative
(C O, 1767 cm  1), and ammonia (963, 933 cm  1), is observed. At
35 min ( 350 1C) the evolution of cyclopentanone increases drasti-
cally along with other above mentioned gases. Around 40 min
( 403 1C) cyclopentanone starts to decrease and hydrocarbon starts
to increase along with ammonia. After 43 min ( 436 1C) there is
only hydrocarbon evolution.
The prole in case of PA66/GFAlPiS400 deviates compared to
neat PA66/GF. Progressive weight loss starts from 21 min ( 244 1C). Fig. 5. Selected pyrolysis GC/MS chromatograms (a) for PA66/GF, pyrolysis at
420 1C; For PA66/GF AlPi S400, (b) pyrolysis at 290 1C, (c) pyrolysis at 350 1C,
Around 29 min ( 322 1C) slightly earlier than in PA66/GF, evolution
(d) pyrolysis at 420 1C. Chemical species (a)(c) are dened in Table 3.
of CO2 begins. At about 34 min ( 370 1C) which is the inection
point of major degradation step, hydrocarbon (2972 cm  1), cyclo-
pentanone (1761 cm  1) and phosphinic acid (3651, 1277, 1240, of ammonia, hydrocarbon and CO2. Weak signals for AlPi (1162,
851 cm  1) starts to evolve. The origin of phosphinic acid is due to 1082 cm  1) are observed at this stage. As the temperature increases,
partial degradation of AlPi additive. Ammonia evolution is seen at AlPi is increasingly detected. Thereafter (40 min, 434 1C) CO2
35 min ( 383 1C). Around 38 min ( 414 1C), it is mainly evolution decreases considerably but hydrocarbon, ammonia, AlPi dominates
 A.D. Naik et al. / Fire Safety Journal 70 (2014) 4660 51

and continues to evolve until 46 min ( 487 1C). A qualitative
comparison of band intensity of cyclopentanone between PA66/GF
and PA66/GFAlPiS400 indicates a decline in its production in the
latter. Evidence of melamine sublimation and subsequent detection
is not evidenced in the formulation. Either this probability is less or
possibility of its condensation in the transfer line of TGA-FTIR cannot
be ruled out. In any case ammonia is unambiguously detected,
which is assumed to be evolved after de-ammonation and subse-
quent condensation of melamine ring which was also conrmed in
the degradation of neat Sares200 [11b].
3.2.2. Pyrolysis GCMS studies
Fig. 5 depicts selected chromatograms showing release of key
volatile species in case of PA66/GF AlPiS400 and neat PA66/GF
under pyrolysis conditions and are grouped in Table 3. Neat PA66/
GF (Fig. 5a), under pyrolysis at 420 1C (corresponds to maximum
weight stage in TGA) shows presence of water (m/z, 18), CO2 (m/z,
44), cyclopentanone (m/z, 64), 1,6-hexanediamine (m/z, 116) and
cyclic monomers of PA66 (Table 3, compound c) predominantly.
Degraded products of 1,6-hexandiamine, and aromatic heterocyc-
lic compound (a and b respectively in Table 3) are also detected.
Pyrolysis at 500 1C (completion of degradation, not shown) shows
comparatively less cyclopentanone [32,37,38] due to further
decomposition of it into CO2. Secondary degradation/rearranged
products of 1,6-hexanediamine like 5-hexaneamine, adiponitrile
(hexane dinitrile, m/z 108) and hydrocarbon fragments are also
identied. Pyrolysis of PA66/GF AlPi S400, is studied at 290 1C,
350 1C, and 420 1C successively. The rst two temperatures corre-
sponds to minor degradation steps in TGA. Until 290 1C, water,
ammonia, CO2 and melamine (m/z, 126) are observed (Fig. 5b).
Around 350 1C which is the end of second minor decomposition
step, shows presence of CO2, melamine and small quantity of
cyclopentanone. In the next pyrolysis step at 420 1C (Fig. 5c) which
is just after the major weight loss in the third step of decomposi-
tion in TGA, shows mainly 1,6-hexanediamine. Direct pyrolysis at
500 1C on this formulation shows more degraded products of 1,6-
hexanediamine (Table 3). Although identication of phosphorus
based species is uncertain due to several unresolved signals,
pyrolysis of neat AlPi at 500 1C shows presence of certain species
like triethylphosphine oxide (m/z, 134) and diethylphosphine (m/z,
90) possibly rearranged products from degrading diethyl alumi-
nium phosphinate.
3.3. Condensed phase analysis
3.3.1. FT-IR spectral results
3.3.1.1. Pyrolysis of S400. The room temperature spectrum of S400
(Fig. 6) shows distinct bands corresponding to NH and NH2
stretching between 3090 and 3400 cm  1. A strong broad band
around 1670 cm  1 is due to v(C N) and (NH2). The characteristic
triazine ring band of melamine appeared at 780 cm  1 [3942].
Additional bands are identied between 1250 and 950 cm  1, and
around 540 cm  1 corresponding to various vibrations from ZnPO
polyhedra from different sources like -meta, -pyro, -ortho phosphate
and most of the bands are overlapped by melamine vibrations
[43,44].
Pyrolysis of S400 in tubular furnace (376 1C, 554 1C and 750 1C)
leads to progressive changes in both melamine component and in
ZnPO polyhedra. Melamine component undergoes de-ammonation
followed by condensation forming more conjugated species or simply
undertake sublimation route. On the other hand depolymerisation of

