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Combustion Characteristics

of Materials and Generation 36


of Fire Products

Mohammed M. Khan, Archibald Tewarson,


and Marcos Chaos

PET polyethyleneterephthalate (Melinex


Abbreviations Mylar)
PFA perfluoroalkoxy (Teflon)
ABS acrylonitrile-butadiene-styrene PMMA polymethylmethacrylate
CDG carbon dioxide generation PO polyolefin
calorimetry POM polyoxymethylene
CPVC chlorinated polyvinylchloride PP polypropylene
CR neoprene or chloroprene rubber PS polystyrene
CSP chlorosulfonated polyethylene rub- PTFE polytetrafluoroethylene (Teflon)
(or CSM) ber (Hypalon) PU polyurethane
CTFE chlorotrifluoroethylene (Kel-F) PVC polyvinylchloride
E-CTFE ethylene-chlorotrifluoroethylene PVCl2 polyvinylidene chloride (Saran)
(Halar)
PVDF polyvinylidenefluoride (Kynar)
EPR ethylene propylene rubber
PVEST polyvinylester
ETFE ethylenetetrafluoroethylene (Tefzel)
PVF polyvinyl fluoride (Tedlar)
EVA ethylvinyl acetate
PVF2 polyvinylidene fluoride (Kynar
FEP fluorinated polyethylene-
Dyflor)
polypropylene (Teflon)
SBR styrene-butadiene rubber
FPA Fire Propagation Apparatus
TFE tetrafluoroethylene (Teflon)
GTR gas temperature rise calorimetry
XLPE cross-linked polyethylene
IPST isophthalic polyester
OC oxygen consumption calorimetry
PAH polyaromatic hydrocarbons Introduction
PAN polyacrylonitrile
PC polycarbonate Hazards associated with fire are characterized
PE polyethylene by the generation of calorific energy and
PEEK polyether ether ketone products, per unit of time, as a result of the
PES polyethersulfone chemical reactions of surfaces and material
PEST polyester vapors with oxygen from air. Thermal hazards
constitute those scenarios where the release of
heat is of major concern. On the other hand,
M.M. Khan (*) • M. Chaos
FM Global Research, Norwood, MA 02062, USA nonthermal hazards are characterized by fire
products (smoke, toxic, corrosive, and odorous
A. Tewarson
Retired from FM Global Research, Norwood, compounds.) Generation rates of heat and fire
MA 02062, USA products (and their nature) are governed by

M. Hurley (ed.), SFPE Handbook of Fire Protection Engineering, 1143


DOI 10.1007/978-1-4939-2565-0_36, # Society of Fire Protection Engineers 2016
1144 M.M. Khan et al.

(1) fire initiation (ignition); (2) fire propagation The chapters are as follows: Chaps. 27, 28, 16,
rate beyond the ignition zone; (3) fire ventilation; and 24. Physical and combustion properties of
(4) external heat sources; (5) presence or selected fuels in air and heats of combustion and
absence of fire suppression/extinguishing related properties of pure substances, plastics,
agents; and (6) materials: (a) their shapes, and miscellaneous materials listed in Appendix
sizes, and arrangements; (b) their chemical 3 should be consulted for information that may
natures; (c) types of additives mixed in; and not be included in this chapter. This chapter
(d) presence of other materials. In this handbook presents the applications of the principles
most of these areas have been discussed discussed in several chapters in this handbook
from fundamental as well as applied views. For to determine the fire properties of materials. Sim-
example, the mechanisms of thermal decomposi- ple calculations have been included in the chap-
tion of polymers, which govern the generation ter to show how the properties can be used for
rates of material vapors, are discussed in Chap. 7, various applications.
generation rate of heat (or heat release rate)
from the viewpoint of thermochemistry is
discussed in Chap. 5, Flaming ignition of the Flammability Apparatuses
mixture of material vapors and air is discussed and Measurement Capabilities
in Chap. 21, and surface flame spread in
Chap. 23. At the scales of relevance to this chapter, there
In this chapter emphasis is placed on small are mainly three heat release rate apparatuses
scale experiments and how such testing can be available: (1) The Ohio State University (OSU)
used to determine the generation per unit of Heat Release Rate Apparatus; (2) FM Global’s
time of (1) the calorific energy, defined as the Fire Propagation Apparatus (previously known
heat release rate, and (2) fire products. From as “Small-Scale Flammability Apparatus”); and
these tests, measurements of so-called “fire (3) NIST’s Cone Calorimeter. These apparatuses
properties” are made that can be used in models are briefly described below.
to predict, under a variety of conditions, (1) heat In 1972, gas temperature rise (GTR) calorim-
release rate, to assess thermal hazards; and etry (details are given in section “Heat Release
(2) generation rates of fire products, to assess Rate” of this chapter) was used by the Ohio State
nonthermal hazards. Fire properties are defined University (OSU) to determine heat release rate
herein that help characterize the flammability of [1, 2]. The apparatus used is now known as the
a given material and relationships are derived, OSU heat release rate apparatus; it is shown in
based on empirical evidence, that elucidate the Fig. 36.1. The OSU apparatus is an ASTM [3]
effect of environmental factors (such as external and an FAA [4] standard test apparatus. In GTR
heat flux and ventilation) on the properties. Also calorimetry, it is assumed that almost all the
important, and discussed in this chapter, is the thermal radiation from the flame is transferred
connection of these properties to the behavior of to the flowing fire products-air mixture, as the
large-scale fire phenomena under well ventilated flames are inside an enclosed space and heat loss
as well as vitiated conditions (i.e., compartment by conductive heat transfer is negligibly small.
fires.). Lastly, with the advent and quick devel- Oxygen consumption (OC) calorimetry (details
opment of computer modeling as applied to are given in section “Heat Release Rate” of this
large scale fires, this chapter also discusses the chapter) has now been adapted to the OSU
value of small scale testing in determining mate- apparatus [5].
rial flammability parameters specific to such Calorimetry methodologies based on carbon
models. dioxide generation (CDG, details are given in
Several other chapters in this handbook relate section “Heat Release Rate” of this chapter),
to the subjects discussed here and should be OC, and GTR calorimetries were used during
consulted for complete information and context. the mid-1970s by FM Global Research
36 Combustion Characteristics of Materials and Generation of Fire Products 1145

Fig. 36.1 Ohio State Combustion


University’s (OSU, ASTM products
E906) heat release rate exhaust
apparatus [1–4] Thermopile

To oxygen
analyzer
By-pass air

Pilot
flames

Glowbars
(radiant heat
source)

Sample

Pilot flame

Air distribution plates Air inlet

(formerly, Factory Mutual Research Corpora- insulation materials, replacing the 7.6 m (25-ft)
tion—FMRC) to determine chemical, convec- corner test (as described in section “Fire Propa-
tive, and radiative heat release rates [6–9]. The gation” of this chapter) [18], for clean room
apparatus used is now known as the Fire Propa- materials used in the semiconductor industry
gation Apparatus (FPA) and is an ASTM [10] [19], and for conveyor belts [20].
and ISO [11] standard; it is shown in Figs. 36.2 In 1982 the National Institute of Standards
and 36.3. Heat release rate from CDG and OC and Technology (NIST) used OC calorimetry,
calorimetries in the FPA was originally defined following the methodology described by
as the “actual heat release rate” until 1986 Hugget [21]. The apparatus developed to use
[9, 12–15]; thereafter, however, it was changed this methodology, known as the cone calorimeter
to “chemical heat release rate” to account for the [22, 23], is shown in Fig. 36.4. The cone
effects of (1) the chemical structures of the calorimeter became an ASTM standard [24]
materials and additives; (2) fire ventilation; test apparatus in 1990. Details about the cone
(3) the two dominant modes of heat release, calorimeter are given in Chap. 28.
that is, convective and radiative; and (4) the Sampling ducts have been designed for the
effects of flame extinguishing and suppressing FPA and the cone calorimeter to measure the
agents. The FPA is a standard test apparatus for mass generation rates of CO2 and CO and mass
electrical cables [16, 17], for wall and ceiling consumption rate of oxygen for use in the
1146 M.M. Khan et al.

Combustion products Combustion products

Product Product
sample sample
analysis analysis

Collection Collection
hood hood

Sample
Infrared Aluminum conveyor
Quartz extension
heaters (4) belt
tube cylinder

Quartz Infrared
tube heaters (4)

Test
sample
Aluminum
support Sample
cylinder support
(on load Aluminum
cell) support Sample
cylinder support
Air + oxygen Air distribution box (on load
cell)
Fig. 36.2 Fire Propagation Apparatus (FPA) [10, 11]
designed by FM Global Research. Sample configuration Air + oxygen Air distribution box
for ignition, pyrolysis, and combustion tests
Fig. 36.3 Fire Propagation Apparatus (FPA) [10, 11]
designed by FM Global Research. Sample configuration
for fire propagation tests; a conveyor belt sample is
calorimetric equations (see section “Heat shown
Release Rate” of this chapter). CDG and OC
calorimetries are used in the FPA. In the OSU
apparatus and the cone calorimeter, only the OC listed in Table 36.1. As shown in the table,
calorimetry is used. For application of GTR cal- the Fire Propagation Apparatus measures flam-
orimetry, a thermopile located in the flue gas mability characteristics of materials under
chimney is used in the OSU apparatus, and a various air flow (ventilation) conditions, in
thermocouple located in the sampling duct is enhanced or reduced oxygen environments, and
used in the FPA, where heat losses by conduction also has the ability to determine flame extinction
are negligibly small. The cone calorimeter has by extinguishing agents. Much of the data
not been designed to use GTR calorimetry. The presented in this chapter takes advantage of all
FPA provides the advantage of determining the of these capabilities.
radiative heat release rate from the difference Figure 36.5 shows an example of typical heat
between the chemical (determined by CDG or release rate profiles measured in the FPA. These
OC) and convective (determined by GTR) heat profiles correspond to the chemical heat release
release rates [25]. Details on sample preparation, rate of polymethylmethacrylate, determined
sample holders, and measurement procedures are from CDG and OC calorimetries, as well as the
provided for each apparatus [3, 10, 11, 24]. convective heat release rate, determined by GTR.
The design features, test conditions, and types The polymethylmethacrylate (PMMA) sample
of measurements for the three apparatuses are was 100 mm in diameter and 9.53 mm in
36 Combustion Characteristics of Materials and Generation of Fire Products 1147

Fig. 36.4 The cone Laser extinction Temperature and differential


calorimeter [22–24] beam including pressure measurements taken
designed at the National temperature here
Institute of Standards and measurement
Technology (NIST)
Soot sample tube location
Exhaust
Exhaust hood
blower

Soot
collection
Gas
filter Cone
samples
heater
taken
Controlled here Spark
flow rate igniter

Sample
Load
cell

Vertical orientation

thickness. It was exposed to an external heat flux When a solid material is exposed to an exter-
of 50 kW/m2 under co-flowing normal air. The nal heat flux, it behaves either as thermally thin
chemical heat release rate profiles from the CDG or thermally thick, depending on its material
and OC calorimetries in the FPA are very similar, properties, dimensions and the magnitude of the
as expected. incident heat flux. Materials typically behave as
thermally thick at high heat fluxes (i.e., at high
heating rates); and behave thermally thin at low
Combustion Characteristics heat fluxes (i.e., at low heating rates) near their
of Materials: Engineering critical heat flux for ignition. A thermally thick
and Modeling Applications material is one having a physical thickness
greater than the depth of thermal diffusion at
Ignition (Fire Initiation) the time of ignition, while the physical thickness
of a thermally thin sample is less than the depth
The fundamental ignition principles are of thermal diffusion at ignition.
described in detail in Chap. 21. These principles The equation for piloted ignition time of
suggest that, for fire initiation, a material has solids under thermally thick conditions may be
to be heated above its critical heat flux (CHF, expressed as [26, 27]:
described below) for ignition. Generally π  2
kρ c p T ig  T 0
speaking, ignition of a combustible solid, heated
tigðthickÞ ¼ 4  00 00 2
ð36:1Þ
by an external source, starts with solid-phase q_ e  χ q_ cr
thermal decomposition and evolution of combus-
tible gases from the surface leading to gas-phase where, tig(thick) is the time to piloted ignition (s);
combustion, resulting in a sustained diffusion k, ρ and cp are, respectively, thermal conductivity
flame. (kW/m/K), density (kg/m3), and specific heat
Table 36.1 Design features, test conditions, and types of measurements for the OSU heat release rate apparatus, the Fire Propagation Apparatus, and the NIST Cone
1148

