materials

Article
Exploring the Modes of Action of Phosphorus-Based
Flame Retardants in Polymeric Systems
Sebastian Rabe, Yuttapong Chuenban and Bernhard Schartel *
Bundesanstalt für Materialforschung und -prüfung (BAM), 12205 Berlin, Germany;
[email protected] (S.R.); [email protected] (Y.C.)
* Correspondence: [email protected]; Tel.: +49-30-8104-1021

Academic Editor: De-Yi Wang

Received: 20 February 2017; Accepted: 20 April 2017; Published: 26 April 2017

Abstract: Phosphorus-based flame retardants were incorporated into different, easily preparable
matrices, such as polymeric thermoset resins and paraffin as a proposed model for polyolefins
and investigated for their flame retardancy performance. The favored mode of action of each
flame retardant was identified in each respective system and at each respective concentration.
Thermogravimetric analysis was used in combination with infrared spectroscopy of the evolved
gas to determine the pyrolysis behavior, residue formation and the release of phosphorus species.
Forced flaming tests in the cone calorimeter provided insight into burning behavior and macroscopic
residue effects. The results were put into relation to the phosphorus content to reveal correlations
between phosphorus concentration in the gas phase and flame inhibition performance, as well as
phosphorus concentration in the residue and condensed phase activity. Total heat evolved (fire load)
and peak heat release rate were calculated based on changes in the effective heat of combustion and
residue, and then compared with the measured values to address the modes of action of the flame
retardants quantitatively. The quantification of flame inhibition, charring, and the protective layer
effect measure the non-linear flame retardancy effects as functions of the phosphorus concentration.
Overall, this screening approach using easily preparable polymer systems provides great insight
into the effect of phosphorus in different flame retarded polymers, with regard to polymer structure,
phosphorus concentration, and phosphorus species.

Keywords: flame retardants; flame inhibition; cone calorimeter; aluminum diethyl phosphinate;
polyester; PMMA; epoxy resin; red phosphorus; BDP

1. Introduction
Nowadays, the ever growing numbers of different flame retardants for all kinds of applications,
along with their variations in concentration, particle size distribution and so on, create a need for
screening methods that allow time and material savings while yielding significant results and enabling
reasonable conclusions. Several different approaches have been taken to accelerate fire testing, such as
the microscale combustion calorimeter, the rapid cone calorimeter and the rapid mass calorimeter [1–4].
These methods are specifically designed for screening the fire performance of large numbers of samples.
However, all of the methods require specific sample preparation, such as extrusion and injection
molding, to ensure homogenous implementation of the flame retardant in the thermoplastic. With the
acceleration of the actual testing method, the bottleneck shifts towards sample preparation. Thus, here
a screening approach is presented that uses cone calorimeter investigations on different thermosets
and on paraffin, which is proposed as a model for polyolefins, to address different phosphorous flame
retardants in different concentrations.
Phosphorus-based flame retardants have been proposed to replace halogenated flame retarding
additives due to their good fire properties and better environmental sustainability [5–7]. They exhibit

Materials 2017, 10, 455; doi:10.3390/ma10050455 www.mdpi.com/journal/materials

Materials 2017, 10, 455 2 of 23

all kinds of flame retardant modes of action, such as flame inhibition in the gas phase and char
enhancement, and intumescence and formation of inorganic glass in the condensed phase [6,8–16].
In many polymers, aluminum diethyl phosphinate (AlPi) is reported to exhibit high activity in the
gas phase by releasing diethylphosphinic acid [17–20]. Often only a small fraction of it remains in the
condensed phase to induce some char or residue formation [21]. Phosphate-based flame retardants are
reported to act in the condensed phase as acid precursors, leading to char formation by esterification
and dehydration [22–24]. Nevertheless, if the phosphate esters are released into the gas phase instead
of reacting with the decomposing polymer, they show high flame inhibiting effects [25,26]. Thus,
phosphate flame retardants such as bisphenol-A bis(diphenyl phosphate) (BDP), triphenyl phosphate
(TPP) and resorcinol bis(diphenyl phosphate) (RDP) have different flame inhibition effectiveness, due
to variations in decomposition behavior and releasability [25,27]. Despite its flammability hazard, red
phosphorus is used as a flame retardant as well. It can act in both the gas phase and the condensed
phase [8,16,28]. Indeed, phosphorous flame retardants often act in the condensed phase and in the
gas phase at the same time [8,10,26,29]. It was also demonstrated that the existence and efficiency of
the mode of action as well as its effect on the performance of the flame retardant depends not only
on its chemical structure, but also strongly on its interaction with the polymeric matrix in which it is
incorporated [8,11,15,26,30].
In this work, two AlPi flame retardants with different particle size distributions were used, as well
as BDP and red phosphorus. Thus, it was possible to investigate and compare a range of different
phosphorus sources with different phosphorus content and particle sizes. To achieve easier and
faster sample preparation, the flame retardants were incorporated into resins, which are cured under
laboratory conditions and into paraffin. Here, epoxy-, polyester- and acrylate-based resins were used
by simply mixing them with the additive and molding in small amounts in the laboratory. It has
to be noted, however, that the used epoxy resin cannot be seen as an example for all epoxy resins,
since burning behavior and behavior of the flame retardants in the respective resin may be different.
The group of polyolefins was replaced by paraffin. The relatively fast compounding aims to shift the
bottleneck in the testing process away from sample preparation. Furthermore, the results obtained by
means of these easily compounded polymeric systems are explained using general model assumptions.

2. Materials and Methods

2.1. Thermogravimetric Analysis Coupled with FTIR

Thermogravimetric analysis was conducted on a TG 209 F1 Iris (Netzsch Instruments, Selb,
Germany). Specimens were provided in 5 mg portions of powder in a ceramic crucible, which were
pyrolyzed under nitrogen at a heating rate of 10 K/min. Pyrolysis was performed in the absence of
oxygen to simulate the oxygen-lean conditions in a laminar flame. To analyze and identify the gases
during pyrolysis, the TGA was coupled via a transfer line with a Tensor 27 infrared spectrometer
(Bruker Optics, Ettlingen, Germany). The gas cell and transfer line were operated at a temperature of
270 ◦ C to ensure transport of the pyrolysis gases without condensation effects [31].

2.2. Cone Calorimeter

Forced flaming combustion tests were performed using a cone calorimeter (FTT, East Grinstead,
UK) in accordance with ISO 5660. Specimens 100 × 100 × 3 mm3 in size were conditioned for 48 h
at 23 ◦ C and 50% relative humidity, wrapped in an aluminum tray, and irradiated with 50 kW/m2
at a distance of 35 mm from the cone heater [32] to ensure sufficient spacing for the greatest possible
residue formation. Samples were measured in triplicate when the first two measurements deviated by
more than 10% in any result.
Materials 2017, 10, 455 3 of 23

2.3. Elemental Analysis

Elemental analysis was performed by Mikroanalytisches Laboratorium Kolbe (Mühlheim an der
Ruhr, Germany).

2.4. Materials

2.4.1. Flame Retardants

Aluminum diethylphosphinate (AlPi) was used in two different varieties, Exolit OP935 and Exolit
OP1230 (Clariant). Exolit OP935 is a fine-grained AlPi developed especially for adhesive applications,
and is established as an effective flame inhibitor in epoxy, acrylic and TPE resins [18,33]. The highly
stable Exolit OP 1230 is widely used for high-temperature polyamides, as well as in polyamide-AlPi
mixtures [34–36]. Both flame retardants contain around 23.5 wt % phosphorus. Red phosphorus
(Exolit RP607, Clariant) is typically used in thermoplastics for electronics applications [28]. As it is the
most concentrated source of phosphorus as a flame retardant, its application concentration generally
lies below 10 wt %, and it is usually applied as encapsulated material. Bisphenol-A bis(diphenyl
phosphate) (BDP) is an oligomeric aryl phosphate ester designed for use in engineering resins such
as PC/ABS [5,6]. Since BDP contains only around 9 wt % of phosphorus, a higher BDP load must be
considered in the material. BDP was used in concentrations of 10, 20, 25 and 35 wt % to reach the
effective range of phosphorus concentration. All other investigated flame retardants were concentrated
at 5, 10, 15 and 20 wt %.

2.4.2. Resin Systems

Epoxy resins have become important materials for electronics and lightweight construction,
especially as fiber reinforced composites [37,38]. Bisphenol-A diglycidyl ether (DGEBA, Araldit
MY740, Bodo Möller Chemie GmbH, Offenbach, Germany) and isophorone diamine (IPDA, Merck
KGaA, Darmstadt, Germany) was used as an example for an epoxy resin [39]. IPDA and the respective
flame retardant were added to DGEBA and stirred until a homogenous mixture was obtained. Forty
grams of the mixture was poured into a 100 × 100 × 6 mm3 aluminum mold and cured for 30 min
at 80 ◦ C and for 70 min at 120 ◦ C. The aluminum frame was stabilized with weights to prevent
deformation during curing. The edges of the finished specimens had to be ground down in order to
obtain a flat surface. The rest of the mixture was also cured as described above, followed by grinding
to obtain powder for TGA-FTIR measurements.
As an acrylate thermoset, a pre-accelerated PMMA resin with an incorporated, UV-induced curing
agent was used (S. u. K. Hock GmbH, Regen, Germany). The respective flame retardant was added
to the methyl methacrylate resin and stirred until homogeneity was achieved. The mixture was then
poured into aluminum molds and cured at room temperature and irradiated by a daylight spectrum
lamp for 12 h. Systems with red phosphorus could not be produced because the curing process was
hindered so that complete hardening could not be achieved.
For preparation of the polyester system, the flame retardant was added to a mixture of polyester
resin L800 and the curing agent methyl ethyl ketone peroxide (MEKP) (S. u. K. Hock GmbH, Regen,
Germany). The mixture was then poured into aluminum molds and cured at room temperature
for 8 h. The edges of the molds were also weighed down to prevent deformation during curing.
Red phosphorus prevented the resin from curing, so that a polyester formulation with RP as flame
retardant could not be manufactured.
Materials 2017, 10, 455 4 of 23

To represent the group of polyolefins, paraffin pellets were melted at 75 ◦ C and combined with
the flame retardant. The hot mixture was poured into the aluminum molds and cooled down to
room temperature. It was not possible to implement BDP into paraffin because the two phases were
immiscible. BDP accumulated as a bubble underneath the paraffin in the mold. All produced materials
were given a label according to Table 1.
Materials 2017, 10, 455 4 of 23

Table 1. Nomenclature
Table 1. Nomenclature ofof
the produced
the producedflame
flameretarded
retardedpolymeric withxx==concentration
materialswith
polymeric materials concentration
of of
thethe
flame
flame retardant, 5, 10, 15 or 20 wt % for Exolit OP935, OP1230 and RP607 and 10, 20, 25 and 35 wt % %
retardant, 5, 10, 15 or 20 wt % for Exolit OP935, OP1230 and RP607 and 10, 20, 25 and 35 wt
forfor
BDPBDPrespectively.
respectively.