Table 3
Key chemical species identied from py/GC/MS by pyrolysis method.

Sample Pyrolysis Species identied

(1C)

PA66/GF 420 H2O, CO2, cyclopentanone, a5-Hexenamine (m/z, 99), 5-aminopentonitrile, 1,6-hexanediamine, b1-methyl-3-formyl-indole
(m/z,159), c1,8-diazacyclotetradecane-2,7-dione (m/z,226)
PA66/GF 500 H2O, CO2, 1-hexanamine (m/z, 101), cyclopentanone, hexane nitrile (m/z, 97), adiponitrile, 1,6-hexanediamine,
N-(6-Aminohexyl)-4-pentenamide (m/z, 198), 1-hexene
PA66/GF AlPi S400 290 H2O, CO2, NH3, melamine, 1,8-diazacyclotetradecane-2,7-dione
(Successively) 350 CO2, Cyclopentanone, Melamine, 1,8-diazacyclotetradecane-2,7-dione
420 1,6-hexanediamine, 1-methyl-3-formyl-indole, 1,8-diazacyclotetradecane-2,7-dione
PA66/GF AlPi S400 500 H2O, NH3, CO2, Cyclopentanone, 1-hexaneamine, Hex-5-enylamine, melamine, 1,6-hexanediamine, 1-methyl-3-formyl-indole,
1,8-diazacyclotetradecane-2,7-dione

Fig. 6. FTIR of S400 and its degradation products.

