Beruflich Dokumente
Kultur Dokumente
ON COMPOSITES
By
NEWCASTLE
204
UNIVERSITY
LIBRARY
----------------06291
6
-------------------------------
June 2005
AbdurazzagLotfi Naas
University of Newcastleupon Tyne (UK), May 2005
Abstract
A
burner
small-scale propane
enable rapid
hot
for
either
conditions
under
reproducible
systems
composite
characterization of
face temperature or heat flux. The burner rig is a low cost device which enables a
its
flux
heat
be
surface.
over
to
100mm square specimen to
subjected a near uniform
The small-scale tests were conducted to measure the thermal conductivities of woven
high
11.8mm
0.13kg
thickness
at
and
roven (WR) glass fiber mats with a weight of
for
derived
the
800C.
An
calculating
was
temperatures up to
empirical equation
fiber
dry
in
the
thermal
mats.
glass
conductivity of
variation
A series of fire resistance tests on composite laminates was carried out using a small
laminated
furnace.
that
During
the
using
tests
the
prepared and
samples were
scale
hand-lay-up techniques were exposed to fire conditions defined by a furnace
temperature versus time curve. Excellent fire resistance under hydrocarbon curve test
conditions was demonstrated for several matrix materials (i. e. isophthalic polyester,
orthophthalic polyester, vinyl ester).
This information was important for the marine sector and companies such as
Devonport group (DML) and Vosper Thorneycroft (VT) to determine if materials
could perform to the A60 requirements. The A60 requirements for fire resisting
fire
60
to
the
testing under the
to
the
structural are refer
minutes
subject
material
SOLAS temperature/time regime. This then press the material for CFRP pipe repair
and metal vessels in petroleum and transportation industries.
AKNOWLEDEGEMENT
His confidence in me and his support for this study throughout these years
111
Table of Contents
Page Number
ACNOWLEDGEMENTs
ABSTRACT
vi
ix
LIST OF TABLES
LIST OF FIGURES
NOMENCLATURE
xv
CHAPTER ONE
INTRODUCTION
1
3
4
1.1 Background
1.2 Objective of the Study
1.3 Structureof the thesis
CHAPTER TWO
LITERATURE REVIEW
2.1 Type of Fire Hazard
2.2 Composite Applications
5
9
2.2.1 StructuralApplications
2.2.2 Applications for Pipes,Tanks andVessels
2.3 Fire Performanceand Behaviour of CompositeMaterials
2.3.1 Fire Reaction
2.3.2 Fire Resistance
2.3.2.1 Method of Testing
2.3.3.2 Fire Protection
11
12
13
14
18
19
22
2.4 Materials
2.4.1 Introduction
2.4.2 Polymer Matrix Composites
2.4.2.1 Reinforcing Fibres
2.4.2.2Matrix Systems
22
22
23
23
25
28
iv
31
33
35
35
37
39
CHAPTER THREE
CALIBRATION OF INCIDENT HEAT FLUX FROM A PROPANE FLAME
3.1 Introduction
3.2 Propane Burner Rig
3.3 Heat Transfer Between the Propane Flame and the Meter
3.4 Temperature Field in Front of the Heat Flux Meter
Created by the Propane Burner
3 4.1 Introduction
3.4.2 Effect of Supply Pressure
3.4.2.1 Results
40
41
42
45
45
45
45
47
50
50
51
61
61
63
65
66
67
67
68
69
71
73
CHAPTERE FOUR
OF DRY
80
81
84
84
86
88
88
93
94
96
99
CHAPTER FIVE
SMALL-SCALE
FIRE TESTING
5.5 Conclusion
100
101
101
102
105
105
110
110
110
111
113
117
117
118
120
121
123
125
127
135
CHAPTER SIX
137
137
138
140
142
148
151
CHAPTER SEVEN
ONE-DIMENSIONAL
MODELLING
OF COMPOSITES IN FIRE
V1
152
152
152
156
158
159
159
161
165
168
169
CHAPTER EIGHT
8.1 Conclusions
8.2 Further Work
170
172
References
174
Appendix I
182
Vll
LIST OF FIGURES
Page Number
Chanter Two
Fig. 2.1
10
Fig. 2.4
12
Fig. 2.5
15
Fig. 2.6
18
irradiance
calorimetervs.
Fig. 2.7
18
19
20
Fig. 2.10
Hydrocarboncellulosics temperature/timecurve
20
Fig. 2.11
21
30
31
34
Fig. 2.15
37
viii
Chapter Three
Fig. 3.1
423testing
apparatus
Fig. 3.2
Fig. 3.3
43
Fig. 3.4
46
Fig. 3.5
47
Fig. 3.6
48
distance
in
two tests
the
meter vs.
of
Fig. 3.7
49
Fig. 3.8
49
Fig. 3.9
50
52
Fig. 3.11
52
Fig. 3.12
53
Fig. 3.13
Fig. 3.14
55
Fig. 3.15
A comparisonbetweenmeasuredHF1 FS temperatures
55
Fig. 3.16
57
57
radiation effects
Fig 3.18
60
Fig. 3.19
60
Fig. 3.20
Fig. 3.21
62
Fig 3.22
64
Fig 3.23
64
ix
62
67
Fig 3.25
67
Fig 3.26
69
Fig 3.27
70
72
Fig 3.24
Fig 3.28
testing condition II
Fig 3.29
C)
h
(W/m2.
heat
transfer
Derived values of
coefficient,
72
Fig 3.30
75
(I)
condition
Fig. 3.31
75
Chanter Four
Fig. 4.1
Dry fibre-mat
81
Fig. 4.2
82
Fig. 4.3
85
(framed glass fibre mat and the front and the rear covers)
Fig. 4.4
85
Fig. 4.5
89
Fig. 4.6
89
k=0.0375
(W/m/K)
initial
fibre
and
of
value
glass
mat with
Pr = 0.3 bar
Fig. 4.7
Fig. 4.8
91
72
91
Fig. 4.10
92
Fig. 4.11
92
Fig. 4.12
93
95
Fig. 4.14
95
96
Fig. 4.16
97
high temperature
Chapter Five
Fig. 5.1
103
Fig. 5.2
103
107
Fig. 5.4
107
Fig. 5.5
Fig. 5.6
108
109
Fig. 5.9
112
Fig. 5.10
115
Fig. 5.11
115
Fig. 5.12
Fig. 5.13
116
63 minutes
Fig. 5.14
122
Fig. 5.15
124
experiment
Fig. 5.16
126
block meter
Fig. 5.17
127
130
Fig. 5.19
131
Fig. 5.20
132
Fig. 5.21
133
Fig. 5.22
134
Fig. 6.1
141
Fig. 6.2
145
Fig. 6.3
146
Fig. 6.4
147
Chapter Six
polyesterresin
Fig. 6.5
xii
147
Chapter Seven
Fig. 7.1
153
Fig. 7.2
162
Fig. 7.3
163
164
167
Chapter Eight
Fig. 8.1
a sample
X111
LIST OF TABLES
Page Number
CHAPTER TWO
Table 2.1
10
Table 2.3
11
Table 2.4
13
in
materials
performancelof
structural applications
CHAPTER THREE
Table 3.1
68
Chapter Four
Table 4.1
87
Table 4.2
87
Table 4.3
98
Table 4.4
98
Chapter FIVE
Table 5.1
104
Table 5.2
104
Table 5.3
Table 5.4
Table 5.5
129
Chapter SIX
Table 6.1
141
Table 6.2
144
Table 6.3
material used.
xlv
150
NOMENCLATURE
Mat
Mg
Cpg
OTjmn,
jace
(1.0 - Vf)
AT
AA
Cp
mat
Cp
Activation energy(J/mole)
he
Heat coefficient from the front face of the meter during the cooling-
hcom
hcylinder
hg
j+1
Kcom
Kf
Kv;a
1
lop/
m;
xv
mf
mo
msj
ms2
qc
qi
qr
Qp
r2
Correlation factor
Tfs
Time (minutes).
T(x, t)
To
Initial temperature(C)
T1
Tb
TCyiinder
Tf
TFire
Tfs
Tmc
TS
Vf
Through-thicknesscoordinate(m)
am
AT
At
Time increment(s)
Ax
xvi
Subscripts
b
Body
Convection
Cf
Cold face
com
Composite material
Cylinder
Cylinder
Final
f
fs
Fibre
Gaseousmass flow
Incident
Initial
Front surface
j+l
Meter
mat
Fibre mat
me
nc
Natural convection
opt
Optimum
Original
Pressure
Pg
Gasesgenerated
Radiation
room
Room
Source
SI
S2
Sc
Water
xvii
Greek Symbols
a
am
ej
em
Er
es
Accuracy coefficient.
pcom
Pmat
pw
Density of water(1000g/cm3)
xviii
Chapter 1 Introduction
CHAPTER ONE
INTRODUCTION
1.1 Background
Fibre reinforced plastic composites offer ideal properties for many structural
applications.
Such materials generally have low through life cost, high specific
strength and stiffness, overall weight savings, and good corrosion. Their resistance
to a wide range of fluids which can attack metals makes them an ideal and attractive
in
for
FRPs
in
extreme
choice
many applications of
many areas, especially
for
in
fire
conditions such as maritime or offshore environments and
protection
transport containers (Gibson and Fahrer, 2000).
Chapter 1 Introduction
"
"
The low thermal conductivity of the residual glass, depleted of resin, which
fire.
in
the
the
surface of
material
remains on
"
"
The use of FRPs in structural applications has given rise to interest in the fire
reaction and fire resistance of such materials.
material's ability to retain structural integrity and to limit the transfer of heat to other
remote objects when exposed to fire (Gibson, 2000).
Interest in fire reactions and fire resistance analysis has led to the development of
numerous standard tests.
limitations.
Both the small scale reaction tests and large scale resistance tests
require expensive test equipment (Gibson, 2003; Babrauskas, 1992). It has been
proposed that the use of a small-scale fire resistance test along with validated
mathematical modelling may be sufficient to replace more expensive test methods
(Gibson, Wu and Naas, 2003).
Composite materials have long been known to show surprisingly good tolerance to
thermal loading and their qualification and acceptance in fire risk applications
depends on satisfying standard tests (Dodds et al, 2000). Standard testing involves
small-scale tests such as non-combustibility,
ignitability,
These
are combined with large scale testing where the material is subject to realistic
thermal insult possibly under load. Large-scale fire resistance tests include furnace
tests under specified temperature/time curves such as the SOLAS curve (SOLAS,
1974 and BS 476 part 20,1990) representative
of a fire driven by cellulosic
materials, or the more severe hydrocarbon fire curve (BS 476 part 20,1990).
Chapter I Introduction
thermal modelling
demonstrate
to
fire
behaviour
the
capability
provides
of
innovative, new designs, to a specified fire rating, with the minimum initial recourse
to expensive fire testing (Dodds et al, 2000).
There are two basic manners in which fires can be fought: active and passive.
Active fire fighting is commonly provided by automatic detection (smoke detectors
fire
deluges
the
heat
use of
and sprays, and
and
sensors), water sprinklers,
is
fire
foam
In
to
protection
addition
and gas.
active measures, passive
suppressive
fire.
being
increasingly
to
the
used
minimise
consequences of a
now
Passive
by
itself,
is
by
design
the
the
or
cladding,
protection
either achieved
of
structure
fire,
is
impede
free
designed
the
that
the
to
of
coating or a
spread
standing system
saving both the structure and life within the fire environment.
"
Chapter 1 Introduction
"
in
fire
protection.
constructionused
"
CHAPTER TWO
LITERATURE SURVEY
This chapter presents a review of the literature related to the fire behaviour of
composite materials, including polymer matrix composites, composite applications,
the fire performance of composites and the modelling of composites in fire.
The use of fire sciencemay improve our ability to predict the behaviour of different
materialsacrossa rangeof possiblefire scenarios.
The growth of a fire in a compartmentmay be illustrated by
1000
Total
Fslsktiss
""'W-1-1
600
Smoks?
.
oxic
lI
Bums
Bums
eoo
400
r_
+.
& Smoks/Toxic
+__"
__
`wem
ti
0I
1985
tIi
1286
1987
1968
1989
1990
1991
1992
1993
,,
1994
1995
Figure 2.1 Annual total number of fire fatalities in the UK (1985-1995) by cause of
death (Irvine and McCluskey, 2000).
Time
Figure 2.2 Schematic representationof a fire vs. time, from ignition and growth,
flashover,full developmentand eventualdecay(Irvine and McCluskey, 2000).
A variety of tests have been developedto ascertainthe manner in which materials
will behavein fire (Irvine and McCluskey, 2000). Theseare principally small scale
standardtests such as BS 476 pt 6 (Troitzsch, 1983), and full scale and newer tests
which examine a material's reaction to fire, such as the cone calorimeter. The
numerouskinds of standardfire tests developedhave been summarisedby Troitzch
(1983).
In
is
other words, what may constitute acceptable
agreed.
universally
products not
behaviour in one test method may be deemed unacceptable in another. Small scale
in
develop
be
a cost
to
to
tests will continue
new materials and products
used
but
fire
behaviour
Full
tests
expensive,
are an alternative,
of
scale
effective manner.
means.
Accidental fires have been a problem throughout human history, and they cause
day.
Prominent recent
loss
life
and property worldwide almost every
major
of
examplesof fire hazards(Tewarson,1995) include:
Casualtiesin the DsseldorfAirport fire: In Germany,April 1996 at Dsseldorf
airport, 17 people were killed, 72 people were injured, and the estimatedfinancial
losses were of 150-500 million Euros. Poisonous smoke killed 17 people and
infected the airport with dioxin-containing debris. The airport was later fire
protectedwith non-combustibleRockwool insulation.
Fire at the Piper Alpha platform oil offshore production facility in the North Sea
(UK), 1988: The offshore oil industry is one which has inherent risks due to the
natureof the work and the isolation of locations. Togetherwith the unpredictability
of offshore weather,thesefactors can, in a fire situation, lead to a disaster.
Wide ranging changesin offshore operating practicesand regulations occurred as a
result of an official report on the explosions and fires aboard Occidental Petroleum
Ltd's Piper Alpha platform, at 11:20 p.m. on July 6th 1988 in the U. K. North Sea,
120 miles northeastof Aberdeen (Cullen, 1990; Oil & Gas Journal, 1988 and The
Engineer, 1990). This causedwhat may turn out to be the heaviestdeath toll in the
history of the offshore petroleum industry. After a series of large explosions,fires
were still burning 17 hours later and flames, which soaredto 700 ft at the peak of the
fire, could be seenfor 25 miles. The fires heavily damagedthe platform. Over 160
workers aboard the platform died and only 61 survived. Following this tragedy,
Cullen (1990) conducteda 13 month inquiry into the reasonsfor the explosionsand
a seriesof detailed recommendationswere given. The major outcomeof the Cullen
report, however, was a retreat from prescriptive design towards performancebased
design. This change in design ideology gives more flexibility in the choice of
to
be
the
operators
used, and places more responsibility on
materials which can
design.
ensurecorrect and safe
There are an infinite number of different fire scenarios due to fire being dependent
however,
Fire,
but
heat
too.
on all other conditions
source and material
not only on
into
be
many categories.
can
grouped
Those which
in
the
may occur
follows:
1997)
(Dewhurst,
are as
offshore/petrochemical environment
"
Pool Fire: A turbulent diffusion fire burning above an upward facing horizontal
has
fuel
fuel
the
zero or
vapour or gas
under conditions where
pool of vaporising
it
fire
is
difficult
little
initial
boiling
A
to
control; may
very
pool
momentum.
jet.
liquid
jet
fire
the
accompanya
where
rains out of
"
Jet Spray Fire: A turbulent diffusion flame resulting from the combustion of a
fuel continuously released with some significant momentum in a particular
direction.
Table 2.1 Potential duration, temperaturesand heat fluxes for different fire types.
Fire Type
Duration
Temperature (C)
Blow-Out
Months
1000-1700
100-1000
Fire Ball/BLEVE
Seconds
1000-1400
113-1200
Pool Fire
Hours
1100-1200
150-220
Running Fire
Hours
800
Jet/SprayFire
Hours
900-1500
80-1550
Their
features can also improve reliability and lead to lower through-life costs.
The most common polymer used in many composites applications are polyester,
vinyl ester and phenolic because of their low cost and good durability in the
environment. Vinyl ester resin is used infrequently instead of polyester in some
applications such as in marine applications, becauseof its higher heat-distortion
temperature,better water resistanceand higher mechanical properties. However,
vinyl esterresins are about 1.5-2times more expensivethen polyester,and therefore
are usedonly for small high-performancerequirements. Phenolic resins are used in
compositesrequiring excellent fire resistance;however their mechanical properties
are inferior to polyester and vinyl ester. Other types of resins, such as epoxies and
thermoplastics (for example polyethersulphoneand polyetherimide), are used in
most compositesapplications,again becauseof their cost. Table 2.2 (Gibson, 2000)
compares the most common types of resins used in composite structural
applications. It appearsthat most resinsare ruled out from use in areaswhere smoke
and toxicity would be a problem (Gibson, 2000). From the viewpoint of toxicity,
phenolic resinsare the most favourablesystems.
Mechanical integrity
Cost
toxicity in fire
Polyester
Vinyl ester
Epoxy
Phenolic
*******
******
*********
*********
*****
****
****
Excellent examples of the use of composites in offshore structures are the two small
scale platforms (see Fig 2.3) deployed in shallow water by Amoco UK (now BPAmoco). The low cost and easy transport were important features in their design,
and minimum topside weight was important because of their monopod from. These
topside assemblies, which included 10% by weight of composites, involved
extensive use of glass/phenolic grating for floors, walkways and handrails, along
with enclosure and heat protection walls.
10
Survey
C'hapler 2 Literature
2000).
(Gibson,
future
Table 2.3 Current and expected
offshore applications
Recent applications
of composite
offshore
Lifeboats
Blast protection
Ilandrails
Corrosion protection
Partition walls
Casings
J-tubes
Loading gantry
Caissons
Pipe refurbishment
Firewater systems
Riser protection
Pipe liners
Accumulator bottles
Bend restrictors
Separator internals
Well intervention
fire
protection
Future
structures
ESDV protection
applications
Rigid risers
Coilable tubing
Flexible risers
Tendons
Primary structure
Separators
Composite materials can provide a cost and weight-effective solution, such as for
blast and fire walls, when used in offshore platforms. Composite materials are also
beginning to be used in the combined corrosion and tire protection of load-bearing
steel structures, as in the platform legs shown in Fig. 2.4 (Gibson, 2000). Pultruded
composite gratings have also been used offshore since the 1980s. Polyester and
vinyl ester resins are still employed today for many applications.
However,
successful pultrusion techniques have been developed for phenolic resin for use
offshore where tire integrity is important.
phenolic gratings during fire, they have the ability to maintain a significant level of
functionality after fire exposure.
II
Figure 2.4 Composite combined corrosion and fire protection applied to a platform
jacket leg (courtesy of Vosper Thornycroft (UK) Ltd).
