Composites: Part A 43 (2012) 793–802

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Composites: Part A
journal homepage: www.elsevier.com/locate/compositesa

Fire structural modelling of fibre–polymer laminates protected with

an intumescent coating
E. Kandare a,b, G.J. Griffin c, S. Feih a, A.G. Gibson d, B.Y. Lattimer e, A.P. Mouritz a,⇑
a
School of Aerospace, Mechanical & Manufacturing Engineering, RMIT University, GPO Box 2476, Melbourne, Australia
b
Cooperative Research Centre for Advanced Composite Structures Ltd. (CRC-ACS), 506 Lorimer St., Fishermans Bend, Melbourne, Australia
c
School of Civil, Environmental and Chemical Engineering, RMIT University, GPO Box 2476, Melbourne, Australia
d
Centre for Composite Materials Engineering, University of Newcastle, Newcastle NE1 7RU, England, UK
e
Department of Mechanical Engineering, Virginia Polytechnic Institute & State University, Blacksburg, VA 24061, USA

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

Article history: This paper presents a new modelling approach to analyse the fire structural response of fibre–polymer
Received 7 January 2011 laminates protected with an intumescent surface coating. The model is designed to predict the temper-
Received in revised form 7 May 2011 ature, decomposition, softening and failure of laminates with an intumescent coating in fire. The model-
Accepted 14 May 2011
ling involves a three-stage analytical approach: (i) thermal-chemical analysis of the intumescent coating,
Available online 19 May 2011
(ii) thermal-chemical analysis of heat transfer through the laminate substrate (beneath the intumescent
coating), and (iii) thermal-mechanical analysis of the softening and failure of the laminate under tension
Keywords:
or compression loading. Fire structural tests were performed on a woven glass/vinyl ester laminate
A. Polymer-matrix composites (PMCs)
B. Thermomechanical
coated with an organic intumescent material to validate the modelling approach. It is shown the model
C. Analytical modelling can predict with good accuracy the temperature distribution and swelling of the intumescent coating
D. Thermal analysis with increasing exposure time to a constant heat flux. The model can approximate the temperature, soft-
ening and failure of the laminate substrate.
Ó 2011 Elsevier Ltd. All rights reserved.

1. Introduction
A problem with using fibre reinforced polymer composites in
structural engineering applications is their susceptibility to soften-
ing and failure in the event of fire. Most polymer matrix systems
soften at elevated temperatures (80 °C < T < 200 °C) due to their
inherently low glass transition temperatures or decompose in
high temperature environments such as those created by fire
(T > 300 °C). It has been demonstrated that structural survivability
of composite engineering structures relies on the composite resist-
ing deformation and failure, rather than on the avoidance of flam-
ing combustion [1]. Thus, thermal softening of the polymer matrix
is the dominant process controlling the structural behaviour of
composites in high temperature and fire environments. Matrix
softening leads to distortion and weakening of the composite
structure and may ultimately cause failure. For this reason, many
composite structures must be thermally insulated when used in
fire prone environments. Examples of composite structures requir-
ing fire protection are building interiors, offshore oil platforms, and
ship bulkheads and decks.
Thermal insulation protection of structural materials can be
placed into two categories: passive and reactive. Passive insulation
⇑ Corresponding author. Tel.: +61 3 992 56269; fax: +61 3 992 56108.
E-mail address: adrian.mouritz@rmit.edu.au (A.P. Mouritz).
involves fire protecting the composite with a surface coating which
has very low thermal conductivity and is thermally inert (i.e. does
not react to the fire). Examples of passive insulation materials are
cement-based coatings, aggregate gypsum (vermiculite, perlite or
expanded polystyrene beads) containing cellulosic particulates or
glass fibre reinforcement, mineral fibres, and insulations boards
(mineral fibreboard with resin or gypsum). Reactive insulation
coatings react when exposed to fire which increases their thermal
insulation properties, thereby protecting the underlying substrate.
Some reactive coatings also release volatiles into the fire which re-
act against the combustion process.
The most common type of reactive insulation is intumescent
coating, which is usually applied onto the substrate as an organic-
based paint or surface tissue. Intumescent coatings provide fire
protection by undergoing an endothermic decomposition reaction
process at elevated temperature that causes the material to swell
and foam into a highly porous, thick and thermally stable char layer
[2–6]. Most intumescent materials contain reactive compounds
which produce large amounts of gas as they thermally decompose
which causes the coating to expand. The solid residue forms a ther-
mally stable and highly porous char, which slows the mass transfer
of volatile combustible gases from the substrate material to the
pyrolysis zone. In addition, the char serves as a thermal insulator
inhibiting conductive heat transfer from the fire to the substrate.
Intumescent coatings are widely used to protect composite
structures from fire, but their efficacy must be determined by

1359-835X/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compositesa.2011.05.012
794 E. Kandare et al. / Composites: Part A 43 (2012) 793–802

Nomenclature

aex expansion factor T temperature (K)