52 A.D. Naik et al. / Fire Safety Journal 70 (2014) 4660
ZnPO polyhedra leads to fragmentation or emergence of crystalline
phase of ZnPO.
There are three main de-ammonation and condensation pro-
ducts of melaminemelam, melem and melon [4042,45,46].
Tentatively, they are formed between 340400, 400450 and
450500 1C, respectively, with certain degree of exibility in
temperature range and shown to vary with experimental condi-
tion [41]. Melam has been considered as the low temperature de-
ammonation product of melamine, which is formed upon linking
two molecules of melamine with concomitant release of one mole
of ammonia. Melamine progressively condenses to give melam
which then further fuses to form melem and via melon to g-C3N3
[4042,45,46]. S400 might pass through one or more of these
phases during its pyrolysis.
The S400-376 spectrum logically represents transition of melam
to melem. There is drastic spectral change compared to neat S400
spectrum. The amine signals are broad, less intense and appear
around 3125 and 3311 cm  1. The shoulder band around 3400 cm  1
disappears. The strong NH2 band at 1673 cm  1 is replaced by a
medium broad band around 1642 cm  1. In addition, new bands
(1550 s, 1436 s, 1374 s, 1334 s, 1247 s) are identied. Pronounced
absorption in this region is assumed to be due to v(CN) and (NH)
from more than one condensed products of melamine. These
observations can be interpreted in line with de-ammonation fol-
lowed by self-condensation leading to the formation of melamine
condensate-melam or coexistence of melammelem.
Spectral pattern changes from S400-376 to S400-554. The vs/as
(NH2), and v(NH) are signicantly reduced and 1642 cm  1 signal
prominent in S400-376 disappears and several overlapped bands
are identied (1618, 1555, 1410, 1318, 1250 cm  1) assigned to
melem dimer/oligomers or melon type species or mixed species.
The bands between 1318 and 1250 cm  1 are of CN stretching and/
or NH bending vibrations characteristic of the CNHC unit in
melem. The triazine ring bend is also shifted to 805 cm  1 suggest-
ing that material consists of non-protonated triazine or heptazine
building blocks [41]. It should be reminded from TG curve (Table 2)
that S400 displays a very gradual weight loss in the second step of
decomposition (430 1C onwards) which possibly involve formation
of multiple melamine condensation products.
In addition to above spectral changes, there are indications of
changes in the composition of ZnPO component. The asymmetric
unresolved envelope between 1257 and 926 cm  1 is specic region
for ZnPO of varying degree of polymerisation [43,44]. The multiple
Fig. 7. FT-IR (expanded region) on selected residues.
bands (broad) in this region (1157, 1094 and possibly overlapped
band at 1257 cm  1) suggest amorphous ZnPO of ortho, pyro or
meta/polyphosphates origin. The 1257 cm  1 band is assigned to
vas(PO2)  and or v(P O) and the 1157 for vas(PO23  ) and or
vs(PO2 ). The strong broad band around 926 cm  1 indicate vas(P
OP) phosphate chain and possibly include v(PO3 4 ) whereas the
low intense band at 739 cm  1 is due to vs(POP). The broad,
strong band around 510 cm  1 is due to (PO) [43,44].
The S400-750 spectrum is relatively simple as most of the
organic part is removed and strong bands around 1068, 868,
501 cm  1 corresponding to phosphate network with or without
zinc coordination can be distinguished. Another noticeable feature
in S400-750 spectrum is a broad distinct band around 2210 cm  1
possibly due to formation of a nitrile or cyanamide derivative
which is also observed in the pyrolysed product of MPP under
similar condition [39]. It was reported that if melamine is
pyrolysed above 650 1C it partially cracked due to de-polymerisa-
tion, leading to cyanamide along with other products [41]. Further
at elevated temperature, heptazine framework may partly collapse
giving dicyandiamide, cyanamide and ammonia [41,45].
3.3.1.2. Degradation of formulations. FTIR on the residues of all the
formulations are presented in Fig. 7. They have nearly similar pattern
with broad, strong bands (except PA66/GF S400) representing
amorphous nature of ZnPO and/or AlPO. The residue obtained from
PA66/GF S400 in tubular furnace (750 1C) is interesting as it shows
relatively sharp bands corresponding to zinc orthophosphate type
structure [43,44]. Although less prominent, same sample from mass
loss calorimeter also exhibit slightly resolved IR pattern. This was
attributed to polymer mediated formation of crystalline ZnPO. In
most of the char forming materials the low intense band around
750 cm  1 is due to COP or CP vibration.
3.3.2. Solid state NMR characterisation of condensed phase analysis
3.3.2.1. Pyrolysis of S400 additive. Degradation in S400 can be
conveniently tracked by solid state NMR thanks to the presence of
NMR sensitive nuclei in both inorganic (31P of ZnPO) and organic
components (13C of melamine) as they provide information [4654]
about fragmentation in phosphorus polyhedra and melamine
condensation/degradation, respectively. 31P MAS-NMR of S400 and
its pyrolysed products are displayed in Fig. 8a. For the 31P isotropic
chemical shift of metal phosphates, there is a trend to lower values
with increase in the number of bridging oxygen atoms attached to a
 A.D. Naik et al. / Fire Safety Journal 70 (2014) 4660
Fig. 8. 31P MAS NMR spectra on (a) neat S400 and its degradation products,
physically mixed AlPi S400 degraded at different temperature. Here number