Composite Pipework: Glass reinforced epoxy (GRE) is the material most used
onshore for both low and high pressure applications with a wide variety of fluids
(Stringfellow, 1992). By contrast, the main offshore applications have been limited
so far to relatively low pressure aqueous services. Beside the best flexible chemical
resistance provided by GRE, a number of other resin types may also be used,
including: (i) isophthalic polyester, for general purpose products; (ii) vinyl ester,
which often shows corrosion resistance approaching that of epoxy, and (iii)
phenolic, which has recently been developed for fire-critical applications;
"
Tanks and vessels: Composites have been used for the manufacture of tanks for
water and diesel storage (Anisdahl et al, 1999; BS 4994,1987 and ASME, 1992).
"
Rigid risers: The development of composite rigid risers has been initiated by a
number of companies, including Conco, Petrobras, Shell and Statoil. The Institute
Francais du Petrol (IFP) has taken a role in research on prototype
riser systems.
12
Composite
Behaviour
Performance
Fire
2.3
of
and
Materials
A kc\
qualit}
of composite
materials
applications
is their
behaviour and response when exposed to severe fire. Three recent conferences have
Gibson
2000,
(Dodds
fire
el (l.,
resistance and reaction of composites
examined the
Testing to obtain both resistance and
fable 2.4 Properties and tests relating to the fire performance of materials in
structural applications.
FIRE REACTION
of fire
Typical Test
I luman survivability
FIRE RESISTANCE
the flammability
types of information
Small-scale
characteristics
of organic
ASTM
-
materials.
Usually,
E 1354, Intermediate-Scale
many
Typical
tests, DTRC
Load.
instead are designed to compare several material systems for a specific application.
The aim of these tests is to model materials, geometry and the fire threat associated
with a specific compartment.
13
Fire reaction relates to the responses of materials, especially in the early stages of a
fire, and their interaction with the environment.
into
be
those that are involved in the progress of fire and
subdivided
reaction can
those that relate to human survivability.
the materials, as opposed to the structure, and can be determined from relatively
small samples of materials.
The industry is currently in the processof standardizingtests that can quantify the
performanceof various compositematerials systemsin a fire. The U. S. Navy has
taken the lead in an effort to certify materials for use on submarines. No single test
method is adequateto evaluate the fire hazard of a particular composite material
system. The behaviour of a given material systemin a fire is dependentnot only on
the properties of the fuel, but also on the fire environment to which the materials
system may be exposed. Proposedstandardizedtest methods for flammability and
toxicity characteristicscover the spectrumfrom small-scaleto large-scaletests.
In 1982 the British StandardsInstitution published BS 6336 (1982) entitled `Guide
to the Development and Presentation of Fire Tests and their Use in Hazards
Assessment'. Examplesof methodsto measurethe key parameters(ignitability, heat
release, flame spread, smoke production and toxic gas production) are the SBI
(single burning item), room/corner test (ISO 9705), spread of flame/LIFT (IMO
FTPC, Part 5 and ISO 5658-2) and the cone calorimeter (ISO 5660). The cone
in
Fig. 2.5 (ISSO 5660) is considered to provide a good
shown
as
calorimeter,
indication of the fire reaction behaviour of materials in a fire and its data would be
expected to present the means to predict fire damage if measurementsof damage
depth and weight loss experiencedby a composite as a result of a fire show good
correlation.
14
"
..
: ,
.,.
"
;.-,-
Liam
15
ATH operates by
Chapter 2 Literature
The decomposition
is
endothermic,
process
develops
that
gradually
the
water
and
decomposition
this
and naturally as a result of
and a blanket against oxygen.
Survey
intumescing
both
effect
an
provides
in conjunction
low
low
have
2000)
Modar
and
viscosity
a naturally
which
with
resins (Dodds el a/.,
toxicity
adopted include
the addition
et (i/, 1999).
of alumina
trihydrate
However,
(ATH)
filler,
techniques
phosphorous
improvements
in one particular
considered non-toxic solutions. For example, Lay and Gutierrez (2001) focused on
the use of tire retardant fillers (alumina trihydrate (ATH)) added to a common
polyester resin. Two types of ATH have been tested, at the same concentration, and
many aspects have been studied such as production processing, mechanical
properties (i. e., static and dynamic tests and fatigue) and fire reaction (i. e., cone
calorimeter tests at different heat flux rates). The properties of polyester composites
with ATI I have been compared to those of standard polyester material. It has been
shown that the use of ATH slightly decreasesthe mechanical properties of polyester
composites, but significantly improves their fire behaviour.
Some experimental work has been done with respect to ATU additives. Lay and
Gutierrez (2001) found that ATH added at a concentration of 60 pph (parts per
hundred), is the best compromise to keep the ease
of processing and good
mechanical properties as well as obtaining a good improvement in the fire reaction
of the composite. Fire reaction tests have shown that adding 60 pph of ATH in a
16
Chapter 2 Literature
lay
hand
by
formed
up, significantly
polyester composite,
Survey
heha\ jour.
Scudamore
by
been
have
studied
resins
mainly
who
important
'003).
concentrated
is readily
heat of combustion,
and Mathys
burning
on their
in
characterising
parameter
Brownen
the flammability
determined
(1997),
characteristics.
is
the rate of
of materials
The most
gas evolution
along with
(Burchill
et al,
The rate of heat release and ignition times are important parameters and can
and
Goransson, 1987).
When fire reaction properties (i. e., time to ignition, heat release and smoke
based
factors,
important
those
on
evolution) are the most
phenolic composites and
Afl1-modified
2.7
2.6
Figures
shows a
the
and
most attractive.
resins are
comparison of time to ignition and heat release values for polyester, vinyl ester,
fibre
laminates
3mm
thick
reinforcement
epoxy and phenolic
of woven glass
of
together with the range of reported results for ATH-modified
toxicity
small
differences between the polyester, vinyl ester and epoxy composites, whereas the
phenolic and Modar/A"hff systems both show clear benefits in terms of both time-toionition and heat release. This is attributable to the high aromatic content, which
promotes the formation of a significant amount of carbonaceous char, which in turn
improves integrity and reduces heat release (Dodds et al., 2000).
In relation to survivability the main short-term to medium-term factors which have
been recognized are smoke generation, which delays escape, and the level of carbon
monoxide which is the most toxic parameter in the short term (Dodds ei al., 2000).
17
Chapter 2 Literature
Survey
100
n
Phenolic
- Epoxy
Polyester
C
O
S.
100
Vinyl ester
01
1I
\TII-T-- e--)}_iIIJII II
I---
1-
Tll_i
--
'114,.
1111
ydY"
LL
I
'Y
I ""-kl
1H
d
E
IDS
hl )al
i
I N-INII'L`-\H
fi
1U
10
Irradiance
100
(kW/sq. m)
300
600
90
Figure ?.7 (a) Peak heat release rate and (b) average heat release rate vs.
irradiance ([)odds et al.. 2000).
ability
to maintain
functionality
more expensive, than those for fire reaction since they require the measurement of
structural
as well
as material
properties.
applications
18
of the
Chapter 2 Literature
the materials
Survey
fire-resisting
properties.
significant
30
25
N
20
a
U
15
10
a)
LL
68
10
12
14
16
18
Figure 2.9 Dire resistance values, measured as a function of thickness, for a range of
different laminates subjected to the HC/arbon fire curve (Dodds et a/., 2000).
The following
(section 2.3.2.1) and standard methods for adding fire protection (section 2.3.2.2).
Testing
There are two principle time-temperature regimes used for furnace testing. those for
cellulosics (BS476, SOLAS. ASTM E-1 19). basically wood, fires and those for
hydrocarbon fires (e.g. Mobil, DoE) and the cellulosics curve). Variations do exist
between the different heating regimes and, in tests carried out by the present author.
all furnace testing was performed to either SOLAS curve such as Eqn. (2.1) (BS
476.1986) or those of the DoE interim hydrocarbon curve (i. e. Eqn. (2.2).
T- To = 345 log,,, (8 1+ 1)
\\ here To = initial room temperature and i= time (seconds).
19
(2.1)
-15.833j
Q1667
T =1100
1- 0.325e111
I -1.41760j
6-0111111
- 0.204e1
0.471e
(2.2)
\I
The furnace test shown in Fig. 2.9 is of a broad range of fire tests. The structural
in
in
furnace
the form of panels which are subjected to a
tested
test
the
are
samples
temperature profile that follows one of the fire curves (i. e., Fig. 2.10). The fire
resistance is measured by the time taken for the cool face of the panels to reach a
temperature of 140 T.
1000
800
600
of
i(
M
400
200
0
-aa-a
40
80
120
280
320 360
Time Amins]
20
(a)
(b)
Figure 2.11 Jet fire test on a steel tubular
during
fire
(a)
composite
protection.
with
21
Fire engineeringis a widely used term in modern building design, but it has many
meanings. The steel industry in the UK has expendedconsiderableresearcheffort
on demonstrating the inherent fire resistance of unprotected steelwork.
Conventionalfire protection can add up to 30% to the cost of the bare steelwork,and
there are many forms of structure where such protection can be shown to be
unnecessary, leading to considerable economies. Historically, iron, as the
predecessorof steel, was developedas a fire-proof material in the early nineteenth
century after terrible fires in large timber mills in the north of England. Currently,
Switzerland, Germany and Swedenhave their own national regulations and design
guidancefor fire and steel structures.In the UK, BS5950 coversthe use of steelwork
in buildings (BS 5950,1990).
2.4 Materials
2.4.1 Introduction
In its most basic form a compositematerial is one which is composedof at leasttwo
elementsworking together to produce material properties that are different to the
properties of those elementson their own. In practice, most compositesconsist of
the matrix, and a reinforcement of some kind, added primarily to increase the
strengthand stiffness of the matrix. This reinforcementis usually in fibre form. The
most common man-madecompositescan be divided into three main groups:
22
(a) Polymer Matrix Composites (PMCs): These are the most common and represent
Reinforced
Fibre
FRP
known
Also
in
discussion
this section.
as
the main area of
Polymers (or Plastics) - these materials use a polymer-based resin as the matrix, and
the
fibres
reinforcement.
as
aramid
carbon
and
such
as
glass,
of
a variety
(b) Metal Matrix Composites (MMCs):
industry, these materials use a metal such as aluminium as the matrix, and reinforce
it with fibres such as of silicon carbide.
This work we only considersthe PMCs, although CMSs are showing potential for
in
field
this
of research.
application
23
have
fibres
for
that
the
The
should
selection are
main criteria
and Clyne, 1996).
Common
be
temperature.
to
processing
resistant
good mechanical properties and
reinforcement fibres are made of carbon, glass and aramid, and they are now used
including
in
there
are others
polymer matrix composites, although
extensively
polyester and polyethylene.
Glass Fibre
Most glass fibres are made by a direct melting process using silica sand, limestone,
fluorspar, boric acid and clay.
C-glass,
E-glass,
be
types
processing parameters, other glass
produced, such as
can
S-glass (Mazumdar, 2002).
24
Aramid Fibres
Aramid fibres consist a man-made organic polymer and are the most important high
modulus polymer fibres developed from aromatic polyamides. They have superior
tensile strength to weight when compared to other reinforced fibres. Several types
of aramid fibres are available commercially, under different names such as Kevlar.
Kevlar fibres provide excellent abrasion resistance in a composite but they are poor
in compression. Hence, they are used in applications where subjection to high strain
compressive or flexural loads are limited.
25
Materials
Thermosetting
a.
Thermosetting matrices or thermosets are formed from a chemical reaction in-suit,
infusible
hard,
form
(hardener)
to
product.
the
a
are mixed
where
resin and catalyst
Once cured, thermosets will not become liquid again if heated, although above a
certain temperature (the Glass Transition Temperature) their mechanical properties
in
1983).
(Powell,
Although
types
there
of resins
are many
will change significantly
use in the composite industry, the majority of composite panel components are made
The
four
types,
resins.
namely: polyester, vinyl ester, epoxy and phenolic
with
main
resins used in this study were polyester and vinyl ester resins.
Polyester Resins
26
Epoxy Resins
Epoxy resins are the most commonly used type in filament wound tubes. Epoxy is
formed by the reaction of epichlorohydrin with bisphenol A in the presence of
sodium hydroxide (Varma and Gupta, 2000).
Epoxy resins are very reactive and can be cross-linked via the epoxy or the hydroxyl
side groups. The choice of curing agent depends on the processing method, curing
conditions,
desired
physical
and
chemical
properties,
toxicological
and
types of phenolic resins: resoles and novolacs. The resole phenolic resin is formed
by the reaction of phenolic with an excess of formaldehyde in the
presence of an
alkaline catalyst. Heating of the resins will cause cross-linking via the methylol
group or more complex routes.
Other resins
Besidespolyesters,vinyl esters,epoxies and phenolics there
are a number of other
thermosettingresin systemsthat are usedwhere their unique propertiesare required:
(i) cyanateestersare mostly used in the aerospaceindustry, but
are very expensive,
typical costs: 40/kg; (ii) polyurethanes are highly tough materials; (iii)
bismaleimides (BMI) are mainly used in
aircraft composites where operation at
higher temperaturesis required (for examplein engine inlets,
and high-speedaircraft
flight surfaces.Typical costs:>50/kg;
and (iv) polyimides are usedwhere operation
at higher temperatures(up to 250C) is required. These are extremely expensive
resinsand typical applications include missile and aero-enginecomponents.
27
dimensional transit heat conduction equation with an additional term to account for
the energy associated with thermal decomposition. Constant thermal properties and
a first order decomposition reaction were assumed. Later, Panton and Ritmann,
(1969) developed a model which accounted for the variable thermal and physical
properties of the material during decomposition.
Spindler (1961) proposed models which accounted both for the variable properties
of the material and the effects of gas flow through the char structure. Kung (1972)
proposed a model which separated the material into its active and residual
components. Kansa et al (1977) utilized a one-dimensional mathematical model to
study the pyrolysis of charring, including porous and permeable structural effects on
the volatile flow.
equations, the Darcy momentum equation, and global Arrhenius decomposition for a
porous, permeable reacting solid. The model was validated with experimental data
and the results indicated good agreement at low surface heating rates (i. e., 0.53 cal
cm-i sec-1), but poor agreement at fire level heat fluxes (2.0 cal cm-1 sec-1). In
contrast, Henderson et al (1985) developed an appropriate mathematical model for
the thermal response of polymer composite undergoing decomposition in the
absenceof surface recession.
28
PCP
T
-k
at x
T )+MG a
p pf
hG -A po
x
ax
po
(E/RT)
-(Qp
+ hc + hG)
(2.3)
fire
furnace
(Dodds
hydrocarbon
tests
11,17
22mm
and
to
the
curve
of
and
exposed
Gibson, 1998). The dotted lines are the calculated temperatures and the solid lines
the experimentally measured temperatures.
laminar temperatures. For each panel thickness the computer model predicts the
cold face temperature responsevery accurately.
One of the objectives in this study is to establish an approach for modelling the fire
behaviour of composite laminates exposed to different fire conditions. This could be
done by validating the existing computer model (i. e., Gibson, 1995) for prediction of
fire resistanceby means of comparison with experimental test results.
Figure 2.12 Experimental and modelling response of HC/curve furnace fire tests
laminated
for
isophthalic
WR
(Dodds
polyester/glass
panels
results
and Gibson, 1998).
One of the products of polymer matrix decomposition is the formation of solid
fire
the
carbonaceous char, which affects
response of laminates in various ways
(Levchik et al, 2000). The char formed can slow the burn-through rate by insulating
the underlying composite from fire.
diffusion rate of volatiles out of the decomposing laminate into the fire, thus
affecting the ignition time and flame spread rate. It can provide stability to burning
laminate by holding the fibres in place after the polymer matrix has been depleted.
This influence reveals that understanding the char formation process is essential in
characterising the fire response of laminated composites. The formation and growth
of char in thermoset laminate composites in fire has been experimentally and
30
(Mouritz
laminate
for
heating
flux
heat
time
increased in char thickness with
a
and
Also
for
thickness.
data
The
the
char
experimental values
points show
et al, 2004).
hot
below
depth
the
shown are theoretical curves of the remaining resin content with
surface of
the
laminate.
McManus
and
Springer
(1992)
proposed a
duration
determine
temperature
of a
the
to
and
thermomechanical model
effects of
fire on the extent of charring in polymer matrix and carbon matrix composites.
500
1000
I
1500
HeatingTime(secs)
Figure 2.13 Thermal damagedepth vs. heatingtime for a heat flux of 50 kW/m2,
for 12mmthick glass-polyesterlaminates(Mouritz et al, 2004).
31
(i.
(2.4)
the
Eqn.
from
derived
be
e.,
(A,
E,
kinetic
The three
n) can
parameters
Arrhenius equation), which describes the decomposition of the polymer matrix
(Freemanand Carroll, 1957).
n
dp__Apo
dt
P-Pf
Po
n
exp
-(EI
RT)
(2.4)
density,
T
time and temperature variables respectively;
the
t
mass
where: p, and are
A, E and n are the rate constant activation energy and the order of the reaction; and R
is the gas constant.
32
r(w
(1/woXdw/dt)
e-ssoooIRr
-wf)/
=1018
-
1,
wo nr:-I
(2.5)
from
data
kinetic
for
Chapter six describes a procedure
evaluating such preliminary
thermogram, and this will be discussed and applied to many cases.
33
2.14) when exposed to a heat source on one side (x=0) (Brian and Jason, 2004).
During the degradation process, three regions will be present: char/glass region,
pyrolysis front region which contains a mixture of virgin material and char/glass
material, and virgin material region.
decomposition material, the physical and thermal properties need to be known for
the virgin material, the char/glass material, and for the pyrolysis region where it is
typically assumed that there is a mixture of the two types of materials (Gibson et al,
1995; Brian and Jason, 2004; Henderson et al, 1985; Boyer and Thomas, 1985;
Boyer 1984). These properties need to be quantified over the temperature range
expected, which could be up to 1000C during a fire exposure.
Due to the increasing use of composite materials in industry, there is an urgent
interest in the theoretical and experimental determination of the effective thermal
conductivity of fibre and particle filled polymer composites. Although the thermal
conductivity of particle filled polymers has been investigated theoretically and
experimentally by many researchers (Tavman, 2000), there are few studies on the
thermal conductivity of fibre filled polymers.
#"LL-o
I
qm
wr
JtlY
TrainMaterial
PyrolysisFront
34
thermal conductivity of GFRP for comparison with the relevant experimental results.
For the temperature range up to 400 K, it seems unnecessary to consider any thermal
inside
the composite materials.
the
voids contained
effect of
On the other hand, the measurement of thermal properties in milli-scale devices such
(DSC)
differential
(TGA)
Thermogravimetric
calorimetry
scanning
and
analysis
as
have been used in previous studies to develop thermal properties for composite
heat
inverse
1981).
(1984)
Boyer
Henderson
1972
(Kung,
used
et al,
and
materials
transfer techniques and carefully conducted experiments to determine a new set of
thermal properties. Using these thermal properties, Boyer was able adequately to
predict temperature profiles through the composite material.
The focus of this thesis is to develop a methodology for determining the thermal
be
in
to
used modelling the thermal response of
conductivity of composite materials,
composites during fires.
transit method was adopted to derive the thermal conductivity of composite material
(i. e. dry fibre mat). Chapter five focuses on using this methodology to determine the
thermal conductivity of non-decomposing samples.