CP,i heat capacity of species ‘i’ (J/kgK) T0.5 temperature at which strength is reduced to 50% of ori-
Eak activation energy for reaction ‘k’ for the intumescent (J/ ginal value (K)
mol) x dimension (m)
Eac activation energy for thermal degradation of the com- zk pre-exponential constant for reaction ‘k’ (s1)
posite (J/mol) Rrc resin content remaining during decomposition
Ai Arrhenius frequency factor for thermal degradation of
species ‘i’ (s1) Greek symbols
hi enthalpy of decomposition of species ‘i’ (J/kg) b heating rate (K/min)
QC heat of decomposition of composite (J/kg) Daex(mk)j change in expansion over time period Dtj
rC compressive strength of laminate at elevated tempera- Dxsub thickness of substrate (m)
ture (Pa) Dh specific enthalpy change due to reaction
rav average strength of laminate at elevated temperature e emissivity
(Pa) ck initial mass fraction of total coating consumed during
rC(0) room temperature measured compressive strength of reaction ‘k’
laminate (Pa) cinert residual mass after reaction ‘k’
rC(R) residual compressive strength of laminate after heat ki thermal conductivity of species ‘i’ (W/mK)
damage (Pa) r Stefan–Boltzmann constant (J/mol K)
rT tension strength of laminate at elevated temperature qi density of species ‘i’ (kg/m3)
(Pa) q0 initial density of intumescent (kg/m3)
rfb fibre strength (Pa) x void fraction of intumescent
rm matrix strength (Pa) U fitting constant
LI thickness of intumescent coating (m) UT load transfer term
h thickness of laminate (m)
b even number of locations at which strength is calculated Subscripts
across laminate I intumescent
tc thickness of composite laminate (m) gas gaseous product from decomposition of intumescent
mk normalised fraction of mass converted during reaction G gaseous product from decomposition of composite lam-
‘k’ inate
m mass fraction of material present at time ‘t’ x, y displacements in the x and y-directions (m)
mf residual mass fraction of material k reaction
n reaction order sol solid phase
Vf volume fraction of fibres in composite sub substrate (composite laminate)
fi fraction of species ‘i’ C composite laminate
m_G mass flux of volatiles rc residual char after laminate decomposition
n0 fitting parameter virgin thermally undamaged material
R Boltzmann gas constant char charred material
rk rate of reaction for reaction ‘k’ (s1)
t time (s)

fire testing, which is slow, expensive, and the results are usually
only valid for the specific test fire scenario. The need exists for a
model that can be used to predict the softening and failure of
composites with an intumescent coating. Such a model will min-
imise the need for fire tests and assist with the design of fire
resistant structures protected with an intumescent coating.
Numerous models have been developed to predict the reduction
to the mechanical properties on the failure of laminates exposed to
fire [7–27]. These models assume that the laminate is exposed di-
rectly to the fire, and they lack the capability to analyse the fire
structural response of laminates with an intumescent coating. Feih
et al. [28] recently developed a model to predict the fire structural
performance of laminates protected with passive surface insula-
tion, but an equivalent model for composites with a reactive intu-
mescent coating is lacking.
This paper presents an approach to modelling the fire structural
behaviour of fibre–polymer laminates with an intumescent surface
coating. The modelling involves a three-stage analytical approach
which combines three existing models:
(i) thermal-chemical analysis of the heat transfer, decomposi-
tion and expansion of the intumescent coating based on
the theoretical work of Griffin [29],
(ii) thermal-chemical analysis of the heat transfer and decom-
position of the laminate substrate (beneath the intumescent
coating) based on the model by Gibson et al. [30], and
(iii) thermal-mechanical analysis of the softening and failure of
the laminate under tension or compression loading based
on the models by Feih et al. [22–24].
An aim of this study is to validate the modelling approach using
a fibreglass laminate protected with an organic intumescent coat-
ing. Fire structural tests are performed on the laminate with or
without the coating under combined one-sided heating (represen-
tative of fire) and static loading (compression or tension). The
model is validated by comparing theoretical predictions against
experimental measurements of the thermal response and intumes-
cence of the coating as well as the temperature and failure time of
the laminate substrate.
2. Fire structural model
2.1. Overview of modelling approach
The approach to model the fire structural response of laminates
with an intumescent coating is shown by the flowchart in Fig. 1.
 E. Kandare et al. / Composites: Part A 43 (2012) 793–802 795

Step 1: Modelling of Intumescent Coating 50 mm

(Equations 1 - 9)
Input:
- heat flux
- thermal & physical properties of the intumescent material

Output:

Radiant Heater
- temperature profile and heating rate of coating
- expansion of coating 600 mm
- porosity of coating
- decomposition (mass loss and mass loss rate) of coating Heated section

Intumescent
coating
Step 2: Thermal Modelling of Laminate Substrate
Laminate
(Equations 10 - 15)
Input:
- interface temperature profile
- thermal & physical properties of laminate

Output:
- temperature profile and heating rate of laminate
- decomposition (mass loss and mass loss rate) of laminate
Tension/Compression
Fig. 2. Schematic of the test specimens used for fire-under-load tests where the
intumescent layer (5 mm thickness) is bonded to a composite laminate of 10 mm
thickness. Only the central 100 mm section of the specimen is exposed to radiant
heating at a constant heat flux. The specimen is loaded in tension or compression.
(For interpretation of the references to colour in this figure legend, the reader is
referred to the web version of this article.)