Exolit
ExolitOP935
OP935 Exolit OP1230
Exolit OP1230 ExolitRP607
Exolit RP607 BDP
BDP
DGEBA/IPDA EP-x-ExOP935 EP-x-ExOP1230 EP-x-ExRP EP-x-BDP
DGEBA/IPDA EP-x-ExOP935 EP-x-ExOP1230 EP-x-ExRP EP-x-BDP
PMMA-resin
PMMA-resin PMMA-x-ExOP935
PMMA-x-ExOP935 PMMA-x-ExOP1230
PMMA-x-ExOP1230 — --- PMMA-x-BDP
PMMA-x-BDP
Polyester-resin
Polyester-resin Pes-x-ExOP935
Pes-x-ExOP935 Pes-x-ExOP1230
Pes-x-ExOP1230 — --- Pes-x-BDP
Pes-x-BDP
Paraffin
Paraffin P-x-ExOP935
P-x-ExOP935 P-x-ExOP1230
P-x-ExOP1230 P-x-ExRP
P-x-ExRP —---

3. Results
3. Results andand Discussion
Discussion

3.1.3.1. Thermogravimetric
Thermogravimetric AnalysisResults
Analysis Results

AllAllinvestigated
investigated systems,
systems, with
with andand without
without flame
flame retardant,
retardant, were
were investigated
investigatedviavia
thermogravimetric analysis in the absence of oxygen. Mass and DTG curves are
thermogravimetric analysis in the absence of oxygen. Mass and DTG curves are displayed displayed in 1
in Figure
Figure 1 and results are listed in Table 2.
and results are listed in Table 2.

Figure
Figure 1. Thermogravimetric(TG)
1. Thermogravimetric (TG)and
andderivative
derivative thermogravimetric
thermogravimetric (DTG)
(DTG)results
resultsfor
forselected flame
selected flame
retarded and non-flame retarded specimens with: epoxy resin (a); polyester resin (b); PMMA
retarded and non-flame retarded specimens with: epoxy resin (a); polyester resin (b); PMMA resin resin (c);(c);
and paraffin (d) as polymer matrix.
and paraffin (d) as polymer matrix.
Materials 2017, 10, 455 5 of 23

Table 2. Results from thermogravimetric analysis (TGA). T5% ML is the temperature at which 5 wt % of
the mass is lost, TDTGmax is the temperature of the maximum of the mass loss rate. The residue was
determined at 800 ◦ C.

T5% ML TDTGmax Residue

Material ◦C ◦C wt %
EP 326 ± 1 360 ± 2 10.7 ± 0.1
EP-10-ExOP935 320 ± 1 355 ± 1 12.1 ± 0.3
EP-10-ExOP1230 320 ± 2 353 ± 1 12.1 ± 0.3
EP-5-ExRP 318 ± 1 349 ± 1 17.0 ± 0.2
EP-10-BDP 265 ± 1 365 ± 1 3.0 ± 0.1
Pes 204 ± 1 380 ± 2 2.9 ± 0.1
Pes-10-ExOP935 211 ± 1 378 ± 1 14.0 ± 0.4
Pes-10-ExOP1230 210 ± 1 382 ± 2 11.7 ± 0.2
Pes-20-BDP 277 ± 2 380 ± 2 2.6 ± 0.1
PMMA 192 ± 1 370 ± 2 1.7 ± 0.1
PMMA-10-ExOP935 229 ± 2 368 ± 1 4.6 ± 0.2
PMMA-10-ExOP1230 228 ± 1 370 ± 2 4.5 ± 0.1
PMMA-10-BDP 246 ± 2 364 ± 1 0.7 ± 0.1
P 223 ± 1 296 ± 1 0.1 ± 0.1
P-10-ExOP935 207 ± 1 274 ± 1 0.2 ± 0.1
P-10-ExOP1230 225 ± 2 454 ± 3 1.4 ± 0.2
P-10-ExRP 207 ± 1 273 ± 1 2.1 ± 0.2

The start of the decomposition T5% ML (at which 5 wt % of the material was lost) for epoxy resin
formulations shifted towards lower temperatures when flame retardants were added. EP-10-ExOP935
and EP-10-ExOP1230 showed decomposition behavior similar to the pure epoxy resin. The temperature
of the maximum mass loss rate, TDTGmax , was shifted to temperatures 5 and 7 ◦ C lower, respectively.
With the non-flame retarded epoxy resin producing 10.7 wt % of residue, replacement of 10 wt % of the
resin with AlPi flame retardants would still produce 9.6 wt % residue. Since residue formation increased
to 12.1 wt %, 2.5 wt % of the residue results from the incorporation of the flame retardant. Epoxy
resin with 5 wt % of red phosphorus flame retardant added began decomposition at an even lower
temperature, exhibiting a lower TDTGmax , and an increase in residue of around 6.8 wt %. This means
that carbonaceous char was produced. Besides the drastic lowering of the temperature at the start of
decomposition, incorporation of 10 wt % of BDP in the epoxy resin resulted in a second decomposition
step prior to the main one. It also formed much less residue than the other epoxy formulations, leading
to the conclusion that this amount of BDP prevents residue production in epoxy resin. The temperature
of maximum decomposition was shifted to temperatures 5 ◦ C higher.
For the polyester system, the beginning of decomposition shifted to temperatures only slightly
higher for Pes-10-ExOP935 and Pes-10-ExOP1230, but the effect was stronger when BDP was added.
Ten weight percent of Exolit OP935 promoted the production of residue, increasing the amount by
11.4 wt %. Carbonaceous char was formed. For 10 wt % of Exolit OP1230 in polyester resin, the residue
formation was promoted by 9.1 wt % compared to the non-flame retarded polyester resin. Pes-20-BDP
produced only 0.3 wt % more residue. The temperatures of maximum decomposition did not alter
much with the addition of a respective flame retardant.
In the PMMA resin, the starting temperature for decomposition shifted to higher temperatures
with the addition of flame retardants. Incorporation of 10 wt % Exolit OP935 or OP1230 increased the
temperature of 5 wt % mass loss by around 37 ◦ C, whereas BDP raised it by more than 50 ◦ C. There
are no differences in decomposition observed between Exolit OP935 and OP1230. Ten weight percent
of either flame retardant in PMMA resin increased the amount of residue by 3 wt %, consisting of
inorganic ash. The amount of residue of PMMA-10-BDP was insignificant. Only for 10% BDP was a
relevant shift of TDTGmax by 6% to lower temperatures observed.
For paraffin, all of the flame retarded formulations showed a two-step decomposition process,
clearly visible in both the mass loss and the mass loss rate curves (Figure 1d). The AlPi flame
retardant Exolit OP935 as well as the red phosphorus caused a decrease in the temperature at which
Materials 2017, 10, 455 6 of 23

Materials 2017, 10, 455 6 of 23

decomposition begins. Furthermore, both flame retardants caused a shift in the maximum of the mass
loss rate to temperatures
decomposition begins.22Furthermore,
to 23% lower. bothInflame
the DTG curves
retardants it becomes
caused a shift clear
in thethat the formulation
maximum of the
with 10 wt %
mass of rate
loss Exolitto OP1230 showed
temperatures 22 the highest
to 23% mass
lower. In loss rate incurves
the DTG the second step of
it becomes decomposition.
clear that the
It wasformulation
even higher than
with 10 what
wt % ofis Exolit
considered
OP1230 the main the
showed decomposition
highest mass step for in
loss rate thethe
other formulations,
second step of
decomposition.
changing the TDTGmax It was
to 454 ◦ C.higher
even than what
The residues is considered
produced the
by all main decomposition
paraffin formulationsstep are for the
negligible.
other formulations, changing the T to 454 °C. The residues produced
These results clarified that the phosphorus-based flame retardants only slightly promote the formation
DTGmax by all paraffin
formulations
of a residue, are negligible.
especially These
at relatively results
low clarified thatofthe
concentrations upphosphorus-based
to 10 wt %, and thusflameare
retardants
mainly only
released
slightly promote the formation of a residue, especially at relatively low concentrations of up to 10 wt %,
into the gas phase. The varied particle size distribution in Exolit OP935 and Exolit OP1230 had no
and thus are mainly released into the gas phase. The varied particle size distribution in Exolit OP935
significant influence on the thermal decomposition properties.
and Exolit OP1230 had no significant influence on the thermal decomposition properties.
3.2. FTIR Spectra of the Gaseous Phase
3.2. FTIR Spectra of the Gaseous Phase
To confirm that phosphorus
To confirm species
that phosphorus werewere
species released into the
released intogas
thephase, the pyrolysis
gas phase, gasesgases
the pyrolysis evolved
from TGA measurements were introduced into an IR cell. It was possible to identify various
evolved from TGA measurements were introduced into an IR cell. It was possible to identify various volatile
phosphorus
volatile phosphorus species. The FTIR spectra of the investigated formulations are shown in Figure These
species. The FTIR spectra of the investigated formulations are shown in Figure 2. 2.
experiments simply serve
These experiments as aserve
simply wayastoa way
enable a discussion
to enable about
a discussion the the
about gasgas
phase
phaseactivity
activity due to the
due to
releasethe
ofrelease of phosphorus
phosphorus species.species.

FigureFigure 2. Fourier
2. Fourier transform
transform infrared
infrared (FTIR)
(FTIR) spectra
spectra at the
at the respective
respective mainmain decomposition
decomposition step
step ofof
flame
flamein:
retardants retardants in: polyester
epoxy (a); epoxy (a); (b);
polyester
PMMA (b);(c);
PMMA (c); and paraffin
and paraffin (d) systems.
(d) systems. DottedDotted lines included
lines were were
included
as an aid as an aidsmaller
to highlight to highlight
peakssmaller
from peaks from phosphorus
phosphorus species. species.

The AlPi flame retardants Exolit OP935 and OP1230 showed peaks at wavenumbers 854, 3650
The
andAlPi
1265 flame
cm−1 inretardants Exolitindicating
the epoxy resin, OP935 and the OP1230 showed
P–O, P–OH peaks at wavenumbers
and P=O-stretch 854, 3650
of diethylphosphinic
and 1265 At−1078
acid.cm 1 in the−1epoxy resin, indicating the P–O,
cm , a weak peak expressed the PO2− anion P–OH and
of the P=O-stretch
AlPi of diethylphosphinic
molecule, whereas the peak at
9521078
acid. At cm−1 cm −1 , a weak
signified the production of ethenethe
peak expressed by PO 2− anion
a P–C bond break
of theinAlPi
AlPi.molecule,
A phosphinate peakthe
whereas waspeak
found− 1at 670 cm −1 [21,40,41]. Red phosphorus showed peaks at 670, 922, 1256 and 2375 cm−1, which
at 952 cm signified the production of ethene by a P–C bond break in AlPi. A phosphinate peak
are representative
was found at 670 cm−for PO43−, P–OP,
1 [21,40,41]. P=O
Red and P–OH vibrations.
phosphorus In the EP-10-BDP
showed peaks at 670, 922,formulation, several
1256 and 2375 cm−1 ,
peaks corresponding to phenolic derivatives of bisphenol-A were found at 1261, 1173, 1490 and
which are representative for PO4 3− , P–OP, P=O and P–OH vibrations. In the EP-10-BDP formulation,
1620 cm−1, which represent aromatic phosphate esters.
several peaks corresponding to phenolic derivatives of bisphenol-A were found at 1261, 1173, 1490
and 1620 cm−1 , which represent aromatic phosphate esters.
Materials 2017, 10, 455 7 of 23