35
interface
flux
heat
the
flux
total
heat
the
Most
solid/fluid
at
measure
sensors
modes.
flux
heat
The
1999).
(Childs
types
sensorsavailableare reviewed
of
et al,
or surface
in this study. Severaltechniquesare in common use, including the following.
(i) Differential temperature sensors. The basis of these techniques is to monitor the
difference in temperature between locations in a component and, with knowledge of
the thermal properties, Fourier's one dimensional law of conduction and an equation
heat
flux
determine
be
Eqn.
(2.6)
through the medium
to
the
then
used
can
such as
(Childs et al, 1999). The limitation of this technique is that the heat flux must be
one-dimensional across the region of concern.
-T2
q=-kdT = -kT
dx
xi - x2
(2.6)
36
Slug
meter
ME
Insulating
cement
FA
Meter body
Copperor
other material
energybalanceduring the
period of initial linear temperatureresponsecan be statedas follows (ASTM E 45796, (1997): Energy Received by the Calorimeter (front face) Energy Conducted
=
Axially into the Slug. It can be expressednumerically by
multiplying the density,
specific heat, and length of the slug by the slope of the temperature-timecurve
obtainedby the data acquisition systemas following:
37
(m
(OT/At)
IA)(OT/Ot)
CP
1
CP
q=p
=
(2.7)
(i.
density
W/m2;
e.
heat
material
slug
of
transfer
p=
rate;
where; q= calorimeter
1=
K;
kJ/kg
(Copper)
heat
Copper) kg/m3; Cp = average specific
of slug material
length or axial distance from front face of slug to the thermocouple location (backK;
heat
during
to
face), m; AT= calorimeter slug temperature rise
source,
exposure
At = time period corresponding to AT temperature rise, s; m=
mass of the
kg;
A=
cross-sectional area of slug, m2.
and
slug,
cylindrical
In order to determine the steady-state heat transfer rate with a thermal capacitance
type calorimeter, Eqn. (2.7) must be solved and calculated based on the known
heat
density
(Tolukian
its
and
the
and
specific
slug material, such as
properties of
Goldsmith, 1961), the length of the slug and the slope (linear portion) of the
temperature-time curve of the calorimeter obtained during the exposure to a heat
by
be
final
initial
The
transient
temperature
eliminated
effect must
and
source.
using the initial linear portion of the curve.
For the maximum linear test time (temperature-time curve) within an allowed
surfacetemperaturelimit, the following relationship may be used(ASTM E457-96):
lq)
Cp(ATln,
0.48p1
Tn,
=
tw
ax.
o,,,.
(2.8)
where; OTfro,jOCeis the calorimeter final front face temperatureminus the initial
front face (ambient temperatureTo). lopt.is the optimum length of the slug, which
can be obtainedby applying the following equation:
lop, =3kLTjm,,,
fi,,,e/5q
(2.9)
38
2.9 Conclusion
This review has discussed the areas where composites are penetrating the onshore
and offshore engineering applications.
The challengesfor the future are the move toward using composite materials as
solutionsfor many applications. Thesechallengesbring with them the possibility of
greatly increasedmarketsfor glassbasedand high performancecomposites.
39
CHAPTER 3
modelling the fire response of systems (Dodds et. al., 2000 and Gibson et. al.,
2003).
The operation of furnace fire resistance tests based on one of the standard fire curves
presents various problems in terms of reproducibility.
of maintaining
good control of temperature in the case of samples which may burn and thus
contribute to the heat release within the furnace. It has been observed, however, that
reliable quantitative information can be obtained on samples of smaller scale. The
cone calorimeter,
for
reproducible
heat release
40
heatflux. The burner rig is a low cost device which enablesa 100mm2specimento
be subjectedto a near uniform heat flux over its surface. Fluxes in the region of
25kwm 2 up to l80kWm'2 are possible. In addition to measuringthe integrity of
in
fire
it
be
laminates
composite
can also
used to measurethe heat flux through a
protectionlaminateinto essentialsurface.
Heat transfer from the flame to a laminate involves both radiation and convection.
Although radiation is the most important factor in fire situations,effects due to heat
convectionmight not be negligible.
To treat flames as a heat radiation source, a characteristic temperaturehas to be
specified, equivalent to the surface temperature for a solid radiating heat to the
surroundings. The characteristictemperatureof a gas flame can be correlatedwith
the heat flux emitted from the flame through the Stefan-Boltzmannlaw (Eastopand
McConkey, 1978).
A surrounding field temperature,Ts, is specified in this study the
as
characteristic
temperatureof a flame in a fire test. The surroundingfield temperatureis defined as
the temperaturemeasuredat a position about 10mm away from the receiving surface
of the sample.
When the surrounding field temperature, T3, is measuredin fire test it
a
can be
correlatedwith the heat flux receivedfrom the flame, and an effective emissivity of
the flame can be derived. The emissivity (c) indicatesthe efficiency of the
emitting
surfaceas a radiator, with a value in the range from zero to 1.0. In fire situations
most hot surfaces,smoke particles or luminous flames have an emissivity between
0.7 and 1.0 (Eastopand McConkey, 1978).
Specifying the surroundingfield temperaturealone
will not uniquely define the heat
flux input to the receiving surfaceof the samplebeing
exposedto the flame. For fire
41
tests in a particular furnace,the effective emissivity of the flame inside the furnace
has to be calibrated. Such an effective emissivity is usually a function of the
surroundingfield temperatureand dependson many furnace factors.
To measurethe heat flux output from a propane flame for calibration purposes,a
thermal capacitance-typecalorimeter (Designation: E457-96,1996) or heat flux
meter was used. The heat flux meter was a block of copper. Figures 3.1 and 3.2
showthe experimentalapparatus.
The heat flux meter consistsof a 100mm diameter cylinder, one end of which was
reducedto 72mm diameterat the region of incoming flux. The coppertemperature
during the test was measuredby three thermocouplesplaced as shown. The outside
was insulatedwith calcium silicate board and Kaowool. The mass of copper was
chosento be large enough to ensure that its temperature during the test did not
generallyexceed70C.
(3.1)
where, q, representsthe total incident heat flux from the propaneflame, qr denotes
the radiation componentand q,, denotesthe convectioncomponent.
The total heat flux, q, receivedby the front face of the sampleis taking into
account
the heat flux part dueto radiation and the convectionpart as follows:
(crctm7d4
q =a
-smTm4)+k(T,
-Tm)
where
42
(3.2)
flame;
E, = emissivity of propane
K4);
W/m2
10.8
(=5.67
Stefan-Boltzmann
x
constant
a=
am= absorptivity of the receiving surface of the meter;
TS= surrounding field temperature;
Em= emissivity of the receiving surface of the meter;
Tm= temperature on the receiving surface of the meter;
h, = forced heat convection coefficient (W/m2 C)
Figure 3.1 The propane burner used as a small scale fire testing apparatus
Insulation
Holder
Sample
20 mm
Cu heat sink
I
T
72 mm
"N
100 mm
Propane flame
70 mm
IIW
Thermocouples
Figure 3.2 Schematicof the heat flux meterusedin the calibration tests.
43
50
IT
45
...
E
Ag
40
Co)
rz
C/
c
m
35
m
E 30
2
LL.
25
20
0.2
0.4
0.6
0.8
1.2
1.4
pressure Pr (bar)
44
Meter
Flux
Heat
Front
the
In
Field
3.4. Temperature
of
Created By the Propane Burner
3.4.1 Introduction.
In order to coordinate reproducible tests with the propane burner, the following
heat
burner
be
be
Can
to
a propane
regarded as a constant
answered.
questions need
flux source when the distance between the sample and the burner, and the gas supply
heat
between
flux
is
fixed?
What
the
the
and the
measured
relationship
pressure are
temperature near to the front surface of the sample?
16 different locations along the centre line to measurethe front field temperatures.
The first position of HF2 (i. e., D= 5mm) was kept for nearly 500 secondsduring
45
Flame
from
Propane
heat
Flux
Incident
a
3
Calibration
Chapter
of
of
The
for
the
positions.
both tests following by about one minute
each of the rest of
testslastedfor nearly 1400seconds.
Propane
Burner
=335mm
3.4.2.1 Results
Figure 3.5 shows typical results for measured temperature vs. time (i. e. CF
40
Within
HF2).
secondsafter the start of the test, the temperature
average/HF1and
became
HF1)
(i.
hot
face
the
the
steady and the averagetemperature
meter e.
on
of
(i. e. between45 and 1175second.) was 780C.
It can be seenfrom Fig. 3.5 that the measuredsteady-statetemperaturessurrounding
the front of the hot face of the meter (i. e. HF2) were all higher than the steady-state
temperatureson the hot face (i. e. HFI) of the meter. This is obviously attributed to
the effects of heat conductionwithin the meter body.
It is clear from Fig. 3.6 that the steady-statetemperaturesalong the central line of
the rig in front of the hot face of the meter (i. e. HF2) from the two tests conducted
are in a good agreementwith one another, indicating that the relevant results are
reliable.
It is also clear from Fig. 3.6 that the steadystatetemperatureincreasedslightly with
increasing(D) or when the thermocouple(i. e. HF2) was moved away from the block
hot surface, until the position of D= 200 mm. As D increased,or the distance
46
between the block hot face (HF) and the propane burner (i. e. S) decreased, the
fact
is
field
increased.
due
in
This
that
to
the
the
temperature
probably
steady-state
fully
developed.
burning
has
the
process
not
at such positions
propane
1000
800
CF1
600
CF2
CF3
400
HF1
HF2
200
200
400
600
800
1000
1200
Time (s)
(a)
1000 1
800
...
V
e
...
600
CF1
CF3
400
HF1
HF2
200
200
400
600
800
1000
1200
1400
Time (s)
(b)
Figure 3.5 The measured temperature profile (a) Test 1 (b) Test 2.
47
1200
1000
I.
_
800
600
f HF2 (Test 2)
400
f HF2 (Test 1)
200
0
0
50
100
150
200
250
300
350
48
HFI
Propane
Burner
CFI
CF3
CFZ
;f
lO mm
HF2
Figure 3.7 Top view of the test arrangement for case two.
1000
800
600
HF1
.. "
4400
HF2
CF
200
0
0
200
600
400
800
Time (s)
49
1000
3.4.3.1 Results
The temperaturesfrom HF2 at nine different positions are shown in Fig 3.9. Based
on the results from this particular test, and having assumedthat the steady-state
temperaturefield in front of the hot face of the meter is axisymmetricalto the central
line of the testingrig, one may concludethat:
"
"
000
600--I
av
G
a
&
AM
p.
ma
-100
-50
50
100
Postion C (mm)
50
Flame
Propane
from
heat
Flux
Incident
3
Calibration
a
Chapter
of
of
from
5mm
line
the
CFO,
the
and
The thermocouple,
central
was positioned along
burner
between
distance
the
body.
Again,
the
inside
propane
front surface
the meter
355mm,
S=
fixed
the
face
pressure
hot
supply
gas
and
the
at
the
was
meter
of
and
I
HF
Meanwhile,
during
thermocouple
was
test.
kept
the
at p=0.49bar
was
body
face
hot
times
the
and
touching
all
the
meter
the
of
centre
right
positioned at
HF2 was positioned along the central line and was 10mm in front of the hot face
during the test.
The test lasted for 1000 seconds. The measured temperature profiles obtained from
thermocouples CFO, CF I, CF3, HF1 and HF2 of the fire test are shown in Fig. 3.11.
3.4.4.1 Results
(A) Generalfeaturesof temperatureprofiles within the meter body.
The three temperature profiles measured at CFO, CF 1 and CF3 are shown in Fig.
3.12. It can be seen from Fig. 3.12 that apart from the first 50 seconds during the
fire test the temperatures measured at CF3 and CF l are nearly the same, whilst the
differences between temperatures measured at CFO and CFI (or between CFO and
CF3) remain almost unchanged. For example, the differences between temperatures
at CFO and CFI are about 7C during the 1000 second long fire test. It can also be
seen from Fig. 3.12 that apart from the initial response stage, the slope of the three
temperature-time curves looks nearly constant, suggesting a linear response time
period.
At the initial responsestageof the test, however, the thermal responsestatusat the
different positions within the meter body looks different. Figure 3.13 shows the
temperaturemeasuredprofiles at CFO,CF1 and CF3 for the first 60 secondsof the
fire test. It can be clearly seen from Fig. 3.13 that the rate of temperaturerise
CFO
measuredat
at this stageis much higher than thosemeasuredat CF1 and CF3.
51
Flame
from
Propane
heat
Flux
Incident
Calibration
a
Chapter 3
of
of
CFO
Heat Flux
Meter
"C
uuu
.:' mm
HFl
------
Propane
Burner
CFI
CF3
CF2
85mm
1000
800
600
200
600
400
800
Time (s)
52
1000
160
140
120
100
m
42
80
4)
60
40
21)
0
200
400
600
800
1000
Time (s)
40
35
30
25
CFO
CH
CF3
20
0
10
20
30
40
50
60
Time (s)
Figure 3.13 Thermal responsesat CFO, CFI and CF3 at the initial
stage.
53
(3.3)
It can be seen from Fig. 3.14 that after the initial response stage of about 50 seconds,
the rate of change of temperature everywhere inside the meter body was almost the
same, declining slightly during the whole course.
Cp
P
aT
(k
(3.4)
where,p denotesdensity of the meter material (i. e., pure copper), Cp specific heat of
copper, k thermal conductivity of copper. For a given time instant after the initial
stage, since the rates of change of temperaturesare nearly the same everywhere
within the meter body, the term on the right hand side of Eqn. (3.4) should be
constant.Therefore,at a given time instant, T (x) can be expressedas
T(x) =Co + C, x+C2x2
3.5)
300
I-
q based on CFO
q based on CF1
250
q based on CF3
200
150
100
50
200
600
400
800
1000
Time (s)
1000
800
/1
I----
600
--
derived FS
measured HF1
400
200
--m
._.-
200
400
600
800
1000
Time (s)
55
Qr=Q(Eram
7-4s-Em 7-4m )
(3.6)
where
qr=
a=
Cr=
radiation sourceemissivity
am=
TS=
Em=
T, =
Having assumedthat Cr= 0.95, am= 1.0,Em= 1.0, and temperaturesof HF2 are taken
as T3,the derived heat flux through radiation effects receivedby the meter during the
test is shown in Fig. 3.17.
56
t--50s
t=1 ON
t--200s
t=300s
t--400s
t=-500s
t--600s
40
t=700s
t--800s
t--sons
t--1ooos
20
0
20
40
60
--l
100
80
Position x (mm)
100
80
60
40
20
0
0
200
400
600
800
1000
Time (s)
57
Flame
from
Propane
heat
Flux
Incident
a
Chapter 3 Calibration of
of
h,
(1'f -T)
q =
where
q, =
h, =
Tf=
T=
lop,=
3kATf,
(3.8)
5q
--
58
where:
k= thermal conductivity of the metermaterial (copper);
Tjs= the meterfront face temperatureminus the initial front face temperature;
q= heat transferrate of the meter.
for
128
(C)
Having noticed that k (copper material) = 399 (W/m/K), Tfronr
the
=
face
current case, and q is about 80 (kW/m2), then the derived lopr= 303 (mm). In reality,
the actual equivalent length of the meter being used is given below:
OT
f,
,,,
rfe
0.48
Cp
tmax,
ou, =
pl
q
(3.9)
404 (sec)
This indicatesthat the estimatedlinear test time is about 400 secondsfor the current
case. One may conclude from Eqn. (3.9) that in general,for a given meter: (i) the
higher the heat flux input is, the shorter the linear test time will be; and (ii) the
thicker the meter is, the longer the linear test time will be.
With different levels of heat flux input for a given meter, the valid length of linear
test time period varies according to the design guidelines. In general,to measurea
higher level of heat flux input, a thicker meter is required. Effects of side heat losses
59
10
E
6
Y
K
d
2
200
600
400
800
1000
Time (s)
Figure 3.18 Heat flux received by the meter through convection effects.
100 ,
-calculated
200
400
600
800
Time (s)
60
1000
3.4.5.1 Results
The measuredtemperaturestime histories at CFO, CFI, CF3, HFI and HF2 are
shownbelow in Fig. 3.20.
Based on the individual temperature measurementsat CFO, CFI and CF3, the
derived heat flux levels are shown in Fig. 3.21. The test lastedfor only six minutes.
One can seeclearly from Fig. 3.21 that for the given lower heat flux input (P, = 0.20
bar) the derived heat flux inputs from CFO, CF1 and CF3 are kept nearly constant
until t= 320 sec.After that, the derived heat flux values start to decrease. The data
for the temperaturesmeasuredat CFO,CF1 and CF3 for the first 50 secondsor so
haveto be ignored in the processof deriving the heat flux input.
61
700 T-
Z 400
300
HF1
hIF2
CF1,CF3
CFO
100
i
100
200
300
400
Time (s)
80
TT
70
60
-q
based on CFO
-q
based on CF1
-q
based on CF3
50
40
30
20
10
50
100
150
200
250
300
350
Time (s)
62
400
Flame
from
Propane
heat
Flux
Incident
3
Calibration
Chapter
a
of
of
=
-Tn)mCP1?
(3.10)
where
m=
A=
(kg)
the
meter
of
copper
mass
front face areaof the meter (m2)
QIEramTs4I = mC
p/A
(3.11)
The following showstypical results from a calibration test (i. e., Pr = 1.Obarand D=
350mm, D is the distancebetweenthe propaneburner head and the front surfaceof
the meter).
The surroundingfield temperaturemeasured,TS,togetherwith temperatureresponse
profiles at M,
TC2 and TC3 are shown in Fig. 3.22. It can be seenfrom Fig. 3.22
that after the initial responseperiod (about 70 - 100 secondslong in the current
case), the surrounding field temperature, T,, becomes practically constant (TS =
992C).
63
1000
soo
600
400
TC1
TC2
ra
Ts
200
50
100
150
200
250
300
350
400
Time (s)
0.2
0
e_
113
H
v
0.1
0.0
100
200
300
400
Time (s. )
Figure 3.23 Derived values of (dT/dt) of the calibration test (Pr = lbar, D= 350mm).
64
Basedon the facts indicated above, in order to derive the incident heat flux input
from the propane flame using the thermal capacitance type calorimeter, the
following procedurewas proposedand adoptedin dataprocessing:
"
"
To derive the heat flux received by the meter according to Eqn. (3.11).
Check the value of ii =(T, /Ts) at the end of the sampling period to ensure that q
< 0.10. If ' is greater than 0.1, the 100 seconds-long sampling time period
should be reduced accordingly.
q= seBTs
(3.12)
Ap
at
530.1
=
(3.6)
at
where:
A= 4060.2 (mm2),
65
emissivity of the propane flame increases gradually with increasing pressure P,, or
temperature Ts,. At P, = 1.2bar, the value of the emissivity is nearly 0.9. For P,
smaller than 0.4bar, however, the effective emissivity
decreasing pressure P,. This trend may be attributed to the fact that at D= 350mm,
when Pr is lower than 0.4 bar, the front face of the meter is out of reach of the
propane flame. Once the flame cannot reach the front face of the meter, there would
be no forced convection effects during the heat exchange. As a result, heat transfer
is achieved purely through heat radiation from the propane flame, leading to an
increase in effective emissivity of the heating source.