corresponds to pyrolysis temperature in tubular furnace. (b) 31P MAS NMR spectra
on degradation samples of formulations from mass loss calorimeter. Numbers 100,
300, 600, and 1000 are time (in second) at which the degrading polymer plates
under the heat ux are dismounted. Symbol (n) denotes spinning side band. Neat
corresponds to undecomposed sample.
phosphorus atom [54]. The HPDEC (High power proton decoupling)
MAS NMR spectrum of S400 shows, an asymmetric doublet at  21.6
and  24.4 ppm representing the Q2 tetrahedra, possibly at different
crystallographic position and are the bases for meta/polyphosphate
chains. There are several intense peaks between  10 to  2 ppm
( 10.7,  7.4,  6.5,  5.5, 2.2). This feature is due to Q1 sites that
are either chain terminals or found in isolated pyrophosphate dimers.
-Zn2P2O7 ( 15.9,  19.1,  21.2 ppm) and -Zn2P2O7 ( 5.5,  7.1,
10.4 ppm) are reported to be found around the same region [52].
A third set of sharp isotropic peaks, are found at 6.7, 6.4,
3.9, 3.1 and 2.3 ppm. CP measurement (Fig. 8a) shows that
these signals ( 2.3 to 3.9 ppm) disappear indicating proximity
of this phosphorus tetrahedra to a proton source like melamine
moiety. These can also be discrete molecules or part of small poly-
meric network with or without zinc coordination. There are few
ZnPO molecules whose chemical shifts falls in this range. Roming
et al. [52] reported signals for -Zn3(PO4)2, around 3.9 ppm and
two signals at 7.6 and 2.8 ppm for -Zn3(PO4)2. Their hydrated
53
counterparts -Hopeite (-Zn3(PO4)2  4H2O) and -Hopeite (-
Zn3(PO4)2  4H2O) are reported between 4.5 and 4.3 ppm which
appeared as a sharp singlet [54]. It is also reported that zinc
hydrogen phosphate (Zn3(HPO4)3  3H2O) show multiple signals
around 2.3, 5.5, and 6.5 ppm [54].
In S400-376, doublet around 21.6 and  24.4 ppm found
in S400 is replaced by a broad band (centred at  24 ppm) and
signals between  10 to  2 ppm decreases considerably. This
indicates collapse of crystalline framework of ZnPO component
of S400 suggesting depolymerisation. The set of signals between
2.3 to 6.7 ppm remains unchanged indicating that these are
independent moieties. In S400-554 spectrum, the metaphosphate
signals around  24 ppm decreases and broadened. Pyropho-
sphate signals are still detected but they are broadened. Interest-
ingly, signals between 2.3 and 6.7 ppm remain unaltered. In
S400-750 spectrum there is a broad signal around 0 ppm indicat-
ing formation of amorphous phase possibly mixture of species
including discrete ortho-phosphoric acid (Fig. 8a).
13
C NMR spectrum of S400 (Fig. 9a) shows two asymmetric
bands at 164.4 and 157.5 ppm assigned to carbon atoms of triazine
ring. Due to tautomeric forms, melamine can exist in two forms
and gives arise to two signals [21]. They have undergone changes
in terms of intensity ratio upon annealing and also broadened
indicating presence of multiple species due to de-ammoniation
leading to condensation products of melamine. The down eld
signal (163.9 ppm) is considerably broadened in S400-376 (163.9,
156.4 ppm). It is likely that it may incorporate signals for con-
densed molecules like melam or melem or even melaminemelam
adduct. Since melam was found to have chelating ability as shown
by several melam-metal complex [41], it is reasonable to assume
that zinc vicinity stabilises this intermediate. Conversion of mel-
amine to any condensation product changes the electronic equiva-
lence of carbon in the triazine ring (CN2(NH)x and CN3 moieties)
and thus separate resonance would appear. Since they are hardly
separable, the signals are very broad. Evidences about these
species were discussed in preceding FTIR section. 13C NMR
spectrum of S400-554 shows further broadening of 13C NMR
signals (163.8, 155.6 ppm) and there is noticeable decrease of
high-eld side signal (155.6 ppm). At this stage condensation of
melem sets in and oligomeric or polymeric heptazine based
materials like melon or even small amount of its proton lacking
counterpart graphitic carbon nitride (CNx) would exist. No sig-
nicant signal was detected in the spectrum of S400-750.
As the S400 degradation materials are collected based on
temperature of maximum degradation in TGA curve it is likely that
the samples are mixture of products rather than single phase of any
melamine condensate. Also thermal treatment time duration (3 h)
may not be sufcient for complete transformation into a single
species. For these reasons distinct identication of de-ammonation
and condensation products from NMR or FTIR is tentative.
3.3.2.2. Degradation studies in manually mixed AlPi S400. 31P MAS
NMR of manually mixed and pyrolysed samples of AlPi and S400 are
shown in Fig. 8a. In AlPiS400-421 spectrum, it can be seen that most
of the pyrophosphate in S400 have transformed and a broad signal
appears around  25 ppm similar to S400-376. The AlPi doublet in
AlPiS400-535 spectrum is completely disappeared and broad signals
around  25 ppm increases in intensity with a shoulder peak at
 9 ppm. The signals between 2.2 to 6.6 ppm remain nearly
unaltered as in S400. The reason for the enhancement of signal
around  25 ppm is due the transformation of AlPi into AlPO4 and
overlapping with phosphate polyhedra from zinc phosphate. The
representative spectra (27Al) from annealed AlPiS400 are depicted in
Fig. 10 which shows presence of two broad signals around 38 ppm
and 12 ppm. The 38 ppm is due to AlPO4 and the 12 ppm is due
54 A.D. Naik et al. / Fire Safety Journal 70 (2014) 4660