Step 3: Mechanical Modelling of Laminate Substrate

(Equations 16 - 19)
Input:
- temperature profile of the laminate Virgin coating
- residual resin content of the laminate Virgin composite
- isothermal property-temperature relationship of the laminate
(a)
Output:
- local tensile or compressive strengths through laminate Intumesced coating
- average tensile or compressive strengths of laminate Virgin coating
- failures time of laminate loaded in tension or compression Virgin composite

Fig. 1. Flow-chart of the three-stage modelling approach to calculate the fire

(b)
structural properties of laminates with an intumescent coating.
Charred coating

The model assumes that the laminate substrate coated with the
intumescent material is exposed to one-sided radiant heating by
fire, as shown schematically in Fig. 2. The intumescent coated
laminate is loaded in compression or tension while simulta-
neously being heated from one side. The first step in the analysis
is to compute the thermal–chemical response of the intumescent
coating to fire. The model assumes that the intumescent coating
and laminate substrate undergo phase changes as they decom-
pose due to the high temperatures generated by fire, as illus-
trated in Fig. 3. The intumescent coating initially decomposes
to form a molten phase with further degradation of the molten
phase forming volatiles and solid-state residual char. This step
in the analysis uses a model adapted from that by Griffin [29]
to calculate heat transfer across the coating as it thermally
decomposes and expands into a porous char due to intumescent
reaction processes.
The second step is to calculate the thermal response of the lam-
inate substrate, using the thermal interface temperature between
the coating and laminate computed in the first step. Calculations
are performed in the second step for the through-thickness tem-
Decomposed composite
Virgin composite
(c)
Fig. 3. An illustration of material phases in the intumescent coated composite
laminate. (a) Virgin state, (b) partially decomposed intumescent coating and virgin
laminate, and (c) fully charred intumescent coating and partially decomposed
laminate.
perature profile in the laminate based on heat conduction, matrix
decomposition, and volatile gas flow using the model by Gibson
et al. [30].
Based on the calculated temperature profile, the final step in the
modelling involves calculating thermal softening of the laminate
with increasing exposure time to fire using the models by Feih
et al. [22,23].
Below is a description of the analysis to each of the three steps
of the model. The failure temperature and time of the laminate
with the intumescent coating is calculated in the final step of the
analysis.
796 E. Kandare et al. / Composites: Part A 43 (2012) 793–802

2.2. Modelling of intumescent coating considered. The three processes are represented by the general
reaction:
Various mathematical models for calculating the heat transfer
across an intumescent coating have been developed [29,31–36], Ai ðsÞ ! residual char þ gaseous products ð4Þ
although many do not adequately analyse all the key processes
that occur during decomposition and expansion of the material. where Ai (i = 1, 2, 3) are the degradable solid components of the
Griffin [29] recently developed a heat transfer model for organic intumescent material that can be transformed into char and gas
intumescent materials that considers the main processes, which products. Mass loss kinetics of the intumescent material must
include heat conduction; decomposition of the reactive agents; be determined experimentally using TGA. Using first-order Arrhe-
gas flow; and formation and growth of the porous char phase. nius rate dependency for the reaction processes, the residual
Griffin showed that the model can accurately analyse the expan- mass fraction (mf) of the intumescent material as a function of
sion behaviour of an organic-based, intumescent coating on an temperature for a constant heating rate is calculated from TGA
inert substrate. However, predictions of the thermal resistance data using [38]:
of intumescent coatings require an accurate description of the dy-
X
3
namic physical and thermal properties of the intumescent mate- mf ¼ ðck mk Þ þ cinert
rial as it undergoes degradation and expansion. In his model, k¼1
Griffin makes several assumptions, with the main considerations 3 
X   
zk Eak
being: ¼ ck exp T 2 exp  þ cinert ð5Þ
k¼1
bEak =R RT
 Heat transfer across the intumescent coating is modelled as a
one-dimensional problem (i.e. through-thickness heat flow). The parameters ck, zk, Eak and cinert are calculated using the Mar-
Planar heat flow in the coating is not considered. quardt–Levenberg method applied to the TGA mass loss-tempera-
 Melting and intumescence are modelled independently and all ture curve for the intumescent material. Griffin [29] outlines the
reactions (primary oxidation, charring and char degradation) assumptions used in deriving these parameters.
are considered first-order Arrhenius reaction processes. The intumescent material used in this research is described
 Mass loss kinetics for each reaction process are modelled using by Asaro et al. [37] who have provided data for the heat
empirical data for the intumescent material obtained using capacity and thermal conductivity of the virgin, intumesced
thermogravimetric analysis (TGA). and char materials. Therefore, the specific heat capacity and
thermal conductivity of the coating is calculated by weighted
The modelling approach uses heat transfer analysis to calculate contributions from the virgin, intumesced and charred phases
the increase in temperature with exposure time of the intumescent of the material.
material when heated from one side. The model calculates the Thermal boundary conditions are imposed on the modelling of
temperature rise in the intumescent coating due to three thermal the intumescent coating bonded to a laminate substrate. These
effects: heat conduction; heat evolved (or absorbed) due to decom- boundary conditions are defined as:
position of the reactive constituents in the coating; and convective
at t ¼ 0; LI;0 P x P 0; T ¼ T 0 ; mk ¼ 1:0;
heat flow due to reaction volatiles (which have a cooling effect on
the coating). For this research, the heat transfer model was formu-
at t P 0; x ¼ LI ; T ¼ T0;
lated so as to best incorporate the available thermal and physical
properties for the intumescent coating which was provided by @T @T
Asaro et al. [37]. The 1D governing equation that combines these x ¼ 0; qsub Dxsub C P;sub ¼ kI ð6Þ
@t dx
thermal effects is expressed as [29]:
    where x = 0 is the exposed intumescent surface. The boundary con-
@T @ @T dition at the rear face of the intumescent was assumed to be poly-
ðqI ðTÞ  C P;I Þ ¼ kI þ Dh I ð1Þ
@t I @x @x mer adhesive, which was used to bond the coating to the laminate
The first term on the right hand side relates to heat conduction substrate.
through the coating, and the second term combines the energy ef- The model for thermal analysis of the intumescent material is
fect of gas flow through the coating with the exothermic (or endo- solved using a forward finite difference (FFD) technique in which
thermic) energy changes from the intumescent chemical reactions. the differential equations are solved at discrete points in the
The final term is calculated using: coating with respect to spatial location and time (xj, tj). A pre-
defined temperature–time heating condition is imposed on the
X front surface of the intumescent coating that defines the thermal
DhI ¼ q0;I ð1  xÞ c k r k Dh ð2Þ
k
boundary condition at x = 0. This defines the radiant heat into
the coating from the fire. Spatial grid points are set up at differ-
and ent locations through the coating, and the model is solved at
each of these locations for increasing heating times using a con-
 