1.6
1.4
1.2
1
0.8
N
m
0.6
0.4
(kW/sq.m)
--o-q/100.0
--o- Ts/1000.0 (C)
0.2
--i
emissivity
0
0
0.2
0.4
0.6
0.8
1.2
66
1.4
1.8
1.6
1.4
1.2
1
0.8
0.6
0.4
0.2
0
20
25
30
35
40
45
Distance (cm)
67
emissivity of the front face of the meter at elevated temperature (60C-140C) were
then derived according to Newton's Law of Cooling and the Stefan-Boltzmann law
of thermal radiation. Finally an assessment of the accuracy of using the meter for
calibrating heat transfer rate from propane flames was made.
71.9(mm)
Cv
384(J/kgC)
99.5 (mm)
4060.2 (mm )
L1
20.3 (mm)
41986.6(mm )
L2
69.9 (mm)
V (total volume)
625959 (mm)
8954 (kg/m )
68
Flame
from
Propane
heat
Flux
Incident
a
Chapter 3 Calibration of
of
L2
_--
-H
A,
1
Ll
Front view
Side view
69
be
have
linear.
Therefore,
to
two
the
carefully reassumptionsmentionedabove
as
heat
flux
do
heat
To
in
transfer
the
this
so,
meter.
particular
examined respectof
front
(A)
in
the
the
the
to
and
emissivity of
meter relation assumption
coefficient of
faceof the meter in relation to assumption(B) have to be measuredor derived.
When the front face of the meter is free from insulation, whilst the rest part of the
surface is insulated by a vermiculate frame and Kaowool layers, the status of the
is
meter referred to as under the insulation condition (I) as schematically shown in
Fig. 3.27a. In Fig. 3.27a, TC1, TC2 and TC3 denote three thermocouples installed
inside the copper block: the tips of TC1 and TO are positioned 3mm from the back
face of the meter, whilst the tip of TC2 is 30mm from the back face.
In addition to the thermal insulation imposed on the meter under condition (I), the
front face of the meter is covered by a thick layer of Kaowool as schematically
shown in Fig. 3.27b. Such a statusof the meter is referred to as under insulation
condition (II). Here, three thermocouples(i. e. TC 1, TC2 and TC3) are locatedat the
samepositions as under condition (I).
Vermiculite frame
Front face of
the Meter
(a)
Vermiculite
frame
W29
Copper
block
TC1
'
Kaowoo
layers
(b)
--
TC2
TC3
Vom'
Figure 3.27 Schematicdiagramof the meter rig for a) condition I, b) condition II.
70
Flame
from
Propane
heat
Flux
Incident
3
Calibration
Chapter
a
of
of
II
Condition
Testing
Meter
Test
the
3.7.3 Cooling-Down
under
of
The meter with its front face exposed to a propane flame was first heated up to a
(II)
down
testing
100C
condition
under
temperature over
and then naturally cooled
(i. e., front face insulated). During the course of the test the initial room temperature
3.28.
in
Fig.
is
The
17.5C.
the
meter shown
measured cooling-down curve of
was
It took more than three and half hours to get the meter body temperature from 104C
down to 75C.
According to Newton's Law of Cooling, the total energy loss from the meter body
layers
heat
due
insulation
insulation
(II)
to
through
the
conduction
condition
under
to the surrounding fluid (or air) at room temperature Tooom
with the meter's total
surfaceareaof A and body temperatureof Tb,is given by
)
(Tb
Q= hA
\rl - T,
m),,,
(3.13)
whereh is the heat transfer coefficient under Testing condition (II). By considering
thermal energy balance,the total energy loss to the surroundings,Q, is equal to the
energyloss of the meter body:
(3.14)
VP
C,p
at
whereV denotestotal volumeof themeterbody.
Combining the two equations(3.13) and (3.14) leadsto:
h=
atn(Tb
)-l
Trood
pCp
A
(3.15)
Basedon Eqn. (3.15) and the experimentaldata shown in Fig. 3.28, the derived heat
transfer coefficients of the meter under condition (II), h, as a function of body
temperatureof the meter, Tb,are shown in Fig. 3.29. It can be seenfrom Fig. 3.29
that the derived values of the heat transfer coefficient of the meter under testing
71
between
in
75C
105C,
(II)
the
temperature
and
range
constant
nearly
condition
are
C).
(W/m2.
being
its
1.63
to
equal
averaged value
with
40
80
120
200
160
240
Time (min)
2.5
U
E2
Q
.21.5
O
0
I'I
cl
+
M
M
,
x
0.5
70
75
80
85
90
95
100
105
110
72
I
Condition
Testing
Meter
Test
the
Cooling-Down
3.7.4
under
of
The secondcooling-down test was carried out with the meter in order to derive the
front
face
the
of the meter.
of
emissivity
Under testing condition (I) the meter was heated up to about 140C and then was
cooled down naturally to about 60C. During this process the room temperature
front
face
20C.
Under
the
recorded was
such a condition,
of the meter was allowed
to radiate thermal energy freely to the surroundings, whilst energy losses from the
meter due to conduction through the insulation layers to the surroundings of the rest
its
total surface area continued.
of
The measured meter body temperature vs. time curve is shown in Fig. 3.30. The
temperature range shown in Fig. 3.30 is greater than that in Fig. 3.28. It took nearly
five hours and forty minutes to get the body temperature of the meter from 140C
down to 57C.
Under the given condition, the thermal energy balanceof the meter can be statedas
follows;
Energy lost by the meter = Energy radiated from the front face of the meter +
Energytransferredthrough the insulation layers to the surrounding.
The abovestatementcan be formulated as follows:
VpCn
ab=
(Tb
)4
(A
)h(Tb
)
(Tb
)
A,
T.,,
h,
A,
T,
+ =41
+
- .
- nom
(3.16)
where Tb denotes the body temperature of the meter, h is the heat convection
coefficient from the meter through insulation layers, a is the Stefan-Boltzmann
constant(= 5.67 x 10 'g W/m2 K4), E is the emissivity of the front face of the meter
and he is the heat coefficient from the front face of the meter during the coolingdown test.
Once heat transfer coefficients h and h, are known, one can derive the emissivity E
of the front face of the meter easily from Eqn. (3.16):
73
[vpcp a
Al(T, b)
"- (A A, )h(Tb T)
-
)
(Tb
h,
T,
A,
- Y,,,
n,
(3.17)
Based on the results given in the previous section, it is assumedin this study for
h=2.0
C)
(W/m2.
that
within the temperaturerangeof concern.
simplicity
Estimation of the heat convection coefficient from the front face of the meter during
the cool-down test, h,, may be achieved by using an approximate equation.
As suggested by Eastop and McConkey, (1978) for natural convection from a
is
it
front
in
like
face
test,
the
this
the
of
meter
cooling-down
vertical surface
laminar.
flow
the
the
to
circulation
air
or
over
remaining
assume
surface
reasonable
The following equation can then be used for the estimation of the heat coefficient:
(Th
hc =1.42
)
T"'
1
1/4
(in: W/m2 C)
(3.18)
74
I VV
S nesl
I 40
Senes2
ci
Series3
20
0
n
E
00
Y
V
80
60
an
0
50
100
150
200
250
300
350
Time (min)
0.8
0.7
0.6
0.5
>
0.4
N
E 0.3
0.2
0.1
0.0
50
70
90
110
130
75
150
Flame
from
Propane
heat
Flux
Incident
Calibration
a
Chapter 3
of
of
Tests
Calibration
the
3.8 Assessment of the Accuracy of
Using the Meter
for
been
has
flux
heat
used
The thermal capacitance-type calorimeter or
meter
As
flames.
from
heat
stated
incident
transfer
propane
rates
steady-state
calibrating
in ASTM E 457-96, a linear temperature response of the meter is expected upon
heat
incident
The
balance.
transfer
rate
thermal
steady-state
energy
consideration of
is then calculated straightforward from the measured slope of the linear temperature
response of the meter.
(--f
)A,
)
)
(A
(Tb
A,
T,,,.
a Ts4- ETh' -h
-
(3.19)
where
Tb
Toomm=
room temperature;
TS
surroundingfield temperature;
Ef
C=
front
face
the
of the meter;
emissivity of
a=
h=
It can be seen from Eqn. (3.19) that only when thermal energy lossesdue to both
heat conduction through the insulation layers and heat radiation from the front face
of the meter to the surrounding are negligible, would a linear temperatureresponse
incident
input.
be
for
the
thermal
of
meterwould
expected a steady-state
energy
Based on the derived values of h and E, the accuracy of using the meter for
calibration of a steady-stateincident heat transfer rate can be assessed:
76
Flame
from
Propane
heat
Flux
Incident
Chapter 3 Calibration of
a
of
aT
n
v,ocp
at
arn,a,
(sfaTs4
QA,
-sTb)-h(A-A,
(vpcPaTh
at
QA, B
XTb
-T, nOIA)
=
(3.20)
faTsa
idea!
The upper term in the left hand of the above equation denotes the energy transfer
body
the
for
temperature
the
the
whilst
only,
meter
of
raising
rate actually received
lower term of the left hand of the equation denotes the incident energy transfer rate
from the steady-state heat radiation source. c may be regarded as an accuracy
coefficient.
During the course of a calibration test on propane flames for a given distance D and
level,
field
TK
P,,
temperature
the
can soon reach a constant
surrounding
pressure
but the body temperature of the meter would rise very gently all the time. This is the
is
in
initial
test
temperature
the
the
not
of
a
calibration
response
meter
reason why
linear.
Equation (3.20) can be reduced to a simpler form. According to Kirchhoff 's Law of
Thermal Radiation, the emissivity of a body radiating energy at a temperature, T, is
equal to the absorptivity of the body when receiving energy from a source at a
temperature, T (Eastop and McConkey, 1978). Therefore, E=a for the meter at any
temperature and so equation (3.20) can be re-written as:
1-
(Th
1
s TS
h(Te-Tinm)
QsfsTf4
A
-1
A,
(3.21)
77
=0.981.
bar):
0.6
burner
Pr
400mm,
D=
the
(distance
(2) CaseII
=
releasingpressureof
20.0C; Ey= 0.89; E=0.42 and h
Substitution of the above data into Eqn. (3.21) leads to: = 0.964
(3) Case III (distance D= 350mm, releasing pressure of the burner P, = 0.30 bar):
h=2.0
Tioom
20.0C;
0.73;
48.4C;
TS= 1061.5K; Tb
and
Ej'
E=0.40
=
=
max=
(W/m2 C).
Substitution of the above data into Eqn. (3.21) leads to:
= 0.963.
3.9 Conclusions
"
"
For heat transfer from the propaneflame to the receiving surfaceof the material
being tested,although thermal radiation is the main mechanism,forced thermal
convectioneffects may also be involved, dependingon: the distancebetweenthe
burner head and the front face of the material being tested; and the pressureat
which the propanegasis released.
"
"
from propane
flames:q= QseffTsa
"
It was found in this study that propane flames have an effective emissivity
between0.73 and 0.88 under the given environmentalconditions in the lab. This
finding is nearly the same as those reported in Perry & Chilton (1973) and
Buchanan(2001).
"
The results from cooling down tests have proven that the use of such thermal
capacitance-typemeters in calibrating incident heat transfer rate from propane
78
The averaged heat transfer coefficient due to conduction from the meter through
the insulation layers to the surroundings under testing condition I is about
2.0W/m2 C in the temperature range from 60C to 100C, and the derived
emissivity of the front face of the meter is a function of body temperature. Its
increases
value
gradually with increasing body temperature from: e=0.42
at
Based on the quantitative results from the two cooling-down tests with the
meter, the estimated error of using the thermal capacitance-type meter for
calibration of incident steady-state heat transfer rates from propane flames is less
then 5%.
"
The surfacecondition of the front face of the meter may be come oxidised and
also some products generated from the decomposition reactions of GRP
laminatesto different types of resin systemmay becomeattached.
"
79
CHAPTER 4
MEASUREMENT OF THERMAL CONDUCTIVITY
OF DRY FIBRE-MATS AT HIGH TEMPERATURE
4.1 Introduction
The mechanical strength of composite materials during a fire is strongly dependent on
temperature, decreasing rapidly
temperature of the matrix material (Ott, 1981). As a result, accurately modelling the
heat transfer through a composite is a critical part of conducting a structural analysis
on the composite when exposed to fire.
One of the major difficulties encountered in modelling the thermal response of GFP
composites in fire is the lack of material property values at high temperatures. In
general, when a composite is exposed to fire, its density, thermal conductivity and
specific heat change. This is attributed not only to the changes in composition
contents of the composite due to decomposition, but also to changes in the material
properties of the matrix and reinforcement materials them selves with increasing
temperature at high temperatures.
The Rule of Mixture has been used to derive the thermal propertiesof compositesat
room temperatureswhen they can be treated as a solid material or a continuum.
During fire exposurethe composite will becomea skeleton that is a new composite
material consisting of three elements: (A) the reinforcement fibres, (B) the resin
undergoing decomposition, and (C) a void filled with air and gases. The Rule of
Mixture may be adoptedagain for deriving the thermal properties the
of
composites
at high temperature. But, investigations have indicated that the application of the
Rule is in particular not accuratefor the evaluation of thermal conductivity
of FRP
composites.
A simple transient responsemethod is introduced in this chapter for
measuringthe
thermal conductivity of dry fibre-mats at high temperatureusing the small scale fire
testing facility. The experimentalresults are then comparedto (1) those derived from
80
its
indicated
Having
literature.
from
(2)
Rule
Mixture,
the
those
the
obtained
and
of
is
investigation
from
it
is
the
that
the
a useful and
method
restrictions,
concluded
fibre-mats.
dry
for
the
thermal
properties of
measuring
reliable means
'.
;2
.3.........
q incident
I,
Ax121Ax23
The mat is exposedto a fire or an incident heat flux (q) at its front side. It is assumed
that the heattransfer inside the mat can be treatedas a one-dimensionalproblem.
In assembling the fibre-mat, a number of thermocouples are inserted into the sheets,
Xi
distances
between
AX23,
AX34...
AX12,
the
the
thermocouples
two
where
adjacent
are
i+1.
It is assumed that the mat can be regarded as a uniform composite consisting of dry
fibre and air in the through-thickness direction with density p and known specific heat
Cp.
81
Based on the above assumptions, the 1D transient heat transfer equation can be given
as follows:
aT
PC, at
ax
aT
(4.1)
ax
where: p (kg/m3), Cp (J/kg K) and K (W/m K), are the density of the mat, the
specific heat of the mat and the thermal conductivity of the mat, respectively. T(x, t)
is the temperature (C) as function of (x) in through thickness and time (t).
Supposethat three thermocouples (i. e., Tc1, Tc2 and Tc3) are inserted into the
mat and
Ex 12= 0x23= Ox. Equation (4.1) is held at Tc2,and can be written as:
PC P
T
at
Ka2
+aK
aX2
_
x
al Tc2
(4.2)
ax
ar Tc2
node
T,
T2
AX
f-6
Through thickness
T3
OX
4t
j+1
Time
t)
i+N
..........
82
Temperatures
High
Fibre-Mats
Dry
Conductivity
Thermal
at
Chapter4 Measurementof
of
(i) Forwarddifference
T
ax
T; - Ti
+I
==T;
x; +I - x;
IxI+Ixi
Ti
+l
AX
x41 -x
(4.3)
aT
x
->
xi-l-xl
T, - T,
T, - T,
T, -T,
-1 =
-1
limxi-l-xi
-' _
xi
Xi
Xi-1
Ox
xi-1
(4.4)
aT
--
ax
Tw -T
xr+i
-I
- x, -I
T, - Tr-1
+l
imx;
-1
-l-+x,+l x, - x,
+l
-I
T, -T
+,
-I
2 Ax
(4.5)
a2T
aT I
ff
I
a..
vr`
..I i-1
L41%,
141
-
&2
7'w - T,
Il%71x-xl
AX
Ax
L1X
Ax
I.
(AX)
LIX
T, - T,
-I
T,+, - 2T, + T.
_,
(4.6)
(&)2
(4.7)
T3' - T'
T3' - 2T2' + T,'
aK2'
+
_K; 2
Ox2
aT
2Ox
(4.8)
ATZ
AZT2 AK
+
PCP
=K CYATZ
At
TZr+
TZ'
_
pc p
t'+' - t'
Here, the term (Ax) is the distancebetweenany two adjacentTcs. The superscriptsj
andj+1 representthe time instants at the beginning and at the end of the time step
83
involved. Since (p Cp) is assumedto be known, one may obtain EK/OT2 from
Meanwhile,
known
is
Ko),
initial
K,
(i.
if
we
or assumed.
e.,
value of
measurement an
have,at a given time t= tt.
(AK
ATZ
Thus
Kj+l - Kj
=
AT2
AK
(ATZ
K;
K; =
+
+l
(4.9)
K;
+
=
AK
(''_T2')
(4.10)
Step by step, the value of Kj+, can be derived from Eqn. (4.10) as a function of
temperature T2. By repeating such an evaluation loop at each time step, values of the
thermal conductivity of the mat at high temperature have been derived.
The advantageof this method is its simplicity. The incident heat flux can be of any
type, for example,constantor stepwise. The disadvantagesof this method are that:
(i) p and Cp haveto be known; (ii) the initial value of K hasto be known or assumed;
and (iii) accuracyis highly dependenton Ax (i. e., the smaller Ax is, the more accurate
the resultsare).
84
are shown schematically in Fig. 4.3. The sample (WR) sheets were kept inside a
Sindanyo frame of 11mm thick with a side-gap for the Tcs wires for the fire test using
the propane burner as a heating source. A steel plate of 1.0mm thick is put on top of
the fibre-mat to ensure that the thickness of the mat is kept fixed.
An insulation
material such as vermiculate is kept attached on the back face of the mat to ensure
that there are no gas flow effects inside the mat during a tests so that only the heat
conduction effect is to be considered. The Kaowool material was placed surrounding
the mat to ensure al -D case.
0.150 m
0.1; 5m
IKGlass
fibre-mat
0.10M
Steel plate of
1.0 mm thick
0.150m
1 I
Ka er
material
al
Sindanyo frame
Vermiculate
Figure 4.3 Specimen used for fire test (framed glass fibre mat and the front and
the rear covers).
D=0.1 19m
Surface
Themxocouple
fi
0,10
m
0050m
I
0 050 m to-010m
#2 #3
incident
--
Insulation
Steel
material
plate
x Ax
85
Three K-type thermocouples (i. e., Tcs1, Tcs2 and Tcs3) were placed inside the fibre
in
4.3,
indicated
Fig.
the
to
Sindanyo
mat
record
through
side-gaps
as
mat
temperature profile at 3 different depths of the mat as following: (i) one thermocouple
(Tcsi) is installed at the interface between the mat and the front steel plate; (ii)Two
thermocouples were fixed inside the sample, one (Tcs2) was placed between layers 5
11
fixed
between
layers
(Tcs3)
10
depth
0.002
6
the
at
was
and
m and
other
and at
depth 0.004m. Before assembly the mats were weighed to estimate the mass density
of the mat. The joint sample was held by the U-shaped channels.