In the polyester resin, Exolit OP935 and 1230 showed peaks at 1105 and 1053 cm−1 , which display
Materials 2017, 10, 455 7 of 23
PO2− vibration. The peak at 1257 cm−1 is attributed to P=O. A peak for a P–O–P vibration was found
at 910 cmIn−1 . In BDP, those vibrations occurred at 1165, 1087, 1230 and 910 cm−1 .
the polyester resin, Exolit OP935 and 1230 showed peaks at 1105 and 1053 cm−1, which
Peaks related to phosphorus
display PO2− vibration. The peak at species
1257 cmare less
−1 is pronounced
attributed to P=O. in the flame
A peak retarded
for a P–O–P PMMA
vibration was resin
formulations. The strong release of methyl methycrylate, verified
found at 910 cm . In BDP, those vibrations occurred at 1165, 1087, 1230 and 910 cm .
−1 by the characteristic
−1 peaks such as
the C–H stretch at around
Peaks related to phosphorus − 1
2950 cm ,species the C=O arestretch −
at 1700 cmin the
less pronounced 1 , the C=Cretarded
flame stretch at 1600 cm
PMMA resin−1 and
formulations.
the C–O stretch at The
aroundstrong release
1200 − 1
cm of, methyl
concealedmethycrylate,
most of the verified by the characteristic
phosphorus-related peaks.peaks
Onlysuchtheaspeaks
the C–H stretch −
at1 around 2950 cm −1, the C=O stretch
2 − at 1700 cm −1, the C=C stretch at 1600 cm−1 and
at 1056 and 1168 cm suggest the existence of PO species in the gas phase. However, Exolit OP935
the C–O incorporated
and OP1230 stretch at around into1200 cm−1, showed
paraffin concealedstrong
most of POthe
2− phosphorus-related
peaks at 1156 andpeaks. 1085 cmOnly
−1 ,the
as well
peaks at 1056 and−11168 cm suggest the existence of PO2− species in the gas phase. However, Exolit
−1
as a peak at 775 cm which is attributed to diethylphosphinic2−acid. Red phosphorus in−1paraffin
OP935 and OP1230 incorporated into paraffin showed strong PO peaks at 1156 and 1085 cm , as
did not exhibit phosphorus-related peaks at the first decomposition step. However, at the second
well as a peak at 775 cm−1 which is attributed to diethylphosphinic acid. Red phosphorus in paraffin
decomposition step, phosphorus
did not exhibit phosphorus-related peaks was released
at theasfirst
mixtures of undefined
decomposition low-oxidized
step. However, at thephosphorus
second
oxides indicated by broad peaks at around 1300 and 950 cm −1 . Earlier work showed that phosphorus
decomposition step, phosphorus was released as mixtures of undefined low-oxidized phosphorus
was released as P4 molecules,
oxides indicated by broad peaksbreaking down
at around to Pand
1300 2 molecules with increasing
950 cm−1. Earlier work showed temperature [16].
that phosphorus
The results from
was released as P4 the FTIR experiments
molecules, breaking down demonstrated
to P2 molecules thatwith
phosphorus
increasingspecies are traceable
temperature [16]. in the
The results from the FTIR experiments demonstrated that phosphorus
gaseous phase and thus are released during pyrolysis of the formulations. This is the premise of the species are traceable in
the gaseous
following phase andinto
investigations thusthe are extent
releasedtoduring
whichpyrolysis
phosphorus of the compounds
formulations. and This the
is the premise of of
concentration
the following investigations into the extent to which phosphorus compounds
phosphorus in the gas phase are attributed to flame inhibition, and whether the remaining phosphorus and the concentration
of phosphorus in the gas phase are attributed to flame inhibition, and whether the remaining
in the residue has any effect on other modes of action in flame retardancy.
phosphorus in the residue has any effect on other modes of action in flame retardancy.
3.3. Forced Flaming Fire Behavior: Cone Calorimeter
3.3. Forced Flaming Fire Behavior: Cone Calorimeter
3.3.1. Comparison of Heat Release Rates
3.3.1. Comparison of Heat Release Rates
Forced flaming
Forced firefire
flaming tests were
tests wereconducted
conducted in in the conecalorimeter.
the cone calorimeter. AtAt first,
first, it was
it was interesting
interesting to to
see the
seedifferences between
the differences betweenthethe
investigated
investigated flame retardantsatatthe
flame retardants the same
same concentration
concentration in different
in different
matrices. TheThe
matrices. heat release
heat releaserate
rate(HRR)
(HRR) curves are displayed
curves are displayedininFigure
Figure3. 3.
TheThe results
results of allofcone
all cone
calorimeter measurements
calorimeter measurements areare
summarized
summarizedin inTable
Table 3.

Figure
Figure 3. Cone
3. Cone calorimeter
calorimeter heat
heat releaserate
release rate(HRR)
(HRR) curves
curves of
offlame
flameretardants in: in:
retardants DGEBA/IPDA (a); (a);
DGEBA/IPDA
Pes-resin (b); PMMA resin (c); and paraffin (d) with a concentration of 10 wt %.
Pes-resin (b); PMMA resin (c); and paraffin (d) with a concentration of 10 wt %.
Materials 2017, 10, 455 8 of 23

Table 3. Cone calorimeter results.

tig PHRR THE EHC Residue at End of Test

System
s kW/m2 MJ/m2 MJ/kg wt %
EP 39 ± 1 1858 ± 41 81.3 ± 0.1 24.7 ± 0.1 0.5 ± 0.0
EP-5-ExOP935 30 ± 1 1632 ± 4 71.1 ± 2.1 21.6 ± 0.4 4.3 ± 0.3
EP-10-ExOP935 32 ± 1 969 ± 57 59.0 ± 1.3 19.2 ± 0.3 6.3 ± 0.3
EP-15-ExOP935 30 ± 1 864 ± 9 57.0 ± 0.3 18.3 ± 0.0 8.6 ± 0.3
EP-20-ExOP935 30 ± 0 817 ± 25 52.3 ± 0.1 17.7 ± 0.1 11.3 ± 0.6
EP-5-ExOP1230 31 ± 2 1105 ± 52 71.6 ± 0.3 19.9 ± 1.4 4.9 ± 0.1
EP-10-ExOP1230 32 ± 1 1097 ± 50 61.1 ± 0.1 19.0 ± 0.0 6.3 ± 0.2
EP-15-ExOP1230 30 ± 0 1007 ± 16 58.9 ± 0.8 18.2 ± 0.2 8.6 ± 0.2
EP-20-ExOP1230 31 ± 2 861 ± 2 54.0 ± 0.3 18.0 ± 0.1 10.8 ± 0.0
EP-5-ExRP 29 ± 1 964 ± 16 51.1 ± 1.9 15.7 ± 0.3 6.3 ± 0.1
EP-10-ExRP 33 ± 1 786 ± 24 47.2 ± 1.0 15.4 ± 0.4 8.0 ± 0.1
EP-15-ExRP 34 ± 2 673 ± 125 42.4 ± 0.9 13.5 ± 0.4 8.7 ± 0.5
EP-20-ExRP 32 ± 2 873 ± 56 50.1 ± 0.4 16.6 ± 0.3 9.9 ± 1.5
EP-10-BDP 25 ± 3 1468 ± 44 74.0 ± 4.1 22.7 ± 1.4 5.0 ± 0.3
EP-20-BDP 26 ± 1 688 ± 3 49.0 ± 0.7 16.9 ± 0.1 14.9 ± 1.1
EP-25-BDP 22 ± 2 660 ± 1 45.0 ± 0.3 15.5 ± 0.1 15.8 ± 1.7
EP-35-BDP 28 ± 1 628 ± 3 42.5 ± 0.6 15.3 ± 0.3 17.3 ± 0.4
Pes 26 ± 1 1017 ± 16 94.3 ± 2.9 19.9 ± 0.9 0.1 ± 0.1
Pes-5-ExOP935 33 ± 2 854 ± 38 85.5 ± 0.4 19.1 ± 0.1 4.1 ± 0.2
Pes-10-ExOP935 32 ± 1 599 ± 6 64.5 ± 1.3 15.7 ± 0.1 7.7 ± 0.5
Pes-15-ExOP935 36 ± 2 577 ± 29 70.9 ± 0.0 16.5 ± 0.2 8.5 ± 0.3
Pes-20-ExOP935 34 ± 1 521 ± 15 60.9 ± 3.2 14.7 ± 0.6 8.6 ± 0.5
Pes-5-ExOP1230 31 ± 2 969 ± 33 89.8 ± 0.1 19.8 ± 0.1 3.7 ± 0.3
Pes-10-ExOP1230 32 ± 5 428 ± 27 69.4 ± 2.2 14.9 ± 2.0 8.5 ± 0.1
Pes-15-ExOP1230 30 ± 2 603 ± 37 73.4 ± 4.0 13.9 ± 2.3 9.4 ± 0.4
Pes-20-ExOP1230 33 ± 1 456 ± 8 61.2 ± 1.7 14.4 ± 0.4 10.0 ± 0.1
Pes-10-BDP 35 ± 1 727 ± 80 77.8 ± 1.4 16.9 ± 0.3 1.1 ± 0.4
Pes-20-BDP 32 ± 1 629 ± 63 66.5 ± 0.7 11.3 ± 3.2 2.1 ± 0.5
Pes-25-BDP 37 ± 6 570 ± 17 59.6 ± 0.6 11.7 ± 1.7 3.5 ± 0.5
Pes-35-BDP 34 ± 5 538 ± 49 55.9 ± 1.4 12.1 ± 0.4 4.8 ± 0.3
PMMA 32 ± 1 1051 ± 41 106.9 ± 0.6 25.1 ± 0.5 0.1 ± 0.0
PMMA-5-ExOP935 26 ± 1 836 ± 1 93.7 ± 2.5 22.8 ± 0.7 1.2 ± 0.2
PMMA-10-ExOP935 25 ± 1 792 ± 21 88.8 ± 0.5 22.8 ± 0.2 2.5 ± 0.1
PMMA-15-ExOP935 24 ± 1 740 ± 37 83.8 ± 0.3 20.9 ± 0.1 3.8 ± 0.0
PMMA-20-ExOP935 22 ± 1 615 ± 33 81.8 ± 1.0 21.0 ± 0.4 5.7 ± 0.5
PMMA-5-ExOP1230 23 ± 1 852 ± 20 97.0 ± 1.0 23.2 ± 1.8 1.5 ± 0.1
PMMA-10-ExOP1230 22 ± 0 722 ± 16 89.2 ± 1.1 22.6 ± 0.4 2.9 ± 0.0
PMMA-15-ExOP1230 24 ± 2 678 ± 63 86.6 ± 3.0 21.6 ± 0.6 3.4 ± 0.1
PMMA-20-ExOP1230 26 ± 2 620 ± 4 82.8 ± 0.6 21.4 ± 04 4.8 ± 0.5
PMMA-10-BDP 29 ± 0 1079 ± 25 108.4 ± 0.3 24.7 ± 2.3 0.5 ± 0.1
PMMA-20-BDP 31 ± 1 994 ± 38 97.4 ± 0.9 23.4 ± 0.4 0.6 ± 0.0
PMMA-25-BDP 28 ± 1 868 ± 48 91.5 ± 1.9 21.7 ± 0.1 0.7 ± 0.1
PMMA-35-BDP 28 ± 1 928 ± 19 93.0 ± 0.2 22.3 ± 0.4 0.8 ± 0.1
P 40 ± 3 2996 ± 24 210.1 ± 2.9 44.1 ± 0.5 0.1 ± 0.0
P-5-ExOP935 32 ± 1 1935 ± 167 198.8 ± 7.1 42.3 ± 0.7 0.0 ± 0.0
P-10-ExOP935 27 ± 2 1593 ± 96 189.9 ± 27.1 41.4 ± 1.0 0.0 ± 0.2
P-15-ExOP935 23 ± 1 1371 ± 101 183.8 ± 1.3 39.4 ± 0.1 2.1 ± 0.3
P-20-ExOP935 23 ± 2 1130 ± 69 187.6 ± 3.7 38.9 ± 0.4 1 ± 0.6
P-5-ExOP1230 37 ± 2 2872 ± 318 197.2 ± 1.5 44.0 ± 0.2 0.1 ± 0.1
P-10-ExOP1230 42 ± 6 2868 ± 123 209.9 ± 2.9 43.3 ± 0.3 1.3 ± 0.8
P-15-ExOP1230 29 ± 1 2559 ± 223 195.8 ± 3.5 42.4 ± 0.7 2.9 ± 0.3
P-20-ExOP1230 27 ± 4 2257 ± 67 188.6 ± 12.6 40.7 ± 1.6 4.3 ± 1.0
P-5-ExRP 33 ± 1 2945 ± 13 212.5 ± 10.9 43.2 ± 0.2 0.5 ± 0.5
P-10-ExRP 34 ± 1 2781 ± 150 201.1 ± 1.6 41.4 ± 0.1 0.5 ± 0.0
P-15-ExRP 29 ± 3 2559 ± 219 191.8 ± 1.5 40.4 ± 0.6 0.2 ± 0.1
P-20-ExRP 35 ± 4 2519 ± 35 189.9 ± 2.6 38.5 ± 0.7 0.3 ± 0.6
Materials 2017, 10, 455 9 of 23

