COMPARISON OF FLAMMABILITY AND FIRE

RESISTANCE OF CARBON FIBER REINFORCED

THERMOSET AND THERMOPLASTIC COMPOSITE
MATERIALS

Jianping Zhang , Michael Delichatsios , Talal Fateh,

B. Karlsson
FireSERT , University of ULSTER
 FireSERT

 FIRE SAFETY ENGINEERING RESEARCH AND TECHNOLOGY

2
 Key research equipments (1)
 Large-scale

20MW Cone calorimeter Large scale fire

resistance furnace
(3×3×4m)
 Key research equipments (2)
 Intermediate-scale (Cone, UFA, SBI, ISO room, etc)

Cone calorimeter Universal flammability

apparatus (infra-red)
Universal Flammability
Apparatus (UFA)
 Key research equipments (3)
 Micro- and small- scale for milligram samples (thermal and toxicity
analysis)

Thermal degradation,
specific heat, heat of
pyrolysis, toxicity,
residue strength

mg samples TGA, DSC, MDSC,

FTIR, ATR, etc Inputs for modelling
large-scale tests
 Overall design

Sampling points

Unheated distance 205mm

(based on ATS furnaces – 28” long with 24” heated length)
 FireSERT

FIRE dynamics and MATERIALS LAB ( FML)

UNIQUE: FROM NANOSIZE TO 20 MW FIRES

INTRINSIC LARGE SCALE

NANOCOMPOSITES
FLAMM. (20MW)
(XRD, TEM, SEM) PROPERTIES
MATERIAL AND
(TGA, FTIR, MDSC, CFD MODELLING
UNIV. FLAMM.
APPARATUS,)
FOUR PHD STUDENTS, TWO POSTDOCS AND
THREE ENGINEERS
Major projects: FIRENET (EU) FAÇADE FIRES (EPSRC, Japan)
PREDFIRE NANO (EU) Industrial R&D , HFFRs, AIRCRAFTFIRES
 AircraftFire Project
Fire risks assessment and increase of passenger survivability
FP7 EASN Project - EU Grant Agreement n° 265612
2011 - 2014
www.aircraftfire.eu

The AircraftFire project

Presentation and Main Results

Contact: jean-michel.most@ensma.fr
 AcF Research Objective

Evaluation of fire threats and passenger survivability in

new generation of aircrafts
 Characterisation of the fire performance of composite
materials (physical/chemical/thermal flammability and burning
properties) for aircraft design and fire safety analysis (modelling)

 Development and validation physical models correlated to

the evolution of the fire scenarios,
 Modelling of the cabin fire growth and passenger
evacuation
 Recommendations for efficient industrial technologies

March 26th, 2014

Througlife, 10
 The fire threat in new
generation of aircrafts
Aluminium is substituted by flammable composites for
decorative panels, hull, wing, cowling, structure, etc.

The fire threat can significantly increase due to…

 The flammability of materials in high temperature environment
 The toxicity of the smokes
 The total aircraft fuel load
With impact on the fire development and the passenger evacuation

Higher energy supply for avionics and electronics

 fire risks (ignition,…)

CAA, Airbus, EADS

March 26th,112014
Througlife,
 Outline

Introduction
 Testing for carbon fiber composite materials
 Comprehensive flammability/toxicity evaluation
 Flammability and toxicity parameters
 Detailed flammability properties for modeling
 Pyrolysis model
 Back surface temperature for fire resistance
 Towards large scale modelling
 Conclusions

12
 Introduction
 Manufacturers of polymers or flame retardants or composites are
constantly looking for improvements in their formulations for
improving people safety and property protection.
 Flame retardants or intumescent paints or carbon fibers are commonly
used to prevent or delay the ignition of polymers and to reduce the
intensity of the fire and prevent burn through. Unfortunately, they
may also introduce new hazards such as an increase in the toxicity of
combustion gases or in smoke production and, over longer periods,
create environmental and toxicological hazards owing to disposal
(e.g., brominated FRs).
 Existing test methods (such as LOI, UL-94, burn through tests ) assess
the ignition and flame spread of a material without considering any
toxicity effects
 Also, most of these methods ranks materials in groups thus does not
differentiate the material behaviour inside a given rank
13
 Introduction (ctd)
 This paper presents a simple method to characterize the
fire performance and toxicity of polymers using parameters
deduced from micro (TGA) and small-scale (Cone
calorimeter) tests, namely

 Fire spread and growth parameter

 Smoke parameter
 Toxicity parameter
 Mass residue
 Heat release rate for thermally thin materials

14
 Literature review
(Numerical modelling)

 Two types of methods have been developed for the

prediction of fire spread due to pyrolysis/burning of
combustible materials:
 Firstly, purely thermal models for upward flame spread have
been used, with input data from the Cone Calorimeter, to
predict flame spread in large scale and the resulting heat release
rate.
 Secondly, more fundamental work has been carried out using
CFD (computational fluid dynamics) models and pyrolysis models
to predict fire growth.