(4.10)
forT<200C
(4.11)
(4.12)
where K, Kf and K0d denote the thermal conductivity of the particular composite
material, the thermal conductivity of glass fibre and the thermal conductivity of the
void respectively,whilst Vf, (1.0 - Vf) denotesthe fibre and void volume fractions
86
High
Temperatures
Fibre-Mats
Dry
Conductivity
Thermal
at
Chapter4 Measurementof
of
in
data
functions
the
Kf
K
temperature
adopted
Both
and
of
are
and
respectively.
Oid
in
for
this study numerical studiesare given the next section.
Table4.1 Set point temperatureat the evaluatedpoint
Test
No
Test No
Pr (bar)
0.1
225
0.2
450
0.2
498
10
0.3
580
0.3
600
11
0.4
654
0.4
652
12
0.5
705
0.5
701
13
0.6
740
0.6
738
14
0.7
773
0.7
777
15
0.8
790
0.8
792
Dimensions
0.033m
Mat thickness(D)
0.011m
0.01 in!
0.002m;
0.130 kg
0.138 kg
0.4
0.000108m
2560 kg.m
1.205kg/m
800kg/m
760 J/kg K
1006 J/kg K
760 J/kg K
0.0375 (W/m. K)
87
Temperatures
High
Fibre-Mats
Dry
Conductivity
Thermal
at
Chapter4 Measurementof
of
temperature, while the other lines (i. e. black, pink and blue) represent the mat
temperature results.
Using a transient method the typical derived values of thermal conductivity of the dry
fibre
high
from
600C)
(up
temperatures
to
the Ist fire test (i. e. Pr =
glass
mat at
0.3bar and q= 53 kW/m2) are shown in Fig. 4.6.
88
500
1000
2000
1500
Time (sec)
Figure 4.5 Measured temperature profiles through the dry fibre thickness,
(Pr = 0.3 bar).
1so
o.
U
k
0.120
e
>
0.080
v
c
O
U
E 0.040
0.000
0
100
300
200
Temperature
400
500
600
(C)
Figure 4.6 Derived values of thermal conductivity of the dry glass fibre mat
with initial value of K=0.0375W/m
89
Figure 4.7 shows the temperature recorded from the fire test (i. e., Pr = 0.5 bar and q=
82 kW/m2). Although the temperature has risen from 875C up to 975C as shown in
Fig. 4.7, the temperature profile shows the same pattern as in Fig. 4.5.
Again Fig. 4.8 shows the derived thermal conductivity of the dry fibre mat under test
from
700C.
The
high
bars
0.5
temperature
to
about
values vary
up
conditions of
at
700C.
22C
0.0145
0.038
temperature
to
temperature
at
about
of
up
about
at a
Also Figs. 4.9 and 4.10 show the stepwise temperature profile through the sample
thickness and the derived thermal conductivity.
consequently, the heat input values also changed. It can be seen from Fig. 4.10 that
the value of thermal conductivity increased almost linearly as the temperature
increased.
Figure 4.11 demonstrates a comparison between two the results obtained from
different tests typically with gas pressure of 0.3 bars and 0.7 bars. The figure shows
that the variation of thermal conductivities of both cases is almost similar. It can be
both
in
from
lines
is
Fig.
It
that
agreement
seen
are good
with each other.
quite clear
4.11 that the value of thermal conductivity is independent of the level of heat input.
1200
1000
.v-.
800
j600
E
400
500
1000
1500
2000
Time (sec)
Figure 4.7 Measured temperature profiles through sample thickness, (Pr = 0.5 bar)
90
0.160
ti
0.120
_/
0.080
qc
7_
0.040
0.000
0
400
200
800
600
Temperature (C)
Figure 4.8 The derived values of thermal conductivity of the dry glass fibre mat
K and Pr = 0.5 bar
1200
0.5
1000
0.6 bar
0.7 bar
HF
0.3
800
Tc2
600
Tc
400
200
0
0
500
1000
1500
2000
Time (sec)
91
0.200
t
0.160
e
0.120
000,
0.080
0.040
m
0.000
0
200
400
Temperature
600
800
1000
(C)
Figure 4.10 The derived values of thermal conductivity of the dry glass fibre
K=0.0375W/m
initial
mat with
value of
0.160T
Temperature (C)
Figure 4.11 The derived thermal conductivity. The light blue line refers to the
results obtained from the fire test at gas pressure of 0.4 bars and the brown
line represents the relevant results from gas pressure set at 0.7 bars.
92
0.160
c)
O8
0.120
0.080
0
U
0.040
Ko=O.0375
Kfio=0.025
Kto=O.05
0.000
200
400
Temperature
600
800
(C)
Figure 4.12 Derived values of K of the dry glass fibre mat from three different initial
value of K, (i. e., 0.025,0.0375 and 0.05W/m K), (Pr at 0.5 bar).
93
High
Temperatures
Fibre-Mats
Dry
Conductivity
Thermal
at
Measurement
Chapter4
of
of
Figure 4.14 show the change in mass density affects the result of the mat thermal
density
from
between
A
the
test
results
obtained
one
at
mat
comparison
conductivity.
(p) of 1300kg/m3 and the results from the secondtest at a density of 1388 kg/m3 are
in
Fig. 4.15.
together
plotted
As can be seenfrom Fig. 4.15, the changesin the thermal conductivity of the mat are
clear. The relative difference between the two curves at low temperatureor at the
start of the test was about 24%. However, as the temperaturethrough mat thickness
increasesat relatively high temperatures,the two curves decline and converge, and
the relative differencewas only 2% at temperaturesabout 600C.
It is worth noting that the mat density has a significant effect on the result of the
thermalconductivity of the dry fibre mat.
94
500
2000
1500
1000
Time (sec)
0.160
...
C)
ei
0.120
t; 0.080
V
c
0
0.040
Ld
F-
0.000
0
100
300
200
400
500
600
700
Temperature (C)
95
0,80
E
0 120
0080
i0
040 "
p=1300 kg/m3
I
0 000 0
_-
p-1388 kg/m3
t-
--- -.
200
400
600
800
Temperature ('C)
Figure 4 15 Derived values of thermal conductivity of the dry glass fibre mat from
two results at different mat density. The lower curve representsthe results
at p= 1300 kg/m3 and the upper curve representsthe results obtained at p=
1388 kg/m3 Both tests were derived at K=0.0375 and Pr = 0.5 bar).
4.5 Discussion
The values of the thermal conductivity
from
fibre
high
dry
temperature
the
mat
at
of
the transient method were compared with those values derived from the Rule of
Mixture and those obtained from the literature, as shown in Fig. 4.16.
It was found that in a temperature range between 0C up 300C the average thermal
conductivity measured by the transient method using the small-scale test was
approximately 10% less than values calculated from the Rule of Mixture and in the
range of 10-17% higher in temperature range between 400C and 800C. However,
by comparing the derived results with those from available published data, the
difference is less than 13% in the temperature range between NOT and 800C.
96
Temperatures
High
Mats
Fibre
Dry
Conductivity
Thermal
Measurement
at
Chapter 4
of
of
high
is
difference
from
Fig.
4.16
it
is
this
that
relatively
On the other hand,
quite clear
Mixtures.
Rule
from
the
of
applying
comparedwith theseresultsobtained
0.200
a, 0.160
E
O
0.120
C 0.080
(3
"a
0.040
x Urature
o Transit-fit-data
A Steady-state-fit-data
o Rule of mixture
0.000
0
400
200
600
800
1000
Temperature (C)
The thermal conductivity in the small-scale testing using the transient method was
found to vary approximately linearly with temperature.
Their experimental values can be described according to the following empirical
equations:
(4.13)
K= 0.0001290 T+0.03414
is
dry
fibre
T
K
the
the
the
thermal
of
mat,
and
value of
conductivity
where represents
local sample temperature (in C); and which has a correlation of r2 = 0.994 with the
transient test data.
The above equation is found to fit very well compared to the experimental values.
These values of thermal conductivity compared to those reported in the literature are
presented in Table 4.4.
97
Density
Specific heat
(p) kg/m3
(Cp) (KJ/kg. K)
(W/m. K)
1.293
1.006
0.024
10
1.247
1.006
0.025
20
1.205
1.006
0.025
30
1.165
1.006
0.026
60
1.060
1.008
0.028
100
0.946
1.011
0.032
200
0.746
1.025
0.039
300
0.616
1.045
0.045
500
0.456
1.093
0.056
1000
0.277
1.185
0.076
Literature-results
(Brian and Jason, 2004)
Transient-
Steady-state
method
method
Rule of
mixtures
0
50
100
200
300
400
500
600
700
800
0.024
0.032
0.041
0.058
0.075
0.092
0.109
0.126
0.144
0.161
0.034
0.041
0.047
0.060
0.073
0.086
0.099
0.112
0.124
0.137
0.021
0.030
0.039
0.058
0.076
0.094
0.113
0.131
0.150
0.168
0.042
0.047
0.051
0.059
0.068
0.076
0.085
0.094
0.102
0.111
98
4.6 Conclusion
"
function
dry
fibre
the
of
mat as a
glass
of
The derived thermal properties of the particular composite mat (dry glass
fibres + air) are in good agreement with relevant published data;
"
The results from this study indicate that, in general,the Rule of Mixture is not
sufficient to evaluatethe thermal conductivity of the particular fibre mat as a
`compositematerial' in the through-thicknessdirection at high temperatures;
"
99
CHAPTER 5
SMALL-SCALE FIRE TESTING
5.1 General Introduction
The design of structures against fire is important, demanding increasing attention as
fire risk and isolation of the structure increases, and their qualification
and
scale testing which includes furnace tests under specified temperature/time such as
the SOLAS curve (ISO 5660-1,1993), or the more severe Hydrocarbon fire curve
(SOLAS, 1974).
100
This chapter describes the main results from the two groups of fire tests and
discussionsof and conclusionsfrom the results are also presented.
-0.167
,
-2.5
60- 0.675.e
60 + To
(5.1)
101
Copper disc
face).
(i.
free
the
the
thermocouples were used on
e., cold
panel
side of
The
thermocouples were bonded on with epoxy resin. The output of each thermocouple
logging
data
the
test
throughout
system of
runs using a
was observed and recorded
the `Pico' type.
It must remembered that this is very small scale testing compared to standard fire
tests conducted under BS 476 and IMO (International Maritime Organization)
requirements, and is intended to offer quicker and cheaper initial screening tests.
The furnace reaches a temperature of 1100C in approximately 25 minutes, which is
very close to the hydrocarbon curve, which reaches a temperature of 1100C in
approximately twenty minutes. This is a preliminary investigation which aims to
show how such a furnace can simply, quickly and cheaply be used to give an
indication of the insulating and fire resistance abilities of GRP panels.
Another group of laminate samples, each approximately 8mm thick, was also
preparedby DML for investigation as possible protection materials. The materials
used and the type of laminated panels used in the fire tests are specified in Tables
5.1 and 5.2, respectively.
102
Chimney
Damper
Electroserv
Test panel
controller
*1
Gas inlet to
burner
1200
1000
...
C)
0
600
E
m
1
400
Hydrocarbon-curve
SOLAS-curve
200
Furnace Temp.
I
05
10
15
20
25
-r-
30
35
Time (min)
103
Catalyst
Resin
Reinforcementused
Conc. (%)
Isophthalicpolyester
Styrene(25-50) Butanox
Type:MSO
Orthophthalic
Styrene(25-50)
Butanox
Type: MSO
polyester
Vinyl ester
Styrene(25-50) ---------
Table 5.2 Type of laminated panels and their volume fraction details.
Thick. (mm)
Laminate Specification
Vf%
Vv %
10.86
46
3.6
10.50
47
3.9
10.21
45
2.8
10.09
46
2.3
Vinyl ester
10.71
45
2.9
GRP/ H polyester(unidirectional)
10.28
50
4.8
Phenolic
8.15
55
7.2
9.73
49
4.1
10.33
48
3.4
10.51
43
3.1
9.87
44
2.1
10.63
49
2.6
12.86
43
104
105
different
based
matrix
for
10mm
on
panel
thick
Typical results
roving
woven
glass
a
figures
The
temperature
the
5.5.
profile
in
5.4
Figs
represent
and
systems are shown
furnace
The
upper curve represents
through the composite panels against time.
face,
hot
the
lower
the
mid-plane and
three
the
represent
curves
temperature, while
the cold side (i. e., free side) temperature response through the composite panel
5.5
from
Figs.
5.4
be
temperature
that
the
It
rise recorded
and
seen
can
respectively.
linearly
increase
the
throughout
face
the
almost
of
panel shows a stable
at the cold
fire tests.
The output from the inter-laminar thermocouple tends to level out to a steady state
face
to
later
in
the
temperature
test,
rise.
the
continues
the
cold
whilst
stages
of
value
In the later stages of the tests the inter-laminar temperature outputs are more
is
depleted.
layers
due
the
the
to
resin
reinforcement
as
separation of
uncertain
There is useful information to be gained by continuing the test for as long as
follow
be
in
to
to
able
order
possible
face
however,
dictated
test
to
terminate
the
the
at cold
need
considerations,
temperatures a little in excess of 200C.
Figures 5.6 and 5.7 shows typical results for compositepanelslaminatedwith some
foil
(ATH)
trihydrate
and aluminum
additive product, such as aluminum
respectively
Figure 5.8 shows a plot of temperature profile responses for different types of
laminates for comparison.
terms of temperature response; however, some show better fire resistance. This is
laminated
those
with additive products such as ATH.
most obvious with
106
1200
1000
,v-.
800
600
400
200
300
600
900
1200
1500
Time (sec. )
107
300
600
900
1200
1500
Time (sec)
Figure 5.5 Experimental furnace fire test results for vinyl ester/glass
woven roving laminated panel (Vf = 49%).
300
600
900
1200
1500
Time (sec. )
108
1200
1000
400
200
300
1500
1200
900
600
Time (sec. )
Figure 5.7 Experimental furnace fire test results for orthophthalic polyester/glass
WR laminated panel with 2 layers of aluminium foil (Vf= 51%).
1200
1000
-(
800
lso-polyester
Orth-Fbyester
600
Furnace terTp.
400
200
0
0
600
300
900
1200
1500
Time (sec)
Figure 5.8 Experimental hydrocarbon curve furnace fire tests results of E-glass WR
panels for different types of laminate, (i. e. orthophthalic polyester resin,
orthophthalic
polyester with
%ATH,
orthophthalic
109
polyester with
110
Two welded tip glass fibre insulatedthermocouplesof type K were installed before
fire testing on eachof the five samplesto measurethe temperaturesof the samples:
layers
(INT),
interface
CFRP/protection
the
the
the
cold
the
other
on
and
of
one at
face (CF).
Before fire testing in each case, a thermocouple (INT) was inserted into position
through a hole of 6mm depth vertical to the back face of the CFRP layer.
One type N mineral insulated thermocouple was positioned inside the small furnace
10mm away from the front face of the samples to measure the furnace temperature.
During fire testing the measured furnace temperature was fed back to a PC and
compared to the standard SOLAS curve, for the control of furnace conditions by
varying the gas flow to the furnace main burner. A computer program was written
using Lab View for this purpose.
The small furnace used is a standard gas heated oven modified to meet the
requirementsof the specified fire testing and was fuelled by the main natural gas
supply.
Originally, the refractory lined door frame of the furnace allowed test panels of
dimensions300mm x 170mm to be clamped securely into place and exposedto the
requiredtemperature/timecurve. The door frame was then modified to keep a steel
frame of dimensions 160 x 160 mm in place, with the opening dimensions being
130mm x 130mm. A panel sampleof dimensions 150mm x 150mm could be then
tightly inserted into the steel frame for fire testing by insulating a thick layer of
Kaowool material aroundthe four sidesof the panel to be tested.
111
The A60 requirements for fire-resisting structural divisions under the Provisions of
the 1974 SOLAS Convention state that "they should have thermal properties such
that the average temperature on the unexposed side will not rise more than 139C
above the original temperature, nor will the temperature at any one point, including
any point, rise more than 180C above the original temperature during the
appropriate fire protection time",
is
t
where the time (in: minutes) and Tois the ambienttemperature(in: C).
112
(5.2)
113
A lot of strong explosive cracking noises were heard during the fire testing.
Material expansion in the through-thickness direction of the sample was also
observed. A simple holding support was applied to keep the specimen in place.
160
191
38.0
180
217
40.9
190
230
44.1
200
243
30
29
32
40
37
44
50
53
67
60
70
86
27
28
40
34
38
50
45
50
60
58
67
91
100
40
110
123
50
136
146
60
159
170
114
Furnace Temp.
SOLAS
CF1
Half thick
10
20
30
50
40
Time (min. )
Figure 5.10 Measured temperature profiles of panel #1 for the first 45 minutes
1200
1000
800
Furnace
Soles
600
INTTemp.
400
CF Temp.
200
-
20
40
60
80
Time (min. )
115
1000
800
600
Furnace
Solas
INT
400
CF Temp.
200
40
20
80
60
Time (min)
Figure 5.12 Measured temperature profiles of specimen #4 for the first 63 minutes
1000
800
Furnace
600
Solas
INT Temp.
400
CF Temp.
200
10
20
30
40
50
60
Time (min. )
Figure 5.13 Measured temperature profiles of specimen #5 for the first 63 minutes
116
Performance
Thermal
the
of
5.4 Qualification of
Composite Fire Protection Laminates
5.4.1 Introduction
This section describes the work carried out on the development and qualification of
(VT).
Plc
Group
to
by
Thorneycroft
Vosper
developed
laminate
system
a composite
Ltd
(UK)
VT
for
transportation.
in
fire
be used
chemical
protection on vessels used
has a track record in composite fire protection systems for use in the offshore and
developments
include
Successful
industries.
composite encapsulation
recent
other
for
legs
for
pressurised risers
the
and
of
platform
spray zone protection
systems
(Gibson, 2000).
117
The laminate thickness was limited to 7mm, which is much thinner than most
previously used fire protection laminates. The testing programme developedwas
therefore aimed at representingwhether the required levels of fire protection and
integrity during fire could be achieved.
For design purposes and according to the IAEA standard fire test
conditions, the
possible heat flux into an unprotected vessel in a pool fire would be calculated from
the following relationship (IAEA Standard fire test conditions):
9-
aEFire
Wire
TCyl;
ECylinder TFire
-
nder)
(TFire
+ heydnder
TCylinder
(5.3)
where:
q=
a=
EFire
Ecyr;
nder =
hcylinder
TFire
= fire temperature
118
In numericalterms,therefore:
(TF;
q=4.0824 x 10-8x
re
Tcylinder
)+ 10(T
Fire-
TCylinder)
(5.4)
Equation (5.3) can be seen to contain terms representingboth the radiation and
dominates.
however,
the
term
radiation
convective components;
Although pool fires vary in intensity according to weather and other conditions, a
fire temperature of 800C (1,073K) was assumed. It is also assumed that the
flux
is
heat
lower
38C.