Except for paraffin, the systems clearly showed improvements in terms of flame retardancy,
such as reduction in peak heat release rate (PHRR) and total heat evolved (THE). In the epoxy resin,
the formulation with 10 wt % of BDP was the least effective; it lowered the PHRR but shortened the
time to ignition. Ten weight percent of Exolit OP935 and OP1230 further reduced PHRR, with OP935
showing slightly better performance. However, their efficiency at 10 wt % was similar. Compared
to the residue analysis results from TGA, the increase in residue was much more evident in the cone
calorimeter, with an increase of 10% for the highest investigated flame retardant load. Red phosphorus
induced the largest reduction in HRR, although an even greater reduction was expected because of the
high phosphorus content. This suggests that not only the phosphorus content of a flame retardant is
responsible for its performance, but also the way the phosphorus is incorporated. Compared to the
results from the thermogravimetric analysis, the residue produced is not as distinct, especially not
for red phosphorus. At the same time, THE is reduced by almost 50% for EP-15-ExRP. This allows
the conclusion that gas phase activity is mainly responsible for the high THE reduction. However,
the residue produced by BDP increased strongly with higher flame retardant load. This suggests
that there is a clear tendency for condensed phase activity of BDP. In the epoxy resin, 15 wt % of red
phosphorus as well as 35 wt % of BDP showed the best HRR and THE reduction.
Polyester resin showed a PHRR of 900 to 1000 kW/m2 without any flame retardant. The flame
retardants Exolit OP935 and BDP caused a similar reduction in PHRR to around 600 kW/m2 , even
though BDP has lower phosphorus content. The performance of 10 wt % Exolit OP1230 in polyester
resin exceeded those of the other polyester formulations, as the PHRR was reduced further, to around
400 kW/m2 . In the PMMA resin, the formulation with 10 wt % of BDP had about the same performance
as the non-flame retarded resin. Residue formation of the polyester resin formulations did not show
salience; amounts increased with increasing flame retardant load, but remained below 10 wt %. It was
found that Exolit OP1230 resulted in the greatest HRR and THE reduction, especially at 20 wt %.
When Exolit OP935 or 1230 were incorporated into PMMA resin, the PHRR decreased but the
time to ignition was shortened. Exolit OP1230 showed slightly lower PHRR but a longer time of
burning. Residue formations were in great accordance with results from thermogravimetric analysis,
and demonstrated that all flame retardants work mainly via gas phase activity. Incorporation of
BDP did not deliver satisfying results in HRR and THE reduction and was thus considered the worst
additive for these purposes.
Forced flaming heat release tests on paraffin and the respective flame retarded formulations did
not differ substantially as a pure system or with 10 wt % flame retardant load. Only the system with
10 wt % of Exolit OP935 showed prolongation of the small plateau of steady burning and a slight
shift of the PHRR to later times. Observation of the burning process of the formulations including red
phosphorus showed a peculiarity—at the end of the burning process the flame became very bright
and smoke production increased. Red phosphorus did not contribute significantly to inhibiting the
burning process. Rather, it burned away at the end of the burning process. Reductions in PHRR were
thus due to fuel replacement by the flame retardant. No significant residue was formed. Only at high
concentrations of the AlPi flame retardants were 2 to 4 wt % of residue measured. However, it was
observed that they formed towards the end of the burning, when the flame was about to extinguish;
thus, they were not able to affect the burning behavior through condensed phase activity. Overall,
20 wt % of Exolit OP935 reduced PHRR from 2972 to 1130 kW/m2 and THE from 210 to 188 MJ/m2 ,
and is thus considered to be the best suited additive in paraffin.
One of the most important characteristics when it comes to the fire performance of a flame
retardant in a polymeric system is the change in PHRR. The reduction in PHRR signifies several
other phenomena: reduction in the effective heat of combustion, reduction in released fuel due to
an increased amount of residue, and the effect of a protective layer are all reflected by this measure.
To illustrate the correlation between PHRR reduction and phosphorus content in a flame retardant,
they were plotted in Figure 4.
Materials 10, 455
2017, 2017,
Materials 10, 455 10 of 23
10 of 23

Figure 4. Peak
Figure of of
4. Peak heat
heatrelease rate (PHRR)
releaserate (PHRR) ofofepoxy
epoxy resin
resin (a), (a), polyester
polyester resin
resin (b), (b), PMMA
PMMA resin (c)
resin (c) and
and paraffin
paraffin (d)(d)systems
systems plotted
plotted against
against amountamount of phosphorus
of phosphorus in the bulkin material.
the bulkThe material. Theare
dotted lines dotted
lines included
are included as guides
as guides for the eyeforanalogous
the eye analogous to the
to the findings fromfindings
Brehme etfromal. forBrehme et al.
comparable for comparable
materials [31].
materials [31].
The DGEBA/IPDA epoxy resin showed a very pronounced leveling off of flame retardancy
effectiveness for all investigated flame retardants. This leveling off set in at around 10 wt %
The DGEBA/IPDA epoxy resin showed a very pronounced leveling off of flame retardancy
phosphorus content for RP, whereas the AlPi flame retardants Exolit OP935 and OP1230 already
effectiveness for all investigated flame retardants. This leveling off set in at around 10 wt % phosphorus
displayed this effect at a lower phosphorus content. For BDP, which had the lowest phosphorus
content for RP,
content whereas
of all the AlPi
investigated flameflame retardants
retardants, Exolit OP935
the reduction in PHRR and wasOP1230
highest,already displayed
but leveled off at this
effectaround
at a lower phosphorus content. For BDP, which had
700 to 600 kW/m2 at even low phosphorus concentrations (Figure 4a). the lowest phosphorus content of all
investigated
The flame
leveling retardants,
off of PHRR the reduction in PHRR was
reduction effectiveness was highest, but leveled
also visible in the off at around
polyester resin.700 to
600 kW/m 2 at even low phosphorus concentrations (Figure 4a).
However, since the absolute reduction in PHRR was not as high as in the epoxy resin, the leveling
off was
The not as off
leveling pronounced.
of PHRR The PHRR reduction
reduction was more
effectiveness was alsoor less the same
visible forpolyester
in the all three incorporated
resin. However,
flame retardants (Figure 4b). Deviations in the Exolit OP1230
since the absolute reduction in PHRR was not as high as in the epoxy resin, the leveling polyester system may derive off wasfromnot as
slight variations in curing time.
pronounced. The PHRR reduction was more or less the same for all three incorporated flame retardants
Flame retardants in the PMMA resin tended to level off in effectiveness in terms of PHRR
(Figure 4b). Deviations in the Exolit OP1230 polyester system may derive from slight variations in
reduction. However, the decay in effectiveness was more gradual, especially since the pure
curing time.
reduction in PHRR was less significant than in the epoxy resin. BDP in the PMMA resin even
Flame
seemed retardants
to have a linearin the
decay PMMAin PHRR resin
withtended to level
increasing off incontent
phosphorus effectiveness in terms of PHRR
(Figure 4c).
reduction.Flame
However, the decay
retardants in effectiveness
in paraffin did not exhibit was more off,
leveling gradual, especially
but rather a linearsince
decaythe pure reduction
in PHRR. Red
in PHRR was less significant than in the epoxy resin. BDP in the PMMA
phosphorus did not lead to a significant reduction in PHRR. Exolit OP935 was the most effective resin even seemed to have
a linear decay
flame in PHRR
retardant, with the
reducing increasing
PHRR from phosphorus content
3000 to around 1000(Figure
kW/m 4c).2 with a phosphorus content of
only 4.7retardants
Flame wt % (Figure in 4d). It would
paraffin did now be interesting
not exhibit leveling to establish how much
off, but rather of thedecay
a linear flamein retardant
PHRR. Red
performance
phosphorus did actually
not leadresulted from gas phase
to a significant activity,
reduction innamely
PHRR.flame Exolit inhibition.
OP935 was the most effective
flame retardant, reducing the PHRR from 3000 to around 1000 kW/m2 with a phosphorus content of
3.3.2. Flame Inhibition Dependency on Phosphorus Content Released into Gas Phase
only 4.7 wt % (Figure 4d). It would now be interesting to establish how much of the flame retardant
performanceTo investigate gas phase
actually resulted activity,
from it was first
gas phase necessary
activity, to determine
namely the amount of phosphorus
flame inhibition.
released into the gas phase. This was calculated by subtracting the measured phosphorus content
3.3.2. Flame Inhibition Dependency on Phosphorus Content Released into Gas Phase
To investigate gas phase activity, it was first necessary to determine the amount of phosphorus
released into the gas phase. This was calculated by subtracting the measured phosphorus content
remaining in the residue from the total amount of phosphorus in the sample. Concentration of
 Materials 2017, 10, 455 11 of 23
Materials 2017, 10, 455 11 of 23

remaining in the residue from the total amount of phosphorus in the sample. Concentration of
phosphorus
phosphorus inside
inside thethe residuewas
residue wasmeasured
measured via
via elemental
elemental analysis.
analysis.For visualization
For purposes,
visualization purposes,
phosphorus release is depicted in a bar graph for every formulation in Figure 5.
phosphorus release is depicted in a bar graph for every formulation in Figure 5.

Figure 5. Bar
Figure graphs
5. Bar of the
graphs percentage
of the of of
percentage phosphorus
phosphorusreleased
releasedininthe
thegas
gasphase
phaseduring
during combustion
combustion for
epoxy
forresin
epoxy(a); polyester
resin resin resin
(a); polyester (b); PMMA resinresin
(b); PMMA (c); and paraffin
(c); and paraffin(d)(d)
formulations.
formulations.