Calorimeter
Design and test conditions OSUa ASTM E2058 Fire Propagation Apparatusb Conec
Inlet gas flow Co-flow Co-flow/natural Natural
Oxygen concentration (%) 21 0–40 21
Co-flow gas velocity (m/s) 0.49 0–0.146 NA
External heaters Electrical resistance elements Tungsten-quartz Electrical coils
External heat flux (kW/m2) 0–80 0–110 0–100
Exhaust product flow (m3/s) 0.04 0.035–0.364 0.012–0.035
Horizontal sample dimensions (mm) 110  150 100  100 100  100
Vertical sample dimensions (mm) 150  150 100  600 100  100
Ignition source Pilot flame Pilot flame Spark plug
Heat release rate capacity (kW) 8 50 8
Measurements
Time to ignition Yes Yes Yes
Material gasification rate No Yes Yes
Fire propagation rate No Yes No
Generation rates of fire products Yes Yes Yes
Light obscuration by smoke Yes Yes Yes
Smoke yield No Yes No
Effective (chemical) heat of combustion No Yes Yes
Chemical heat release rate Yes Yes Yes
Convective heat release rate Yes Yes No
Radiative heat release rate No Yes No
Flame extinction No Yes No
_______________________________
NA not available
a
As specified in ASTM E906 [3] and by DOT/FAA [4]
b
As specified in ASTM E2058 [10] and ISO 12136 [11]
c
As specified in ASTM E1354 [24]
M.M. Khan et al.
36 Combustion Characteristics of Materials and Generation of Fire Products 1149

Fig. 36.5 Heat release 10


rates determined
employing the OC Calorimetry
methodologies described CDG Calorimetry
8
in the text (CDG, OC, GTR Calorimetry

Heat Release Rate (kW)


and GTR) for a 9.53-mm
thick slab of
polymethylmethacrylate 6
(PMMA) exposed to an
external heat flux of
50 kW/m2 and 0.09 m/s 4
co-flowing normal air
in the Fire Propagation
Apparatus
2

0
0 100 200 300 400 500 600

Time (s)

(kJ/kg/K) of the solid; their product represents the for a black surface, where σ is the Stephan-
thermal inertia of the solid. Tig and T0 are Boltzmann constant (kW/m2/K4).
the surface ignition temperature (K) and ambient The value of χ approximates the effect of heat
00 00
temperature (K), respectively, q_ e and q_ cr are the losses during heat up of the solid. It was
incident heat flux (kW/m2) and the critical heat recommended [27] that χ ¼ 0.64 for thermally
flux for ignition (CHF) (kW/m2), and χ is the thick conditions assuming surface re-radiation
00
average heat loss as a fraction of the critical heat losses close to q_ cr are dominant. After analyzing
flux and takes into account the fact that heat losses various materials, and considering both radiant
are initially zero and increase as the solid is heated and convective losses Khan et al. [29] proposed a
to its ignition temperature. The square root of single value of χ ¼ 1.0 for both thermally thin
the term in the numerator of the right hand side and thermally thick solids. A thermal diffusion
of Equation 36.1 is sometimes referred to as the time, τth (s), can be defined to demarcate the
Thermal Response Parameter (TRP) [28]: transition between thermally thick and thermally
thin responses as [26, 29]:
π 1=2  
TRP ¼ kρ c p T ig  T 0 ð36:2Þ 4ρ c p d2
4 τth ¼ ð36:4Þ
πk
Under thermally thin conditions for solids Using Equations 36.1 and 36.4, the relationship
of thickness d (m), the time to piloted ignition, between thermally thick and thin ignition behav-
tig(thin), is based on the energy required to heat ior is given by [29]:
the material to its ignition temperature assuming
a uniform temperature throughout the material:  1=
tigðthinÞ ¼ τth tigðthickÞ 2
  π 1=2  
ρ c p d T ig  T 0 kρ c p T ig  T 0 4ρ c d2  =2
1
tigðthinÞ ¼ 00 00 ð36:3Þ 4 p
q_ e  χ q_ cr ¼ 00 00
q_  χ q_ cr πk
 e 
Tig in Equations 36.1 and 36.3 is evaluated here ρ c p d T ig  T 0
¼ 00 00
assuming that reradiation heat losses dominate q_ e  χ q_ cr
00  
the ignition process so that q_ cr ¼ σ T ig 4  T 0 4 ð36:5Þ
1150 M.M. Khan et al.

A generalized form applicable to both regimes


is [29]:

82 34 2 38 91=4
>
> >
>
<6 7 =
00 00 00 00
q_  χ _
q 7 1 6 q_  χ q_
tigðthick=thinÞ ¼ 64
e cr 7 þ 6 e cr 7 ð36:6Þ
> 1=  5 τth 2 4π 1=2  5 >
: π kρ c p 2 T ig  T 0
>
kρ c p T ig  T 0
>
;
4 4

The exponents ¼, 4, and 8 in Equation 36.6 pro- sample. Empirically, the CHF is obtained by
vide a good fit to exact numerical solutions for collecting piloted ignition data in a flammability
transition between thermally thin and thick apparatus, such as the FPA, over a range of (low)
behavior [29]. In Equation 36.6, if tig is less heat fluxes. By plotting the inverse of time to
than τth the response of the material becomes ignition versus heat flux and using Equation 36.3,
thermally thick; whereas, if tig is greater than τth the intercept of a best-fit line on the heat flux axis
the response becomes thermally thin. Thus τth corresponds to the CHF. Alternatively, ignition
provides the transition between thermally thin tests may be also performed in search of the heat
and thermally thick behaviors. flux for which no ignition occurs after a specified
threshold (e.g., 15 min).
Critical Heat Flux (CHF)
The ignition and subsequent burning of a solid Thermal Response Parameter (TRP)
sample is sensitive to heat losses from the rear TRP is a very useful parameter for engineering
surface of the sample being tested. This heat loss calculations to assess resistance to ignition and
depends on the sample holder and its surrounding fire propagation. For thermally thick materials,
environment. Theoretical studies of ignition and the inverse of the square root of time to ignition
pyrolysis in flammability apparatuses show that is expected to be a linear function of the external
the construction of the sample holder has a sur- heat flux away from the CHF value (see Equa-
prisingly large effect on measured parameters, tion 36.1). The inverse of the slope of the line is
especially for solids having thermally thin behav- the TRP (see Equations 36.1 and 36.2). Most
ior near the critical heat flux [30]. This makes commonly used materials behave in a thermally
flammability measurements apparatus depen- thick manner at practical fire conditions and,
dent. One naturally wishes to minimize any such thus, satisfy Equation 36.1. This behavior is
heat losses, but to whatever extent such losses shown in Fig. 36.6 for polymethylmethacrylate
remain, they must be made reproducible and (PMMA) [31]; in Fig. 36.7 for heavy corrugated
quantifiable so that one can correct for their pres- paper sheets; and in Fig. 36.8 for cone calorime-
ence. To minimize apparatus dependencies, de ter data [32].
Ris and Khan have designed an insulated sample The TRP value is determined, for example, in
holder [30] that minimizes heat losses from the the Fire Propagation Apparatus, by (1) measuring
rear and sides of the sample being heated. The the time to ignition for 100 mm  100 mm
holder ensures that thermal processes remain square or 100-mm diameter and up to 25-mm-
one-dimensional so as to conform to most theo- thick samples at different external heat flux
retical analyses used to interpret data. values. The sample surfaces are blackened with
The critical heat flux may provide a measure a very thin layer of black paint or fine graphite
of the ignition temperature of a given material if, powder to avoid errors due to differences in the
as stated above, one assumes that all heat losses radiation absorption characteristics of the
near the CHF are dominated by radiation; this, materials, and (2) performing a linear regression
again, reinforces the need for a well-insulated analysis of the data away from the critical heat
36 Combustion Characteristics of Materials and Generation of Fire Products 1151

Fig. 36.6 Square root of 0.35


the inverse of time to
Natural flow
ignition versus external Co-flow; vg = 0.18 m/s
0.30
heat flux for 100-mm  Co-flow; vg = 0.18 m/s
100-mm  25-mm-thick Co-flow; vg = 0.18 m/s
polymethylmethacrylate 0.25

(Time to ignition)–1/2
(PMMA) slab with a
blackened surface. Data

No ignition
0.20

(s)–1/2
measured in the Fire
Propagation Apparatus [31]
0.15

0.10

0.05 CHF

0.00
0 10 20 30 40 50 60 70 80 90 100
External heat flux (kW/m2)

Fig. 36.7 Square root 0.5


of the inverse of time
0% Coating
to ignition versus 10% Coating
external heat flux for two 15% Coating
100-mm  100-mm  0.4
20% Coating
11-mm-thick sheets of
(Time to ignition)–1/2

heavy corrugated paper


with various levels of fire 0.3
No ignition
(s)–1/2

protection coating. Data


measured in the Fire
Propagation Apparatus.
Lines are linear fits to the 0.2
data; TRP values derived
from the fits are given
in Table A.35 0.1

0.0
0 20 40 60 80
External heat flux (kW/m2)

flux condition, following Equation 36.1, and boundary condition, provided by an appropriate
recording the inverse of the slope of the line. high absorptivity surface coating, in ignition tests.
The TRP for a surface may vary depending Uncoated samples may be subject to other phe-
on whether or not it is blackened. For example, nomena such as in-depth radiation [33] as well as
for nonblackened and blackened surfaces of the spectral characteristics of both sample surface
polymethylmethacrylate (PMMA), TRP ¼ 434 and radiation source [34, 35]. It is for these
and 274 kW · s1/2/m2, respectively [31]. The reasons that standard FPA tests [10, 11] require
TRP value for a blackened surface of PMMA is that samples be coated with high emissivity paint
close to the value calculated from the known Tig, to ensure surface absorption of imposed heat flux.
k, ρ, and cP values for PMMA [31]. These results TRP depends on the chemical as well as the
highlight the importance of a well-defined physical properties of materials, such as the
1152 M.M. Khan et al.

Fig. 36.8 Square root 0.5


of the inverse of time
to ignition versus PVEST
PVEST—glass
external heat flux for 0.4 Epoxy
100-mm  100-mm Epoxy—glass
nonblackened surfaces of Wood

(Time to ignition)–1/2
10-mm  11-mm-thick
polyvinyl ester (PVEST), 0.3

(s)–1/2
11-mm-thick epoxy, and
6-mm-thick wood
(hemlock). Data measured 0.2
in the cone calorimeter [32]

0.1

0.0
0 20 40 60 80 100
External heat flux (kW/m2)

chemical structure, fire retardants, etc. For exam- highly halogenated polymers, the TRPcal values
ple, Fig. 36.9 shows that TRP increases with are significantly lower than the TRPmeas values.
sample thickness for a composite material (poly- There is strong flame retardation by the fuel
ester/fiberglass) and increases in the amount of vapors of the highly halogenated polymers with
passive fire protection agent used, such as that a significant reduction in the fuel vapor concen-
provided by a surface coating to a heavy tration due to charring. Thus, for the ordinary
corrugated paper sheet (see Fig. 36.7). The TRP polymers, thermal arguments to describe the
response versus thickness shown in Fig. 36.9 is ignition behavior (Equations 36.1 and 36.2) are
counterintuitive given that TRP is strictly defined sufficient, but not for the highly charring, high-
for thermally thick materials; this response is a temperature, engineered polymers and highly
result of the composite material considered and halogenated polymers.
evidences the effect of physical structure and The effects of the fuel vapors of the highly
nonhomogeneity of the material. charring, high-temperature, engineered polymers
CHF and TRP values for several materials and highly halogenated polymers on the ignition
derived from data for time to ignition versus exter- behavior can be compensated by performing the
nal heat flux are listed in Table A.35. The ranges ignition experiments under enhanced oxygen
of CHF and TRP values in Table A.35 are due to concentration and, thus, thermal arguments
differences in the compositions of materials hav- again can be used to describe the ignition behav-
ing similar generic natures and differences in the ior. This is supported by the data reported by
test procedures, such as the use of an insulated Khan and de Ris [36], which are listed in
sample holder, as described above. Table 36.2.
Examples of calculated TRP values, using
available Tig, k, ρ, and cp data and Equation 36.2, Example 1 In a fire, newspaper and polypropyl-
and those measured are listed in Tables A.36 and ene are exposed to a heat flux value of 50 kW/m2.
A.37. The calculated and measured TRP values Estimate which material will ignite first, assum-
(TRPcal and TRPmeas, respectively) are plotted in ing physical conditions to be very similar for
Fig. 36.10. For ordinary polymers that do not both the materials.
contain halogen atoms and do not char signifi-
cantly, the TRPcal value is only about 17 % lower Solution From Table A.35, for newspaper and
than the TRPmeas value, but for highly charring, polypropylene, CHF ¼ 10 and 15 kW/m2, respec-
high-temperature, engineered polymers and tively, and TRP ¼ 108 and 193 kW · s1/2/m2,
36 Combustion Characteristics of Materials and Generation of Fire Products 1153

Fig. 36.9 Thermal


response parameter versus S–2 Polyester/fiberglass
500

Thermal response parameter


thickness for S-2 polyester/
fiberglass sample and
weight percent of surface
450

(kW·s2/m2)
coating for the heavy
corrugated paper (see
Fig. 36.7). Data measured
in the Fire Propagation 400
Apparatus. w weight %

350

300
0 5 10 15 20 25 30 35 40 45 50
Sample thickness (mm)

800 Heavy corrugated paper


Thermal response parameter

600
(kW·s2/m2)

400
TRP = 24.5 w + 181

200

0
0 5 10 15 20 25
Surface coating (weight percent)

Fig. 36.10 Calculated 900 Ordinary


versus measured values of 800 High temperature
TRPmeas (kW-s1/2/m2)

the thermal response Halogenated


700
parameter
600
500
400
300
200
100
0
0 100 200 300 400 500 600
TRPcal (kW-s1/2/m2)

respectively. Substituting these values in Example 2 Halogenated materials are obtained


00
Equation 36.1 with q_ e ¼ 50 kW/m2, the times to by replacing hydrogen atoms with halogen atoms
ignition are calculated to be 6 and 24 s for in the chemical structures of the materials. For
newspaper and polypropylene, respectively. example, a unit in polyethylene (PE) consists of
Thus, newspaper will ignite first. C2H4. If a hydrogen atom (H) is replaced by a
1154 M.M. Khan et al.