The
the
than
temperature
of
exposure
at
start
no
cylinder
2,
into an unprotected cylinder under these conditions from Eqn. (5.4), is 6lkWm
heat
transfer coefficient, therefore, is 81W m2 K''.
the
and
corresponding
To
qualify as fire protection laminate, therefore, the overall heat flux and the heat
transfer coefficient into the vessel should be no higher than 50% of these values
during a 30 minute exposure to a fire at least as severe as this (i. e. a pool fire).
sox=0.375.
The target values of heat flux and heat transfer coefficient to qualify the protection
laminate are therefore 0.375 of the values mentioned above, (i. e. 22.9kWm2 and
30.4Wm2 K", respectively). For the protection laminate to qualify, these values
should not be exceededat any point during a 30 minute fire test. This standardwas
further refined by specifying that the HTC, averagedover any 1 minute period,
shouldnot be exceededduring the test.
119
The front face temperatureof the samplewas measuredduring the test with a k-type
thermocouple. During the earlier measurementsthe gas supply was adjustedduring
each run to keep the front face thermocouple reading a steady value. Later on,
however, the gas supply was fixed and not adjusted during the test. In
order to
examinethe effect of varying the hot face temperature,one run was carried out at a
120
lower hot face temperature (average 788C) and one at a higher temperature
(average 1000C).
A burner-to-sample distance of 350 mm was used throughout the tests. The fuel
hot
face
For
desired
the
temperature.
the
of
to
most
maintain
supply was adjusted
below
just
face
hot
temperature
the
was maintained at a value
steady state
runs
below 1000C.
2
A net heat flux of 85kWm was measured for a front face
temperature of 1000C.
The test duration was 30 minutes, during
which
thermocouples were recorded, along with the front face temperature, at 5 second
intervals. There was very little difference between the three copper block sensor
temperatures, indicating that the heat flux between the exposed part of the sample
and the block was uniform. These three temperatures were therefore averaged when
calculating the test results. Experimental scatter was reduced by applying a 5-point
formula
to the averaged temperatures.
mean smoothing
5.4.4 Materials
The laminates tested were all supplied by Vosper Thornycroft.
150mm square by approximately 7mm thick.
They measured
121
Holder
Figure 5.14 Experimental rig used to determine the heat flow into the copper
block via the laminate, for a particular hot face temperature.
122
1=
where
p=
IpC
AT
+
Ot
gLoss
AT
At
hLoss
(T
)
To
-
(5.5)
block
thickness
sink or
density
block)
(cooper
sink
Cp
block
heat
of
= specific
T, AT
increment
temperature,
= sink material
At
increment;
time
=
To
qLoss
dT
(T TO)
=1 PC n dt --hLoss -
(5.6)
f dt
1P C
dT
IT-To
hLoss
J=rR
where TRis the heat sink temperatureat a referencetime, tR. Integrating this gives
123
IpCp
t-tR
It
TR-To
becomes
on
re-arranging,
which,
T- To
TR-To
h,
=-e
(L-fR)
SO
IpCp
C
T= To+ (TR- To)exp IhPp
(t
)
tR
-
(5.7)
Figure 5.15 showsthe fitted prediction of Eqn. (5.7), from the cooling curve. This
fit was achievedby pinning the curve to the experimentalvalue at a referencetime
value of 100 minutes. The fit was achievedwith a heat transfer coefficient of 10.98
W/m2C. Subsequently,the value obtained for the heat transfer loss was then used
in the correction term of Eqn. (5.5) for derived the net heat flux from the sample
into
the copperblock meter (i. e.. the secondterm).
underquestion
400
300
200
d
a
I.100
100
200
300
400
Time (min)
124
for
fire
h,
calculated
heat
was
`apparent'
protection
transfer
An
coefficient,
overall
from the net heat flux value into the copperblock, using the relationship
q
(5.8)
T, -T
face
is
T
face
temperature.
hot
is
the
T1
temperature,
cold
the
and
measured
where
This was plotted as a function of time along with the other test results in the
figures.
PowerPoint
Excel
spreadsheetand
accompanying
In addition, an average heat transfer coefficient for the 30 minute test was calculated
by using the average hot and cold face temperatures in Eqn. (5.8).
It was agreed that, for design and qualification purposes,the maximum apparent
heat transfer coefficient, rather than the average, would be used. This value,
2C''.
Wm
30.4
averagedover a period of 1 minute, should not exceeda value of
125
lower
has
laminate
By
in
the
160C
a much
the calibration tests.
contrast,
conductivity andwill reachhigher temperatures.
This effect was counted in test runs 12-17. For these runs the propane flame was
heat
hot
face
800C
the
temperature
copper
of
using
adjusted to give a measured
flux block. The same gas setting was then maintained, without adjustment, in a heat
flux test on a laminate specimen.
temperature in the test could exceed the initial 800C value by up to 100C. It was
therefore concluded that most of the difference between the heat flux vs. hot face
temperature curves, and the IAEA Pool fire equation in Fig. 5.17 could be accounted
for by this effect. The key factor on which the qualification relies is that the propane
burner rig should give a heat flux intensity which is at least as great as that in the
IAEA Pool fire. It was therefore decided that, for final qualification purposes, the
be
12-17
results of runs
would
used.
1200
1000
5r 800
..,
Y
CM
600
mw
400
Z
w
0
'
200
0
0
10
15
20
Time (min)
Figure 5.16 Results of the heat flux calibration on the copper block meter,
showing the hot face temperature (upper curve), the block
temperature(pink) and the calculatedheat flux (red).
126
180
160
140
E
120
100
=
80
60
40
700
900
800
1000
1100
Figure 5.17 Heat flux data plotted against hot face temperatureduring the copper
block calibration test (squares). The predictions of the IAEA pool fire
for
block
(Eqn.
5.2),
(upper
38C
temperatures
model
of
curve) and
160C(lower curve) havebeenaddedfor comparison.
127
128
leaving a residue of clean glass. The conditions of Fig. 5.22, however, were above
the design temperature.
Details
Max. HF
Max.
Temp.C
Details
C'n
Max. HF
Max.
Temp. C
kWm-2
kWm'2
Q-1
Laminate
980
22.5
Q-9
Laminate
791
18.2
Q-2
Laminate
944
27.0
Q-10
Lam. w. mesh,
795
14.1
871
17.6
883
17.8
868
19.0
852
19.9
852
19.9
852
15.8
833
20.3
Laminate
966
35
Q-12
Laminate w.
w. mesh
Q-4
Laminate
mesh
966
35.2
Q-13
Laminatewith
w. mesh
Q-5
Laminate
mesh
958
32.5
Q-14
Laminatew.
mesh
Q-6
Laminate
980
33.9
Q-15
Laminate/mesh
w. mesh
Q-7
Laminate
no gel coat
960
28.2
Q-15
Laminate/mesh
no gel coat
Q-8
Laminate
802
18.7
Q-16
Laminate/mesh
w. mesh
no gel coat
Q-17
Laminate/mesh
no gel coat
Table 5.5 Qualification valuesof heat transfer coefficient.
Sample
Details
Q-12
Laminatew. mesh
23.1
Q-13
Laminatew. mesh
23.4
Q-14
Laminatew. .mesh
24.9
Q-15
Laminate/meshno gelcoat
26.1
Q-16
Laminate/meshno gelcoat
20.7
Q-17
Laminate/meshno gelcoat
26.6
129
1000
--
800
600
400
200
0
0
30
20
10
Time (min)
(a)
U
40
cr
30
E
20
10
20
10
30
Time (min)
(b)
Figure 5.18 Results of the test on laminate, Q-5, nominal hot face temperature
950C. The upper curves show hot face and block temperaturevs. time. The lower
figure shows the heat flux (lower curve) and apparent heat transfer coefficient
(upper curve) vs. time. The HTC was calculatedassuminga temperaturedifference
of 762C.
130
1000
800
600
400
200
20
10
30
Time (min)
(a)
50
v
40
3
= 30
3 20
Y
x
qV 10
0
0
20
10
30
Time min
(b)
Figure 5.19 Results of the test on laminate with mesh, Q-4, nominal hot face
temperature950C. The upper curvesshow hot face and block temperaturevs. time.
The lower figure shows the heat flux (lower curve) and apparent heat transfer
coefficient (upper curve) vs. time. The HTC was calculatedassuminga temperature
differenceof 762C.
131
30
3
v 20
F
M
3
o
LL.
30
20
10
Time (min)
(a)
1000
8
a
800
600
400
200
x
F
0
0
10
20
30
Time (min)
(b)
Figure 5.20 Results of the test on laminate with mesh, Q-8, nominal hot face
temperature800C. Upper curves show hot face and block temperaturevs. time.
The lower figure shows the heat flux (lower curve) and apparent heat transfer
The
HTC was calculatedassuminga temperature
(upper
time.
coefficient
curve) vs.
differenceof 762C.
132
1000
800
600
400
200
20
10
30
Time (min)
(a)
Time (min)
(b) laminate
Q-17. For testsQ-12 to Q-17, the gaswas adjustedto achievea hot face temperature
flux
heat
in
block.
The
test
the
800C
thermocouple
contactwith
copper
of
with the
hot
The
the
then
gas setting.
carried out without changing
was
upper curve shows
face temperaturevs. time (which rises significantly above 800C. The lower figure
flux
heat
(lower curve) vs. time. The HTC was
(upper
HTC
the
the
shows
curve) and
difference
temperature
of 762 C.
calculatedassuminga
133
laminate
face
(lower
(upper
a
photo)
of
photo) and rear
Figure 5.22 Front
testing.
after
sample
134
following
for
the
It should be noted that the results are regarded as conservative
reasons:
been
has
laminate
assumed
flux
heat
the
through
protection
The maximum test
been
this
it
has
that
However,
quantity
observed
test.
the
throughout
to apply
"
the
HTC
flux
heat
the
over
The
calculated
and
average
rises throughout the test.
full test period would be only about 75% of the maximum value.
been
has
the
assumed,
between
Good contact
the protection and
vessel wall
This
the
fact
surface.
poor contact or no contact will apply over most of
when in
by
25%
been
has
flux
heat
or more.
the
overestimated
could mean that
"
"
be
the
fact
in
upper
of
some
there
space
over
vapour
or
a
gas
probably
will
when
into
for
heat
the
is
This
transfer
vessel.
the
case
worst
surface.
"
The main factor limiting the speed and accuracy of the experimental procedure
block
be
temperature, equal to the specimen
the
to
achievement of a steady
appeared
large
block
insulated
Because
of
temperature, at the start of each experiment.
a well
for
hours
12
it
found
the
that
was
needed
of
more
a period
or
mass was chosen, was
block cool to reach ambient temperature after each run.
5.5 Conclusion
The form of the cold face responseof sampleswas preparedand manufacturedby
hand lay-up using WR glassreinforcementsbasedon different types of resin such as
orthophthalicand isophthalic polyesters. Vinyl estersresins are similar with slightly
differenceresponsesfrom thoselaminatedwith aluminum foil which provide a delay
in the transmissionof heat into the zone or componentprotectedby the laminate.
Despite the loss of most of the resin, the material close to the cold face remains
laminate
The
the
structurally
sound.
undamagedand
showed good
panel remains
integrity of the front face material, and only a very small amount of glass fibre was
135
level
indicating
black,
becomes
face
a certain
lost. Also the rear
was undamagedand
formation.
of char
The fire resistanceperformance of the five composite samples tested as a part of the
DML development of fire protection according to the standard `SOLAS' timefive
by
fire
be
indicated
A60
the
two
that
temperature curve,
of
rating can
well met
samples.
foam
E-glass/phenolic
5mm
35mm
the
phenolic
syntactic
with
and
glass/epoxy skin
skin specimens can meet A60 requirements.
layer
On
be
largely
Rockwool
the
the
the
thickness
of
might
reduced.
requirements,
other hand, the experimental results show that the 20mm E-glass WR/epoxy meets
A30 requirement only, whilst the 4mm Technofire 60853 intumescent/epoxy failed
to meet the requirements.
136
CHAPTER 6
When composite components are exposed to fire, their polymeric matrix materials
high
decomposition
temperatures. To predict the thermal response
may undergo
at
behaviour of composites in fire, the kinetic parameters of pyrolysis reactions are
required for the analysis. These include: (1) a rate factor, A (in 1/sec. or 1/hour); (2)
the order of the pyrolysis reaction, n, (non-dimensional); (3) the activation energy of
the polymeric material in decomposition, E, (in: J/mole) and (4) the nondimensional ratio of final mass, mf over initial
decomposition process, (mlmo).
FORTRAN) has been developed at Newcastle University for the prediction of the
fire resistanceof composite laminates in fires (Gibson et. al., 1994). To run the
code,the kinetic parametersof the relevant resin systemof composite materials are
requiredas a part of the input.
The kinetic parameterscan be calculatedfrom thermogravimetric data obtainedfrom
TGA tests of the sample materials under air or under nitrogen. The mass change
rate of polymeric materials in decomposition is given by an nth order Arrhenius
equationof the following form (Friedman, 1965):
(-1/mo ) (am/at)
(MIM")
f
=A e-EIeT
(6.1)
137
for
derived
The
group
based
a
technique.
data
this
for
results
the
on
processing
used
further
for
GRP
use.
compositesare presented
of polymeric materialsor
The method and the modified technique adopted in this study are described as
follows. In general,the Arrhenius equation (i. e. Eqn. (6.2)) is used to describethe
pyrolysis reactionof a polymeric material at high temperatures:
[m_mf]
dm
exp
mo
-A
dt
-(EIRT)
(6.2)
where;m, moand mf (in: mg) are the instant massof the sample,the original massof
the sampleand final mass of the sample at the end of decomposition respectively;
and t (in: s) and T (in: K) are the time and temperaturevariablesrespectively.
Or, in a more generalform:
ca-W
dt
-(EIRT)
[w-wf
]n
exp
=-A
(6.3)
Ow=
log log (A) +n log [w-
at
138
w1
J-E
RT
loge
(6.4)
T2 where
decomposition takes place, and hence (- w/t) > 0. For any temperature outside
the decomposition region (&/t)
= 0.
Alog
=nAlog[w-wf]-2.302E
RA T
(6.5)
A log 0log
ET
at
01
n2.302R 0log
w-wf
(6.6)
w-wf
A log -W
Y=
at
0 log w- wf
),
and x=
)
0(1/T
01og w- wf
(6.7)
y-n-2.302Rx
Basedon Eqn. (6.7), one may derive the kinetic parameters(n
and E).
Having derived the two values n and E, the rate factor A
139
The specificationdata-sheetsfor all resins are presentedin Table 6.1. The Thermobalance Stanton Redcroft Model (STA 780 Series equipment, Chemistry
Department, Newcastle University) as shown in Fig. 6.1, was used to measure
its
STA
780
in
The
the
systemare ease
major advantagesof
changes sampleweight.
investigation,
loss
in
In
this
sample weight was
of operation and speed of use.
function
furnace
time,
temperature was
temperature
and
while
of
as
a
recorded
25C/min
60C/min.
increased
fixed
and
at
of
rates
continuously
In all cases,the thermogravimetric data refer to approximately 100 milligrams of
in
Coors
(000)
glazed porcelain crucibles and
representativeresin material placed
heated at a rate of 25C/min or 60C/min after tarring the balance in a flow of
50cm3/minin an atmosphereof dry nitrogen. The mass of resin was recordedfrom
ambient temperature, under the same flowing gas conditions, to the desired
maximum heating temperature. The loss in mass was recorded as a function of
temperature and time using Pico-log software, while furnace temperature was
continuouslyincreasedat the desiredfixed rate (i. e. 25C/min or 60C/min).
The total duration of such a test is about 20 minutes, but approximately 5 further
minutesare requiredto cool the furnaceand clean the crucible.
140
Table 6.1. Specification data sheet for all resin systems used in TGA tests.
Type of sample (glass-free)
Type of Matrix System
Series no.
Supplier
Isophthalic polyester
420-100
NORPOL (V-TC)
Orthophthalic polyester
440-M750
NORPOL (V-TC)
Vinyl ester
9100-700
NORPOL (V-TC)
Type of fibre-glass
Supplier
Phenolic
Unidirectional F 4010
FIBRELINE
Halogenated polyester
FIBRELINE
141
involves two steps. The first step is to derive mass change rate as function of
temperature, so that the main decomposition region of concern in terms of
temperature can be properly defined. The second step is to get all four parameters,
having input the defined decomposition region. For a resin system like phenolic,
two separated phases of the chemical reaction may be involved.
To derive the
kinetic parameters for both phases,the second step of the program must be run twice
basedon the defined decomposition region.
Figure 6.2 shows a plot of the TGA data of the sample materials (i. e. isophthalic and
orthophthalic polyester, vinyl ester, phenolic and halogenated polyester resin) cured
according to the manufacture's specifications, where mass is given in a nondimensional mode (i. e. iv = (m/m,,) as a function of temperature. The tests were
carried out at nominal heating rates of 25C/min and 60C/min in nitrogen.
The initial weight loss curve presentedin Fig. 6.2 was due to water (% moisture),
and the reactionwas initiated at a temperatureapproximately at 230C/min., and was
from
320 to 480C. To define the decomposition region more
relatively rapid
from
the TGA data, the mass change rate of some resin systems, (-dw/dt)
clearly
were calculatedas a function of temperature. Apart from the phenolic system,it is
quite clear that the major decompositionregion takes place betweenTl - 300C and
T2 =- 480C, and, in most cases, the rate of decomposition passes through a
maximum at 430C after which it decreasesrapidly. After this point only slight
change occurred and the decomposition was substantially complete when the
temperaturehad risen above 600C (for most resin systems). The weight loss which
142
in
is
burnt
the
off
is
as
carbon
to
the
carbon content,
equal
occurs after that
oxygenated atmosphere.
T2
300C
T1=
between
decomposition
=
the
and
Within the major
resin
region of
It
6.3.
in
Fig.
data
from
TGA
Y
X
the
480C, the calculated values of and
are shown
is
between
figure
from
be
the
not
that
y
the
x and
actual relationship
seen
can
linear.
but
only approximately,
exactly,
The rates of change in sample weight of the phenolic resin as a function of
temperature under nitrogen shows markedly different decomposition behaviour. The
in
decomposes
two stages over a wider temperature range than other
phenolic resin
first
The
ester.
and
vinyl
stage of the reaction mainly
systems such as polyester
interval
150
370C,
to
the
temperature
of
while the second stage of the
occurs over
The
690C.
440C
to
the
temperature
range of approximately
reaction occurs over
maximum decomposition in this stage of the reaction occurred at temperatures above
555C. After that, constant decomposition was observed and the reaction was
finished
completely
when the temperature reached about 1200C.
Based on the four kinetic parametersderived, the mass change rate of the resin
samplecan be calculatedas a function of temperaturefrom Eqn. (6.3):
iv=[
---
9,v
1/n
eE/RT)
+W
et
(6.8)
The simulated TGA curve based on the Arrhenius equation is shown in Fig. 6.4
togetherwith the original TGA curve for comparison. The discrepancybetweenthe
two curvesis attributed mainly to varying heating ratesduring the courseof TGA.