dmk Eak stant time step increment of 103 s between successive analyti-
rk ¼ ¼ zk exp mk ð3Þ cal iterations. As the coating expands due to the intumescent
dt RT
reactions then the spacing between the grid points increases
The specific enthalpy change (Dh) due to reactions leading to according to:
mass loss are assumed independent of the type of reaction, as pro-
posed by Asaro [37]. It is also assumed all reactions are indepen- xiþ1;j  xi;j ¼ aex ðmk Þðxiþ1;0  xi;0 Þ ð7Þ
dent and first order, and that their rate is independent of oxygen
concentration in the gaseous environment. where aex(mk) is a variable expansion parameter. For the intumes-
In the thermal model describing the decomposition process of cent coating used in this research, the expansion of the coating is
the intumescent coating, three independent and concurrent reac- assumed to be directly proportional to the mass loss during the
tions related to melting, intumescence and char formation are melting and intumescence processes.
 E. Kandare et al. / Composites: Part A 43 (2012) 793–802
The thickness of the intumescent coating, LI, during expansion is
calculated using:
X "
LI ðxi ; tj Þ ¼ LI;0 þ aex ðmk ÞDx0
i ¼ ðqv irgin  qchar Þ
and the porosity, x, of the coating is determined using:
P The order of reaction, n, is assigned a value of unity in this
aex  c
k k mk
x¼
aex
2.3. Thermal modelling of laminate substrate
A 1D heat transfer model was used to calculate the temperature
rise in the through-thickness direction of the laminate substrate due
to heat flow into this material from the intumescent coating. This
model was originally developed by Henderson et al. [39,40] and later
modified by Gibson et al. [30]. The analysis has been described in
numerous papers [20–28] and therefore is only briefly explained
here. The 1D governing equation for the laminate substrate is similar
to Eq. (1) for the intumescent coating, and is expressed as:
   
@T @ @T @T @q
qC C p;C ¼ kC _ G C p;G
m  ðQ C þ hC  hG Þ
@t @x @x @t @t
The first term on the right hand-side represents heat conduc-
tion into the laminate from the coating. The second term describes
the mass flow of volatile products generated by decomposition of
the polymer matrix into the coating. A third term analyses the heat
absorbed during thermal decomposition of the polymer matrix,
which is assumed to be an endothermic reaction process. The fibres
are assumed to be thermally inert and do not decompose at high
temperature, although Eq. (10) can be modified to analyse lami-
nates containing organic fibres.
For accurate modelling of heat flow from the intumescent coat-
ing into the laminate substrate, appropriate thermal boundary con-
ditions at the interface (coating/laminate) are required. The
intumescent coating is assumed to be perfectly bonded to the lam-
inate. Thus, the coating/laminate interface is treated as the back-
side of the intumescent coating, and the temperature calculated
at that location is taken to be the same as the front face of the lam-
inate (i.e. there is no temperature change across the interface).
The temperature profile through-the-thickness of the laminate
and the extent of thermal degradation of the polymer matrix are cal-
culated using the thermal model described by Eq. (10). During ther-
mal decomposition of the polymer matrix, the phase states present
within the laminate are the fully decomposed (char) phase repre-
sented by the mass fraction, fchar, and the virgin (undecomposed)
phase represented by the mass fraction, fvirgin. Assuming that there
is no significant change in the volume of the laminate due to the
phase change from virgin material to char, then the instantaneous
mass fraction of solid material present at any time in relation to
the original mass of virgin material can be calculated using:
q  qchar
f ¼
qv irgin  qchar
If the mass density is assumed to follow rule-of-mixtures, then:
f ¼ fv irgin ðqv irgin Þ þ fchar ðqchar Þ
The thermal conductivity and specific heat capacity of the lam-
inate are respectively calculated using:
kC ðTÞ ¼ fv irgin kv irgin ðTÞ þ fchar kchar ðTÞ
C p ðTÞ ¼ fv irgin C P;v irgin ðTÞ þ fchar C P;char ðTÞ
where the first term on the right hand side of Eqs. (13) and (14) rep-
resents the contribution from the virgin phase while the second
term represents the contribution from the char phase.
797
Matrix decomposition is assumed to follow a single-stage
Arrhenius rate equation of the form:
#n
ð8Þ  
@q q  qchar
 Ac eEac =RT ð15Þ
@t qv irgin  qchar
ð9Þ study; i.e. decomposition follows first-order reaction kinetics.
Mass-loss kinetic (Arrhenius) parameters are determined by TGA
of the laminate material.
2.4. Mechanical modelling of laminate substrate
After the second step in the modelling approach is complete –
calculating the temperature profile in the through-thickness direc-
tion of the laminate substrate as a function of exposure time to the
fire – then the third and final step of calculating the strength and
failure under axial compression or tension loading is performed.
Various mechanical models can be applied in this step to calculate
the load response of the hot laminate [7–21], although in this study
the average strength-based analysis by Feih et al. [22–24] is used.
ð10Þ Feih and colleagues developed a strength-based model that can be
applied to a laminate under combined one-sided heating and static
compression [22] or tension [23] loading to predict softening and
failure. The analysis involved with these models is described in de-
tail elsewhere [22,23], and therefore is only briefly outlined here.
In the analysis of a hot, decomposing laminate under compres-
sion loading, Feih et al. [22] assume that the reduction in compres-
sive strength in the through-the-thickness direction due to thermal
softening and decomposition is dependent on the temperature
profile. The analysis involves determining the local strength at
many locations through the laminate based on the local tempera-
ture. At any location in the laminate, the local strength is related
to the local temperature by:
 