Table 36.2 Thermal response parameter values measured in normal air and 40 % oxygen concentration and calculated
from physical properties [23, 37]
TRPmeas (kWs1/2/m2)
Polymer Normal air 40 % oxygen TRPcal (kWs1/2/m2)
Ordinary polymers
Polymethylmethacrylate (PMMA) 239 230 264
Polyoxymethylene (POM) 252 260 269
Polypropylene/fire retarded 276 301 242
Halogenated polymers
Polyvinylchloride (PVC)—rigid 498 200 171
Chlorinated PVC (CPVC)—rigid 435a 230 280
Polyvinylchloride (PVDF) 447–508 324 301
a
Data from Table A.35

chlorine atom (Cl) in a PE unit, it becomes a unit Fire Propagation


of rigid polyvinylchloride (PVC), that is,
C2H3Cl. If two H atoms are replaced by two The fundamental surface flame spread principles
fluorine atoms (F) in a PE unit, it becomes a are described in Chap. 23. According to these
unit of Tefzel (ethylene tetrafluorethylene), that principles, the fire propagation process, as
is, C2H2F2. If all the hydrogen atoms are replaced indicated by surface flame spread, can be
by four F atoms in a PE unit, it becomes a unit of explained as follows. As a material is exposed to
Teflon (polytetrafluoroethylene), that is, C2F4. heat flux from internal and/or external heat
Show how the replacement of hydrogen atoms sources, a combustible mixture is formed that
by the halogen atoms affects the ignitability of ignites, and a flame anchors itself on the surface
the materials. in the ignition zone. As the vapors of the material
burn in the flame, they release heat with a certain
Solution From Table A.35, for PE (high rate, defined as the chemical heat release rate. Part
density), PVC (rigid), Tefzel, and Teflon, the of the chemical heat release rate is transferred
CHF values are 15, 15, 27, and 38 kW/m2, beyond the ignition zone as conductive heat flux
respectively, and the TRP values are 321, 406, through the solid and as convective and radiative
356, and 682 kW · s1/2/m2, respectively. In heat fluxes from the flame. If the heat flux trans-
the calculations, it is assumed that these ferred beyond the ignition zone satisfies CHF,
materials are exposed to a uniform heat flux TRP, and gasification requirements of the mate-
of 60 kW/m2 in a fire under very similar rial, the pyrolysis and flame fronts move beyond
physical conditions. From Equation 36.1, using the ignition zone, increasing the burning surface
00
q_ e ¼ 60 kW/m2, the times to ignition for PE area. Consequently, flame height, chemical heat
(high density), PVC (rigid), Tefzel, and Teflon release rate, and heat flux transferred ahead of the
are calculated to be 40, 64, 91, and 755 s, respec- pyrolysis front all increase. The pyrolysis and
tively. Thus, resistance to ignition increases as flame fronts move again, and the process repeats
the hydrogen atom is replaced by the halogen itself further increasing the burning area. Fire
atom in the chemical structure of PE. The higher propagation on the surface continues as long as
the number of hydrogen atoms replaced by the the heat flux transferred ahead of the pyrolysis
halogen atoms in the structure, the higher front (from the flame or external heat sources)
the resistance to ignition. When all the satisfies CHF, TRP, and gasification requirements
hydrogen atoms are replaced by the fluorine of the material.
atoms, the material becomes highly resistant to The rate of movement of the pyrolysis front is
ignition. generally used to define the fire propagation rate:
36 Combustion Characteristics of Materials and Generation of Fire Products 1155

Fig. 36.11 Pyrolysis front 400


versus time for downward
fire propagation for a
300-mm-long, 100-mm-
wide, and 25-mm-thick 300
PMMA vertical slab under
opposed airflow conditions
in the Fire Propagation

Xp (mm)
Apparatus. Airflow
200
velocity ¼ 0.09 m/s.
Oxygen mass
fraction ¼ 0.334 (Figure
is taken from Ref. [31])
100

0
0 200 400 600 800 1000
Time (s)

Fig. 36.12 Pyrolysis front 700


versus time for upward fire
propagation for a 600-mm-
600
long, 100-mm-wide, and
25-mm-thick PMMA
vertical slab under 500
co-airflow conditions in
the Fire Propagation
Xp (mm)

400
Apparatus. Airflow
velocity ¼ 0.09 m/s.
Oxygen mass 300
fraction ¼ 0.233
(Figure is taken from 200
Ref. [31])

100

0
0 100 200 300 400 500
Time (s)

dX p In Fig. 36.14, heat release rates increase linearly


u¼ ð36:7Þ
dt with time during downward fire propagation,
very similar to the pyrolysis front values for the
where u is the fire propagation rate (mm/s or downward fire propagation in Fig. 36.11.
m/s), and Xp is the pyrolysis front length The trends of the lines in Figs. 36.11, 36.12,
(mm or m). 36.13, and 36.14 represent fire propagation
The fire propagation rate can be determined in rates. The upward fire propagation rate is much
one of several apparatuses: (1) the LIFT [37] faster than the downward fire propagation rate.
described in Chap. 23; (2) the Fire Propagation For downward fire propagation, linear increases
Apparatus [10, 11] shown in Fig. 36.3. Examples in the pyrolysis front and heat release rates
of the type of data obtained from the FPA are indicate decelerating fire propagation behavior.
shown in Figs. 36.11, 36.12, 36.13, and 36.14. For upward fire propagation, nonlinear increases
1156 M.M. Khan et al.

Fig. 36.13 Pyrolysis front 700


height versus time for
upward fire propagation for
600
a 600-mm-long and
0.446 0.279
25-mm-thick diameter
PMMA cylinder under 500
co-airflow conditions
in the Fire Propagation
400

Xp (mm)
Apparatus. Airflow
velocity ¼ 0.09 m/s.
Numbers inside the frames 300 0.233
are the mass fractions of
oxygen in air (Figure is 200
taken from Ref. [31])

100

0
0 100 200 300 400
Time (s)

Fig. 36.14 Chemical (top) 12


and convective (bottom) Flame Entire
heat release rate versus spread surface
time for downward fire 10 0.446 0.233 burning
propagation, combustion,
and flame extinction for a
300-mm-long, 100-mm- 8
wide, and 25-mm-thick
Qch (kW)

PMMA vertical slab under


opposed airflow conditions 6 0.201
in the Fire Propagation

0.178
Apparatus. Airflow
velocity ¼ 0.09 m/s. 4
Numbers inside the frames
are the mass fractions of
oxygen in air (Figure is 2
taken from Ref. [31])
0 0.233

6 Unstable Flame
flame extinction
5
Qcon (kW)

4

0
0 200 400 600 800 1000 1200 1400
Time (s)
36 Combustion Characteristics of Materials and Generation of Fire Products 1157

in the pyrolysis front indicate accelerating fire cables. For example, for upward fire propagation
propagation behavior. in the CSA FT-4, a damage length of less than
60 % of the total length of the cable tray for a
Empirical Relationship Between Fire 20-min exposure is used as the acceptance crite-
Propagation Rate, Flame Height, Pyrolysis rion. For horizontal fire propagation in the
Front, and Heat Release Rate UL-1581 test, a flame length of less than 40 %
Numerous researchers have found the following of the total length of the cable tray is used as the
relationship between the flame height and acceptance criterion.
pyrolysis front (as discussed in Chap. 13, and The relationship between the flame height
reviewed in Refs. [31, 38]): and the chemical heat release rate, expressed
as the normalized chemical heat release rate
X f ¼ aX np ð36:8Þ (NCHRR), is defined as
where 0
Xf ¼ Flame height (m) Q_ ch
NCHRR ¼ ð36:9Þ
a ¼ 5.35 3=
ρc p T a g =2 X p2
1

n ¼ 0.67–0.80
for steady wall fires [31]. Xp is in m.
Fire propagation data for PMMA from the where
0
FPA and for electrical cables from several stan- Q_ ch ¼ Chemical heat release rate per unit width
dard tests (ICEA [39], CSA FT-4 [40], and (kW/m)
UL-1581 [41]) satisfy Equation 36.8, as shown ρ ¼ Density of air (g/m3)
in Fig. 36.15, with a ¼ 5.32 and n ¼ 0.78. The cp ¼ Specific heat of air (kJ/g · K)
visual measurement of the pyrolysis front as Ta ¼ Ambient temperature (K)
damage length is used for the acceptance crite- g ¼ Acceleration due to gravity (m2/s)
rion in many of the standard tests for electrical Xp is in m.

Cable (ICEA; YO = 0.233)


Cable (CSA FT–4; YO = 0.233)
Cable (UL–1581; YO = 0.233)
PMMA (FMRC–Cylinder 1; YO = 0.233)
PMMA (FMRC–Cylinder 2; YO = 0.233)
PMMA (FMRC–Slab; YO = 0.233)
Flame height (mm)

103 PMMA (FMRC Cylinder 1; YO = 0.445)

102

101 102 103


Pyrolysis front (mm)

Fig. 36.15 Flame height versus pyrolysis front height and UL-1581) and for 600-mm long PMMA slabs
for upward fire propagation in normal air. Data are for the (100-mm-wide and 25-mm-thick) and cylinders (25-mm
vertical fire propagation for electrical cables contained in diameter) in the Fire Propagation Apparatus. Data for fire
2.44-m-long, 310-mm-wide, and 76-mm-deep trays in propagation in an oxygen mass fraction of 0.445 are also
standard tests for electrical cables (ICEA, CSA FT-4, included (Figure is taken from Ref. [31])
1158 M.M. Khan et al.

Many researchers have shown that the height show that (1) for 0.2 < NCHRR < 5, n ¼ 2/3
ratio of the flame to the pyrolysis front is a and 1.5 < Xf/Xp < 20 (PMMA fire propagation
function of the heat release rate, such as the and methane combustion); and (2) for
following relationship (as discussed in NCHRR > 5, n ¼ 1/2 and Xf /Xp > 20 (ethane
Chap. 13, and reviewed in Refs. [31, 38]): and propylene combustion). Thus, the ratio of
the flame height to pyrolysis front height is a
Xf
¼ aðNCHRRÞn ð36:10Þ good indicator of the fire propagation
Xp characteristics of the materials. Materials for
where a and n are constants. This relationship which flame height is close to the pyrolysis
reported in the literature (as reviewed in Ref. front location during fire propagation can be use-
[31]) for methane, ethane, and propylene is ful indicators of decelerating fire propagation
shown in Fig. 36.16. The data for the upward behavior.
fire propagation for PMMA [31] and for electri- Researchers have also developed many
cal cables from several standard tests (ICEA correlations between the flame heat flux trans-
[39], CSA FT-4 [40], and UL-1581 [41]) also ferred ahead of the pyrolysis front and heat
satisfy this relationship as indicated in Fig. 36.16. release rate for downward, upward, and horizon-
In Fig. 36.16, data in the lower left-hand cor- tal fire propagation (as discussed in Chap. 23,
ner are for low-intensity polyvinylchloride and reviewed in Refs. [31, 38]). For example,
(PVC) electrical cable fire propagation in stan- small- and large-scale fire propagation test data
dard tests for cables. These data show that for suggest that, for thermally thick materials with
NCHRR < 0.2, Xf/Xp < 1.5 and n ¼ 1/10. This highly radiating flames, the following semiem-
is a characteristic property of materials for which pirical relationship is satisfied [28]:
there is either no fire propagation or limited fire  1=3
00 χ rad _ 0
propagation beyond the ignition zone. The data q_ f / Q ð36:11Þ
for higher-intensity fire propagation in Fig. 36.16 χ ch ch

Cable (UL–1581)
102 Cable (ICEA)
Cable (CSA FT–4)
Ethane, Propylene n = 1/2
Flame height/pyrolysis front

Methane
PMMA (FMRC)

101

n = 1/10
n = 2/3

100

10–2 10–1 100 101 102


Normalized chemical heat release rate

Fig. 36.16 Ratio of flame height to pyrolysis front tests for electrical cables (ICEA, CSA FT-4, and
height versus the normalized chemical heat release rate UL-1581). Data for PMMA are from the Fire Propaga-
for upward fire propagation in normal air. Data for dif- tion Apparatus for 600-mm-long vertical PMMA slabs
fusion flames of methane, ethane, and propylene are (100-mm-wide, 25-mm-thick) and cylinders (25-mm-
from the literature. Data for cables are from standard diameter) [31]
36 Combustion Characteristics of Materials and Generation of Fire Products 1159

00
where q_ f is the flame heat flux transferred ahead
of the pyrolysis front (kW/m2) and χ rad is the
radiative fraction of the combustion efficiency,
χ ch. The fire propagation rate is expressed as [28]
 1=3
1= 1 χ rad _ 0
u / 2
Q ð36:12Þ
TRP χ ch ch