Figure 6.5 shows the heating rate derived from the TGA data. It can be seenfrom
Fig. 6.5 that in the decompositionregion 300C-480C,the heating rate was not kept
constantand was generally higher than the nominal value of 25C/min.
The kinetic parametersof the resinsas derived are presentedin Table 6.2.
143
From the intercept and slope of the line, the order of reaction for each systemwas
obtained,and the correspondingorders of reaction and energiesof activation were
determinedfrom the interceptsand slopesof the lines.
E (J/mol)
A (1/sec)
mf/mo
IsophthalicPE resin
0.288E+06
0.539 E+24
0.040
1.7
0.222E+06
0.118 E+11
0.644
1.1
0.104 E+06
0.79 E+08
0.533
0.111 E+06
0.579 E+09
0.791
OrthophthalicPE resin
1.8
0.144 E+06
0.989 E+13
0.041
Vinyl-ester resin
3.5
0.197 E+06
0.518 E+14
0.038
stageI
12
0.613 E+05
0.129 E+08
0.415
stageII
3.1
0.134 E+06
0.739 E+26
0.776
0.431 E+06
0.662 E+38
0.080
Phenolicresin
Epoxy resin
144
1.2 ,
1.2
25C/mn
a
0.8
60*
25Gmn
60Gmn
0.8
E 0.6
0
E 0.6
0.4
0.4
d 0.2
0.2
0
400
200
Temperature
600
(C)
800
400
200
Temperature
800
600
(C)
(ii)
(1)
1.1
N
ql
O
T
25CJmn
In
R
0.9
0.8
60C/nin
E
>
0.7
oc
0.20
0.6
200
400
Temperature
b
to
0
600
(C)
(iii)
(iv)
1.2
250Chin
0.8
0.9
in
E 0.6
E 0.8
O
>
60C/min
> 0.4
R
600
800
(C)
25C/min
60C/min
I
p
R 0.7
d
0.2
400
200
Temperature
800
0.6
200
400
600
800
200
400
600
Temperature (C)
Temperature (C)
(v)
(vi)
Figure 6.2 The Original TGA Data of the resin systemsof (i) Isophthalic polyester,
(ii) Orthophthalic polyester (iii) Vinyl ester resin, (iv) Phenolic (Vf= 36% iv),
(v) Halogenated polyester/CSM E-glass and (vi) Halogenated polyester
Unidirectional E-glass (P4506 lamina Vf= 49%).
145
2.0E+01
O.0E+00
-2.0E+01
-1.0E+01
(i)
-6.0E+01
0.0E+00 1.0503 2.0503 3.0&03 4.OE-03 5.0503
x
2.0E+01
0.0E+00
-2.0E+01
:" -4.0E+01
-6.0E+01
-8.0E+01
(1i)
-1.0E+02
0.0E+00
2.0E-03
4.0E-03
8.0&03
6.0E-03
(iii)
1
-6.0E-+Ol
0.0E+00 5.OB.04
1.0&03
1.51103 2.0E-03
2.5E03
146
0.8
0 (i
i
ii4
U.2
0
O
100
200
3(X)
400
500
600
700
TemperatureC
Figure 6.4 The original and derived mass-loss curves of the polyester resin.
The red line represents the experimental data and the yellow
line is the derived data.
40
3O
E
3
0
20
1 10}
0
0
200
400
600
TemperatureC
147
To calculate the composite specific gravity, the mass of the sample was measured
both in the air and in a liquid of known density, typically water. It must be noted
here that the void content values calculatedmay be subject to large error. This was
fact
immersed
in the water were open ended,so that
by
that
the
the
samples
caused
into
ingress
open voids. It was expectedthat this was likely to lead to a
water would
large error, particularly in poorly impregnatedsamples. The test routine as such is
liquid
between
is able to go through and those
distinguish
the
to
unable
voids which
which it is not. From the recordedvalues of the mass of the sample in the air and
the mass of the sample in water, the specific gravity for the sample may be
calculated:
Pc (meas) _m
-m
Si
ms2
sl
* ptivater
(6.9)
where pC, p,Vare the density of the sample measuredand density of water being
equal to 1000 g/cm3,respectively; and msi and mS2are the mass of sampleweighed
in air and the mass of sample weighed in water, respectively. The value of Eqn.
(6.9) is then correctedfor the density of the liquid at the test temperature(for water
at 25C multiplied by 0.9975). The ratio of the glass matrix in the samplemust also
be measured;this was carried out on the samesampleused for the measurementof
the specific gravity. The sample is weighed and then burned-off at 550C for five
148
Modelling
for
Preparation
6
Data
Chapter
leading
the
to
mass
is
then
recorded,
hours. The weight of the glasswhich remains
fraction of the polymer and glassin the sample.
the
known
respective
densities
fibre
constant,
and
were
Assuming matrix and
determined
be
V,
Vjand
using:
fraction
also
can
the
matrix
glass
of
volume
V_
mf *Pc(measured )
ntJ. P f_
/p
ms
(100,,,/)
(6.10)
ms * Pf
c (measured )
Thus the volume fraction of the matrix can also be calculated by:
(6.11)
Vw =(1-V1)
The theoreticaldensity (for a material with zero void content) can be calculated for
the samplecompositeusing the rule of mixtures:
)
(1000
)]
V
[(Vf
+
gcm-3
p,
pf
Pc cJhe.
(6.12)
The void content (Vv) can be measuredby the difference between the theoretical
densities:
and measured
Vv-
Pc(theor.)
Pc(meas.)
100 %
(6.13)
Pc(theor.)
The meanvalue was then calculatedfor the five samplesfor eachtest conducted.
The density, fibre volume fraction and void content of the composite panels are
for
in
6.3
Table
be
in
Table
6.3.
It
that
the
results
clearly observed
can
shown
volume fraction varied between36% and 54%. The highest value of void content
was exhibited by the phenolic system. This is probably related to the nature of this
resin, which has a high void content due to condensedwater formed during the
forms
in
forms
is
This
the
trapped
the
water
resin.
reactionprocesswhich
resin and
micro-voids after resin curing.
149
V, %
10.7
44
thickness(mm)
Code
I
Vf%
Sample
SampleType
GRP/orthophthalic polyester +4
GRP/orthophthalicpolyester+3
layersfrom aluminium foil
9.62
37
2.1
GRP/orthophthalicpolyester+2
10
54
1.6
GRP/orthophthalic polyester)
10
GRP/isophthalicpolyester
10.8
GRPNinyl ester
10.1
HalohenatedGRP/polyester
9.98
GRP/Phenolic
8.5
GRF/orthophthalicpolyester+
9.73
41
1.6
10.33
42
1.1
1.8
44
1.4
2.3
46
2.9
5
GRF/orthophthalicpolyester+
TXCV7050 1 layer
GRF/orthophthalicpolyester+
TXCV7129 1 layer
10.51
46
GRF/orthophthalicpolyester+
9.87
38
2.6
GRF/orthophthalicpolyester+
TXCV7161 Superwoodsteelwire
reinforced 607 max fabric 1 layer
150
9.96
2.2
Modelling
for
Preparation
Data
6
Chapter
6.5 Conclusion
of
kinetic
the
systems
resin
relevant
of
COM_FIRE
the
parameters
To run the
code,
kinetic
input.
These
parameters
the
of
a
part
as
required
are
composite materials
TGA
by
tests.
out
carried
were obtained
kinetics
the
to
of the thermal
The Freeman technique was applied
calculate
decomposition of the polyester, vinyl
is
60
C/min.
in
loss
form
found
It has been
curve nitrogen at
that the
of the weight
is
initiated
but
25C/min.,
the
at
and
completed
reaction
that
to
of
at
a
rate
similar
for
begins
decomposition
NOT
The
the
higher
of
most
at
temperature.
slightly
kinetics
500C
The
is
the
in
of
approximately.
at
complete
samples question and
Freeman
Carroll.
by
the
of
and
method
reactionwere evaluated
The apparentactivation energiesof isophthalic polyester, orthophthalic polyester,
be
0.288E+06,0.144E+06,0.197E+06
to
and
vinyl ester,and epoxy were estimated
0.431E+06(J/mol) respectively. However, phenolic resin has two stageof reaction,
for
first
for
E=0.134E+06
E=0.613E+05
it
found
the
the
that
stage
and
and vas
secondstage.
The density, fibre volume fraction and void content of the composite panels were
determinedaccordingto the testing method describedearlier in this chapter. It was
fraction
from
for
the tests varied between 36% and
that
the
volume
observed
results
54%. The highestvalue of void contentwas exhibited by the phenolic system. This
is probably related to the nature of this resin, which has a high void content due to
condensedwater which is formed during the reaction processwhich forms the resin.
151
Fire
in
Composites
Modelling
7
Chapter
of
CHAPTER 7
OF
MODELLING
ONE-DIMENSIONAL
COMPOSITES IN FIRE
7.1 The 1-D Finite Difference Model
7.1.1 Introduction
The computer program COM FIRE, version 3.4,2004 (developed at the Centre of
Composite Materials Engineering (CCME), School of Mechanical, and System
Engineering, University of Newcastle, UK), is used in this chapter for the
laminates
in
fire.
the
thermal
composite
of
responses
predictionsof
ProgramCOM FIRE was initially developedin 1994 for predictions of the thermal
its
faces)
(with
laminates
to
GFRP
two
exposed
one
of
thick
when
resistanceof
hydrocarbon fire only, based on the one-dimensional (1D) model (Gibson et al,
1995) using a finite difference (FD) numerical analysis approach. Now the new
be
the
used to predict the thermal responsesof composite
can
version of
program
laminates exposed to different heating sources, and the resin systems and fibre
different
be
involved
types.
of
can
reinforcements
152
Fire
in
Composites
Modelling
7
Chapter
of
laminate
a
with
from
examination
under
the
FD
composite
cut
element
"AID
direction
in
(Ax)
through-thickness
length
the
of
a
and
unit cross-sectionalarea
is shownbelow:
Through thickness direction
*
Cold side
Hot side
i
x
iX+eX
"
a (p.
li,. )(Ax)
(7.1)
hco,
density
denotes
the
material,
composite
whilst
of
representsenthalpy
wherepro,,,
of the material.
"
(7.2)
C)
(in:
T
k,,
the
thermal
composite material and
conductivity of
where
represents
denotestemperatureof the body.
"
Internal energy changeof the element due to gaseousmass flow (from the cold
side to the hot side):
153
("g
(AY)
h,
(7.3)
denotes
hg
flow,
flux,
and
denotes
At,
mass
of
gaseous
or
rate
mass
gaseous
where
decomposition.
during
enthalpy of the gasesgenerated
"
LP7,(aY)
Q,
-
(7.4)
is
for
decomposition
heat
denotes
Q.
and
endothermicreaction.
negative
of
%%-here
Having assumedthat there is no accumulation of gasesgeneratedin the composite
during fire exposure, a consideration of the energy conservation of the element
following
differential
leads
to
the
non-linear
partial
equation:
underexamination
a (,)
-ak
""
ar
ar
`"'ax
(it
+a
g:
gP
ax
Qp
(7.5)
at
The teen on the left hand side of Eqn. (7.5) can be re-written as:
apahn,
+h
Pco.
=f)T+
Ct
P
at
COM
at
apc')M
hCUM
at
(7.6)
and the secondterm on right hand side of Eqn. (7.5) can be re-written as:
c'It'
(Cps)
Here,
+li
("ifs
cl
1lig(CPj
aT
+hg
Mg
(7.7)
Through considering mass conservation over the element, one may derive the
follo%%ing
equation:
154
ap
(7.8)
a"r9=
aT
&I,
0
be
time,
t,
AM,
flux,
may
any
and
at
position,
x,
at
any
the
therefore,
mass
gas
and
Eqn.
(7.8):
integrating
by
calculated
"j
(Pro.,)dx
(7.9)
COi. wY
governing
in
equation adopted the program:
L
rt! ,
'p
T
lot
&c
_k
ax)
+ Ili rC
aT
G
aP`m(Q
at
+h-com hg)
(7.10)
'at
-An? o
- n: f
mo
xm
exp(-E /R T)
(7.11)
where:
m=
mo
mf
A=
pre-exponentialfactor (1/sec),
T=
temperature
of theresin(K),
n=
155
Fire
in
Composites
Modelling
7
Chapter
of
E=
(J/mole),
activation energy
R=
J/mole/K).
8.314
(=
gasconstant
(7.11).
Eqn.
be
The governingequation(i. e. (7.10)) must solved simultaneouslywith
E,
(i.
in
Eqn.
(7.11)
pree. activation energy,
The four kinetic parameters appearing
final
the
at
resin
factor,
A,
of
mass
and
the
n
reaction,
chemical
of
order
exponential
from
derived
thermogravimetric
be
the
decomposition,
processing
can
nit)
the end of
data using Anderson's single heating rate technique as described in Chapter 6.
)+k(T,
156
TpJ
-
(7.12)
here
%%
heat flux into the hot face of the material sample(W/m2);
q
T,
heating
temperature
source;
of
surrounding
temperatureon hot face of the material sample;
h,
T,
heating
(-);
source
emissivity of
hlF
the
material of the sample;
of
absorptivity
Cm
lf
Ci
The first term on the right hand side of Eqn. (7.12) representsthe energy transfer to
the sample from the heating source through thermal radiation, which follows the
familiar Stefan-Boltzmannlaw. The secondterm representsthe energy transfer to
from
the heating source.
thermal
through
the sample
convection
natural
For prediction purposes, the evaluation of flame emissivity under specified
is
its
is
usually a complex function of field
value
conditions necessary,since
temperatures.
To measurethe surrounding temperature of a heating source in a fire test, Ts,
thermocouplesshould be placed in such positions which are close to the front hot
faceof the samplewithin the boundarylayer thicknessof the fluid flow.
As indicated by Buchanan (2001), in fire situations most hot surfaces, smoke
between
have
luminous
flames
0.7 and 1.0. This was
emissivity
particlesor
an
may
also the finding revealedby Gibson et al, (2003).
In general, the emissivity of the hot face of an FRP composite laminate sample, en,,
be
taken as 0.8, and in most practical cases, the absorptivity of the hot face of
can
the sample, a,,,, can be taken as 1.0.
There are three options in this program for thermal boundary conditions on the cold
faceof the laminatedsampleunder examination: (1) thermally insulated; (2) natural
convectionplus free radiation; (3) connectedwith a steel plate of a given thickness.
Thermal boundary condition on the back face of the steel plate can be either
thermally insulatedor natural convectioncombinedwith free radiation.
157
Prwn"' Pi l i+ P. P.
Y.
if+C,.
P.
Pf
C
Cpf
".
Pf Vf+P. Y.
I_f
iz
tM
158
"
is
flux,
by
heat
incident
heat
flux
the
which
specified
value
of
constant
and
"A
the relevantemissivity of the heatingsource;
"
"
The final type above is associatedwith no particular heating source. This special
type of 'heating source' is designedfor predictions to be comparedwith predictions
from
FEA
FDA
or
obtained
packagesin a conventional thermal
running commercial
thermal boundaryconditions are usually defined as temperatureson
analysis,%%here
boundarysurfacesas a function of time. For thermal analysis in most commercial
packages,the effects of decompositionreactions in materials at high temperatures
areusually not included.
159
define
is
type
It
the
to
reinforcement
of
glass
used
also
resin).
resin or phenolic
involved (such as E-glass fibres, carbon fibres or Kevlar fibres). Also the fire
laminate
GFRP
the
(in
under
thickness
the
of
and
time
minutes)
period
exposure
laminate
GFRP
fraction
fibre
the
(in:
the
of
volume
mm) as well as
examination
input.
in
be
this
to
specified
underexaminationare
For printing out the relevantresults, sevennode numbers(chosen from 2 to 51) are
to be specified. For example,ND4 = 26 meansthat the correspondingresults for the
in
layer
laminate
for
25'h
those
the middle column
the
the
of
are
mid-plane node or
of the file.
The three kinetic parametersof the first stage of the reaction (such as AA, EE and
li) are also to be specified. The type of heat sourceunder examination also has to be
for
heating
for
for
tIC
instance;
the
the
curve;
case
where
=I
specified;
source
=0
is defined by the input data file (unit=32); =2 for a constant heat flux; =3 for
SOLAS fire curve. Finally, the emissivity of the heating source, and both the
laminate's
GRP
front
the
the
surface have to be
emissivity and
absorptivity of
specified.
The input data file (unit=32, file=fort-32) is used for the case where the heating
sourceis defined from experimentaldata. This contains four main inputs. The first
input is usedfor identification of thejob, the secondinput is the total number of data
lines, the third input indicatesthe time unit adopted(i. e. =1 if the time unit adopted
in this input file is minutes;=2 if the time unit adoptedin this input file is seconds).
The last input from input unit 32 indicatesthe environmentaltemperatureat a given
time.
There are five output files from running this program. However, the main output
files are the temperatureprofiles in the through-thicknessdirection of the laminate at
the chosensevennode positions for the specified fire exposuretime period, and the
predictedRRCs as functions of time at the chosensevenlayers of the laminate. The
RRCs are expressedas the percentageof remaining resin content over the initial
resinweight.
The input and output data files are describedin detail in Appendix 1.
160
in
Fires
Laminates
Composite
Results
7.3 Some Experimental
of
WR
lay-up
hand
specimens using a small
Fire tests were conducted with some
furnace and the results are illustrated in Fig. 7.2.
Values for the kinetic parameters of the samples were taken as standard from
factor
in
The
6).
Chapter
in
the
(i.
stage one
pre-exponential
e.
work
previous
0.144E+06
(J/mol),
),
0.98E+13
(1/sec.
the
energy
activation
and the
reaction was
heat of decomposition 2344600 (J/kg).
face
be
data,
the
to
and
constant,
was assumed to
rear
or
assumed
experimental
free
heat
(no
insulated
be
to radiation and natural
transfer)
or
thermally
either
convection. The emissivity and absorptivity of the samples were given arbitrary
0.8
1.0
Figure
7.3
based
of
and
respectively.
shows the
values
upon past experience
typical model output for 10mm thick WR based laminates for (a) orthophthalic
(c)
isophthalic
(b)
resin,
and
polyester
vinyl ester resin. The test
polyester resin,
behaviour
throughout the laminates
temperature
profile
conditions yielded similar
regardless of the resin t}.
be
temperature
can
seen to become gentler.
the
the gradient of
profile
This is
attributed to the cooling effect of the volatile products of the resin decomposition
moving towards the flame.
Both the gas flow and the endothermiceffects are neglected. The gas flow term in
Eqn. (7.10) requires a significant amount of computation. Current work on the
dimensions
from
to
two
the
means that the possibility of
one
extensionof
model
neglecting gas flow %%illconsiderably simplify computation. Another very
here
by
the
observed
model
significant result predicted
concernsthe effect of glass
content. Up till now, for fire protection applications, great efforts have been made
by severalcompaniesto achieve laminateswith the highest possible glass content.
Of course,the greaterstructural integrity of WR will be of prime importance when
laminatesare under load in a fire. One of the main reasonsfor developing the fire
fire
testing when developing laminates for specific
to
the
model was saveon
cost of
fire protectionapplications.