rCð0Þ þ rCðRÞ rCð0Þ  rCðRÞ 0
rC ðTÞ ¼  tanhðUðT  T 0:5 ÞÞ Rrc ðTÞn
2 2
ð16Þ
The first term on right-hand side considers thermal softening of
the laminate, which is assumed to occur over as a single-stage brit-
tle-to-rubbery phase transformation of the polymer matrix. The
parameters – rC(o), rC(R), U, T0.5 – must be measured from isother-
mal compressive strength tests on the laminate over the tempera-
ture range of interest. The second term considers further softening
due to matrix decomposition, where the term Rrc is the residual
mass fraction of polymer in the decomposing laminate. The expo-
nent n0 to Rrc(T) is dependent on the relationship between polymer
decomposition and residual strength, and is assumed to equal
three. Rrc is calculated using Eq. (15) based on the change in mate-
rial density due to decomposition.
After the local compressive strengths have been calculated at a
number of locations through the laminate, the bulk (average) com-
ð11Þ
pressive strength is determined using the Simpson integration
technique:
Z h
1
ð12Þ rav ¼ rðxÞdx ð17Þ
h 0
where
Z h
ð13Þ h
rðxÞdx ¼ ½rðx0 Þ þ 4rðx1 Þ þ 2rðx2 Þ þ    þ 2rðxy2 Þ
0 3b
ð14Þ þ 4rðxy1 Þ þ rðxy Þ ð18Þ
In Eq. (18), b defines an even number of locations where the lo-
cal compressive strength values are calculated, and was set at 50 in
this study. Eq. (17) is solved for stepped increments of time to
798 E. Kandare et al. / Composites: Part A 43 (2012) 793–802

calculate the reduction in the average compressive strength of the

(a) 4000
laminate substrate with increasing exposure time to fire. The time- Intumesced Material
Charred Material
to-failure is calculated using the fire exposure time needed for the

Specific Heat Capacity (J/Kg C)

3800
average strength of the laminate substrate to reduce to the applied

o
compressive stress. This failure criterion assumes that at this point 3600
all the ply layers in the laminate fail in compression at the same
time. 3400
Calculating softening and failure of the laminate substrate un-
der tensile loading follows a similar analytical approach to com- 3200
pression loading. Using the temperature profile calculated in the
second step of the modelling, the residual tensile strength of the 3000
laminate is determined at many locations in the through-thickness
direction. Tension modelling must consider thermal softening of 2800
both the fibre reinforcement and polymer matrix, with fibre
strength degradation being the dominant factor. Fibre strength loss 2600
0 100 200 300 400 500 600
occurs at higher temperatures than resin softening and is a time-
o
dependent process. Calculating the reduction in fibre strength as Temperature ( C)
a function of temperature and heating time and the reduction in
matrix strength as a function of temperature is described by Feih
(b) 0.35
Intumesced Material
et al. [23]. Using modified rule-of-mixtures analysis that combines Charred Material
the local strengths of the fibres and matrix, the local tensile 0.30

Thermal Conductivity (W/m C)

strength of the laminate substrate is calculated as:

o
0.25
rT ðT; tÞ ¼ UT ðTÞV f rfb ðT; tÞ þ ð1  V f Þrm ðTÞ with UT 6 1 ð19Þ
Once the tensile strength values at many locations in the 0.20
through-thickness direction have been calculated, the bulk resid-
ual tensile strength of the laminate is again computed using Simp- 0.15
son integration (Eqs. (17) and (18)). The reduction to the bulk
tensile strength is calculated in incremental steps of increasing 0.10
exposure time. When the bulk tensile strength is reduced to the
0.05
applied tensile stress, then the laminate substrate is assumed to
fail. In this study, the heating time taken for the residual tensile
0.00
strength to decrease to the applied stress is taken to be the time- 0 100 200 300 400 500
to-failure. As in the compressive analysis, tensile failure is assumed o
to occur by simultaneous failure of all the ply layers in the Temperature ( C)
laminate. Fig. 4. (a) Specific heat and (b) thermal conductivity of the intumesced and charred
It is assumed in the analysis of both the compression and tensile coating material phases as a function of temperature.
strengths that the intumescent coating is not structural and does
not contribute to the stiffness and strength. It is also assumed that
heat-induced damage (e.g. delaminations, matrix voids, fibre/ma- high-temperature adhesive were taken into account for the pur-
trix interfacial cracking) and visco-elastic creep softening of the fi- poses of modelling the coating/laminate interface and were pro-
bres or matrix do not affect the strength properties of the laminate. vided by the supplier.
The physical, thermal and mechanical properties of the intu-
mescent coating and laminate needed to solve the model are given
3. Materials and experimental methods in Tables 1 and 2. The temperature-dependent thermal conductiv-
ities for the virgin laminate and charred laminate were optimised
3.1. Polymer laminate with intumescent coating for each heat flux condition.