On the basis of the discussion above, an emprical


parameter termed fire propagation index (FPI)
[16, 17, 28, 42–46] has been defined:
0 =3
1

Q_
FPI ¼ 750 ch ð36:13Þ
TRP
FPI describes the fire propagation behavior of
materials under flame-radiating conditions prev-
alent in large-scale fires. Small- and large-scale
fire propagation test data of various materials
along with understanding of fire propagation
phenomena suggest that the FPI values can be
used to classify materials as either propagating
(fire propagates rapidly beyond ignition zone)
and non-propagating (there is no fire propagation
beyond the ignition zone) [28, 31, 43–46].
These FPI-based determinations have been
validated by using intermediate-scale parallel
panel tests (e.g., [19]) as shown in Figs. 36.17 Fig. 36.17 Nonpropagating fire between two vertical
and 36.18 and described below. parallel panels of a polymer (FPI < 6) for a test duration
of 15 min [19]. The panels are about 0.61 m (2 ft) wide,
Application of the Fire Propagation Index 2.44 m (8 ft) high, and 25 mm (1 in) thick separated
by 0.30 m (1 ft). The ignition source is a 60-kW,
(FPI) to Classify Materials 0.30-m-wide, 0.61-m-long, and 0.30-m-high propane
The FPI values for the upward fire propagation, sand burner. The tip of the flame from the burner reaches
under flame-radiating conditions, have been a height of about 0.91 m (3 ft). Marks on the scale are
determined for numerous materials at reduced in feet
scales in the Fire Propagation Apparatus. The
highly radiating conditions, representative of are performed in the FPA (materials are
large-scale fires, are created in the FPA by burn- arranged as in Fig. 36.3). About 300–600-
ing the materials in an enhanced oxygen environ- mm-long, up to about 100-mm-wide, and up
ment (0.40 oxygen mass fraction). Two sets of to about 100-mm-thick samples are used.
tests are performed: The bottom 120–200 mm of the sample is in
1. Thermal response parameter test: Ignition the ignition zone, where it is exposed to
tests are performed in the FPA (materials are 50 kW/m2 of external heat flux in the presence
arranged as in Fig. 36.2), and the TRP value is of a pilot flame. Beyond the ignition zone, the
determined from the time to ignition versus fire propagates by itself under co-airflow con-
external heat flux as described in the subsec- dition with an oxygen mass fraction of 0.40.
tion “Thermal Response Parameter (TRP)”. During upward fire propagation, the chemical
2. Upward fire propagation test: Fire propaga- heat release rate is measured as a function
tion tests for vertical slabs, sheets, or cables of time.
1160 M.M. Khan et al.

parallel panel intermediate scale test configura-


tion was first introduced in 1988 [28] to verify
the fire propagation behavior of electrical cables
based on the fire propagation index (FPI),
derived from bench-scale FPA measurements. It
consists of two parallel panels of test material,
each 0.61 m wide and 4.9 m long facing each
other with a separation of about 0.31 m (keeping
an aspect ratio of the panel width to the separa-
tion distance as 0.5). A 60 kW propane sand
burner continuously provides an exposure fire at
the base of the two panels. This intermediate
scale test scenario contains the essential features
of fire phenomena expected at larger scales, most
notably enhanced radiant fluxes due to the
radiation feedback between the panels. This test
configuration provides sufficient size and
confinement of flames to yield realistic flame
heat transfer to the materials (see Figs. 36.17
and 36.18).
The nonpropagating fire condition is satisfied
for FPI  10.0 for electrical cables (classified
as Group 1) [17] that do not exhibit flame propa-
gation beyond the vicinity of the ignition
source in the parallel panel tests. In a recent
study [46], plenum rated cables, having FPI
values of 7.0, did not exhibit flame propagation
in the parallel panel tests. Table 36.3 lists FPI
Fig. 36.18 Rapidly propagating fire between two verti- values for selected electrical cables and
cal parallel panels of a polymer (FPI > 20) [19]. The conveyor belts.
panels are about 0.61 m (2 ft) wide, 2.44 m (8 ft) high,
and 25 mm (1 in.) thick separated by 0.30 m (1 ft). The
ignition source is a 60-kW, 0.30-m-wide, 0.61-m-long,
Example 3 What type of fire behavior is
and 0.30-m-high propane sand burner. The tip of the represented by a 300-mm-wide, 8-m-high, and
flame from the burner reaches a height of about 0.91 m 25-mm-thick vertical cable array with a TRP
(3 ft). Marks on the scale are in feet. The photograph was value of 95 kW · s1/2/m2 if the peak chemical
taken a few seconds before flames extended far beyond
the top of the panels
heat release during upward fire propagation is
50 kW?
The TRP value and the chemical heat release
rate so determined are used in Equation 36.13 to Solution Fire propagation behavior is assessed
calculate the FPI; the maximum (peak) measured by the FPI value. For the cable material,
chemical heat release rate value is used in the the chemical heat release rate per unit width,
0
calculation. Q_
ch ¼ 50/0.3 ¼ 167 kW/m. Substituting
this value in Equation 36.13, with TRP ¼
Electrical Cables The FM Approval standard 95 kW · s1/2/m2, FPI ¼ 43. The cable material
for cable fire propagation [17] is used to classify will propagate fire.
electrical cables, based on their upward fire prop-
agation behavior, under highly flame-radiating Conveyor Belts A conveyor belt standard has
conditions (0.40 oxygen mass fraction). A been developed at FM Global [20]. In this
36 Combustion Characteristics of Materials and Generation of Fire Products 1161

Table 36.3 Fire propagation index for cables and Con- Example 4 Conveyor belts are made of solid
veyor belts, determined in the Fire Propagation Apparatus woven or piles of elastomers, such as styrene-
Diameter/ butadiene rubber (SBR), polychloroprene rubber
thickness (mm) FPI (CR), polyvinylchloride (PVC), reinforced with
Power cables fibers made of polymers, such as nylon. In large-
PVC/PVC 4–13 11–28 scale fire propagation tests in a tunnel, fire on the
PE/PVC 11 16–23
surface of a CR-based conveyor belt was found to
PVC/PE 34 13
be nonpropagating, whereas for a CR/SBR-based
Silicone/PVC 16 17
conveyor belt fire was found to be propagating.
Silicone/XLPO 55 6–8
Small-scale tests showed that the CR- and
EP/EP 10–25 6–8
XLPE/XLPE 10–12 9–17
CR/SBR-based conveyor belts had the following
XLPE/EVA 12–22 8–9
fire properties, respectively: (1) CHF ¼ 20 and
XLPE/neoprene 15 9 15 kW/m2, (2) TRP ¼ 760 and 400 kW · s1/2/m2,
0
XLPO/XLPO 16–25 8–9 and (3) peak Q_ ¼ 114 and 73 kW/m under
ch
XLPO, PVF/XLPO 14–17 6–8 highly flame-radiating conditions (0.40 oxygen
EP/CLP 4–19 8–13 mass fraction). Show that small-scale test results
EP, FR/none 4–28 9 are consistent with the large-scale fire propaga-
Communications cables tion behaviors of the two conveyor belts, using
PVC/PVC 4 36 the criterion that, for nonpropagating fire behav-
PE/PVC 4 28 ior, the FPI is equal to or less than 7.
PXLPE/XLPO 22–23 6–9
Si/XLPO 28 8 0
EP-FR/none 28 12 Solution Substituting the TRP and Q_ ch values
PECI/none 15 18 in Equation 36.13, the FPI values for the CR-
ETFE/EVA 10 8 and CR/SBR-based conveyor belts are 5 and
PVC/PVF 5 7 8, respectively. Thus, the CR-based conveyor
FEP/FEP 8 4 belt is expected to have a nonpropagating fire
FEP/FEP 10 5 behavior, whereas the CR/SBR-based conveyor
Conveyor beltsa belt is expected to have a propagating fire
Styrene-butadiene 8–11 behavior. The small-scale test results, there-
rubber (SBR) fore, are consistent with the large-scale fire
Chloroprene rubber (CR) 5
propagation behaviors of the two conveyor
CR/SBR 8
belts.
PVC 4–10
a
3–25 mm thick
Polymeric Materials For Cleanrooms -
Microchip devices are manufactured, in bulk,
standard, as with the cable standard [17], TRP on wafers of semiconducting materials. Wafers
and upward fire propagation tests are performed, are manufactured in several stages: material
and Equation 36.13 is used to calculate the FPI. preparation, crystal growth and wafer prepara-
Conveyor belts are classified as propagating tion, wafer fabrication, and packaging. Wafers
or non-propagating. For an approximately are fabricated in cleanrooms where cleanliness
600-mm-long and 100-mm-wide vertical con- is highly controlled in order to limit the number
veyor belt, the data measured in the FPA under of contaminants to which the wafer is exposed.
highly flame-radiating conditions show that the The stringent requirements of the solid-state
nonpropagating fire condition is satisfied for devices define levels of cleanliness that far
FPI  7.0 for belts that show limited fire propa- exceed those of almost any other industry. Con-
gation in the large-scale fire propagation tests tamination in a cleanroom is defined as anything
[45, 47]. Table 36.3 lists FPI values for selected that interferes with the production of wafers
conveyor belts taken from Refs. [45, 47]. and/or their performance. The overall cleanroom
1162 M.M. Khan et al.

design principle is to build a sealed room that chapter). The FPI and SDI values for various
is supplied with clean air, is built with polymeric materials (including composites)
polymeric materials that are noncontaminating, determined from FPA tests are listed in
and includes systems to prevent accidental Table 36.4 [19, 43, 44, 48, 49].
external contamination, interactions of the poly- It can be noted from Table 36.4 that specialty
meric materials and wafer cleaning liquids, oper- polymeric materials (highly halogenated
ator error, and accidental fires. thermoplastics and high temperature
In 1997, FM Global Research introduced thermosets) have low FPI and SDI values and
a new methodology, identified as the FM several of them satisfy the 4910 test protocol
Approval Standard 4910 Test Protocol [19], for criteria (FPI  6 (m/s1/2)/(kW/m)2/3 and SDI
testing the fire propagation and smoke develop-  0.4 (g/g)(m/s1/2)/(kW/m)2/3) for acceptance
ment behaviors of polymeric materials for use as cleanroom materials [19]. These polymeric
in cleanrooms for the semiconductor industry. materials have high thermal stability with
For the acceptance of polymeric materials, reduced release of carbon, hydrogen, and halo-
two criteria need to be satisfied: (1) Fire Propa- gen atoms, as can be noted from their decompo-
gation Index FPI  6 (m/s1/2)/(kW/m)2/3 sition temperatures listed in Table 36.5 [50].
and (2) Smoke Development Index Ordinary thermoplastics (such as PE, PP, and
SDI  0.4 (g/g) (m/s1/2)/(kW/m)2/3. PVC) can also be modified such that they behave
In the 4910 Test Protocol [19], the Fire Prop- similarly to the specialty polymeric materials
agation Index (FPI) is formulated from (1) the and have low FPI and SDI values to satisfy the
thermal response parameter (TRP), which relates 4910 Test Protocol criteria for acceptance as
the time to ignition to the net heat flux, and cleanroom materials.
(2) the chemical heat release rate measured dur-
ing the upward fire propagation in air having a Composites and Fiberglass-Reinforced
40 % oxygen concentration to simulate flame Materials Composites and fiberglass-reinforced
heat transfer at large scale, as described above. materials are very attractive because of their low
SDI is related to the smoke release rate and is weight and high strength characteristics and have
obtained by multiplying the FPI value by the found practical applications in a large number of
smoke yield as shown in Fig. 36.19. The smoke sectors such as in aircrafts, submarines, naval
yield is defined as the ratio of the total mass of ships, military tanks, public transportation
smoke released per unit mass of burned vapors vehicles including automobiles, space vehicles,
from the polymeric material (see section “Gener- tote boxes, pallets, chutes, and so forth. Fire prop-
ation of Fire Products and Smoke Yields” of this agation, however, is one of the major concerns for

Fig. 36.19 Peak smoke 10


release rate measured in
Smoke release rate (g/m2·s)

combustion tests in normal Composites


air with imposed external Polymers
heat flux of 50 kW/m2 1
versus peak FPI values
from the propagation tests
in 40 % oxygen
environments multiplied by 0.1
the smoke yields from the
combustion tests. Tests
were performed in the Fire
Propagation Apparatus
0.01
0.001 0.01 0.1 1 10
FPI x ys (g/g)(m/s1/2)/(kW/m)2/3
36 Combustion Characteristics of Materials and Generation of Fire Products 1163