15
 Flammability and toxicity parameters

16
 Flammability and
toxicity parameters
 It is desirable and cost effective to be able to assess the
flammability of materials by means of small scale-tests
before new formulations progress in large-scale production
of products made out of these materials;
 This can be achieved by combining experiments with CFD
modelling; but performing CFD modelling including
deducing all the required material properties is very time
consuming;
 In this work, we developed, based on measurements, a set
of fundamental parameters that can characterize and
compare the flammability and toxicity of materials

17
 Key flammability
properties 2
 These properties are determined using a combination of:
 TGA
 TGA-FTIR
 MDSC
 Cone calorimeter
 Universal flammability apparatus (UFA)
 Two stage tube furnace
 A numerical model describing the pyrolysis of materials that
form char upon degradation
 Flammability and
toxicity parameters

 Fire spread and growth parameter

 Smoke parameter
 Toxicity parameter
 Mass residue
 Heat release rate for thermally thin materials

19
 Flammability and
toxicity parameters
 Fire spread and growth parameter = square of peak heat
release rate divided by time to ignition
PHRR 2
tign
This parameter is proportional to FIGRA as measured in SBI

 Q max  PHRR 2
FIGRA    
 t max  SBI tign

20
 Flammability and
toxicity parameters
 Smoke parameter = smoke yield / effective heat of
combustion

𝑦𝑠 /∆𝐻𝑐

The product of the smoke parameter and the fire growth

parameter is proportional to the SMOGRA measured in SBI

 PHRR2 y   Q max ys 
SMOGRA ~   s  ~   
 t    
 ign H c   t max H c 

21
 Flammability and
toxicity parameters
 Toxicity parameter = the ratio of the effective heat of
combustion of the fire retarded polymer to the effective
heat of combustion of the neat polymer.
H c , FR _ polymer
1
H c , neat _ polymer

In the case where the polymer weight percentage is different

for different formulations, the following should be used

𝑤𝑡% 𝑜𝑓 𝑝𝑜𝑙𝑦𝑚𝑒𝑟 𝑖𝑛 𝒏𝒐𝒏 𝐹𝑅 𝑓𝑜𝑟𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛

∆𝐻𝑐 𝑜𝑓 𝐹𝑅 𝑓𝑜𝑟𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛 𝐹𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑚𝑎𝑠𝑠 𝑝𝑦𝑟𝑜𝑙𝑦𝑠𝑒𝑑 𝑖𝑛 𝒏𝒐𝒏 𝐹𝑅 𝑓𝑜𝑟𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛
1− ×
∆𝐻𝑐 𝑜𝑓 𝒏𝒐𝒏 𝐹𝑅 𝑓𝑜𝑟𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛 𝑤𝑡% 𝑜𝑓 𝑝𝑜𝑙𝑦𝑚𝑒𝑟 𝑖𝑛 𝐹𝑅 𝑓𝑜𝑟𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛
𝐹𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑚𝑎𝑠𝑠 𝑝𝑦𝑟𝑜𝑙𝑦𝑠𝑒𝑑 𝑖𝑛 𝐹𝑅 𝑓𝑜𝑟𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛

22
 Flammability and
toxicity parameters
 Mass residue = how much of the initial material is left
behind as residue after combustion.

 This is not significant for fire spread and growth but it can
provide the amount of total fuel load in a fully developed fire.
 Values for this parameter are not presented in this paper but are
included in other publications for the materials examined in this
work.

23
 Flammability and
toxicity parameters
 Heat release rate for thermally thin materials = maximum
mass loss rate in Nitrogen (appropriately normalized by the
initial mass and heating rate) In TGA multiplied by the heat
of combustion in the Cone Calorimeter

1  dm 
  H c / Heating rate
minitial  dt  max

24
 Materials and
experiments
 Experiments were performed in a Cone Calorimeter for
sample exposed to an external heat flux of 50kW/m2.
 In parallel, experiments of the same formulations were
performed in TGA /FTIR/ATR/ tube furnace but only results
from TGA at 10 °C/min in Nitrogen are employed in this
paper.
 We have established the variability (uncertainty) in our
apparatus to be a number between 3-5% for individual
measurements.