In the epoxy resin, there were no differences in phosphorus release between Exolit OP935 and
In the epoxy resin, there were no differences in phosphorus release between Exolit OP935 and
OP1230. At any flame retardant load in the sample, around 70% of the phosphorus was released into
OP1230. At any flame retardant load in the sample, around 70% of the phosphorus was released into
the gas phase. Phosphorus release at 10 wt % flame retardant load was similar to that of the AlPi
the gas phase.
flame Phosphorus
retardants release at 10 wt
at any concentration, but%with
flame retardantBDP
increasing loadload,
wasthis
similar to that
amount wasofsignificantly
the AlPi flame
retardants at any concentration, but with increasing BDP load, this amount was
reduced to less than half of the phosphorus released into the gas phase. Red phosphorus released significantly reduced
to less than
over 90%half of the
of its phosphorus
phosphorus released
into the into the
gas phase andgas phase.
showed Red phosphorus
a slight increase withreleased over
increasing 90% of
flame
its phosphorus
retardant load into the gas
(Figure 5a).phase and showed a slight increase with increasing flame retardant load
(Figure 5a).
Exolit OP935 in polyester resin had a higher phosphorus release than Exolit OP1230. The
highest release in
Exolit OP935 of phosphorus
polyester resin washadalso aathigher
the highest flame retardant
phosphorus releaseload.
than By contrast,
Exolit formulations
OP1230. The highest
withofBDP
release had the highest
phosphorus was alsophosphorus release flame
at the highest at 10 wtretardant
% of BDPload.
load, By
which gradually
contrast, decreased towith
formulations
BDParound
had the80% with increasing
highest phosphorus amounts
releaseofatBDP (Figure
10 wt 5b). load, which gradually decreased to around
% of BDP
In the PMMA resin, Exolit OP935 showed the maximum phosphorus release at the lowest
80% with increasing amounts of BDP (Figure 5b).
amount of flame retardant. This decreased with increasing flame retardant load. The phosphorus
In the PMMA resin, Exolit OP935 showed the maximum phosphorus release at the lowest amount
release of Exolit OP1230 was constant at around 80 to 85% at all investigated flame retardant loads.
of flame retardant. This decreased with increasing flame retardant load. The phosphorus release of
For BDP the phosphorus release was at a very high level, at around 90 to 95% with increasing load in
Exolit
theOP1230 was constant
matrix (Figure 5c). at around 80 to 85% at all investigated flame retardant loads. For BDP the
phosphorus release was
Exolit OP935 and OP1230 at a very high level, atboth
in paraffin around 90 to decreasing
showed 95% with increasing
phosphorusload in thewith
release matrix
(Figure 5c). flame retardant load. However, this effect was more significant with Exolit OP1230. The
increasing
highest OP935
Exolit phosphorusand OP1230 in paraffin
release into both showed
the gas phase was at 10 decreasing
wt % of flamephosphorus
retardantrelease with increasing
load. Formulations
flame retardant
with RP left no load. However,
residue at all; this
thus,effect was morewas
all phosphorus significant
released with Exolit
into gas OP1230.
phase during The highest
burning
(Figure 5d).
phosphorus It was
release observed
into the gas that,
phase towards
was atthe end%ofofthe
10 wt burning
flame process,
retardant theFormulations
load. flame turned withvery RP
bright.
left no It is assumed
residue at all; thus,thatall
thephosphorus
red phosphorus waswas burning
released separately,
into gas phaseresulting
during inburning
this bright flame, 5d).
(Figure
and thus did not take part in any pyrolysis reaction with the matrix. This is
It was observed that, towards the end of the burning process, the flame turned very bright. It is supported by monitoring
assumed that the red phosphorus was burning separately, resulting in this bright flame, and thus did
not take part in any pyrolysis reaction with the matrix. This is supported by monitoring the effective
heat of combustion (EHC) during the test. As seen in Figure 6, the EHC is split into two areas, the first
 Materials 2017, 10, 455 12 of 23
Materials 2017, 10, 455 12 of 23

the effective heat of combustion (EHC) during the test. As seen in Figure 6, the EHC is split into two
oneareas, the first
attributed to one
the attributed
burning of tothe
the paraffin
burning of the paraffin
matrix matrix
at around 40 at aroundAfter
MJ/kg. 40 MJ/kg. Afterthe
reaching reaching
PHRR
the PHRR at around 200 s, the EHC curve features a second, lower plateau at approximately
at around 200 s, the EHC curve features a second, lower plateau at approximately 20 MJ/kg with a
20 MJ/kg with a final decay, which is associated with the burning of red phosphorus. This is in
final decay, which is associated with the burning of red phosphorus. This is in analogy to the different
analogy to the different burning phases observed for example in polymer blends [42]. Contrarily, the
burning phases observed for example in polymer blends [42]. Contrarily, the EHC of 20 wt % AlPi
EHC of 20 wt % AlPi incorporated in paraffin features a constant EHC throughout the entire period
incorporated in paraffin features a constant EHC throughout the entire period of burning. This shows,
of burning. This shows, that the decomposition temperatures of red phosphorus and the paraffin
that the decomposition temperatures of red phosphorus and the paraffin matrix were not overlapping
matrix were not overlapping and thus did not ensure an active flame retardancy.
and thus did not ensure an active flame retardancy.

Figure 6. Effective
Figure heat
6. Effective of combustion:
heat of combustion:for
forP-20-ExRP
P-20-ExRPexhibiting
exhibiting aa two-part progression(a);
two-part progression (a);and
andfor
for
P-20-ExOP935 as an example for a constant EHC
P-20-ExOP935 as an example for a constant EHC (b).(b).

Overall,
Overall, it isit demonstrated
is demonstratedthat thatphosphorus
phosphorusrelease
release is
is controlled
controlled byby the
the polymer
polymermatrix,
matrix,thethe
phosphorus species itself and the concentration of phosphorus in the specimen.
phosphorus species itself and the concentration of phosphorus in the specimen. To learn about the way To learn about the
flameway flame inhibition
inhibition is influenced
is influenced by the amount
by the amount of phosphorus
of phosphorus release
release into theinto the gasthe
gas phase, phase, the
effective
effective heat of combustion (EHC) is plotted versus phosphorus concentration in the gas phase
heat of combustion (EHC) is plotted versus phosphorus concentration in the gas phase (Figure 7).
(Figure 7). The EHC measured by the cone calorimeter includes the effective heat of the combustion
The EHC measured by the cone calorimeter includes the effective heat of the combustion of the volatiles
of the volatiles multiplied by the combustion efficiency of the flame, and thus is a measure for the
multiplied by the combustion efficiency of the flame, and thus is a measure for the efficiency of a flame
efficiency of a flame retardant in terms of flame inhibition and gas phase activity in general.
retardant in terms of flame inhibition and gas phase activity in general.
As seen in Figure 7a especially, the curve progression of EHC levels off with increasing
As seen in Figure 7a especially, the curve progression of EHC levels off with increasing phosphorus
phosphorus content in the gas phase. The model curve in Figure 8 is proposed as a basis for the
content in the discussion
following gas phase. The and model
is basedcurve in Figurein
on findings 8 is proposed
previous as a basis
works for in
[31,43], thewhich
following discussion
the EHC first
anddwindles
is based on findings in previous works [31,43], in which the EHC first dwindles in
in a linear fashion (I), up to a certain level where the effectiveness in EHC reduction levelsa linear fashion
(I), up to a This
off (II). certain
effectlevel where
is very the effectiveness
prominent in EHC
in epoxy resin, andreduction levels off
less pronounced in (II). This effect
the polyester is very
system.
prominent
The phase is described as (III) in Figure 8, which depicts an increase in EHC with even higheras
in epoxy resin, and less pronounced in the polyester system. The phase is described
(III)amounts
in Figure of8, which depicts
phosphorus in thean increase
gas in EHC
phase. This with effect
converse even higher amounts
occurs due of phosphorus
to increased burning ofinthethe
gas phosphorus
phase. Thisspecies
converse effectexhibiting
without occurs dueanytoflame
increased burning
inhibiting of the phosphorus species without
effect.
exhibiting any flame inhibiting effect.
Materials 2017, 10, 455 13 of 23
Materials
Materials 2017,
2017, 10,
10, 455
455 13
13 of
of 23
23

In
In epoxy
Inepoxy resin,
epoxy resin,
resin, RPRP showed
showed aaahigher
RPshowed higher reduction
higher reduction
reduction in in EHC
in EHC than
EHC than the
than the AlPi
theAlPi flame
AlPiflame retardants
flameretardants
retardantsExolitExolit
Exolit
OP935
OP935 and
and OP1230.
OP1230. MoreMore phosphorus
phosphorus was was released
released into into
the the
gas gas phases,
phases,
OP935 and OP1230. More phosphorus was released into the gas phases, contributing strongly contributing
contributing strongly
strongly to EHCto
to
EHC
EHC reduction.
reduction. However,
reduction. However, BDP
BDP displayed
BDP displayed
However, a similar
displayed aa similar EHC
EHC reduction
EHC reduction
similar while
while releasing
while releasing
reduction less
less phosphorus
less phosphorus
releasing into the
phosphorus
into
gas the
the gas
intophase, gasandphase, and
and the
the leveling
phase, leveling
theoff off
set in at
leveling set
set in
offaroundin at
15around
at MJ/kg.15
around MJ/kg.
This
15 This
This demonstrated
demonstrated
MJ/kg. that
that not only
demonstrated thatthenot only
notpure
only
the
the pure amount of phosphorus but also the nature of the phosphorus species had an influence on
pure
amount ofamount of
phosphorus phosphorus
but also but
the also
nature the
of nature
the of the
phosphorus phosphorus
species had species
an had
influencean influence
on the flame
on
the
the flame
inhibition inhibition
flame [23]. [23].
At higher
inhibition At
At higher
higher concentrations,
[23]. concentrations, all
all formulations
all formulations
concentrations, showed
showed a leveling
formulations showedoff aa leveling off
off of
of the EHC
leveling of the
the EHC
reduction
EHC
reduction
in the samein
reduction in the
the same
range (Figure
same range
7a). (Figure
range EHC was
(Figure 7a). EHC
EHC was
reduced
7a). reduced
by around
was by
by around
reduced55–65% before
around 55–65% before
beforeinan
an increase
55–65% an increase
increase in
phosphorus in
phosphorus
content content
in thecontent
phosphorus in
gas phase the gas
ceased
in the phase ceased
to haveceased
gas phase to have
a beneficial
to have a beneficial
effect. effect.
a beneficial effect.

Figure
Figure7.7.
Figure Effective
7.Effective heat
Effectiveheat of
heatof combustion
ofcombustion plotted
combustionplotted versus
plottedversus the
versusthe actual
theactual amount
actualamount
amountof of phosphorus
ofphosphorus released
phosphorusreleased into
releasedinto
into
the gas
thegas
the phase
gasphase during
phaseduring combustion
duringcombustion in:
combustionin: DGEBA/IPDA
in:DGEBA/IPDA
DGEBA/IPDA (a); (a); polyester
(a); polyester resin
polyester resin (b);
resin (b); PMMA
(b); PMMA resin
PMMA resin (c);
resin (c); and
(c);and
and
paraffin (d).
paraffin(d).
paraffin (d).

Figure
Figure8.8.
Figure Proposed
8. Proposed model
Proposed model for
model for the
for the dependency
thedependency
dependency of of effective
ofeffective heat
effectiveheat
heatofof combustion
ofcombustion
combustionon on the
onthe phosphorus
thephosphorus
phosphorus
content
content released
contentreleased
released into
into
into the
the the gas phase
gas phase
gas phase based
basedbased on previous
on previous
on previous work
work bywork
Brehme by Brehme
byetBrehme et al.
et al.
al. [31]. The [31]. The
The curve
[31].progression
curve curve
progression
progression
follows follows
follows
a linear a linear
a linear
decrease of EHCdecrease
decrease of EHC
of EHC
(I) and leads (I)
to a (I) and leads
and leads
leveling to
off of to
EHCa leveling
a leveling
reduction off of
off(II). EHC
of Furtherreduction
EHC reduction
phosphorus(II).
(II).
Further
increase phosphorus
Further is
phosphorus
proposed toincrease
increase is
have a is proposed
proposed
negative to have
to have
impact a negative impact
a negativethus
on efficiency, impact on
theon efficiency,
efficiency,
increase thus the
the increase in
thus(III).
in EHC increase in
EHC
EHC (III).
(III).
Materials 2017, 10, 455 14 of 23
Materials 2017, 10, 455 14 of 23