Table 36.4 Fire propagation index and smoke development index for polymeric materials
FPI (m/s1/2)/ SDI (g/g)(m/s1/2)/
Polymeric material (kW/m)2/3 (kW/m)2/3
Fire-retarded or unmodified electrical cables
Polyvinyl chloride(PVC/polyvinylchloride PVC) 36 4.1
Polyethylene (PE)/polyvinyl chloride (PVC) 28 3.8
Silicone/polyvinyl chloride (PVC) 17 2.0
Modified electrical cables
Polyvinylchloride (PVC) 8 1.2
High-temperature polyvinylchloride (PVC) 7 0.69
Polyethylene (PE)/ethylvinylacetate (EVA) 5 0.40
Ordinary polymeric materials
Fire-retarded polystyrene (FR-PS) 34 5.60
Fire-retarded polybutyleneterephthalate (FR-PBT) 32 2.20
Unmodified polymethylmethacrylate (U-PMMA) 23 1.1
Unmodified polyoxymethylene (U-POM) 15 0.03
Fire-retarded (FR) vinyl ester 10 2.5
Unmodified wood slab 14 0.20
Unmodified polyethylene (U-PE) 30 1.4
Polyethylene with 25 % chlorine 15 1.7
Polyethylene with 36 % chlorine 11 1.5
Polyethylene with 48 % chlorine 8 1.9
Modified polyethylene (M-PE)-1 7 0.64
Modified polyethylene (M-PE)-2 6 0.65
Unmodified polypropylene (U-PP) 31 1.7
Fire-retarded polypropylene (FR-PP) 30 2.1
Modified polypropylene (M-PP)-1 11 3.0
Modified polypropylene (M-PP)-2 7 0.95
Modified polypropylene (M-PP)-3 7 0.35
Modified polypropylene (M-PP)-4 6 0.41
Modified polypropylene (M-PP)-5 5 0.40
Modified polypropylene (M-PP)-6 5 0.19
Modified polypropylene (M-PP)-7 5 0.21
Modified polypropylene (M-PP)-8 4 0.19
Fire-retarded flexible polyvinylchloride (FR-PVC) 16 1.6
Unmodified rigid polyvinylchloride (U-PVC)-1 8 0.86
Unmodified rigid polyvinylchloride (U-PVC)-2 7 1.2
Modified rigid polyvinylchloride (M-PVC)-1 6 0.31
Modified rigid polyvinylchloride (M-PVC)-2 5 0.64
Modified rigid polyvinylchloride (M-PVC)-3 4 0.15
Modified rigid polyvinylchloride (M-PVC)-4 3 0.16
Modified rigid polyvinylchloride (M-PVC)-5 3 0.29
Modified rigid polyvinylchloride (M-PVC)-6 2 0.11
Modified rigid polyvinylchloride (M-PVC)-7 2 0.04
Modified rigid polyvinylchloride (M-PVC)-8 2 0.06
Modified rigid polyvinylchloride (M-PVC)-9 1 0.03
Chlorinated rigid polyvinylchloride (CPVC, Corzan) 3 0.13
(continued)
1164 M.M. Khan et al.

Table 36.4 (continued)


FPI (m/s1/2)/ SDI (g/g)(m/s1/2)/
Polymeric material (kW/m)2/3 (kW/m)2/3
Highly halogenated specialty polymeric materials
Unmodified polyvinylidenefluoride (U-PVDF Kynar)-1 5 0.14
Unmodified polyvinylidenefluoride (U-PVDF)-2 4 0.08
Unmodified ethylenechlorotrifluoroethylene (U-ECTFE, Halar) 4 0.15
Unmodified ethylenetetrafluoroethylene (U-ETFE, Tefzel) 7 0.17
Unmodified perfluoroalkoxy (U-PFA, Teflon) 2 0.01
Unmodified fluorinated ethylene-propylene (U-FEP, Teflon) 3 0.01
High-temperature specialty polymeric materials
Phenol formaldehyde 5 0.06
Polyether ether ketone (PEEK) 4 0.03
Melamine 7 0.24
Unmodified polycarbonate (U-PC) 14 4.2
Modified polycarbonate (M-PC)-1 10 4.2
Modified polycarbonate (M-PC)-2 7 4.0
Unmodified polysulfone (U-POS) 18 1.49
Modified polysulfone (M-POS)-1 11 1.4
Modified polysulfone (M-POS)-2 11 0.32
Modified polysulfone (M-POS)-3 7 1.2
Modified polysulfone (M-POS)-4 7 0.25
Modified polyetherimide (M-PEI)-1 6 0.24
Modified polyetherimide (M-PEI)-2 6 0.04
Modified polyetherimide (M-PEI)-3 5 0.46
Unmodified polyphenyleneoxide (U-PPO) 9 1.6
Glass fiber–reinforced ordinary polyesters
Glass fiber–reinforced fire-retarded polyester (FR-PES)-1 21 5.4
Glass fiber–reinforced fire-retarded polyester (FR-PES)-1 16 7.4
Glass fiber–reinforced fire-retarded polyester (FR-PES)-1 14 4.0
Glass fiber–reinforced modified polyester (M-PES)-1 11 5.5
Glass fiber–reinforced modified polyester (M-PES)-1 10 5.2
Glass fiber–reinforced modified polyester (M-PES)-1 9 3.1
Composites
Fire-retarded polyester (30 %)/glass fibers (70 %)-1 13 0.91
Fire-retarded polyester (30 %)/glass fibers (70 %)-2 10 0.68
Unmodified phenolic (16 %)/Kevlar fibers (84 %) 8 0.33
Modified phenolic (20 %)/glass fibers (80 %) 3 0.07
Fire-retarded epoxy (35 %)/glass fibers (65 %)-1 11 2.1
Fire-retarded epoxy (35 %)/glass fibers (65 %)-2 10 0.94
Fire-retarded epoxy (35 %)/glass fibers (65 %)-3 9 1.2
Modified epoxy (24 %)/glass fibers (76 %)-1 5 0.61
Modified epoxy (29 %)/graphite fibers (71 %) 5 0.54
Modified epoxy and phenolic (18 %)/glass fibers (82 %) 2 0.18
Modified polyphenylenesulfide (16 %)/glass fibers (84 %) 3 0.29
Modified cyanate (27 %)/graphite fibers (73 %) 4 0.41
Note: Data taken from Refs. [19, 43, 44, 48, 49]
36 Combustion Characteristics of Materials and Generation of Fire Products 1165

Table 36.5 Decomposition temperature, char yield, and limiting oxygen index for polymeric materials
Decomposition Char Limiting oxygen
Polymeric material temperature ( C) yield (%) index (%)
Polybenzobisoxazole (PBO) 789 75 56
Polyparaphenylene 652 75 55
Polybenzimidazole (PBI) 630 70 42
Polyamideimide (PAI) 628 55 45
Polyaramide (Kevlar) 628 43 28
Polyetherketoneketone (PEKK) 619 62 40
Polyetherketone (PEK) 614 56 40
Polytetrafluoroethylene (PTFE) 612 0 95
Polyether ether ketone (PEEK) 606 50 35
Polyphenylsulfone (PPSF) 606 44 38
Polypara(benzoyl)phenylene (PX) 602 66 41
Fluorinated cyanate ester 583 44 40
Polyphenylenesulfide (PPS) 578 45 44
Polyetherimide (PEI) 575 52 47
Polypromellitimide (PI) 567 70 37
Polycarbonate (PC) 546 25 26
Polysulfone (PSF) 537 30 30
Polyethylene (PE) 505 0 18
Polyamide 6 (PA6)-nylon 497 1 21
Polyethyleneterephthalate (PET) 474 13 21
Acrylonitrile-butadiene-styrene (ABS) 470 0 18
Polyurethane elastomer (PU) 422 3 17
Polymethylmethacrylate (PMMA) 398 2 17
Polychlorotrifluoroethylene 380 0 95
Polyvinylchloride (PVC) 370 11 50
Polystyrene (PS) 364 0 18
Polyoxymethylene (POM) 361 0 15
Polyvinylidenefluoride (PVDF) 355 0 44
Note: Data are taken from Ref. [50]

composites and fiberglass-reinforced materials; (7.6 m) corner test as a standard test to evaluate
therefore, the FPI concept discussed above for the burning characteristics of interior finish wall
electrical cables and conveyor belts can also be and ceiling materials [18]. The 25-ft (7.6 m) corner
applied to these materials [43, 44]. In the case of test is performed in a 7.6-m (25-ft)-high, 15.2-m
composites and fiberglass-reinforced materials (50-ft)-long and 11.6-m (38-ft)-wide building cor-
the nonpropagating fire condition is satisfied for ner configuration [51, 52]. The materials tested are
FPI  6.0, for about 600-mm-long and 100-mm- typically panels with a metal skin over an insula-
wide vertical composites and fiberglass- tion core material. The materials installed in the
reinforced materials, under highly flame-radiating corner configuration are subjected to a growing
conditions (0.4 oxygen mass fraction), very exposure fire (peak heat release rate of about
similar to the conveyor belts. Table 36.4 lists FPI 3 MW) comprised of about 340 kg (750 lb) of
values for selected composites and fiberglass- 1.2-m (4-ft)  1.2-m (4-ft) wood (oak) pallets
reinforced materials [43, 44]. stacked 1.5 m (5 ft) high at the base of the corner.
The material is considered to have failed the test if
Interior Finish Wall/Ceiling Materials Since within 15 min either (1) fire propagation on the
1971, FM Global Research has used the 25-ft wall or ceiling extends to the limits of the structure,
1166 M.M. Khan et al.

or (2) flame extends outside the limits of the struc- Xt ¼ Total available length [11.6-m (38 ft)] in
ture through the ceiling smoke layer. the 25-ft (7.6 m) corner test
00
The fire environment within the 25-ft (7.6 m) Q_ ¼ Convective heat release rate (kW/m2)
con
corner test structure has been characterized measured in the small-scale test
through heat flux and temperature measurements The right-hand side of Equation 36.14 with
[51, 52]. It has been shown that the fire propaga- the convective heat release rate measured
tion boundary (pyrolysis front) measured by (through GTR, see above) for a material exposed
visual damage is very close to the critical heat to 50 kW/m2 of external heat flux in the Fire
flux (CHF) boundary for the material, as shown Propagation Apparatus is defined as the convec-
in Fig. 36.20 [52]. This relationship is in agree- tive flame spread parameter (FSPc) [51, 52].
ment with the general understanding of the fire Figure 36.21 shows a correlation between the
propagation process. Through small- and large- convective flame spread parameter obtained
scale fire propagation tests for low-density, from the FPA and the normalized fire propaga-
highly char-forming wall and ceiling insulation tion length in the FM Global 25-ft (7.6 m) corner
materials, a semi-empirical relationship has been test. Pass/fail regions, as determined from the
developed for fire propagation rate for a 15-min 25-ft (7.6 m) corner test, are indicated in the
test in the 25-ft (7.6 m) corner test [51, 52]. figure. Materials for which FSPc  0.39 pass
00 the 25-ft (7.6 m) corner test, and materials for
X p Q_ con
¼ ð36:14Þ which FSPc  0.47 are judged to be unaccept-
Xt TRP able (i.e., fail); the region where the FSPc values
where are greater than 0.39 but less than 0.47 is uncer-
Xp ¼ Average fire propagation length along the tain [18, 51, 52].
eaves (Fig. 36.20) of the 25-ft (7.6 m) corner The correlation and pass/fail criterion
test (pyrolysis front) measured visually (m) shown in Fig. 36.21 have been adopted in the

X5
X5
X6 X6
X5 X6
X9 X15 X9
X4 X6 X10 X4
X10
4 X15
X6 X10 X34 X10
X52 X18
X49
9 X120
X187 X69
100 X118
X2

East wall X2 X2 South wall


X6 X193
97

X146 X3
X3 84

Visual damage evaluation


Critical heat flux boundary

Fig. 36.20 Critical heat flux boundary and visual observations for the extent of fire propagation in the FM Global 25-ft
corner test for a product that passes the tests [52]
36 Combustion Characteristics of Materials and Generation of Fire Products 1167

Fig. 36.21 Normalized 1.0


fire propagation length
measured in the 25-ft Xp /Xt = 0.82 * FSPc0.25
corner test versus the
convective flame spread 0.8
parameter obtained from
the ASTM E2058 fire
propagation apparatus
(Figure is taken from 0.6
Refs. [51, 52])

Xp /Xt
0.4

0.2 Pass
Fail

0.0
0.0 0.2 0.4 0.6 0.8 1.0
FSPc

FM Approval Standard Class No. 4880 for surface regression becomes steady after fire
insulated wall or wall and ceiling panels [18]. propagates throughout the available surfaces.
In this standard, the 25-ft (7.6 m) corner test The surface regression continues until all the
has been replaced by the Fire Propagation Appa- combustible components of the material are
ratus tests along with a new intermediate-scale exhausted. During fire propagation and surface
parallel panel test [53], which are a cost-effective regression, the material generates vapors at a
alternative and considerably simplify the test transient or steady rate. The generation rate of
protocol. Two sets of tests are performed in the the material vapors is measured by the mass loss
FPA [18, 51, 52]: rate. In the presence of a flame and/or external
1. Thermal response parameter test: Ignition heat flux, the mass loss rate, under steady state, is
tests are performed using approximately expressed as [14, 31, 44]:
100-mm  100-mm and up to 100-mm-thick
samples. Times to ignition at various external 00 00 00 00
00 q_ e þ q_ f r þ q_ fc  q_ rr
heat flux values are measured to determine the m_ ¼ ð36:15Þ
TRP as described earlier. ΔH g
2. Convective heat release rate test: Combus-
tion tests are performed using about where
100-mm  100-mm and up to 100-mm-thick ṁ00 ¼ Mass loss rate (g/m2 · s)
00
samples. Samples are burned in normal air q_ f r ¼ Flame radiative heat flux transferred to the
under an external heat flux exposure of surface (kW/m2)
50 kW/m2. During the test, measurement is 00
q_ fc ¼ Flame convective heat flux transferred to
made for the convective heat release as a
the surface (kW/m2)
function of time. 00
q_ rr ¼ Surface re-radiation loss (kW/m2)
ΔHg ¼ Heat of gasification (kJ/g)
Flaming and Nonflaming Phenomena 00 00 00
During fire propagation, the surface of the mate- total flame heat flux to the surface q_ f ¼ q_ f r þ q_ fc
rial regresses in a transient fashion with a rate According to Equation 36.15, the generation
slower than the fire propagation rate [31]. The rate of material vapors is governed by the
1168 M.M. Khan et al.