25
 Materials and
experiments

ACF1, type 1: epoxy (thermoset) +carbon fiber(~70%)

ACF2 , type 2 :epoxy ( thermoset) +carbon fiber(~70%)
ACF6 PEEK ( thermoplastic) +carbon fiber (~70%)
ACF7 , type 3 : epoxy (thermoset) +carbon fiber (~70%)

NOTE : exact composition has not been provided being

prorietary

26
GLOBAL FLAMMABILITY PARAMETERS
FOR THE COMPOSITE MATERIALS

27
FLAME SPREAD AND SMOKE

28
ACF7

29
 Materials and
experiments
Fire
growth smoke CO CO2 Initial Final Residu
Materials PHHR tig parameter yield yield yield THRR TML HoC mass mass e
kW/m
Units 2 s kW2/m4-s g/g g/g g/g MJ/m2 g kJ/g g/kJ g g %
ACF1-1 194.8 49 774.43 0.0627 0.03690 1.263 33.75 18.66 18.09 0.00347 64.1 45.44 70.89
ACF1-2 194.1 49 768.87 0.0652 0.04590 1.277 33.71 17.86 18.87 0.00345 64.1 46.24 72.14
ACF1-3 213.2 47 967.11 0.0762 0.04560 1.337 33.38 16.9 19.75 0.00386 64.4 47.50 73.76
ACF1-
AVE 200.7 48.333 836.80 0.0680 0.04280 1.292 33.61 17.807 18.90 0.00359 64.2 46.39 72.26
ACF2-1 314 65 1516.86 0.0878 0.05920 1.469 28.51 16.52 17.26 0.00509 60.9 44.38 72.87
ACF2-2 355.1 73 1727.34 0.0844 0.06140 1.52 28.85 16.36 17.63 0.00479 60.8 44.39 73.07
ACF2-
AVE 334.55 69 1622.10 0.0861 0.06030 1.4945 28.68 16.44 17.45 0.00494 60.8 44.39 72.97
ACF6-1 103.2 121 88.02 0.0451 0.04940 1.383 28.09 15.71 17.88 0.00252 63.4 47.69 75.22
ACF6-2 128.4 128 128.80 0.0483 0.04280 1.39 31.15 17.46 17.84 0.00271 66.7 49.26 73.83
ACF6-
AVE 115.8 124.5 108.41 0.0467 0.0461 1.3865 29.62 16.585 17.86 0.0026148 65.06 48.48 74.53
ACF7-1 336.8 66 1718.70 0.1705 0.06420 1.69 34.66 16 21.66 0.00787 61.0 45.00 73.77
ACF7-2 352.5 63 1972.32 0.1448 0.05030 1.75 30.99 14.12 21.95 0.00660 61.0 46.88 76.85
ACF7-
AVE 344.65 64.5 1845.51 0.1577 0.05725 1.72 32.825 15.06 21.81 0.00723414 61 45.94 75.31

30
 Materials and experiments
Flame spread parameter versus smoke yield
10000
(kW /m -s)
4

1000
2

ACF1
ACF2
PHRR /tig

ACF6
2

ACF7
100
ACF1-Pprime
ACF3
ACF9-1
ACF9-2
ACF1 (2mm)

10
0.00 0.05 0.10 0.15 0.20

ys (g/g)

31
 Materials and experiments

Flame spread parameter versus smoke parameter

10000
(kW /m -s)
4

1000
2

ACF1
ACF2
PHRR /tig

ACF6
2

ACF7
100 ACF1-Pprime
ACF3
ACF9-1
ACF9-2
ACF1 (2mm)

10
0.000 0.002 0.004 0.006 0.008 0.010

ys/HoC (g/kJ)

32
COMPARISON WITH OTHER
POLYMERS

33
THERMALLY THIN PARAMETER

34
 TGA and DTG curves at 10 oC/min for ACF1,ACF2,ACF7 (
different epoxy thermoset carbon fiber composites) and
ACF6 ( PEEK thermoplastic carbon fiber composite).