Glass–vinyl ester laminates with and without an intumescent

coating were used to validate the model. The laminates were fab-
ricated from plain woven E-glass fabric (800 g/m2) and vinyl ester
resin (Derakane 411-350; Ashland Composite Polymers). The lam-
inates were produced using the vacuum bag resin infusion process,
and then cured under ambient conditions (20 °C, 55% RH) followed
by an elevated temperature post-cure (80 °C for 2 h). The laminates
had a fibre stacking sequence of [0/90] and a fibre volume fraction
of 55%.
A 5 mm thick organic intumescent coating (Zero Inc., Type
FS2002) was applied to one surface of the laminate. The chemical
composition and thermal properties of the intumescent material
are given by Asaro et al. [37]. The temperature dependent specific
heat capacity and thermal conductivity properties of the coating in
the virgin, intumescent and charred conditions needed to solve the
model are provided by Asaro et al. [37] and are shown in Fig. 4. The
coating was bonded to the laminate substrate using a thin layer of
high-temperature adhesive. The thermal properties of the cured
3.2. Fire structural testing
The model was validated using data from fire structural tests
performed on the laminate with and without the intumescent
coating. The fire structural test method basically involves subject-
ing a laminate specimen to combined one-sided radiant heating
and static loading (tension or compression), as shown schemati-
cally in Fig. 5. The specimens are long, slender beams (600 mm
long, 50 mm wide and 9 mm thick without the coating). The spec-
imens were insulated with an inert ceramic fibre material (Fibref-
raxÒ 550 K) except for a 100 mm section at the centre, which was
exposed directly to the heat source. A 5 kW conical radiant heater
operated at incident heat fluxes of 25 kW/m2 (maximum surface
temperature of 440 °C) and 50 kW/m2 (700 °C) was used as the
heat source. The heat source was located 25 mm from the test
specimen, and both were aligned in the vertical orientation. When
exposed to the heat source, the specimen is loaded to a constant
 E. Kandare et al. / Composites: Part A 43 (2012) 793–802 799

Table 1 compressive or tensile stress using a 250 kN MTS machine fitted

Thermo-physical and material properties for the intumescent coating and laminate. with a smoke exhaust system. Specimens were tested at different
Material property Material Value Source compressive load levels between 10% and 80% of the buckling
state stress at room temperature (21 MPa). Specimens were also tested
Intumescing coating in tension at loads between 10% and 80% of the tensile failure
Thermal conductivity Virgin 0.4 [34] stress at room temperature (470 MPa). The time the specimen
(W/m °C) Intumesced 3.00  104T + 0.1 [34] can sustain the combined heating and applied load was used to
Charred 3.00  104T + 0.1 [34]
Specific heat capacity Virgin 2200 [34]
validate the model. Two specimens with or without the intumes-
(J/kg °C) Intumesced 1.5T + 3000 [34] cent coating were tested for each fire structural condition. Further
Charred 2.0T + 2800 [34] details on the fire structural test method are given by Feih et al.
Original thickness (mm) – 5.00 Measured [22–24].
Density (kg/m3) Virgin 1392 [34]
The expansion of the intumescent coating during fire testing
Heat of decomposition (J/kg) – 0.24  106 [34]
Glass-vinyl ester laminate was measured using a digital camera. A grid placed behind the
Fibre volume fraction – 0.55 [23] specimen provided reference distances to measure the amount of
Rate constant (1/s) – 5.59E13 [23] expansion. Temperature measurements were taken during testing
Activation energy (J/kg mol) – 2.13E5 [23] at the exposed surface, the intumescent/laminate interface, mid-
Order of decomposition – 1 [23]
thickness of the laminate, and the unexposed laminate surface
Remaining mass fraction (%) – 3.0 [23]
Thermal conductivity Virgin 0.32 + 1.36E4T using K-type thermocouples.
(W/m °C)
Char 0.27 + 2.82E5T
Specific heat capacity {45 °C} Virgin 960 [23] 4. Results and discussion
(J/kg °C)
Specific heat capacity Virgin/char 1210 [23] 4.1. Thermal analysis
{140 °C} (J/kg °C)
Specific heat capacity Virgin/char 1360 [23]
{290 °C} (J/kg °C) The thermal response of the laminate with or without the intu-
Original thickness (mm) – 9.00 Measured mescent coating when exposed to the incident heat fluxes of 25
Density glass (kg/m3) Virgin 2560 [23] and 50 kW/m2 are shown in Figs. 6 and 7, respectively. The solid
Density vinyl ester (kg/m3) Virgin 1140 Supplier
Heat of decomposition (J/kg) – 378, 800 [23]
(a) 500
Hot front