Fig. 36.22 Specific heat


of polymethylmethacrylate 2.4
versus temperature
measured by a differential

Specific heat (kJ/g·K) × 103


scanning calorimeter at the
2.1
flammability laboratory of
FM Global Research

1.8

1.5

1.2

250 300 350 400 450 500 550 600 650 700
Temperature (K)

external and flame heat flux, surface re-radiation such as the OSU heat release rate apparatus, the
loss, and the heat of gasification. FPA, or the cone calorimeter. The following are
some examples of the techniques:
Heat of Gasification The heat of gasification 1. Heats of gasification of polymers from differ-
for a melting material is expressed as [6] ential scanning calorimetry: Values for cp,s,
cp,l, ΔHm, and ΔHv for polymers have
Tðm Tðv
been quantified in the FM Global Research
ΔH g ¼ c p, s dT þ ΔH m þ c p, l dT þ ΔH v Flammability Laboratory [6]. The techniques
Ta Tm involve measurement of the specific heat as a
ð36:16Þ function of temperature, such as shown in
Fig. 36.22 for polymethylmethacrylate. Further
where measurements are also made of the heats of
ΔHg ¼ Heat of gasification (kJ/g) melting and vaporization. Some examples of
cp,s ¼ Specific heat of solid in kJ/gK the data measured at FM are listed in
cp,l ¼ Specific heat of molten solid in kJ/gK Table 36.6.
ΔHm ¼ Heat of melting at melting temperature 2. Heat of gasification from literature data
in kJ/g for the heats of gasification for various
ΔHv ¼ Heat of vaporization at vaporization tem- molecular weight hydrocarbons (alkanes):
perature in kJ/g The CRC Handbook of Chemistry and Phys-
Ta ¼ Ambient temperature ics [54] listing for the heats of gasification
Tm ¼ Melting temperature for liquid and solid hydrocarbons (alkanes)
Tv ¼ Vaporization temperature in K satisfies the following relationship in the
For materials that do not melt, but sublime, molecular weight range of 30–250 g/mol:
decompose, or char, Equation 36.16 is modified
accordingly. The heat of gasification can be
ΔH g ¼ 0:164 þ 0:0042M  3:72  106 M2
determined from (1) the parameters on the
right-hand side of Equation 36.16, which can be ð36:17Þ
quantified by thermal analysis techniques or cal-
culated from the properties listed in the litera- where M is the molecular weight of the hydro-
ture; and (2) nonflaming tests using apparatuses, carbon (g/mol).
36 Combustion Characteristics of Materials and Generation of Fire Products 1169

Table 36.6 Surface re-radiation and heats of gasification of various materials

Surface re- Heat of gasification (kJ/g)


Materials radiation (kW/m2) Flam. App.a Coneb DSCc Cald
Distilled water 0.63 2.58 – 2.59 2.58
Hydrocarbons (alkanes)
Hexane 0.50 – – – 0.50
Heptane 0.63 – – – 0.55
Octane 0.98 – – – 0.60
Nonane 1.4 – – – 0.64
Decane 1.8 – – – 0.69
Undecane 2.3 – – – 0.73
Dodecane 2.8 – – – 0.77
Tridecane 3.0 – – – 0.81
Tetradecane 3.0 – – – 0.85
Hexadecane 3.0 – – – 0.92
Natural materials
Filter paper 10 3.6 – – –
Corrugated paper 10 2.2 – – –
Wood (Douglas fir) 10 1.8 – – –
Plywood/FR 10 1.0 – – –
Particleboard – – 3.9 – –
Synthetic materials
Epoxy resin – – 2.4 – –
Polypropylene 15 2.0 1.4 2.0 –
Polyethylene (PE) (low density) 15 1.8 – 1.9 –
PE (high density) 15 2.3 1.9 2.2 –
PE foams 12 1.4–1.7 – – –
PE/25 % chlorine (CI) 12 2.1 – – –
PE/36 % CI 12 3.0 – – –
PE/48 % CI 10 3.1 – – –
Rigid polyvinylchloride (PVC) 15 2.5 2.3 – –
PVC/plasticizer 10 1.7 – — –
Plasticized PVC, LOI ¼ 0.20 10 2.5 2.4 – –
Plasticized PVC, LOI ¼ 0.25 – – – – –
Plasticized PVC, LOI ¼ 0.30 – – 2.1 – –
Plasticized PVC, LOI ¼ 0.35 – – 2.4 – –
Rigid PVC, LOI ¼ 0.50 – – 2.3 – –
Polyisoprene 10 2.0 – – –
PVC panel 17 3.1 – – –
Nylon 6/6 15 2.4 – – –
Polyoxymethylene (Delrin) 13 2.4 – 2.4 –
Polymethylmethacrylate (Plexiglas) 11 1.6 1.4 1.6 –
Polycarbonate 11 2.1 – – –
Polycarbonate panel 16 2.3 – – –
Isophthalic polyester – – 3.4 – –
Polyvinyl ester – – 1.7 – –
Acrylonitrile-butadiene-styrene (ABS) 10 3.2 2.6 – –
Styrene-butadiene 10 2.7 – – –
Polystyrene (PS) foams 10–13 1.3–1.9 – – –
PS (granular) 13 1.7 2.2 1.8 –
(continued)
1170 M.M. Khan et al.

Table 36.6 (continued)

Surface re- Heat of gasification (kJ/g)


Materials radiation (kW/m2) Flam. App.a Coneb DSCc Cald
Polyurethane (PU) foams
Flexible polyurethane (PU) foams 16–19 1.2–2.7 2.4 1.4 –
Rigid polyurethane (PU) foams 14–22 1.2–5.3 5.6 – –
Polyisocyanurate foams 14–37 1.2–6.4 – – –
Phenolic foam 20 1.6 – – –
Phenolic foam/FR 20 3.7 – – –
Ethylenetetrafluoroethylene (Tefzel) 27 0.9 – – –
Fluorinated ethylene propylene (FEP, Teflon) 38 2.4 – – –
Tetrafluoroethylene (TFE, Teflon) 48 0.8–1.8 – – –
Perfluoroalkoxy (PFA, Teflon) 37 1.0 – – –
Composite and fiberglass-reinforced materials
Polyether ether ketone–30 % fiberglass – – 7.9 – –
Polyethersulfone–30 % fiberglass – 1.8 – – –
Polyester 1–fiberglass – – 2.5 – –
Polyester 2–fiberglass 10 1.4 – – –
Polyester 3–fiberglass 10 6.4 – – –
Polyester 4–fiberglass 15 5.1 – – –
Polyester 5–fiberglass 10 2.9 – – –
Phenolic fiberglass (thick sheet) 20 7.3 – – –
Phenolic Kevlar (thick sheet) 15 7.8 – – –
a
From the Fire Propagation Apparatus under nonflaming conditions
b
Calculated from the cone calorimeter data reported for the mass loss rate at various external heat flux values in flaming
fires [13, 32]
c
From the flammability laboratory using the differential scanning calorimetry
d
Calculated from the data reported in the CRC Handbook [54]

The heats of gasification calculated from Using differential scanning calorimetry, the
Equation 36.17 for various alkanes are listed heat of gasification of water determined in
in Table 36.6. the FM Global Research Flammability Labo-
3. Heat of gasification from literature data for the ratory is 2.59 kJ/g, which is in excellent agree-
specific heats and heats of vaporization: Water ment with the calculated value. These two
will be used as an example. The specific heat of values for the heat of gasification of water
liquid water, cp,l, which is assumed constant, is are listed in Table 36.6.
0.0042 kJ/g-K [55] and the heat of vaporization 4. Heat of gasification from nonflaming tests
of water at 373 K is 2.26 kJ/g [54]. Assuming using the Fire Propagation Apparatus: The
the ambient temperature to be 298 K and the measurement for the heat of gasification from
vaporization temperature to be 373 K, the heat the nonflaming tests in the ASTM E2058 [10]
of gasification of water from Equation 36.16 is fire propagation apparatus was introduced in
00
calculated as follows: 1976 [6]. In the absence of flames, q_ f ¼ 0, and
Tðv Equation 36.15 simplifies to:
ΔH g ¼ c p, l dT þ ΔHv 00
00
q_ e  q_ rr
00

m_ ¼ ð36:18Þ
Ta ΔH g
¼ c p, l ðT v  T a Þ þ ΔHv
where mass loss rate is now extrictly a linear
¼ 0:0042ð373  298Þ þ 2:26 ¼ 2:58kJ=g function of the external heat flux. Therefore,
36 Combustion Characteristics of Materials and Generation of Fire Products 1171

this equation provides a convenient method to Heats of gasification determined from mass
determine the heat of gasification in nonflaming loss rate as a function of external heat flux at
tests, where mass loss rate of the sample is nonflaming conditions in the FPA are listed in
measured at various external heat flux values. Table 36.6 for selected materials. Excellent
The heat of gasification is determined from linear agreement can be noted between the heats of
regression analysis of the average steady-state gasification determined from the FPA data and
mass loss rate as a function of external heat those obtained from differential scanning
flux, using Equation 36.18. In the Fire Propaga- calorimetry.
tion Apparatus, samples can be exposed to radi- Heat of gasification can also be determined
ant fluxes in 100 % nitrogen atmospheres, from flaming fires if high external heat flux
00 00 00 00
allowing the application of this methodology values are used such that q_ e >> q_ f r þ q_ fc  q_ rr
Figure 36.23 shows a plot of the vaporization in Equation 36.15. This method has been used to
rate (i.e., mass loss rate), as a function of time, of calculate the heat of gasification from cone
water in a 0.0072 m2 Pyrex glass dish exposed to calorimeter data using mass loss rates
50 kW/m2, measured in the Fire Propagation measured in flaming fires reported in the litera-
Apparatus. The figure also includes the predicted ture [13, 32]. The values calculated from
mass loss rate using Equation 36.18, where the cone calorimeter data are also listed in
00   Table 36.6 and show a general agreement with
q_ rr ¼ εσ T 4v  T 4a ð36:19Þ the values from the FPA.

where ε is the emissivity of water (0.95–0.963 Example 5 Estimate the ignition temperature of
in the temperature range 298–373 K), [56] a material with a CHF of 11 kW/m2. Assume its
and σ is the Stefan-Boltzmann constant surface emissivity to be unity, ambient tempera-
(56.7  1012 kW/m2-K4). For water, Tv ¼ 373 K ture to be 20  C, and vaporization temperature
00
and Ta ¼ 298 K, and thus q_ rr ¼ 1 kW/m2. to be approximately equal to the ignition
00
From Equation 36.18, using q_ e ¼ 50 kW/m2, temperature.
00
q_ rr ¼ 1 kW/m2, and ΔHg ¼ 2.59 kJ/g,
ṁ00 ¼ 19.0 g/m2s. There is excellent agreement Solution Following the assumption that at the
between the measured and predicted values at the CHF reradiation is the only mode of heat loss,
steady state in Fig. 36.23. from Equation 36.19,

Fig. 36.23 Vaporization 25


rate of water versus time
measured in the Fire Predicted
Propagation Apparatus
20
using 99.69 g of water in
Vaporization rate (g/m2·s)

a Pyrex dish with an area


of 0.0072 m2. Water was
exposed to an external 15
heat flux of 50 kW/m2

10

0
0 200 400 600 800 1000 1200
Time (s)
1172 M.M. Khan et al.