Fig. 9. (a) Expanded region around aromatic carbon in 13C CP MAS NMR of neat S400 and pyrolysed products of S400. (b) 13C MAS NMR spectra on S400 and some selected
formulations. Also shown are char formation in the residue.

Fig. 10. 27Al MAS NMR spectra on degradation samples of PA66/GF AlPi S400
from mass loss calorimeter. 100, 300, 600, and 1000 are time (in second) at which
the degrading polymer plates under the heat ux are dismounted. Representative
spectra of PA66/GF S400-1000 and manually mixed samples (AlPi S400) at 421,
and 535 1C carried out in tubular furnace are also shown.
to undecomposed AlPi. Presence of a weak band around  10 ppm
indicates AlO5(PO) intermediate in the formation of AlPO4.
3.3.2.3. Degradation studies in PA66/GF S400. 31P NMR of PA66/
GF S400 and its degradation products collected based on HRR
curve are shown in Fig. 8b. Compared to neat S400 spectrum,
Fig. 11. (a) XRD pattern for S400 and its pyrolysed samples (b) XRD pattern on
selected residues obtained in tubular furnace (750 1C) and mass loss calorimeter
(1000 s).
pyrophosphate signal is more prominent than other signals in
PA66/GF S400. This trend increases progressively from PA66/
GFS400-100 spectrum to PA66/GFS400-300 spectrum indicat-
ing fragmentation. Further in PA66/GF S400-300 spectrum, signals
are broad and there is an additional broad signal at  30 ppm. The
PA66/GFS400-600 spectrum displays signicant changes with a
 A.D. Naik et al. / Fire Safety Journal 70 (2014) 4660 55

Fig. 12. PA66/GF AlPi S400 sample from mass loss calorimeter: (a) BSE image on shiny intumescence surface, (b) optical microscope image on upper surface of char layer
showing random distribution of white islands. (c) BSE image on white lumps seen on image (b). ((d)(g)) Elemental mapping (N, Zn, P and Al respectively) on intumescence
surface.

weak broad signal around  10 ppm and sharp intense peaks at
26.2 ppm and  35.2 ppm. The  10 ppm signal is due to
fragmented pyrophosphate species whereas  26.2 and  35.2 ppm
are assigned to re-structured crystalline form of zinc polyphosphate.
The 13C NMR spectrum of PA66/GF S400 (Fig. 9b) shows signals that
corresponds to carbon source of PA66 whereas signals from S400 are
very weak. Multiple peaks between 42.1 to 25.4 ppm are seen
indicating CH2 groups of PA66 and the carbonyl function appear at
173.3 ppm. Additive insertion into PA66/GF increases the overall
thermal stability of PA66/GF and thus decomposition of PA66/GF is
delayed and signals corresponding PA66/GF is still seen in PA66/
GF S400-300 spectrum (not shown). At PA66/GFS400-600, a broad
weak resonance around 130 ppm is seen which is assigned to char
formation.
In PA66/GFS400-468 (from tubular furnace) pyro- ( 11.2 ppm)
and metaphosphate (25.3 ppm) have equal proportion compared
to dominant pyrophosphate in PA66/GFS400. Further in PA66/
GF S400-578, there is major transformation into meta/polypho-
sphate ( 30.1 ppm as unresolved doublet) which also corresponds
to completion of 3rd step of degradation in TGA. Small amount of
pyrophosphate present appears as multiplet between  15.8 and
7.1 ppm. These signals are relatively sharp and may indicate
crystalline nature of products. In addition less intense signals are
also present around 5 ppm due to zinc orthophosphate.
3.3.2.4. Degradation studies in PA66/GF AlPi S400 formulation. In
31
P MAS NMR spectrum of PA66/GFAlPiS400 (Fig. 8b), an intense
symmetric doublet from AlPi is observed at 43.6 and 41.6 ppm,
whereas weak signals are seen for S400 and this pattern is retained
in PA66/GF AlPi S400-100 spectrum. In PA66/GFAlPiS400-
300 spectrum, AlPi signals decrease and appear as asymmetric
doublet which mark the onset of its decomposition and there
appear also a very broad weak signal around  30 ppm. This signal
is mainly due to zinc phosphate but may also include AlPO4 as
beginning of AlPi decomposition can contribute to it. AlPi signals
disappear in PA66/GFAlPi S400-600 spectrum and the broad
signal around  30 ppm is prominent which further increases in
intensity in PA66/GF AlPi S400-1000 spectrum. This broad signal
may have contribution from stable species like AlPO4 and ZnPO or
even mixed phosphates.
Spectrum of 27Al MAS NMR of PA66/GF AlPi S400 shows
two signals (Fig. 10), a broad resonance around 50 ppm and a
sharp peak at  12.3 ppm. These are respectively assigned to
alumina in glass bre and octahedral aluminium of AlPi [26,29].
56 A.D. Naik et al. / Fire Safety Journal 70 (2014) 4660