Inthe
In thepolyester
polyesterresin,
resin,BDP BDPshowed
showedhigher higherefficiency
efficiencythan thanExolit
ExolitOP935
OP935and andOP1230,
OP1230,reducing
reducing
theEHC
the EHCtotoaround
around11 11MJ/kg
MJ/kg (Figure
(Figure7b). 7b). Nevertheless,
Nevertheless, in inthis
thissystem,
system,too, too,ititbecame
becameclear clearthat,
that,with
with
increasing phosphorus concentration in the gas phase, the reduction in EHC, i.e., the effectiveness of of
increasing phosphorus concentration in the gas phase, the reduction in EHC, i.e., the effectiveness a
a flame
flame retardant
retardant in in terms
terms of of
gasgas phase
phase activity,
activity, reached
reached itsits limit.For
limit. Forthe
thepolyester
polyesterresin, resin,thetheminimum
minimum
EHCwas
EHC wasfound
found to to
bebe at around
at around 50 to5065%to 65%
of theofnon-flame
the non-flame retarded retarded formulation,
formulation, depending depending
on which on
which flame retardant
flame retardant is used. is used.
Incontrast,
In contrast,formulations
formulationswith withPMMAPMMA resin
resin asasthethe polymer
polymer matrix
matrix showed
showed no noclearclear differences
differences in
in EHC reduction behavior, and a slight tendency toward leveling
EHC reduction behavior, and a slight tendency toward leveling off is possible (Figure 7c). off is possible (Figure 7c).
Paraffindiffered
Paraffin differedfromfromthe theother
otherinvestigated
investigatedsystemssystemsin inthat
thatno noleveling
levelingoff offininEHC EHCreduction
reduction
wasapparent.
was apparent.All Allthree
threeof ofthe
theflame
flameretardants
retardantsused usedexhibited
exhibitedapproximately
approximatelylinear linearbehavior
behaviorwith with
increased concentrations in the gas phase, as also observed for the decrease
increased concentrations in the gas phase, as also observed for the decrease in PHRR with increasing in PHRR with increasing
phosphorusload
phosphorus load(Figure
(Figure 7d).7d).
From Fromthese these investigations,
investigations, it canitbecan be concluded
concluded that, forthat,the twofor systems
the two
systems
epoxy epoxy
resin andresin and polyester
polyester resin, there resin,
is athere is a maximum
maximum concentration concentration
of phosphorusof phosphorusat which at flame
which
flame inhibition has its highest efficiency as a mode of action. After
inhibition has its highest efficiency as a mode of action. After that point, a higher load of flame that point, a higher load of flame
retardantand
retardant andthus
thus phosphorus
phosphorus concentration
concentration will more
will more likely likely contribute
contribute to condensedto condensed phase
phase activity.
activity. Furthermore, the polymeric matrix in which the flame retardants
Furthermore, the polymeric matrix in which the flame retardants are used can alter their efficiency are used can alter their
efficiency significantly. The PMMA systems showed a slight tendency
significantly. The PMMA systems showed a slight tendency towards a non-linear EHC reduction with towards a non-linear EHC
reductionphosphorus
increasing with increasing contentphosphorus content no
and for paraffin, and for paraffin,
tendency toward no leveling
tendencyofftoward leveling Rather,
was observed. off was
observed. Rather, it was found that paraffin does not seem to be qualified
it was found that paraffin does not seem to be qualified as a suitable polymeric matrix to investigate as a suitable polymeric
matrix to investigate
phosphorus-based flamephosphorus-based flame retardants
retardants in polyolefinic polymers. in polyolefinic polymers.
Additionally,the
Additionally, the effective
effective heatheat of combustion
of combustion depending
depending on phosphorus
on phosphorus content content in the
in the gas gas
phase
phase was checked by comparing the different polymeric matrices
was checked by comparing the different polymeric matrices flame retarded with the same flame flame retarded with the same
flame retardant.
retardant. This enables
This enables to maketoamake statementa statement
about whichabout flamewhichretardant
flame retardant
is most is most effective
effective in which in
which system. Since all systems exhibit different initial values for the non-flame
system. Since all systems exhibit different initial values for the non-flame retarded equivalent, the EHC retarded equivalent,
the to
had EHC had to be normalized
be normalized in order toin order tothe
compare compare the effectiveness.
effectiveness. The results The of the results of the comparisons
comparisons are shown
are
in shown
Figure 9. in Figure 9.

Figure9.9. Effective
Figure Effective heat
heat of
of combustion
combustion versus
versus the
the phosphorus
phosphorus content
content inin the
the gas
gas phase
phase for
for the
the
different polymeric systems flame retarded with: Exolit OP935 (a); Exolit OP1230 (b); BDP
different polymeric systems flame retarded with: Exolit OP935 (a); Exolit OP1230 (b); BDP (c); and red (c); and
red phosphorus
phosphorus (d). Dotted
(d). Dotted lines lines are included
are included as a guide
as a guide to thetoeyes.
the eyes.

In order to compare the differences occurring with varying particle size distributions, both AlPi
flame retardants Exolit OP935 and Exolit OP1230 are compared in the four different polymer
Materials 2017, 10, 455 15 of 23

In order to compare the differences occurring with varying particle size distributions, both AlPi
flame retardants Exolit OP935 and Exolit OP1230 are compared in the four different polymer matrices.
Exolit OP935 is least efficient in paraffin, achieving only a reduction in EHC to 90%. In PMMA,
a reduction to 85% is observed, followed by a reduction to around 75% in polyester resin. Exolit OP935
performs best in epoxy resin, when it comes to reduction in EHC.
Exolit OP1230 shows only a minor effect in paraffin, reducing the EHC to 95% at the highest
loading. In PMMA resin, the efficiency is higher. The EHC is reduced up to 85%. In epoxy resin and
polyester resin, Exolit OP1230 exhibits equally good EHC reduction, making both the ideal matrix for
this flame retardant.
This comparison showed that there are slight differences in effectiveness depending on the
polymer matrix resulting from different particle size distributions of Exolit OP935 and Exolit OP1230.
Due to incorporation of BDP into the polymeric systems (Figure 9c), the EHC was reduced to around
60% in the epoxy resin at around 1 wt % of phosphorus in the gas phase. In the polyester resin, a higher
phosphorus content in the gas phase was observed, reducing the EHC to around 55% at 1.5 wt % of
released phosphorus. In the PMMA resin, only a reduction to around 85% was achieved.
Red phosphorus was incorporated into epoxy resin and paraffin. Both systems exhibit a totally
different behavior. As shown in Figure 6, the EHC of the separately burning red phosphorus is lower
than the EHC of the paraffin matrix. The mean EHC depicted here is decreasing with higher flame
retardant load, because the duration of burning red phosphorus increases. It is not a result of an active
flame inhibiting effect. In the epoxy system, red phosphorus shows a maximum reduction of EHC to
around 55% while releasing 13 wt % of phosphorus into the gas phase.
This matrix comparison for each flame retardant showed, that the effectiveness with increasing
flame retardant load and thus phosphorus content is highly dependent on the polymer matrix.
All systems, except for paraffin, exhibit a more or less distinctive non-linear leveling off behavior.
In addition, modifications such as the particle size distributions may play a minor role in whether a
flame retardant is more effective in one or another polymeric matrix. Furthermore, paraffin was shown
to be unsuitable to simulate the fire behavior of a polyolefinic polymer matrix.

3.3.3. Dependency of Condensed Phase Activity on Phosphorus Content

Phosphorus remaining in the residue after burning reacted during pyrolysis to contribute to
condensed phase activity. The residue at the end of the cone calorimeter measurement is plotted versus
the phosphorus content remaining in the residue in Figure 10. This plot gives information about the
influence of increasing phosphorus content in the residue on residue formation.
We propose that the curves resulting from all of the measured formulations take S-shapes, or are
assumed to take an S-shape, as depicted in Figure 11. This is because the buildup of a protective layer
is ever more significant with increasing amounts of flame retardant, in this case phosphorus content.
The point of inflection of the sigmoidal curves, described by area II in Figure 11, is considered to be the
amount of phosphorus needed to induce formation of a protective layer. After this inflection point,
the amount of residue flattens again and results in a continuous increase with increasing phosphorus
content (Figure 11 III).
In epoxy resin, the curve of residue increase for the BDP formulations has its point of inflection at
a relatively low phosphorus concentration in the residue. This means that a protective layer effect, and
thus the level of decomposition, started to influence the burning behavior after the inflection point,
found at around 7 wt % of phosphorus in the residue. This is in accordance with previous results, in
which BDP was shown to be a good precursor for condensed phase activity [6]. Depending on the step
height of the sigmoidal curve, the degree of decomposition changes, up to a point, where the material
is incompletely pyrolyzed [44–46]. For BDP in epoxy resin, this step height is observed from around
5 wt % to 15 wt % of residue. For Exolit OP935 and OP1230, the highest concentration of phosphorus
in the investigated samples was at around 13 wt %. Up to this point, it is observed that the slope of
the curve gradually increases. It is imaginable, that with higher flame retardant load, and thus higher
Materials 2017, 10, 455 16 of 23

concentrations of phosphorus found in the residue, the curve will exhibit a point of inflection as well,
and continue as a sigmoidal curve. Red phosphorus incorporated in epoxy resin released more than
Materials
90% 2017, 10, 455 into the gas phase during burning. Nevertheless, the concentration of phosphorus
of phosphorus 16 of 23

in theMaterials
residue increased
2017, 10, 455 with higher flame retardant load. Since this increase was not as significant16 of 23
load. Since this increase was not as significant as for the AlPi flame retardants, the point of inflection
as for the AlPi flame retardants, the point of inflection will occur at a much higher concentration of
will occur at a much
load. Since higherwas
this increase concentration of phosphorus
not as significant in flame
as for the AlPi the residue (Figure
retardants, 10a).of inflection
the point
phosphorus in the residue (Figure 10a).
will occur at a much higher concentration of phosphorus in the residue (Figure 10a).

Figure 10. Residue plotted against the phosphorus content in the residue: DGEBA/IPDA (a); polyester (b);
FigurePMMA (c); andplotted
10. Residue paraffinagainst
(d) system.
the phosphorus content in the residue: DGEBA/IPDA (a); polyester
Figure 10. Residue plotted against the phosphorus content in the residue: DGEBA/IPDA (a); polyester (b);
(b); PMMA (c); and paraffin (d) system.
PMMA (c); and paraffin (d) system.

Figure 11. Proposed progression of residue formation with increasing phosphorus in the residue.
Figure
The curve is 11. Proposed
divided into:progression of residue
an approximately formation
linear with increasingrelation
phosphorus-residue phosphorus
(I); aninarea
the residue.
of inflection
of the curve (II); and a continuous increase of residue with phosphorus content afteranthe
The curve is divided into: an approximately linear phosphorus-residue relation (I); area of
inflection
inflection
point (III) [45]. of the curve (II); and a continuous increase of residue with phosphorus content after the
inflection point (III) [45].
Figure 11. Proposed progression of residue formation with increasing phosphorus in the residue.
The BDP
BDP curve
in isthe
divided
theinpolyester
polyesterinto:
resin an had
had
resin approximately
a similar effect
a similar linear
as in
effect phosphorus-residue
asthe epoxy
in the epoxyresin, relationthe
exhibiting
resin, exhibiting (I); an area of
sigmoidal
the sigmoidal curve
inflection
progression of the curve
at relatively
curve progression (II);
at low and a continuous
concentrations
relatively increase
of phosphorus
low concentrations of residue with phosphorus
in the residue.
of phosphorus content
However,
in the residue. after
the amount
However, the
the of
inflection
amount
residue ofpoint
was relatively (III)
residuelow[45].
was relatively
as well, with low
onlyas well,
4 wt % atwith only 4 wt
the highest % at the concentration
phosphorus highest phosphorusmeasured.
concentration
The area of inflectionmeasured.
in thisThe area lies
system of inflection
at around in this
7 wtsystem
% to 9lies
wtat%around 7 wt % to in
of phosphorus 9 wt
the%residue.
of
BDP in the in
phosphorus polyester
the residue. resin had
Since theaheight
similar effect
of the as increases
curve in the epoxy resin, exhibiting
only slightly the sigmoidal
during the inflection,
curvebyprogression
around 2%, the change in decomposition
at relatively low concentrationslevel wasof much less thanin
phosphorus in the
the epoxy
residue.resin system. the
However,
amount of residue was relatively low as well, with only 4 wt % at the highest phosphorus
concentration measured. The area of inflection in this system lies at around 7 wt % to 9 wt % of
phosphorus in the residue. Since the height of the curve increases only slightly during the inflection,
by around 2%, the change in decomposition level was much less than in the epoxy resin system.
Materials 2017, 10, 455 17 of 23
Materials 2017, 10, 455 17 of 23