Table 2 400 Centre

Reaction kinetic data for the intumescent material determined using TGA performed
Temperature ( C)

at a heating rate of 40 °C/min in N2.

o

300 Back face

Degradation stages ck zk (s1) Eak (kJ/mol)
‘Melting’ 0.061 1.71  105 56.4
Intumescence 0.151 1.06  104 66.4 200
Char formation 0.268 5.50  106 122.9

Note: The final mass of the char (cinert) was measured at 0.519.
100
No intumescent coating
2
q = 25 kW/m

0
0 600 1200 1800 2400 3000 3600
Grips Time (s)

Fiberfrax (b) Hot face

500
blanket

400 Centre
Temperature ( C)

Interface
o

300
Back face
Radiant
heater

Composite
specimen 200

100 Intumescent coating

2
q = 25 kW/m

0
0 600 1200 1800 2400 3000 3600
Time (s)

Grips
Fig. 5. Schematic of fire-under-load test. (For interpretation of the references to
colour in this figure legend, the reader is referred to the web version of this article.)
Fig. 6. Temperature-time profiles for the laminate at a heat flux of 25 kW/m2 for (a)
non-insulated and (b) intumescent coated specimens. The measured and predicted
temperature profiles are shown by the data points and solid line, respectively. The
dashed line is the fitted front temperature profile. (For interpretation of the
references to colour in this figure legend, the reader is referred to the web version of
this article.)
800 E. Kandare et al. / Composites: Part A 43 (2012) 793–802

modelling approach gives an approximate estimation of the ther-

(a) 700 mal response of the laminate protected from radiant heating by
Hot front
600 an intumescent coating.
Centre The inability of the modelling approach to exactly calculate the
500 thermal response is due to several assumptions made in the anal-
Temperature ( C)

ysis together with limitations in the experimental measurements

o

400 Back face of the temperatures. The thermal model for the intumescent mate-
rial (Eq. (1)) assumes one-dimensional flow of volatile gases
300 through the coating towards the hot surface. However, in the tests
the gases were free to flow towards the hot face as well as the sides
200 of the coating, which will affect the measured temperature–time
No intumescent coating profiles of the coating. The sides of the test specimens were not
100 2 sealed, and gases were able to escape as the coating decomposed
q = 50 kW/m
and intumesced. Therefore, the gas flow conditions in the experi-
0 ments are three-dimensional, which is different to the one-dimen-
0 600 1200 1800 2400 3000 3600
Time (s) sional case assumed in the model. Similarly, the thermal model for
the laminate (Eq. (10)) assumes that gases generated in the decom-
position of the polymer matrix can only flow towards the coating/
(b) 800 Hot face substrate interface. During fire testing, delamination cracks devel-
op in the test specimens due to the build-up of internal gas pres-
700
sure, and these cracks provide a pathway for the planar flow of
600 volatiles out of the laminate which will affect the measured tem-
Temperature ( C)

Centre peratures. The presence of delaminations, which are not consid-

o

Interface
500 ered in the model, will also slow the heat conduction rate
through the laminate substrate. Delaminations create air gaps be-
400
tween the ply layers which slow heat conduction through the lam-
Back face
300 inate, and this is not accounted for in the model. It is also assumed
in the thermal model that the intumescent coating is perfectly
200 bonded to the laminate substrate, but during testing interfacial
Intumescent coating de-bonding can occur due to differences in the coefficients of ther-
100 2
q = 50 kW/m mal expansion of the coating and laminate substrate as well as
0 decomposition of the two materials. These and other factors (e.g.
0 600 1200 1800 2400 3000 3600 heating rate) are responsible for the lack of exact agreement be-
Time (s) tween the calculated and measured temperature-time profiles.
Fig. 7. Temperature-time profiles for the laminate at a heat flux of 50 kW/m2 for (a)
non-insulated and (b) intumescent coated specimens. The measured and predicted
4.2. Analysis of expansion of the intumescent coating
temperature profiles are shown by the data points and solid line, respectively. The
dashed line is the fitted front temperature profile. (For interpretation of the
references to colour in this figure legend, the reader is referred to the web version of Modelling expansion of the intumescent coating is important
this article.) for analysing the fire structural response of the laminate substrate.
The amount of expansion controls the rate of heat flow through the
coating and into the substrate, and therefore it is essential that
curves show the temperature–time response at different locations
the intumescence process is accurately modelled. Fig. 8 compares
through the coating and laminate calculated using the thermal
the calculated and measured expansion of the intumescent coating
modelling approach (described in Section 2.1). The data points
on the laminate substrate when exposed to heat fluxes of 25 and
are the temperature-time profiles measured experimentally using
thermocouples attached to the surfaces or embedded within the
specimens. Agreement between the calculated and measured tem- 28 2
perature profiles is good, but not exact, at the different locations in 25 kW/m
2
50 kW/m
the specimens tested at the two heat flux levels. The difference be-
Intumescent Thickness (mm)