The PA66/GF AlPiS400-100 spectrum shows broadening of low
eld signal with the appearance of two maxima indicating presence
of another species. This additional signal is more prominent in
PA66/GFAlPiS400-300 and very distinct in PA66/GFAlPi
S400-600. This species is due to formation of AlPO4 and AlPi
disappears completely at this stage. No further change is observed
in PA66/GFAlPiS400-1000 spectrum. 13C NMR of PA66/GF
AlPiS400 (Fig. 9b) shows signals that corresponds to carbon of
PA66 and AlPi. Spectrum is similar to that of PA66/GF S400 but
with additional signal for AlPi which shows a multiplet between
22.4 and 20.4 ppm and a strong peak at 8.6 ppm assigned respec-
tively to CH2 and CH3 groups. Signals of PA66/GF are still found in
the spectrum of PA/GF AlPi S400-300 indicating thermal stabili-
zation of PA66 by additives. In PA66/GFAlPiS400-600 spectrum,
a broad weak resonance around at 130 ppm is seen which is
assigned to char formation [26].
3.3.3. X-ray powder diffraction studies (XRD)
XRD pattern of selected residues were displayed in Fig. 11. XRD
of S400 is well dened indicating crystalline nature of the material.
As the temperature increases (376 1C to 554 1C to 750 1C) the
diffraction peaks weaken due to amorphozation. The XRD pattern
of S400-750 shows a broad band around 251 due to char formation.
It is found that ZnPO framework has a pronounced tendency to
collapse upon removing the amine template from the framework by
dry heating unlike AlPO. It is also possible that presence of acid
source like H3PO4 lead to degradative transformation of ordered
molecular network in S400 into low dimensional amorphous solids
[53]. The residues obtained from formulation involving AlPi also
display broad band due to char formation. Although few sharp
diffraction peaks are seen in AlPiS400-750, assigning to specic
crystalline phase is difcult as other peaks are overlapped in the
broad band from char. Interestingly, residue from PA66S400-750
obtained from tubular furnace under controlled condition shows
well dened diffraction pattern. Comparison with the literature and
database search [14,5358] reveals that it is a mixture of several
species like dehydrated form of -hopeite (Zn3(PO4)2, Zn(PO3)2 and
Zn2(P2O7). It has been observed that polymer medium often acts as
a sacricial matrix to generate crystalline, phase pure ZnPO.
3.3.4. Texture studies
The intumescence surface, underlying char and its upper surface
were investigated by EPMA to determine the constituents of the
char. This also shows the migration and distribution of chemical
species under re scenario. The BSE image on intumescence is
shown in Fig. 12a and corresponding elemental mapping are shown
in Fig. 12dg. There is random distribution of white granules
throughout the surface. The needle shaped structures seen at certain
places are glass-bres. EPMA analysis conrms that the surface is
rich in nitrogen, oxygen, carbon, zinc, phosphorus, and aluminium
distributed over the entire surface. There is hardly any difference in
terms of elemental composition between white patches and the
surrounding dark matrix. Further, it is observed that the upper
surface of underlying char also display random distribution of white
lumps of 23 mm width (Fig. 12b). Same elements that were
mapped on intumescence surface are detected except carbon.
A cross-section on the char layer is shown in Fig. 13a, which shows
a highly porous structure. A 3D image constructed from optical
microscope (Fig. 13b) shows numerous interconnected pores. A BSE
image over one such area is shown in Fig. 13c and an elemental
mapping performed over this surface are shown in Fig. 13df. The
skeletal framework is constructed from glass bres, carbon and all
the key elements like P, Al and Zn making a robust solid sponge. The
voids that can be seen in the images are assumed to be developed
during burning which acts as escape channels for gases.
4. General discussion
Under re scenario virgin PA66 due to its inherent ammability
burns easily. Despite its rich carbon framework which could be
source of char it fails to build sufcient stable cross-linking and
subsequent thermally stable char. Adipic acid based polymers like
PA66 were proposed to thermally degrade via a H-transfer to the
nitrogen atom with formation of compounds having amine and
keto-amide ends groups (Scheme 1). Successively, secondary