00  
q_ rr ¼ CHF ¼ εσ T 4v  T 4a Flame Heat Flux For flaming fires, in the
absence of external heat flux, from Equation 36.15
 1=4
CHF 00 00 00
T v ¼ T ig ¼ þ Ta 4
00 q_ f r þ q_ fc  q_ rr
εσ m_ ¼ ð36:20Þ
ΔH g
" #1=4
11kW 4
T ig ¼ þ ð298KÞ The results from numerous small- and large-
m 2

56:7  1012 mkW


2 K4 scale fire tests show that, as the surface area of the
T ig ¼ 670K material increases, the flame radiative heat flux
increases and reaches an asymptotic limit,
Example 6 A material with a surface re-radiation whereas the flame convective heat flux decreases
loss of 10 kW/m2 and heat of gasification of and becomes much smaller than the flame radia-
1.8 kJ/g was found to be involved in a fire with an tive heat flux at the asymptotic limit in large-scale
exposed area of 2 m2. The combined flame and fires [57]. It is also known that, in small-scale
external heat flux exposure to the material was fires of fixed size with buoyant turbulent diffusion
estimated to be 70 kW/m2. Estimate the peak flames, as the oxygen mass fraction is increased,
mass loss rate at which the material may have the flame radiative heat flux increases and reaches
been burning in the fire in terms of g/m2 · s and g/s. an asymptotic limit comparable to the asymptotic
limit in large-scale fires, whereas the flame con-
Solution From Equation 36.15, vective heat flux decreases and becomes much
smaller than the flame radiative heat flux [13].
00 00 00 00
00 q_ e þ q_ f r þ q_ fc  q_ rr The effect of the mass fraction of oxygen
m_ ¼
ΔHg on the flame radiative and convective heat
00 00 00 kW fluxes in small-scale fires is shown in Fig. 36.24
q_ e þ q_ f r þ q_ fc ¼ 70 for 100-mm  100-mm square  25-mm-thick
m2
kW slabs of polypropylene. The data were measured
ð70  10Þ in the Fire Propagation Apparatus [13]. The
00
m_ ¼ m2 ¼ 33 g
kJ m2 s increase in the flame radiative heat flux with
1:8 increase in the mass fraction of oxygen is due
g
to the increase in the flame temperature and soot
The estimated peak mass loss rate of the burn- formation and decrease in the residence time in
ing material is 33 g/m2/s, or 33  2 ¼ 67 g/s. the flame [13]. The oxygen mass fraction

Fig. 36.24 Flame 60


radiative and convective
heat fluxes at various Radiative
oxygen mass fractions for 50 Convective
the steady-state
Flame heat flux (kW/m2)

combustion of
100-mm  100-mm 40
square  25-mm-thick
slabs of polypropylene in
the FPA under co-airflow 30
velocity of 0.09 m/s (Data
taken from Ref. [13]). Mass
fractions of oxygen are 20
indicated by the numbers
inside the frames
10
0.196

0.208

0.233

0.266

0.310

0.370

0.427

0.507

0
36 Combustion Characteristics of Materials and Generation of Fire Products 1173

variation technique to simulate large-scale flame- high molecular weight oligomers, the asymptotic
radiative heat flux conditions in small-scale fires flame heat flux values increase substantially to
is defined as the flame radiation scaling tech- the range of 49–71 kW/m2, regardless of their
nique [44]. This methodology forms the basis chemical structures. The independence of the
for the approaches described above regarding asymptotic flame heat values from the chemical
the flame propagating behavior of materials structures of materials is consistent with the
using the FPI concept. dependence of flame radiation on optical thick-
In the flame radiation scaling technique, ness, soot concentration, and flame temperature
the flame radiative and convective heat in large-scale fires.
fluxes are determined from (1) mass loss rate
measurements at various oxygen mass fractions Example 7 Calculate the peak mass loss rate for
in the range of 0.12 (close to flame extinction) to polypropylene in large-scale fires, burning in
about 0.60, under co-airflow conditions; (2) the the open, with no external heat sources in the
convective heat transfer coefficient for the FPA, surroundings.
derived from the combustion of methanol; (3) the
mass transfer number; and (4) Equation 36.20. Solution In the calculation Equation 36.21 will
00
In the Fire Propagation Apparatus, the asymp- be used. From Table 36.6, q_ rr ¼ 15 kW/m2
totic limit is reached for oxygen mass fractions in and ΔHg ¼ 2.0 kJ/g, and from Table 36.7,
excess of 0.30. At the asymptotic limit, Equa- 00
q_ f , asy ¼ 67 kW/m2. Using these values in
tion 36.20 can be expressed as
Equation 36.21,
00 00
00 q_ f , asy  q_ rr 00 00
q_ f , asy  q_ rr
m_ asy ¼ ð36:21Þ 00
m_ asy ¼
ΔHg ΔH g
kW
where subscript asy represents the asymptotic ð67  15Þ
00
m_ asy ¼ m2 ¼ 26 g
limit. The asymptotic values for mass loss rate kJ m2 s
and flame heat flux determined using the flame 2:0
g
radiation scaling technique in the FPA are listed in
Table 36.7. The measured asymptotic values for Example 8 Calculate the peak mass loss rate for
mass loss rate reported in the literature and flame polypropylene in large-scale fires burning in the
heat flux in large-scale fires are also listed in open in the presence of a burning object, which
Table 36.7. Flame heat flux values for the large- provides 20 kW/m2 of heat flux to the polypro-
scale fires are derived from the asymptotic values pylene surface, in addition to its own flame heat
of the mass loss rate and known values of surface flux of 67 kW/m2.
re-radiation losses and heats of gasification.
The data in Table 36.7 show that asymptotic Solution In the calculation, Equation 36.15 will
00
flame heat flux values, determined in the FPA be used with q_ e ¼ 20 kW/m2. From Table 36.6,
00
using the flame radiation scaling technique, are q_ rr ¼ 15 kW=m2 and ΔHg ¼ 2.0 kJ/g and from
00
in good agreement with the values measured in Table 36.7, q_ f , asy ¼ 67 kW/m2. Using these
large-scale fires. The asymptotic flame heat flux
values in Equation 36.15,
values vary from 22 to 77 kW/m2, depending 00 00 00 00
primarily on the mode of decomposition and 00 q_ e þ q_ f r þ q_ fc  q_ rr
m_ ¼
gasification rather than on the chemical ΔH g
structures of the materials. For example, for 00 00 00 kW
liquids, which vaporize primarily as monomers q_ e þ q_ f r þ q_ fc ¼ ð67 þ 20Þ 2
m
or as very low molecular weight oligomers, the kW
ð87  15Þ 2
asymptotic flame heat flux values are in the range m_ ¼
00
m ¼ 36 g
of 22–44 kW/m2, regardless of their chemical 2:0
kJ m2 s
structures. For polymers, which vaporize as g
1174 M.M. Khan et al.

Table 36.7 Asymptotic values of mass loss rate and flame heat flux
00 00
ṁasy (g/m2/s) q_ f , asy (kW/m2)
Material Sa Lb Sa Lb
Aliphatic carbon-hydrogen atomsc
Polyethylene 26 – 61 –
Polypropylene 24 – 67 –
Heavy fuel oil (2.6–23 m) – 36 – 29
Kerosene (30–80 m) – 65 – 29
Crude oil (6.5–31 m) – 56 – 44
n-Dodecane (0.94 m) – 36 – 30
Gasoline (1.5–223 m) – 62 – 30
JP-4 (1.0–5.3 m) – 67 – 40
JP-5 (0.60–17 m) – 55 – 39
n-Heptane (1.2–10 m) 66 75 32 37
n-Hexane (0.75–10 m) – 77 – 37
Transformer fluids (2.37 m) 27–30 25–29 23–25 22–25
Aromatic carbon-hydrogen atomsc
Polystyrene (0.93 m) 36 34 75 71
Xylene (1.22 m) – 67 – 37
Benzene (0.75–6.0 m) – 81 – 44
Aliphatic carbon-hydrogen-oxygen atomsc
Polyoxymethylene 16 – 50 – –
Polymethylmethacrylate (2.37 m) 28 30 57 60
Methanol (1.2–2.4 m) 20 25 22 27
Acetone (1.52 m) – 38 – 24
Aliphatic carbon-hydrogen-oxygen-nitrogen atoms
Flexible polyurethane foams 21–27 – 64–76 –
Rigid polyurethane foams 22–25 – 49–53 –
Aliphatic carbon-hydrogen-halogen atoms
Polyvinylchloride 16 – 50 –
Tefzel (ETFE) 14 – 50 –
Teflon (FEP) 7 – 52 –
Note: Mass loss rates are from the data reported in the literature
a
Small-scale fires, pool diameter fixed at 0.10 m, flame radiation scaling technique was used in the Fire Propagation
Apparatus, YO  0.30
b
Large-scale fires in normal air
c
Numbers in m in parentheses are the pool diameters used in large-scale fires

Pyrolysis and Determination of “Model- chapter such behavior is referred to as pyrolysis.


Specific” Material Properties Pyrolysis is a complex process that involves a
number of coupled physical and chemical phe-
One of the most prevailing observations made nomena, which include, among many others,
with the bench-scale apparatuses discussed in phase changes, char formation, water desorption/
section “Flammability Apparatuses and Measure- migration (e.g., in cellulosic fuels), gas diffusion,
ment Capabilities” of this chapter is the rate of gas-solid heat exchange, oxidation, etc. (refer to
thermal degradation of condensed phase materials Chaps. 21 and 23). These processes determine the
under a prescribed heating scenario. This behavior formation of gradients (thermal, species, etc.)
is captured in the tests through the measurement within a given material which control ignition,
of a mass loss rate (MLR). In the context of this heat release, and flame propagation in fires.
36 Combustion Characteristics of Materials and Generation of Fire Products 1175

There is strong and continued interest in the measured in this manner may not be directly
fire community in the development of predictive used even in the most advanced models since
fire modeling capabilities for practical large- they cannot reflect the true complexity and het-
scale fires through the use of new-generation erogeneity of the physical processes taking place
computational fluid dynamics (CFD) tools during pyrolysis. To some degree models must
[58–60]. Such modeling can provide measures always conceptualize and aggregate complex
to interpret, interpolate, and extrapolate informa- interactions by the use of only relatively simple
tion obtained from limited experimental data as mathematical equations. Therefore, in that sense,
well as providing cost-effective alternatives by pyrolysis models cannot use “true” material
reducing the number of large-scale tests neces- properties if all the physics are not fully captured.
sary to develop fire protection requirements or Finally, in the context of large CFD simulations,
standards. To reach this objective, physical use of comprehensive and complex models may
models for fluid mechanics, gas phase combus- be computationally prohibitive.
tion, soot formation and oxidation, radiation, On the basis of the above discussion, then, one
solid phase heat transfer and pyrolysis, and sup- of the major challenges posed to the end user of
pression need to be incorporated into an appro- CFD pyrolysis models is to make simplifications
priate CFD solver to properly represent the and approximations to keep the number of
multi-scale, multi-physics phenomena taking parameters manageable and the model computa-
place in large-scale fires. Given the mathematical tionally efficient while maintaining sufficient
complexity of these CFD tools, it is important model generality and applicability to a given
that such fire models be verified and validated practical scenario. By following this approach
against experimental data [59, 60]. the input parameters to the model can be consid-
Of relevance to the present chapter is how ered “effective” or “model-specific” material
bench-scale experiments may contribute to the properties which are sensitive to the physical
development of pyrolysis models to be used in processes included in the model. The methodol-
the CFD tools described above. Models have ogy by which these model-specific properties are
become recently available [61–64] which repre- obtained is detailed in the following sections.
sent the current state of the art of pyrolysis
modeling; these are comprehensive models Optimization
which share similar robust mathematical and The main requirement regarding the performance
numerical frameworks. These models, due to of CFD pyrolysis models is that they should
their complexity, require a potentially large num- properly reproduce aspects of the condensed-
ber of adjustable input parameters, i.e., material phase material behavior, such as pyrolysis gas
properties. Many applications (e.g., large-scale (i.e., fuel) generation rates, surface temperatures,
industrial fires) involve fuels for which such etc., which may be critical to the successful per-
properties are unknown. In certain cases formance of the CFD fire simulation. These
(e.g., [65–67]) detailed property measurements material response characteristics can in principle
may be performed (via thermogravimetric be measured via bench-scale tests such as those
analyses, TGA, and differential scanning calo- conducted in the Fire Propagation Apparatus.
rimetry, DSC, for example) and successfully The model-specific material properties alluded
used in the comprehensive models. However, to above are obtained by coupling a simplified
experimental venues such as TGA and DSC, pyrolysis model to optimization algorithms and
although extremely useful in providing funda- the input parameters (i.e., the material properties)
mental material information, are often not are adjusted in order to obtain the best possible
representative of practical applications as they agreement between model outputs and experi-
feature relatively slow heating rates and preclude mental bench-scale pyrolysis data. In the
the formation of mass and thermal gradients general framework of flammability properties
within the material. Furthermore, properties this approach has been seldom used [68, 69]
1176 M.M. Khan et al.