100

95

90

Weight (%) 85

80

75

70
Weight loss rate (%/min)

-1

-2

-3
ACF1
ACF2
ACF6
-4
ACF7

-5
200 300 400 500 600 700 800
o
Temperature ( C)

35
 10000
Thermally thin parameter
𝟏 𝝏𝒎
(kW /m -s)
4

1000

( × 𝒎𝒂𝒙 )
2

ACF1
𝒎𝒊𝒏𝒊𝒕𝒊𝒂𝒍 𝝏𝒕
× ∆𝑯𝒆𝒇𝒇
ACF2
PHRR /tig

ACF6
2

𝒉𝒆𝒂𝒕𝒊𝒏𝒈 𝒓𝒂𝒕𝒆
ACF7
100 ACF1-Pprime
ACF3
ACF9-1
ACF9-2
ACF1 (2mm)

10
0.000 0.002 0.004 0.006 0.008 0.010

ys/HoC (g/kJ)

36
DETAILED FLAMMABILITY PROPERTIES
AND PYROLYSIS MODEL

37
Deduced effective ignition and thermal properties of ACF1, ACF2, ACF6 and ACF7.

Material Critical Specific Ignition Heat of

s Thickness heat flux Diffusivity Conductivity Density heat temperature HoC pyrolysis
mm kW/m2 m2/s W/m-K kg/m3 J/kg-K K kJ/g kJ/g
ACF1 4.12 13 0.8X10-7 0.236 1480 1993 697 19 =0.2
ACF2 3.95 11 1.9X10-7 0.52 1550 1860 668 18 = 0.2
ACF6 4.16 31 1.9X10-7 0.38 1480 1366 860 18 =1
ACF7 4.16 11 1.9X10-7 0.51 1420 1890 658 22 = 0.2

Pre-expon.
Material Average Average Stoichio. Smoke point Activation Factor, Reaction
s ys yco Residue MLR HRR Ratio, S a height b energy, Ea Ln(A) order, n
g/g g/g % g/m2-s kW/m2 mm kJ/Mol s-1
ACF1 0.0680 0.0428 72.26 Fcn( ) c Fcn( ) c 6.3 9.05 149 21.4 1
ACF2 0.0861 0.0603 72.97 17 300 6.0 6.83 169 26.1 1
ACF6 0.0467 0.0461 74.53 6.5 120 6.0 12.59 261 32.3 1
ACF7 0.1577 0.0573 75.31 11 250 7.3 4.44 160 24.7 1

38
PYROLYSIS MODELS FOR DIFFERENT
FORMULATIONS

39
One of the objectives of this paper is to develop a simple model that can be incorporated in
CFD models for full scale modelling. In this work, it is found that the heat flux ratio between
   Tign ) and the actual heat
the heat flux assuming that there is no carbon fibre layer ( qext
4

flux between the carbon fibre layer and the virgin layer ( qint erface ) can be related to the depth of
the material pyrolysed in the following three cases:

a) Heat flux ratio increases linearly with the pyrolysed depth (ACF1) independent of the
heat flux, as found for typical charring materials
b) Heat flux ratio increases non-linearly with the pyrolysed depth independent of the
heat flux (ACF2 and ACF7)
c) Heat flux ratio initially increases linearly the pyrolysed depth but then remain nearly
constant independent of the heat flux (ACF6)

40
 PREDICTIONS
ACF1
0.18

0.16

0.14
Mass loss rate (g/s)

0.12 70kW/m2

0.10

0.08

0.06

0.04
30kW/m2
0.02

0.00
0 50 100 150 200 250 300 350 400 450 500
Time (s)

41
EXPERIMENTS

42
INSULATED BACK SURFACE TEMPERATURE AND NET HEAT
FLUX

43
 700
Back surface temperature (oC)

2
600
50kW/m
500

400

300

ACF1
200 ACF2
ACF6
100 ACF7

0
0 100 200 300 400 500 600

Time (s)

44
After 100 s , ignition starts and the net heat flux into the solid can be estimated for the slope
of temperature histories , the mass remaining ( 45 g over an area of 0.01 m 2) and the specific
heat of carbon fibers C= 0.5kJ/kg K . This net heat flux is equal to 4.5 *0.5* 300/200 = 3.4
kW/m2. This heat flux will be imposed on the insulated material behind the fuselage. We
expect and have shown ( for heat fluxes up to 75 kW/m2) that same proportional reduction of
the imposed heat flux ( by 90 %) occurs at higher imposed heat fluxes and therefore, no flame
through or flame spread will occur behind the fuselage.