Fig. 13. Char layer from PA66/GF AlPi S400 obtained from mass loss calorimeter: (a) optical microscope image showing cross sectional view on char, (b) 3D view on
porous char. As a guide, dark blue color indicates presence of cavities leading to internal channels created from escaping gases. (c) BSE image on cross-section of char
embedded in epoxy resin. White spots are glass bres whereas grey areas represent presence of other elements mixed with carbon skeleton. ((d)(f)) Elemental mapping
(Zn, P and Al) on image (c) showing distribution of elements. (For interpretation of the references to color in this gure legend, the reader is referred to the web version of
this article.)
 A.D. Naik et al. / Fire Safety Journal 70 (2014) 4660
thermal fragments leads to compounds like cyclopentanone, CO2,
compound with azomethine and isocyanate. Cyclopentanone, a
volatile product is shown to result from cyclization of adipic acid
portion. When this happens at adipic acid terminated chain end of
polyamide 66, there is concomitant release of carbon dioxide.
Literature reveals that there may be several types of competitive
reaction in the thermal degradation of PA66 and additives often
found to inuence this degradation pathway in a favourable way
[26,27,3033,37,59,60].
Scheme 1. A simplied, tentative degradation pathway and decomposition pro-
ducts in PA66/GF.
Scheme 2. Tentative degradation pathway and prominent decomposition products in the gas phase action of PA66/GF AlPi S400.
57
In the preceding section, it is noted that synergy between S400
and AlPi has improved ame retardancy of PA66/GF (Fig. 3a)
in PA66/GF AlPi S400. Otherwise susceptible PA66/GF shows
 80% reduction in rate of heat release in mass loss calorimeter
and moreover the ignition time is signicantly prolonged (111 s). It
is evident from pyrolysis GCMS that melamine is released from
S400 at an earlier stage that might trigger destabilization of
polyamide network (Scheme 2). The other potential species are
ammonia, a de-ammonationcondensation side-product of S400
that is detected in TGA-FTIR performing the same role. In the
following section, the identications of key intermediates that were
discussed in the previous sections are gathered and results are
converged to frame a tentative sequence in ame retardancy
mechanism. This covers both gas and condensed phase actions with
remarkable physical response of protective intumescence.
The rst obvious and visual indication of ame retardancy is
intumescence. Only AlPiS400 combination offers a signicant
intumescent phenomenon to PA66/GF (Fig. 3c). The breathing
effect of swelled char largely regulates the increasing pressure
created by the gases underneath thereby regulating control release
of ammable/non-ammable gases. This also acts a physical
barrier against external heat ux. Since both S400 and AlPi have
high probability of sublimation, it also contributes to swelling of
intumescence due to pressure developed underneath an action
called blowing effect. This effect might bring some elements to the
intumescence surface contributing to the dense coating of ele-
ments. The intumescence is vitreous, strong and exible enough to
withstand gaseous pressure thanks to the glass-bres as at no
point of time the hollow intumescence collapses. EPMA conrms
that all the key elements (P, Al, Zn, N, C, O) that were part of the
58 A.D. Naik et al. / Fire Safety Journal 70 (2014) 4660

additives/polymer were found on the surface of intumescence. The
dispersion of these vitreous-glass forming materials cement the
intumescence and along with densely interwoven glass-bre gives
cohesiveness and robustness to intumescence. It is interesting to
note that 3 mm thick polymer plate under mass loss calorimeter
experiment develop  4 cm hollow intumescence (Fig. 3c) provid-
ing protection to the underlying polymer.
Alongside, the underlying polymer degrades to form a porous
char (Fig. 13). Analysis on collected condensed phases based on HRR
curve is a trail of sequence of events that had taken place during the
course of thermal degradation of ame retarded polymer. Elemental
mapping by EPMA (Fig. 13) conrms presence of all elements (P, Al,
Zn, N, C, O) embedded in carbon matrix. These elements along with
glass bres reinforce the char layer. PA66 is the main source of carbon
partly contributed from S400 and AlPi. Solid state NMR was useful as
true molecular identities of the elements in char could be established
(Section 3.3.2) that are formed at different steps in the course of
thermal degradation. S400 alone is found to have higher tendency to
form low dimensional phosphate products like ortho/pyro phos-
phates (ZnPO). On the other hand polymer mediated decomposition
shows formation of crystalline meta/polyphosphate chains (Fig. 8b).
The source of identied AlPO4 is AlPi and its evolution is traced:
(AlO6(PO) to AlO5(PO) to AlO4(PO)) [29] and obviously ZnPO is
obtained from S400. Although amorphoziation is evident from XRD
pattern, dehydrated form of -hopeite (Zn3(PO4)2, Zn(PO3)2 and
Zn2(P2O7) is identied underlining the role of polymer matrix in
shaping the crystallinity of zinc phosphate. The upper surface of char
bears interesting islands of white lumps whose elemental identica-
tion indicates all the expected elements except carbon. This probably
indicates some sort of migration and accumulation of elements. The
role of phosphorus-containing compounds in ame retardancy in
condensed phase is multi-modal. They are known to be involved in
branching and cross-linking of decomposition products of polyamide
thus reducing combustible gaseous products [27]. Their role in