161
1200
1000
IFums T
800
0
600
-ace
J
400
Half-thi
200
(a)
400
800
1200
1600
Time (sec)
(b)
Time (sec)
Figure 7.2 Experimental furnace fire test results on WR laminates for: (a)
(b)
Vinyl
(Vf
48%),
ester resin (Vf = 50%).
=
polyester
orthophthalic
162
1000
800
400
200
(a)
200
600
400
800
1000
Time (sec)
"
E
i
(b)
Cold-
300
600
900
1200
1500
Time (sec)
1200
1000
00
P
600
400
(c)
163
The predicted
of a 10mm thick
ablation
45%
volume
fraction
polyester/glass
resin percentages at
the hot face and at five points through the laminate thickness are shown against time
for the simulated furnace fire test.
completely spent after only a few minutes of exposure to the furnace fire.
percentages at the five
decomposition
points
the
through
laminate
show
gradually
The resin
broader
The thermal response model validated against standard furnace tests can be extended
to predict the responsesto other fire situations or to provide information relevant to
the structural behaviour of composites in fire.
300
600
900
1200
1500
Time (sec)
Figure 7.4 The predicted amount of resin remaining at fifth points through
the thickness for a 10.0mm thick, 48% volume fraction polyester /
glass laminate during furnace fire test.
164
dimensions
higher
to
would allow
Extensionof the one-dimensionalthermal model
in
distribution
shaped
complex
a
temperature
the
a complete prediction of
in
the
the
thermal
knowledge
stresses
This
of
calculation
allow
would
component.
for
in
fire;
due
an overall structure.
assessment
thus assisting risk
to the
structure
be
boundary
the
knowledge
may
used
Subject to a
model
conditions,
of the relevant
jet-fires
fires,
fire
to
or
materials
pool
other
to predict the responses of composite
incidents. An example of the use of the thermal model is the preparation of design
information for the use of composite materials in fire sensitive applications.
165
in
thickness
laminates
thinner
would not
of
It should, however, be pointed out that
(i.
>12mm)
thick
since
a
in
e.
behave
ones
be
the
as
way
same
to
any case expected
degradation
to
take
for
is
place
process
the
thickness
progressive
critical
needed
(Gibson and Wu, 1994). It has beenfound for thicker specimens(> 10mm) that the
This
is
face
size effect can
temperatureresponse reproducedvery accurately.
cold
be explainedby the reducedstructural integrity of thinner sectionsof laminates. The
layers.
for
delamination
The
does
directly
the
of
composite
slow
model
not account
bum-througheffect causedby the endothermicdecomposition of the resin is allowed
to develop as the panel maintains its structural integrity. For thinner panels, the
insulation failure criterion of a temperaturerise of 140C is breachedvery rapidly,
is
laminate
integrity
the
the
quickly reduced as the surface
of
and
structural
reinforcementlayersare delaminated.
The form of the cold face responseis similar in all the samplestested. Following an
initial temperaturerise there is a prolonged plateau, correspondingto the removal of
the volatile material from the laminate. The main significance of the results is the
presenceof this plateau,which in the field would provide a delay in the transmission
of heat into the zone or componentprotected by the laminate. The temperature of
the plateauregion, and most especiallythe time it lasts, are of course key features of
the fire resistanceof a laminate.
It was probable that the Arrhenius constants for the decomposition reaction,
calculated from TGA data, would require adjustment in order to fit the model
predictionsto realistic fire test results. The experimentalscatteris seenin the interlaminar thermocouple outputs, due to delamination of the panels as resin is
decomposedlocally to the thermocouples. The predicted inter-laminar temperatures
do not follow the thermocouple outputs exactly, due to the modelling of the
delaminationsby averaging the transport properties, but the cold face temperature
prediction is accurate.
166
C)
.
I
(a)
200
600
400
Time (sec)
800
1000
tiiF-cal.,vlat
dictedl
200
400
600
800
1000
Time (sec)
(c)
200
CF-predicted
200
400
600
800
1000
Time (sec)
Figure 7.5 A comparison of the experimental and calculated fire test results
for. (a) WR/orthophthalic polyester resin (Vf 48= %, (b) Isophthalic
Vinyl
(c)
45%)and
(Vf
ester resin system (Vf = 50%).
resin
=
polyester
167
high
temperatures may
The use in the modelling of constant thermal properties at
laminated
the
of
composition
be
the
chemical
changing
as
wholly adequate,
not
introduction
of
gases
and
thereto-chemical
expansion
the
associated
material,
fire
during
fibres
to
between
are thought to
exposure
(including air)
the exposed
degraded
laminate.
the
in
large
composite
changes the thermal conductivity of
cause
This creates doubt concerning the derivation of thermal conductivity for degraded
laminate from the rule of mixtures is found. Glass fibres are known to be almost
isotropic individually, with values of thermal conductivity in the region of 1.05-1.09
W/mC. However, when they are formed as an insulating board the thermal
drops
direction
0.035-0.048
W/mC
(Bejan,
in
to
thickness
through
the
conductivity
1993). The elimination from the model of the change in thermal conductivity of the
fibres due to contact, especially in the later stages of the decomposition where some
fibre melting has been noted, could form a major uncertainty in the prediction (Wu
et al., 2004). Using the value of thermal conductivity of the undamaged laminate at
high temperatures might prove an over-estimation, thus leading to a conservative
prediction of thermal response.
7.5 Discussion
Despitevibrant debateover the approximationsof input parametersand assumptions
madein the computationsof the thermal model presentedfor analysis,the agreement
betweenmodelledand measuredresponsesis consideredvery good indeed.
168
Fire
in
Composites
Modelling
7
Chapter
of
the
a
non
with
through
samples
heat
transfer
occurs
be
It can
seen that significant
the
and
decomposition
the
resin
composite
of
insulated rear face, thus slowing the
laminate
Therefore,
the
and
conditions
under
breakdown of the ablative protection.
barrier
fire
than
be
polyester.
suitable
a
more
would
tested
thicknesses
vinyl ester
Under
the
well.
fluxes
equally
lower
heat
However at
polyester may perform
by
100
the
with
seconds,
ester
vinyl
outlast
the
would
tested
polyester
conditions
decomposition behaviour up to that point being almost equal.
dimensional
heat
transfer
the
two
truly
that
represents
A modification to the program
improve
the
the
laminates
in
agreement
of
model and measured
the
would
effects
results.
in
during
the
is
It
or
air
voids
generated
the
of
gases
that
existence
suggested
decomposition of the composite material is taken into account in formulating a
Mixture:
Rule
of
modified
7.6 Conclusions
has
been
found
be
FD
dimensional
to
model
capable of
simple one
"A
behaviour
thermal
of polyester/WR and vinyl
the
response
modelling
fire
laminates
to
tests.
subject
esterAVR
The most important term in the model and the most significant effect is that
delays
heat
decomposition
the
which
endotherm,
conduction through
of
resin
face
in
the
the paneland producesa plateau
cold
response.
"
"
169
CHAPTER 8
CONCLUSIONS AND FUTURE WORK
8.1 Conclusions
From the study conducted using the small scale propane burner as the fire testing
facility, the following conclusions can be drawn:
"
"
Flames are selective emitters. The effective emissivity Eef of the flames
is
fire
in
by
function
burner
test
the
a
complex
a
produced
of the
propane
`surrounding field temperature', Ts, which is the temperature measured at a
The
from
10mm
the
surface.
receiving
emissivity is a
position about
away
function of (i) pressure,and (ii) the distance between propane burner and the
objective.
"
It was found from this study that the effective emissivity rangedfrom 0.7-1.0 for
the given environmentalconditions in the laboratory. This finding is nearly the
sameasthosereportedby Perry and Chilton (1973) and Buchanan(2001).
"
data.
Furthermore,
in
an
air) are a good agreementwith relevant published
in
for
the
thermal
derived
the
variation
estimating
empirical equation was
conductivity of dry glassfibre mats.
Five composite samples have been fire tested to examine fire resistance
"
from
The
DML.
Those
the
samples were exposed to
performance.
are produced
the standard `SOLAS' time-temperature curve. The results indicate that A60 fire
rating can be well met by two of the five samples. For instance, the performance
of 100mm Rockwool with lmm E-glass/epoxy skin and the 35mm syntactic
phenolic foam with 5mm E-glass/phenolic skin specimens can meets A60 with
just
is
A60
It
to
that
requirements.
meet
requirements, the thickness of the
noted
Rockwool layer might be largely reduced. On the other hand, the experimental
results show that the 20mm E-glass WR/epoxy meets A30 requirements only,
whilst the 4mm Technofire 60853 intumescent/epoxy was failed to meet the
requirements.
"
The actual meanvalue was 24.1Wm 2K71,with a 95% upper confidence limit of
26.4Wm2K71,which is significantly lower than the required value. Qualification
hasthereforebeenachieved.
There is no systematic difference between gel-coated and non-gel-coated
samples,so the gel-coat used is unlikely to damagefire protection performance.
The laminatescontaining steelmeshare slightly less effective than those without
it. Sincethe main qualification was achievedwith the mesh samples,both types
of laminatequalified from a thermal performanceviewpoint.
"
To run the 1D FD fire code in FORTRAN, COM FIRE, the kinetic parameters
of a relevant resin system of composite materials are required as a part of the
programinput. Thesekinetic parametersof polyester, vinyl ester, phenolic and
171
Freeman
technique
TGA
the
tests
by
using
carrying out
epoxy were obtained
dry
the
in
60C
and
nitrogen,
25
of
heating
atmosphere
an
and
under a
rate of
based
data
the
for
the
on
TGAP2,
processing
FORTRAN program, i. e.,
was used
Freeman technique.
The apparent activation
energies of
isophthalic
polyester,
orthophthalic
be
0.288E+06,0.144E+06,
to
estimated
were
polyester, vinyl ester, and epoxy
0.197E+06 and 0.431E+06 (J/mol), respectively. However, phenolic resin has
for
first
E=0.613E+05
found
it
the
that
stage
two stages of reaction, and was
and E=0.134E+06 for the second stage.
"
is
finite
difference
dimensional
that
the
capableof
model
concluded
existing one
modelling the thermal responsebehaviour of polyester/WR and vinyl ester/WR
like
furnace
heating
fires,
including
the
to
small
or the small
source
exposed
University
Newcastle
lab.
in
CCME,
burner
the
of
scalepropane
used
"
The work carried out in this study has proved that the small scale fire testing
facility based on the use of a simple propane burner for examining thermal
responseof FRP laminatesin fires provides a cost-effective way of conducting
in
thermal
the
of
composites
experimentalassessments
resisting performance
of
fire. Although incident heat flux levels have beencalibrated,the outcome of the
calibration tests are to be further confirmed using other approachessuch as the
conecalorimeter.
"
The small scale fire testing facility developed can be used not only for
examiningthe fire resistanceof compositesexposedto a heating source,but also
to measure thermal properties for example, the thermal conductivity of
compositematerial at high temperatures,as shown in this study, based on the
transient response method. Further improvement of the transient response
method adopted and also other potential methods can be explored to use this
172
facility for measuring thermal properties (including both K and Cp) of composite
laminates at high temperatures which are usually not available in the literature.
"
further
be
laminates
for
facility
fire
The small scale
could
composite
testing
loads
further
fire
in
fire
to
testing
composite
under
on
modified to carry out
develop the capacity of this novel facility as schematically shown in Fig. 8.1.
Pressure
gauge
_
Propane
burner
Insulation
material
I-
O
Sample
material
:
_:
Load
Insulation
J.
Load
Figure 8.1 Front view of the layout of the testing facility including a sample.
173
References
References
Adams M. C., "Recent Advances In Ablation" American Rocket Society, 1959.
vol. 29: pp. 625-631.
Anisdahl D.T.; Wang w. and Stokke R., "In Composite Materials for Offshore
Operations-2 (CMOO-2)", eds. Wang S.S., Williams J.G. and Lo K. H.,
American Bureau of Shipping, Houston, USA, ISBN 0-943870-01-1,pp. 261274,1999.
ASME, "Boiler and Pressure Vessel Code", Section X: Fibre Reinforced Plastic
PressureVessels", 1992. The American Society of Mechanical Engineers.
ASTM E 422-99, "Standard Test Method for Measuring Heat Flux Using a
Water-Cooled Calorimeter", 1999. American Society of Testing and Materials,
pp. 435-438.
ASTM: E 457-96, "Standard Test Method for Measuring Heat-Transfer Rate
Using a Thermal Capacitance(Slug) Calorimeter", 1997. American Society of
Testing and Materials, pp. 454-458.
Bamford C. H., Crank J. and Malan D.H., "The Combustion of Wood. Partl"
CambridgePhil. Soc.Proc., 1946.vol. 42: pp. 166.
Bejan A., "Heat Transfer", Appendix D: Properties of Gases,John Wiley &
Sons,Inc., 1993.
174
References
Boyer
G.
T.,
"An
Analytical
and Experimental
Investigation
of
the
Brian Y. L. and Jason 0., "Thermal Properties of Composites for Heat Transfer
Modelling During Fires", in SAMPE 2004. May 16-20,2004. Long Beach, CA.
USA.
Brown N. A. and Tipping G. " Fire Safe Polyester Composites Using Aluminium
Hydroxide" in Composite in Fire 1.1999. Newcastle University, Newcastle,
England.
BS 476 part 20, "British Standard Fire Tests on Building Materials and
Structures",1987.British StandardsInstitution.
BS 5950: "The Structural use of Steel in Buildings Part 8: Code of Practice for
Fire ResistantDesign", 1990.British StandardsInstitution.
BS 6336, "Development and Presentationof Fire Tests and their Use in Hazzard
Assessment",1982. British StandardsInstitution.
BuchananA. H., "Structural Design for Fire Safety", Wiley J. & SonsLtd, 2001.
pp. 35-56.
175
References
Convention for Safety of Life at Sea (SOLAS) 1974, Consolidated Edition 1992,
IMO London.
Cullen H. L., "The public Inquiry into The Piper Alpha Disaster" HMSO,
London, V. 2,1990.
Curtis, P.T. "Crag Test Methods for the Measurement of the Engineering
Properties of Fibre Reinforcement Plastics". Royal Aerospace Establishment,
Technical report, 1988.
176
xeferences
177
References
Gibson A. G., Wu Y-S and Naas A. L., "A Low Cost Burner Technique for the
Development and Modelling of Laminates in Fire", in Composites in Fire 3,
2003. Newcastle upon Tyne, England.
HendersonJ. B., Wiebelt J. A. and Tant M. R., "A Model for the Thermal
Responseof Polymer Composite Materials with Experimental Verification"
Journalof CompositeMaterials, 1985.vol. 19: pp. 579-595.
Hill P. S. and White G. C., in Composite Materials for Offshore Operations-2
(CMOO-2)', eds. S.S. Wang, J, J.G. Williams and K. H. Lo, American Bureaue
of Shipping, HoustonTX 77060, ISBN 0-943870-01-1.pp. 623-634,1999.
Hull D. and Clyne T. W. "An Introduction to CompositeMaterials", Cambridge
University Press,1996.
178
References
179
References
McManus
HLN,
Springer
GS.,
"High
Temperature
Thermomechanical
180
References
Van Krevelen, D. W., Van Heerden C., and Huntjens F. J., "Physicochemical
Aspects of the Pyrolysis of Coal and Related Orgainc Compounds" Fuel, 1951.
vol30: p. 253.
Varma I. K. and Gupta V. B., "ThermosettingResin Properties.Chapter 2.01 of
comprehensiveComposite Materials", Eds A Kelly and C Zweben, Elsevier,
2000.
181
Appendix
Appendix
COM FIRE PROGRAM INPUT AND
OUTPUT DATA
The main input data file to the program are( unit = 31, file = fort. 31) and (unit = 32,
file = fort. 32).
= 3,
= 4,
THICK,
VOLFR:
is the
thickness of the GFRP laminate under examination (in: mm). VOLFR is the
fibre volume fraction of the GFRP laminate under
examination.
182
Appendix
Set 7. NDI, ND2, ND3, ND4, ND5, ND6, ND7: ND1, ND2, and ND7 are the seven
from
for
2
51)
(chosen
to
printing out relevant results with these
node numbers
for
26
ND4
For
the midthe
that
means
corresponding results
nodes.
example,
=
layer
for
25th
the
plane node or
of the laminate are those in the middle column of the
file.
Set 8. KDEGRA:
= 1,
Set 10. AA, FE, II: This set is used to define the three kinetic parametersof the
first stageof the reaction.
AA The pre-exponentialfactor in the Stage-1 reaction (in: 1/sec)
EE The activation energyin the Stage-1 reaction (in: J/mol).
II
Set 11. AA2, EE2,112: This set hasto be usedto define the kinetic parametersfor
the secondstageof reaction. This set usedfor the caseof Phenolic resin.
Set 12. RC12: The residual resin content (RRC) value at the end of stage I
reaction
during the decomposition process is specified in this set. This is
only
applying for phenolic resin system.
Set 13. K FUR, K CF: The K FUR input indicator for the control the type
of
of
the heat sourceunder examination:
for
HC
curve;
o,
=
for the casewhere the heating sourceis defined by the input data file
=1,
(unit=32);
= 2, for a constantheat flux;
= 3, for SOLAS fire curve.
The K
input indicator for the control of thermal boundary
conditions
on
_CF
the CF of the laminate:
= 0,
183
fippenu"
= 1,
= 2,
for
CF;
free
the
radiation
natural convectioncombinedwith
connectedto a steelplate of a given thickness.
Set 14. EMIS HTSO, EMIS GRP, ABSORP GRP: In this set, the emissivity of
front
laminate's
GRP
EMIS
HTSO,
heating
the
the
the
emissivity of
source
front
laminate's
GRP
EMIS_GRP
the
the
surface
and
absorptivity
of
surface
ABSORP_GRP have to be specified.
Set 15. K WATER:
due
transfer
to water vaporization:
content on energy
= 0,
= 1,
Set 16. Q FLUX: Is the constantheat flux input (in: kW/m2). This set has to be
heat
is
heat
flux.
if
type
source
not
as
a
constant
of
omitted
Set 17. THICK
STEEL,
(in:
laminate
the
mm);
of
under examination
For K_CFST the input indicator for the control of the type of thermal
boundaryconditions on the CF of the steelplate:
= 0,
= 1,
from experimentaldataresult.
Set 1. JOB: Is usedfor identification of thejob.
184
Appendix
N
Set 2. FUR:
Is the total number of the data lines in this input file. Each of the
FUR(I):
One should note that the input maximum value, TIME FUR, in this file has to be
input
input
defined
in
TIMED
the
than
the
to
value of
main
either equal or greater
file (unit=3 1).
The input data file (ui: it=32, file fort. 32)
There are five output files from running this program.
unit=30, unit=40, unit=50, unit=60 and unit=70. All output files are self-explained.
Through combining the data in this output file with those contained in output file
`fort.30', one may obtain the messageson RTMs as functions of temperatureat the
layers,
which are very similar to the experimentaldata obtained from
chosenseven
TGA tests.
185