45
APPLICATION TO LARGE SCALE SITUATIONS:
BURNING RATE IN THE SBI EXPERIMENT

46
 120
EXP Test 1
EXP Test 2
90
Burner HRR = 30kW
HRR (kW)

Integral model
60

30

0
0 200 400 600 800 1000 1200

Time (s)
Comparison of the predicted HRR of Flaxboard in SBI by a numerical
model and the experimental data using the calculated flammability
properties

47
 CONCLUSIONS

 Comprehensive flammability/toxicity evaluation

 Flammability and toxicity parameters
 Detailed flammability properties for modeling
 Pyrolysis model
 Back surface temperature for fire resistance
 Towards large scale modelling

48
Thanks for your attention!

Any questions?
 TOXICITY PARAMETER WHEN IT SHOWS A DIFFERENCE

50
 Toxicity assesment based on effective Heat of combustion

1.0 Inefficiency of combustion

0.8

PG2
0.6

0.4

0.2 PG4
PG3B
PG1
0.0
Percentage of initial mass left after tests in Cone calorimeter at 30kW/m2
40

PG3B
PG2 PG4A
30
PG1
Mass left (wt%)

20

10

0
Percentage of initial mass left after tests in Cone calorimeter at 30kW/m2
5 Mass of Glass fibres was substracted

PG3B
Mass left (-GF)

2
PG2 PG4A

PG1
0
 Results and discussions
 Fire growth and smoke parameters (all formulations)

54
 Results and discussions
 Toxicity parameter (all formulations)

55
 Heat release parameter for thermally thin conditions calculated as
𝟏 𝝏𝒎
(𝒎 ×𝒎𝒂𝒙 𝝏𝒕 )
𝒊𝒏𝒊𝒕𝒊𝒂𝒍
× ∆𝑯𝒆𝒇𝒇 , where 𝒎𝒊𝒏𝒊𝒕𝒊𝒂𝒍 is initial mass of sample (mg),
𝒉𝒆𝒂𝒕𝒊𝒏𝒈 𝒓𝒂𝒕𝒆
𝝏𝒎
𝒎𝒂𝒙 𝝏𝒕 is peak mass loss rate (mg/s) and ∆𝑯𝒆𝒇𝒇 is effective heat of
combustion (kJ/g) taken from Cone calorimeter

World Rescue Challenge 2012 Page 56

 Results and discussions
 Heat Release Rate for thermally thin materials (PBT+GF
and PA66+GF)

57
 Conclusions
 Five parameters were deduced based on micro- and small-scale tests
in order to characterize ignition and flammability behaviours of any
material, namely, fire spread and growth parameter, smoke parameter,
toxicity parameter, mass residue and heat release rate for thermally
thin materials
 These parameters (except mass residue which is not relevant in this
work) were applied to polymers fire retarded with brominated fire
retardants (BFRs) or halogen free fire retardants HFFRs) and it is found
that:
 In terms of fire growth and smoke parameters (i) base polymers have
the highest fire growth parameter but with minimum production of
smoke, (ii) BrFRs reduce the fire growth parameter but increase the
smoke production considerably and (iii) HFFRs achieve similar and
smaller fire growth parameter but with less smoke production
compared to BrFRs.

58
 Conclusions

 In terms of the toxicity parameter, BrFRs have highest inefficiency of

combustion because of their strong gaseous action, whereas HFFRs
have higher combustion efficiency because they mostly act in the solid
phase by modifying the char formed on the surface of the polymer.
 In terms of the heat release rates at thermally thin conditions, PBT+GF
and PA66+GF formulations behave differently, where the formulation
containing BrFRs has the lowest value for PBT+GF whilst the highest for
PA66+GF. The opposite behaviour by PA66+GF is due to the fact that
brominated PA66+GF has a maximum mass loss rate about twice that of
neat PA66+GF. This result demonstrates the limitation of TGA data
which is obtained under thermally thin condition as opposed to real
burning conditions where the material behaves as a thermally thick
material as typically found in the Cone Calorimeter tests.

59
60
61
 Acknowledgements
 The authors acknowledge the EU for financially supporting the ENFIRO
project under Grant No 226563 and AircraftFire Project under Grant
No 265612. The authors also thank Mr M McKee and W Veighey for
helping with the Cone experiments.

62
Thanks for your attention!

Any questions?