24
tween the calculated and measured temperatures is generally less
than 50 °C, with the largest disparity occurring at the interface be-
tween the intumescent coating and laminate substrate. Previous 20
studies have shown that the thermal model (Eq. (10)) can predict
the temperature of unprotected laminates [15–25] and laminates 16
protected with passive surface insulation [28]. The results pre-
sented in Figs. 6 and 7 demonstrate that the coupled thermal mod- 12
els for the intumescent coating and laminate provide an
approximate prediction of the temperature for composites pro-
8
tected with an intumescent material. The agreement indicates that
the thermal model for the intumescent coating can estimate heat
flow through this material as it decomposes, expands and trans- 4
0 200 400 600 800 1000
forms into a highly porous char phase, which begins at tempera-
tures above 150 °C. Likewise, the thermal model for the Exposure Time (s)
laminate can estimate the temperature profile as the polymer ma- Fig. 8. Intumescent coating thickness as a function of exposure time at incident
trix decomposes above 350 °C. The comparison of the calculated heat fluxes of 25 and 50 kW/m2. The data points and dashed lines are the measured
and measured temperature-time profiles proves that the thermal and calculated thickness values, respectively.
 E. Kandare et al. / Composites: Part A 43 (2012) 793–802 801

50 kW/m2. The agreement between the calculated and measured 500

expansion is good, but like the temperature predictions is not ex-
act. The model for the intumescent gives an approximate estima-

Applied Tensile Stress (MPa)

tion of the amount of expansion to the coating with increasing 400
heating time. The model also predicts with good accuracy the final
Insulated
thickness of the fully intumesced coating.
300

4.3. Mechanical and failure analysis

200
No insulation
The modelling approach for predicting structural failure of lam-
inates with an intumescent coating was validated by comparing
100
calculated time-to-failure values against experimental failure
2
times for specimens loaded in compression or tension while ex- q=50 kW/m
posed to one-sided radiant heating. Calculated and experimental 0
failure times for the laminate with or without the intumescent 10 100 1000 10000
coating under compression and tension loading are shown in Figs. 9 Time-to-failure (s)
and 10, respectively. As expected, the failure times increase when
Fig. 10. Measured and predicted failure times for laminates with and without an
the incident heat flux and/or the applied stress are reduced. The
intumescing coating tested in tension at 50 kW/m2. Data points show the
intumescent coating prolongs the failure time of the laminate, par- experimentally measured failure times and solid lines give theoretical time-
ticularly at the lower stress levels. The coating insulates the lami- to-failure predictions.
nate from the radiant heat, which slows the thermal softening and
decomposition rates of the substrate and thereby extends the fail- several reasons for the inability of the modelling approach to accu-
ure time. rately calculate the failure times under compression or tension
The model predicts the general trend of increasing failure time loading. An important reason is that the model only provides an
with decreasing heat flux and stress level, although the agreement approximate calculation of the temperature in the laminate,
with the experimental data is (in most cases) not exact. There are although highly accurate prediction of the temperature profile is
required due to the strong dependency of the failure time on the
temperature, especially for compressive failure which occurs in a
(a) 20 shorter time. Several assumptions used in the model also affect
q=25kW/m 2
Applied Compressive Stress (MPa)

the accuracy of the failure times, including the assumption that

failure does not occur by progressive failure, heat-induced delam-
inations do not affect the failure time, simplified strength-mass
15 Insulated
loss correlation, and time-dependent creep softening of the poly-
mer matrix and fibres is ignored. Despite the many simplifying
assumptions, the modelling approach provides an approximate
10 estimate of the failure times for the laminate protected with an
intumscent coating.

5 5. Conclusions
No insulation
A new modelling approach to predict the thermal response,
0 softening and failure of laminates protected with a polymer-based
500 1000 1500 2000 2500 3000 3500 4000 intumescent coating when exposed to fire has been validated. The
Time-to-failure (s) modelling approach provides an approximation of the temperature
rise, decomposition and expansion of the intumescent coating and
(b) 20
q=50kW/m
2 the temperature rise, softening and failure of the laminate sub-
Applied Compressive Stress (MPa)

strate when exposed to combined one-sided radiant heating and

axial compression or tension loading. The failure times predicted
15 using the model are approximate, but not exact, due to simplifying
Insulated
assumptions made in the analysis. It is expected that better accu-
racy in the failure time predictions could be achieved by improved
10
analysis, such as modelling of three-dimensional gas flow, delam-
ination cracking, and creep-induced elasto-plastic flow of the lam-
inate. While the modelling approach only gives approximate
No insulation
estimates of the softening and failure time of the laminate, it pro-
5 vides the foundation for further development of the analysis to im-
prove the accuracy of the predictions.

0 Acknowledgements
0 400 800 1200 1600 2000 2400
Time-to-failure (s) The study was funded by the United States Office of Naval Re-
search (Grant No. N00014-07-10514) under the direction of Dr L.
Fig. 9. Measured and predicted failure times for non-coated and coated laminates
tested in compression at (a) 25 and (b) 50 kW/m2. Data points show the
Couchman. The authors thank the following: Prof Robert J. Asaro
experimentally measured failure times and solid lines give theoretical time- (University of California – San Diego) for the application of the
to-failure predictions. intumescent coating to the laminate specimens; Mr Robert Ryan
802 E. Kandare et al. / Composites: Part A 43 (2012) 793–802
and Mr Peter Tkatchyk (both of RMIT University) for technical
assistance in the manufacture and testing of the specimens. This
research was performed as part of a larger project (P2.1.2) within
the Cooperative Research Centre for Advanced Composite Struc-
tures (CRC-ACS).
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