Scheme 3. Tentative degradation pathway and decomposition products in the condensed phase action of PA66/GF AlPi S400.
 A.D. Naik et al. / Fire Safety Journal 70 (2014) 4660
formation of inorganic glasses is well documented. They are also
found to obstruct the gasication of char. It could be expected that
char/intumescence further undergo oxidation in air at elevated
temperature ruining its signicant contribution. FTIR indicates that
there may be formation of CP or COP bonds (Scheme 3) which
might explain the stability of char layer towards oxidation. It was
reported by McKee et al. [61,62] that carbonaceous materials treated
with ortho-phosphoric acid lower their oxidation rate because raising
the temperature results in the decomposition of the adsorbates and
the formation COP bonds. Hence, carbon active sites are blocked
and oxidation of carbon is limited. Often such phosphate glasses
were incorporated with metal ions like aluminium, zinc or zirconium
to enhance performance [6163].
Independent studies on S400 degradation points to the forma-
tion of conjugated aromatics upon de-ammonation. There is visual
indication of chromic response upon annealing. White S400
changes to cream in S400-376, grey in S400-554 and light brown
in S400-750. All these intermediates are in powder form. This is
attributed to the formation of melamine condensation products.
The color may also have contribution from light yellow hydrated
zinc phosphate. In the deammonationcondensationdegradation
of S400, formation of melam, melem, oligomers of melem or
melon/carbon nitride, cyanamide/nitrile derivatives are possible
[4042]. There is high possibility of zinc coordination to these
species and formation of stable species. As the de-ammonation
products in the condensation cascade of melamine are regarded as
ame retarding materials, it is reasonable to assume the presence
and action of these species in the condensed phase ame retar-
dancy of S400 based formulations.
Factors and chemical species that affect the re cycle constitute
gas phase action in ame retardancy are evidenced mainly from
TGA-FTIR [3436] and pyrolysis GCMS [32,37,38,64]. Endothermic
decomposition of S400 helps to reduce pHRR and thus acts as heat
sink. The non-ammable gases identied can dilute the oxidant.
AlPi is found to sublimate or release phosphonic acid or produce
diethyl phosphine, triethyl phosphine oxide which might interrupt
radical chain mechanism of combustion process [4]. It is observed
from TGA-FTIR (Fig. 4) that production of ammable cyclopenta-
none is reduced in FR formulation compared to neat PA66/GF. This
would mean either deviation of usual degradation pathway of
polyamide or utilization of cyclopentanone, towards a chemical
reaction (e.g. formation of a Schiff base) with melamine or other
amine side-products and subsequent usage in cross-linking process.
It is also possible that under air atmosphere it undergoes oxidation
to form carbon dioxide as seen in TGA-FTIR under air atmosphere
(not shown). Braun et al. also reported decrease in cyclopentanone
production in case of PA66/GFMPP or PA66/GFAlPi [26]. PA66
degradation without cyclopentanone detection and formation of
only polymer chain fragments, NH3, H2O, CO2 are also discussed in
literature [27]. Levchik et al. discussed that chain scission might also
occur at the alkylamide bond CH2CONH and formation of
carbodiimide structures with relatively large amount of CO2 [27].
Gijsman et al. reported that cyclopentanone may cross-link with
melamine cyanurate degradation product, mainly ammonia result-
ing in less ammable high molecular weight structures [59]. Taken
these facts into account, tracing cyclopentanone evolution is con-
sidered an equally important factor in ame retardancy of PA66.
5. Conclusion
Expansion of FR melamine family continues to provide stimu-
lating results. Chemical renovation of these molecules under the
platform of inorganicorganic hybrids is found to be an ideal
strategy to amalgamate the inherent ame retardancy of indivi-
dual members and upgrade overall performance. Non-halogen
59
S400 is a tailored multi-component molecular system with each
component capable of contributing to ame retardancy. S400
inuence processability, improves color of extrudate, shows syner-
gism with additives, and enhances re performances. A detailed
investigation on how S400 is able to execute itself in the
strengthening of polyamide 66 towards ame retardancy is extra-
polated in this work. The inclusive aspects extracted in this work
to delineate the mechanism of action in ame retardancy would
be an impetus for further redesign strategy for novel metal based
melamine polyphosphates.
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