Residue
Since theformation
height of the wascurve
muchincreases
higher for only Exolit OP935
slightly and the
during OP1230, but the
inflection, by amount
around 2%, of phosphorus
the change
remaining in the residue
in decomposition level was varied
much moderately,
less than inasthe was the case
epoxy resinfor the amount
system. Residue of phosphorus
formation was released
much
into the gas phase (Figure 10b).
higher for Exolit OP935 and OP1230, but the amount of phosphorus remaining in the residue varied
In the PMMA
moderately, as was resin,
the case BDPforformed
the amountalmost no residue atreleased
of phosphorus all. Only 1 wt
into the%gas was built(Figure
phase up at around
10b).
13 wtIn%the of phosphorus
PMMA resin,inBDP the residue. For Exolit
formed almost OP 935 and
no residue at all.OP1230
Only 1awt residue
% was formation
built up at of around
5 wt %
was
13 wtobserved at a phosphorus
% of phosphorus concentration
in the residue. For Exolit of OP
around
935 and14 OP1230
wt % inathe residue,
residue whichofwas
formation 5 wtthe%
highest flame at
was observed retardant load investigated
a phosphorus concentration (Figure 10c).14
of around Inwt
paraffin,
% in the the AlPi flame
residue, whichretardants Exolit
was the highest
OP935 and OP1230
flame retardant exhibited a (Figure
load investigated very high 10c).concentration
In paraffin, the of AlPi
phosphorus in the residue.
flame retardants Exolit OP935 The
phosphorus
and OP1230 concentration
exhibited a very stagnated at around 24ofwtphosphorus
high concentration %, while the amount
in the residue.of residue formation
The phosphorus
increased
concentration up tostagnated
4 wt %. Formulations
at around 24 wt with %,red phosphorus
while the amount didofnot form formation
residue any residue from which
increased up toa
sample could be taken for elemental analysis. Thus, it was assumed
4 wt %. Formulations with red phosphorus did not form any residue from which a sample could be that all of the phosphorus
content
taken forwas released
elemental into the
analysis. gas itphase
Thus, (Figure that
was assumed 10d).allInofthe
the PMMA
phosphorus resincontent
and paraffin system,
was released a
into
trend
the gassuch
phaseas(Figure
the one 10d).proposed
In the PMMA in Figureresin and11 was not system,
paraffin recognizable.
a trend Insuch fact, theone
as the phosphorus
proposed
concentration
in Figure 11 was in not
the recognizable.
residue was In observed
fact, theto be constant
phosphorus in the rangeinofthe0 residue
concentration to 20 wt % observed
was of flame
retardant load.inHowever,
to be constant the range itofis0 conceivable,
to 20 wt % ofthat flamewith even higher
retardant load, the amount
load. However, of phosphorus
it is conceivable, that within
the residue will increase additionally to the amount of residue.
even higher load, the amount of phosphorus in the residue will increase additionally to the amount
For the epoxy and polyester resin formulations, it was observed that with increasing flame
of residue.
retardant
For the load, the amount
epoxy of phosphorus
and polyester remaining initthe
resin formulations, was residue
observed increased
that withas well, up to a flame
increasing point
where the concentration of phosphorus stagnated. Because of the
retardant load, the amount of phosphorus remaining in the residue increased as well, up to a point increase in residue formation, it
was
whereassumed that this isofthe
the concentration point where
phosphorus the effect
stagnated. of a change
Because in decomposition
of the increase level, up to
in residue formation, the
it was
presence of incompletely pyrolyzed polymer due to a protective layer
assumed that this is the point where the effect of a change in decomposition level, up to the presence effect contributes more and
more to the overall
of incompletely flame retardancy
pyrolyzed polymer due performance.
to a protective layer effect contributes more and more to the
Residue
overall flame pictures
retardancy of flame retarded epoxy resin formulations reveal the influence of a protective
performance.
layer Residue
on burning performance
pictures of flame(Figure
retarded12).epoxy
Whereas resinresidues from EP-15-ExOP935
formulations reveal the influence and EP-15-ExOP1230
of a protective
show
layer onbeginnings of a closed(Figure
burning performance residue12). surface
Whereas thatresidues
can serve fromasEP-15-ExOP935
a protective layer, the residue of
and EP-15-ExOP1230
15 wt beginnings
show % of RP inof the epoxy residue
a closed resin issurface
loose and thatbrittle
can servewithasno significantlayer,
a protective sign theof aresidue
protective
of 15layer.
wt %
In contrast to those examples, the completely closed surface of the residue
of RP in the epoxy resin is loose and brittle with no significant sign of a protective layer. In contrast to of EP-25-BDP is evidence
of a protective
those examples,layer effect on burning
the completely performance,
closed surface which of
of the residue prevented
EP-25-BDP theiscomplete
evidence combustion
of a protective of
some of the material.
layer effect on burning performance, which prevented the complete combustion of some of the material.

Figure 12.
Figure Residue pictures:
12. Residue pictures: EP
EP (a);
(a); EP-15-ExOP935
EP-15-ExOP935 (b);
(b); EP-15-ExOP1230
EP-15-ExOP1230 (c);
(c); EP-15-ExRP
EP-15-ExRP (d);
(d); and
and
EP-25-BDP (e).
EP-25-BDP (e).

Exolit OP935 and OP1230 in polyester resin produced a residue that was very compact and had
a closed surface, even though it was very light (Figure 13). However, due to the strong deformation
during
during burning,
burning, the
the residue
residue broke
broke and
and aa significant
significant effect
effect of
of aa protective
protective layer
layer was
was lost.
lost. Pes-25-BDP,
Pes-25-BDP,
on the other hand, did not produce significant residue, but only a small, but compact and shiny char
of 3.5 wt %. This demonstrates that the main flame retardancy effect has to come from gas phase
Materials 2017, 10, 455 18 of 23

on the other
Materials hand,
2017, 10, 455 did not produce significant residue, but only a small, but compact and 18 shiny
of 23 char
of 3.5 wt %. This demonstrates that the main flame retardancy effect has to come from gas phase
activity, namely
activity, namely flameflame inhibition.
inhibition. In
In the
the next
next segment,
segment, this
this effect
effect is
is quantified,
quantified, along
along with
with charring
charring and
and protection layer
protection layer effects. effects.

Figure13.
Figure Residue
13.Residue pictures:
pictures: PesPes
(a);(a); Pes-15-ExOP935
Pes-15-ExOP935 (b); (b); Pes-15-ExOP1230
Pes-15-ExOP1230 (c); Pes-25-BDP
(c); and and Pes-25-BDP
(d). (d).

3.4.
3.4. Quantification
Quantification ofofCone
ConeCalorimeter
CalorimeterResults
Results
Flame retardancy
retardancy effects
effects have
have been
beenquantified
quantifiedfor
forvarious
variousflame
flameretarded
retardedpolymeric
polymericmaterials
materials in
previous works [46,47]. Equations (1) and (2) were used to calculate the theoretical values forfor
in previous works [46,47]. Equations (1) and (2) were used to calculate the theoretical values PHRR
PHRR
and and THE.
THE.
0
H RR ∼ χ (1· (1−) µh)c0 · hc
HRR (1) (1)

THE ∼ χ · (1 − µ) · h0 · m0
TH E    (1   )  hc0  mc 0 (2)
(2)

In these equations, χ is the combustion efficiency, h0c0 is the heat of complete combustion of the
In these equations,  is the combustion efficiency, hc is the heat of complete combustion of
fuel gases, µ is the char yield and m0 the mass of the specimen. The main premise is that the reduction
the fuel gases, μ is the char yield and m0 the mass of the specimen. The main premise is that the
of the effective heat of combustion χ · h0c is influenced by flame inhibition, and this is displayed along
reduction of the effective heat of combustion   hc0 is influenced by flame inhibition, and this is
with the effect of fuel reduction (1 − µ) and the altered density due to addition of a flame retardant.
displayed
By measuring along with
the the effect
formed of fuel
residue reduction
as well as the(1reduction
− μ) and the altered
of EHC anddensity due toin
the change addition
sampleofweight,
a
flame retardant. By measuring the formed residue as well as the reduction of EHC and the change in
a value for THE can be calculated. Comparing this calculated THE with the measured THE almost
sample weight, a value for THE can be calculated. Comparing this calculated THE with the
always shows perfect accordance. The values of measured and calculated reduction are expressed
measured THE almost always shows perfect accordance. The values of measured and calculated
as percentages in Table 4, in which the non-flame retarded material is always set to 100%. Together
reduction are expressed as percentages in Table 4, in which the non-flame retarded material is
with the effect of a protection layer, all three modes of action are displayed in the reduction of PHRR.
always set to 100%. Together with the effect of a protection layer, all three modes of action are
The reduction in PHRR is calculated using Equation (1); however, this does not include the protective
displayed in the reduction of PHRR. The reduction in PHRR is calculated using Equation (1);
layer effect.
however, Thus,
this doesthe
notdifference
include the between calculated
protective and measured
layer effect. PHRR reduction
Thus, the difference betweenis calculated
a quantitative
measure for a protective
and measured layer effect.
PHRR reduction To provide ameasure
is a quantitative better understanding
for a protectiveoflayer
the approach,
effect. To the calculation
provide a
of the percentage of protective layer effect in EP-35-BDP is presented. The char
better understanding of the approach, the calculation of the percentage of protective layer effect in yield of EP-35-BDP
amounted
EP-35-BDPto is 17.3 wt %. Since
presented. the yield
The char pure ofepoxy resin produced
EP-35-BDP amounted0.5 towt
17.3%wtof char, the the
%. Since effective char yield
pure epoxy
resulting from addition
resin produced 0.5 wt %ofof35char,
wt % ofeffective
the BDP amounts to 16.9%.
char yield Thisfrom
resulting equates to a fuel
addition reduction
of 35 wt % of (1BDP− µ) to
83.1%
amounts of the fuel released
to 16.9%. from pure
This equates to a epoxy resin. The
fuel reduction (1 effective heat of
− μ) to 83.1% of combustion χ · h0c from
the fuel released was measured
pure
in the cone
epoxy resin.calorimeter
The effective and was
heat of combustion   hc0 of
reduced to 62.0% wasthemeasured
EHC from in pure epoxy
the cone resin. Multiplication
calorimeter and was
of (0.831 ×
reduced to 62.0% of the EHC from pure epoxy resin. Multiplication of both values (0.831 ×pure
both values 0.620) leads to a calculated PHRR of 51.5% of the PHRR from epoxy
0.620)
resin. However, the measured PHRR was 33.8% of the PHRR from pure
leads to a calculated PHRR of 51.5% of the PHRR from pure epoxy resin. However, the measured epoxy resin, which means
PHRR was 33.8% of the PHRR from pure epoxy resin, which means that this further reduction has to be
Materials 2017, 10, 455 19 of 23

that this further reduction has to be the result of other effects than fuel reduction and flame inhibition,
which is mainly a protective layer effect. While more than those indices play a role in reducing the
PHRR, it is considered to be one approximation to monitor protective layer effect. The change in steady
state burning phase would be more accurate, but hardly any of our materials exhibited such a phase.
The efficiency of a protective layer is also different, when the measurement method changes, leading
to deviant behaviors in the cone calorimeter, UL94 and LOI tests.

Table 4. Quantification of the reduction in THE and PHRR due to the flame retardancy modes of action:
charring, gas phase action, and residual protection layer for all of the examined systems.

(1 − µ) Ø·h0c m0 Cal. THE THE Cal. PHRR PHRR Prot. Layer

Material
% % % % % % % %
EP 100.0 100.0 100.0 100.0 100.0 100.0 100.0 0.0
EP-5-ExOP935 96.1 87.7 103.8 87.5 87.5 84.3 87.9 −4.3
EP-10-ExOP935 94.2 77.9 98.9 72.5 72.6 73.3 52.2 28.9
EP-15-ExOP935 91.9 74.3 102.7 70.1 70.1 68.3 46.5 31.9
EP-20-ExOP935 89.2 71.7 100.7 64.4 64.4 63.9 44.0 31.2
EP-5-ExOP1230 95.6 80.6 105.5 81.3 88.2 77.1 59.5 22.8
EP-10-ExOP1230 94.1 77.1 103.6 75.2 75.2 72.5 59.0 18.6
EP-15-ExOP1230 91.8 73.8 107.0 72.5 72.5 67.8 54.2 20.0
EP-20-ExOP1230 89.7 72.9 101.7 66.5 66.5 65.4 46.3 29.2
EP-5-ExRP 94.2 63.7 104.8 62.9 62.9 60.0 51.9 13.5
EP-10-ExRP 92.4 62.3 101.0 58.1 58.1 57.5 42.3 26.5
EP-15-ExRP 91.8 54.8 103.7 52.2 52.1 50.3 36.2 27.9
EP-20-ExRP 90.5 67.2 101.4 61.7 61.6 60.8 47.0 22.7
EP-10-BDP 95.4 92.0 103.7 91.1 91.0 87.8 79.0 10.0
EP-20-BDP 85.5 68.6 102.8 60.3 60.3 58.7 37.0 36.9
EP-25-BDP 84.6 63.0 104.0 55.4 55.4 53.3 35.5 33.3
EP-35-BDP 83.1 62.0 101.4 52.3 52.3 51.5 33.8 34.4
Pes 100.0 100.0 100.0 100.0 100.0 100.0 100.0 0.0
Pes-5-ExOP935 96.0 95.9 101.3 93.3 90.7 92.1 84.0 8.8
Pes-10-ExOP935 92.4 78.7 96.6 70.2 68.4 72.7 58.9 18.9
Pes-15-ExOP935 91.6 82.9 102.3 77.6 75.2 75.9 56.8 25.2
Pes-20-ExOP935 91.5 73.6 98.9 66.6 64.6 67.4 51.2 24.0
Pes-5-ExOP1230 96.4 99.5 102.4 98.2 95.2 95.9 95.3 0.5
Pes-10-ExOP1230 91.6 74.8 102.4 70.2 73.7 68.6 42.1 38.6
Pes-15-ExOP1230 90.8 69.7 101.1 63.9 77.8 63.2 59.3 6.2
Pes-20-ExOP1230 90.1 72.4 101.3 66.1 64.9 65.3 44.8 31.3
Pes-10-BDP 99.0 84.6 100.3 84.0 82.5 83.8 71.5 14.7
Pes-20-BDP 98.0 56.5 100.3 55.5 70.5 55.4 61.8 -11.7
Pes-25-BDP 96.6 58.9 99.3 56.5 63.2 56.9 56.0 1.4
Pes-35-BDP 95.4 60.8 98.9 57.3 59.3 58.0 52.9 8.8
PMMA 100.0 100.0 100.0 100.0 100.0 100.0 100.0 0.0
PMMA-5-ExOP935 98.9 90.9 97.5 87.6 87.6 89.9 79.6 11.4
PMMA-10-ExOP935 97.6 91.2 93.4 83.1 83.1 89.0 75.4 15.2
PMMA-15-ExOP935 96.3 83.6 97.4 78.4 78.4 80.5 70.4 12.6
PMMA-20-ExOP935 94.4 83.9 96.5 76.4 76.5 79.2 58.6 26.0
PMMA-5-ExOP1230 98.6 92.6 99.4 90.8 90.7 91.3 81.1 11.1
PMMA-10-ExOP1230 97.2 90.3 95.0 83.4 83.4 87.8 68.7 21.7
PMMA-15-ExOP1230 96.7 86.3 97.1 80.9 81.0 83.4 64.5 22.6
PMMA-20-ExOP1230 95.3 85.3 95.2 77.4 77.4 81.3 59.0 27.4
PMMA-10-BDP 99.6 104.6 97.6 101.7 101.4 104.2 102.6 1.5
PMMA-20-BDP 99.5 93.5 97.9 91.1 91.1 93.0 94.6 -1.7
PMMA-25-BDP 99.4 86.8 99.2 85.6 85.6 86.3 82.6 4.3
PMMA-35-BDP 99.3 89.1 98.3 87.0 87.0 88.5 88.3 0.2
P 100.0 100.0 100.0 100.0 100.0 100.0 100.0 0.0
P-5-ExOP935 100.1 95.9 98.2 94.2 94.7 96.0 64.6 32.7
P-10-ExOP935 100.1 93.2 96.3 90.4 90.4 93.9 53.2 43.4
P-15-ExOP935 98.0 89.4 99.1 86.8 87.5 87.5 45.8 47.7
P-20-ExOP935 98.1 88.3 103.3 89.5 89.3 86.6 37.7 56.5
P-5-ExOP1230 99.9 99.7 94.5 94.1 93.9 99.7 95.9 3.8
P-10-ExOP1230 98.7 98.2 102.9 99.8 99.9 97.0 95.7 1.3
P-15-ExOP1230 97.1 96.3 98.0 91.6 93.2 93.5 85.4 8.6
P-20-ExOP1230 95.8 92.3 102.2 90.4 89.8 88.5 75.3 14.9
P-5-ExRP 99.6 97.9 103.1 100.5 101.1 97.5 98.3 -0.8
P-10-ExRP 99.5 93.9 102.5 95.8 95.7 93.5 92.8 0.7
P-15-ExRP 99.8 100.7 100.1 91.5 91.3 91.4 85.4 6.5
P-20-ExRP 99.8 87.3 104.2 90.8 90.4 87.1 84.1 3.5
Materials 2017, 10, 455 20 of 23

For most of the specimens investigated, the effect of a protective layer was quite low. In the case
of BDP in epoxy resin, the share of flame retardancy performance coming from a protective layer mode
of action increased with increasing BDP load. This confirms the previous conclusions and complies
with the conclusions from observing the residue pictures. Both AlPi flame retardants gave similar
results in the epoxy resin, reducing the PHRR to around 45% at a flame retardant load of 20 wt %.
They worked mainly in the gas phase. Red phosphorus, at a load of 20 wt %, was calculated to have the
lowest protective layer effect of all tested flame retardants in epoxy resin, while achieving a satisfactory
reduction in PHRR.
The ratio between PHRR reduction and the share in effectiveness that does not come from a
protective layer effect was especially good in the polyester resin-BDP system. The PHRR was reduced
to around 53%, and only 9% of this reduction is due to a protective layer effect. Twenty weight percent
of ExOP1230 showed a slightly better PHRR reduction than ExOP935, but the share of the protective
layer effect was also higher, at 39% compared to 26%.
BDP incorporated in the PMMA resin had the worst performance of any BDP formulation. At a
load of 20 wt %, the PHRR was reduced to only 88%. Practically no protective layer effect could be
detected. Both AlPi flame retardants showed about the same PHRR reduction at 20 wt % load, and the
share in protection layer effect was similar as well.
In paraffin, a reduction of PHRR of around 64% was achieved with 20 wt % of Exolit OP935.
However, 59% of the flame retardant effect was due to a protective layer. Those calculated values are
not in accordance with the observations made during burning. No protective layer was formed during
the forced flaming combustion tests in the cone calorimeter. Rather, the residue formed right before
the flames extinguished.
According to the results depicted in Table 4, BDP and red phosphorus are the most effective flame
retardants in epoxy resin. Up to a load of 25 wt %, the flame inhibition efficiency of BDP reaches its
maximum. For red phosphorus, 15 wt % were concluded to be the optimal concentration in this system.
In the polyester resin, Exolit OP1230 at a load of 10 to 20 wt % was most efficient. In the PMMA resin,
the AlPi flame retardants showed their best performance at 20 wt %, while the incorporation of BDP
did not result in satisfactory results even at high loads of 35 wt %. Differences in both tested AlPi flame
retardants were most pronounced in paraffin. Twenty weight percent of Exolit OP935 in paraffin was
concluded to be the best combination.

4. Conclusions
The use of easily preparable thermosets for investigating flame retardant modes of action,
particularly flame inhibition in this work, was shown to be an effective method. Commercially
available resins as well as paraffin were used to replace the time-consuming extrusion and injection
molding of specimens. Although some flame retardants could not be implemented in certain matrices
due to interferences with the curing process, much was learned from thermogravimetric analysis,
infrared spectroscopy and burning behavior under forced flaming conditions. The dependence of EHC
reduction and residue formation on phosphorus content in the gas phase and on residue, respectively,
was revealed and investigated for each polymer matrix. Additionally, the performance in terms of
EHC of a single flame retardant was compared among the different polymeric matrices. It was found
that paraffin is not a suitable matrix for the rapid incorporation and investigation of modes of action
of flame retardants and failed as a model for polyolefinic systems. The other polymer matrices gave
great insight into the leveling off of flame inhibition efficiency of phosphorus-based flame retardants.
Furthermore, the effect of particle size distribution was observed by comparing Exolit OP935 and
Exolit OP1230 in epoxy resin and polyester resin, respectively. It was found that the finer grained
Exolit OP935 is most effective in epoxy resin, whereas incorporation of Exolit OP1230 does not exhibit
a large difference in epoxy resin and polyester resin. To investigate and explain the behavior of
residue formation with increasing phosphorus content in the residue, a thesis for a crucial phosphorus
concentration inducing a protective layer effect was proposed and proven in certain formulations, such
Materials 2017, 10, 455 21 of 23

as for BDP in epoxy or polyester resin. It was proposed that, for these specific formulations, there is a
critical phosphorus concentration, at which the level of degradation changes significantly, up to the
retention of incompletely pyrolyzed polymer due to a protective layer. The results were quantified with
simple calculations and it was shown that they are in great accordance with observed and measured
outcomes. However, it has to be mentioned that flame retardant behavior and performance in a
polymeric system is not easy to generalize. There are noticeable trends when it comes to the changes in
effectiveness and flame retardant mode of action of varying loads of BDP in epoxy resin, for example,
but they do not allow predictions of behavior for a different epoxy-based polymeric system. These
systems do not give a statement about the fire behavior of any epoxy-, acrylate- or polyester-based
polymer, besides the ones studied. Overall, several new relations between polymer matrix, phosphorus
species, phosphorus concentration and results under forced flaming conditions were clarified.

Author Contributions: Sebastian Rabe conceptualized the working packages for this project and the scientific
work. Sebastian Rabe carried out specimen preparation, experiments and data evaluation as well as the
scientific discussion. Sebastian Rabe wrote this publication. Yuttapong Chuenban performed sample preparation,
experiments, and data evaluation, and contributed to the interpretation of the results. Bernhard Schartel acquired
the project and conceived the basic idea of the project. Bernhard Schartel supervised the work and contributed
to the scientific discussion of the results and the conclusions. Bernhard Schartel collaborated on the writing of
this publication.
Conflicts of Interest: The authors declare no conflict of interest.

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