True Bench-Scale True Observed algorithm is the Shuffled Complex Evolution


Input Experiment Response Response
(SCE) [85]. This is a method that has been mostly

Output
applied to hydrological problems [86] but, as will
Observed Simulated
Input
Model Response Time be shown below, it is general and robust enough
to show considerably good performance in
Parameters Optimization
flammability applications. Chaos et al. [73–75]
Fig. 36.25 Optimization approach found SCE to be superior to other global
optimization tools, such as genetic algorithms, a
finding that has been confirmed by other
although it has recently received renewed atten- researchers [87].
tion [70–76]. Numerous similar efforts, though, A schematic flowchart of the SCE algorithm
exist in the literature mostly aimed at determin- is shown in Fig. 36.26. Similar to genetic
ing a limited set of thermal properties and for algorithms, SCE is based on a process of natural
specific applications [77–82]. evolution. A population of s points (i.e., vectors
A schematic of the optimization approach is of “material properties” in the present context) is
shown in Fig. 36.25. An experimental process is randomly sampled from the feasible parameter
captured via a numerical model subject to a space (given the bounds for each parameter) and
driving input (e.g., external radiation) and a set the value of the objective function to be
of parameters (“material properties”). In the fig- optimized (e.g., minimization of the sum of
ure, an important distinction is made between the squares between model outputs and experimental
true input to and true response of the experiment data) is computed. The points are ranked from
and what is actually observed, or measured, in smallest to highest objective function value and
order to represent experimental uncertainty. It are then partitioned into p complexes each
is because of this uncertainty that parameters containing m points (note s ¼ pm) so that the
determined through optimization procedures first complex contains every (l – 1)p + 1 ranked
such as the one discussed herein are sensitive to point, the second every (l – 1)p + 2 ranked point,
the accuracy of the experimental data used as etc. where l ¼ 1, 2, . . ., m. Each of these
optimization targets. As can be expected, the complexes is then allowed to evolve indepen-
optimization problem is complex and highly dently according to a competitive complex evo-
non-linear. Therefore, local search methods lution (CCE) algorithm [85], described below.
such as direct search [83] and gradient search After the CCE process, all the points in each
[84] algorithms are not applicable; however, complex are combined back into a single popula-
such methods have been used widely for property tion, ranked according to their objective function
estimation [68, 69, 77, 81, 82]. Global methods value, and re-partitioned following the procedure
are needed which can tackle the major above; this effectively “shuffles” the complexes.
complications of high-dimensionality optimiza- This procedure is iteratively repeated until
tion such as local optima, multiple attraction specified convergence criteria are met. SCE
basins, discontinuities, etc. allows for more extensive (i.e., in different
An optimization algorithm with high effi- directions) and freer exploration of the feasible
ciency and robustness is needed if one is to space due to the partition of complexes. Shuffling
perform multiobjective and multivariable opti- enhances survivability by sharing information
mization as little or no a priori knowledge is about the space gained independently by each
available of the structure of the model response complex.
surface. Furthermore, these qualities allow opti- The key component of the SCE method is the
mization algorithms to be easily generalized so CCE algorithm which is based on the Nelder-
as to provide consistent performance over a wide Mead simplex downhill search scheme [83]. In
range of problems, even if optimization target the CCE algorithm q points are randomly
data are limited. Here, the selected optimization selected within each complex according to a
36 Combustion Characteristics of Materials and Generation of Fire Products 1177

Assign triangular probability to each


point in complex
2(m+1−j)
σj = j = 1,... , m
m(m+1)

Form a subcomplex by selecting q


points (u1, … ,uq) according to σ
and sort
(f1 < f2 < … < fq)

Sample s random points


in feasible space, Ψ Compute centroid g
Compute objective (do not include uq)
function value, f
1 q −1
g= ∑u j
q − 1 j =1
Sort points
(f1 < f2 < … < fs)
Reflection step
r = 2g - uq
Partition into p
complexes Generate random point
containing m points No x in hypercube H
r within Ψ ?
Combine formed by the q points
complexes Evolve each in subcomplex. Set r = x
Yes
complex
(CCE algorithm) Set uq = r and Yes
fr < fq ?
fq = fr

No
No Contraction step
Convergence
satisfied? c = (g + uq)/2

Yes Generate random


No
fc < fq? point x in H.
STOP Set uq = x and fq = fx
Yes

Set uq = c and
fq = f c

Sort all points


in complex

No, τ = τ +1
τ >= β ?
Yes

Fig. 36.26 The Shuffled Complex Evolution algorithm

trapezoidal probability distribution so that the than the worst point, the worst point is replaced.
best and worst points in the complex have the In the case that the latter two steps do not gener-
highest and lowest chance, respectively, of being ate a better point or if the reflection through the
chosen. The centroid of the subcomplex formed centroid yields a point outside the feasible space,
by the set of q points is calculated without con- a point is generated randomly which replaces the
sidering the worst point in the subcomplex; then, worst point. This procedure is repeated a specific
this worst point is reflected through the centroid. number of times, β, before the complexes are
If the new point so computed is better (i.e., its shuffled as described above. In this manner,
objective function value is improved) than the each complex evolves independently as a whole.
worst point, the worst point is replaced. Other- The SCE process is shown graphically in
wise a point is computed halfway between the Fig. 36.27 by using a two-dimensional example.
centroid and the worst point; if this point is better A test function was generated (left pane in
1178 M.M. Khan et al.

Fig. 36.27 SCE application to a two-dimensional problem

Fig. 36.27) by distorting selected regions of a one-dimensional pyrolysis model was used to
convex quadratic function so as to introduce generate synthetic experimental data for a sup-
local minima with varying regions of attraction, posed charring material. One-dimensionality is
following the methods of Gaviano and Lera [88]. assumed as this is representative of tests
A three-minima function was generated with one conducted in the Fire Propagation Apparatus or
global minimum located at (X,Y) ¼ (0.312,0.598). cone calorimeter where the thickness of samples
SCE was run with three complexes (denoted by tested is small compared to their diameter and
stars, circles, and triangles in Fig. 36.27) consisting edge effects can be considered negligible.
of 5 points each (i.e., p ¼ 3, m ¼ 5, s ¼ 15). The specific details of the pyrolysis model used
Note the effect of shuffling in Fig. 36.27. The are beyond the scope of this chapter, and the
overall distribution of points from the end of an reader is referred to [63, 64, 73–75] for further
evolution to the beginning of the next is information; only the simplifications made to
unchanged; however, the distribution within each the model are described here for brevity. The
complex changes. Also note that some points model employs a control volume approach and
converge towards the local minimum at the governing mass and energy conservation
(X,Y) ¼ (-0.412,-0.351) in the first two evolutions equations are solved numerically using a fully
but shuffling efficiently directs their convergence implicit scheme. Only three species are treated:
towards the global minimum. virgin solid, char, and pyrolytic gas and it is
assumed that the virgin solid decomposes to
Application char and/or gas through a single heterogeneous
Synthetic Data and Target Selection nth-order Arrhenius-type reaction. Pyrolysis gas
Foremost, it is important to illustrate the features is assumed to be in thermal equilibrium with the
and limitations of the SCE optimization algo- solid and to immediately escape once formed.
rithm when applied to problems of practical All material properties are assumed to be temper-
interest herein. In order to do this, a simplified ature-independent.
36 Combustion Characteristics of Materials and Generation of Fire Products 1179

Table 36.8 Parameters used to generate synthetic data (Fig. 36.28) and parameters returned by optimization

SCE optimization
Property Synthetic LB UB Case 1 Case 2 Case 3 Case 4
Virgin Thermal conductivity (W/m/K) 0.10 0.01 1.00 0.04 0.09 0.10 0.10
Density (kg/m3) 500 100 1000 521 571 660 510
Heat capacity (J/kg/K) 1500 500 5000 684 1390 1210 1470
Emissivity 0.5 0.0 1.0 0.30 0.49 0.59 0.50
Char Thermal conductivity (W/m/K) 0.25 0.01 1.00 0.21 0.30 0.33 0.25
Density (kg/m3) 100 50 500 120 169 260 95
Heat capacity (J/kg/K) 1000 500 5000 5000 1166 2071 1053
Emissivity 0.9 0.0 1.0 0.49 0.99 1.00 0.90
Arrhenius Log [pre-exponential factor (s1)] 10 6 12 10.7 7.6 8.9 10.0
decomposition Activation energy (kJ/mol) 150 50 250 160 119 141 150
Reaction order 2 0 5 1.3 1.8 1.5 2
Log [heat of pyrolysis (J/kg)] 5.81 4 7 5.52 5.87 5.85 5.81
Average deviation (%) 57.8 17.1 35.2 1.2

The synthetic dataset consists of mass loss 100 kW/m2 case. Note that by increasing the
rate and surface temperature data generated for filter window size by a factor of two the first
a 5-mm thick material subjected to external radi- mass loss rate peak, which is narrower, is
ation levels of 25, 50, and 100 kW/m2. For sim- “washed out” whereas the second peak is still
plicity, the back boundary of the material was properly captured.
assumed to be perfectly insulated (adiabatic) and Several optimization runs were preformed by
a constant convective heat transfer coefficient of selecting specific subsets of the data shown in
15 W/m2/K was assumed for the front surface. Fig. 36.27. This was done in order to test the
The material properties used in the model to robustness of the SCE algorithm as it is often the
generate the data are listed in Table 36.8. The case, especially with complex practical
model-generated curves were modified by materials, that target experimental data may be
adding Gaussian error with standard deviations limited and/or difficult to measure accurately.
representative of experimental uncertainty: An algorithm that can reach the global optimum
100 mg for mass loss and 15 K for temperature with the least amount of target data can be
measurements [75, 89], In order to obtain mass extremely useful as it can allow one to limit
loss rate, the modified mass loss curve was the target metrics to only those data that can
differentiated using Savitsky-Golay filters [37, presumably be measured more accurately with-
90, 91]. As opposed to previous applications of out considering data with higher uncertainty.
this methodology [36, 91] in which a fixed filter Four target data subsets were selected: Case
window size was recommended, the window size 1—mass loss rate at 50 kW/m2; Case 2—mass
of the filter was kept between one and two times loss rate, cumulative mass loss, and surface
the full-width-half-magnitude size of the temperature at 50 kW/m2; Case 3—mass loss
narrowest transient peak of interest [92] in rate at 25, 50, and 100 kW/m2; and Case 4—
order to avoid introducing unwanted bias in the mass loss rate, cumulative mass loss, and sur-
derived MLR data. This approach ensured that face temperature at 25, 50, and 100 kW/m2. SCE
the magnitude of these peaks was preserved after was run subject to the property bounds shown in
application of the filter. Figure 36.28 shows plots Table 36.8 and with algorithmic parameters
of the synthetic data prior to and after adding (i.e., p, m, q, and β, see above) selected
Gaussian error. Also in the figure, the effect of according to the guidelines of [86]; the popula-
varying the smoothing filter size is shown for the tion size was 150.
1180 M.M. Khan et al.

6 800 parameters are not recovered in most cases. A


25 kW/m2
clear trend can be observed, nonetheless; the
5
700 deviation from the original parameters is reduced
4 when more target metrics are added (compare
600
Case 1 to Case 2 and Case 3 to Case 4) and
3
when more heat fluxes are considered for the
500
2 same target metric (compare Case 1 to Case
3 and Case 2 to Case 4). This trend is an obvious
400
1 manifestation of how the target data are able to
0 300
constrain the model and, thus, the optimization
0 200 400 600 800 1000 algorithm. By considering mass loss rate alone
16 50 kW/m2
(Case 1 and Case 3) parameters, most notably
14
900 physical properties such as thermal conductivity
Mass Loss Rate (g/m2/s)

Surface Temperature (K)


12 800
and heat capacity, cannot be accurately deter-
mined. This is to be expected as these parameters
10 700
are coupled through the thermal inertia and ther-
8
600 mal diffusivity of the material. Introducing tem-
6
500
perature as an optimization target improves
4 agreement against these properties and the same
400
2 can be said about considering additional heat flux
0 300 levels. It is noted that, in a similar synthetic data
0 50 100 150 200 250
exercise as that discussed here, SCE was found to
100 kW/m2 recover the input parameters using datasets
30 1050 consisting of mass loss rate, front and back sur-
25 face temperatures at two heat flux levels [87];
900
20
back surface temperature measurements may
750 present a experimental challenge, however.
15 The discussion above should persuade the
600
10 reader that the process of obtaining model-
450 specific properties through optimization will be
5
most successful when considering multiple
0 300 experimental data (mass loss rate, temperature,
0 25 50 75 100
Time (s) etc.) over as wide a range of practical conditions
as possible [60]. Furthermore, availability of
Fig. 36.28 Synthetic data. Lines show model outputs properties that can be easily measured
and symbols denote the model data after Gaussian error
was added (see text). The dashed line for mass loss rate at
(e.g., virgin density) will further improve the
100 kW/m2 shows the effect of varying the smoothing results by reducing the dimensionality of the
filter window size from 25 s to 50 s (see text) problem. Yet, there are cases in the literature
(e.g., [76]) where optimization is performed
The values for the optimized property against very limited datasets. As a last word of
parameters obtained for each of the four cases caution it is reiterated that the “material
are listed in Table 36.8. For the sake of brevity properties” obtained using the methodology
and in lieu of showing plots it is noted that for all described herein depend on the choice of pyroly-
cases a near perfect match was obtained against sis model as well as the accuracy of the experi-
each of the corresponding datasets used for mental data and are not universally applicable to
optimization; the R-squared values for all cases other models or to scenarios that considerably
were in excess of 0.99. However, regardless depart from the experimental conditions used to
of the good agreement obtained, the original derive the model-specific properties.
36 Combustion Characteristics of Materials and Generation of Fire Products 1181

Fig. 36.29 Experimental (symbols) and computed (lines) parallel panel heat release rates for single-wall corrugated
cardboard [96]. The experimental configuration is shown on the left panel

FPA Data and Intermediate-Scale Fire importance of oxidative pyrolysis in certain


Growth Simulations applications [35, 89, 97]. Considerable progress
The approach outlined above has been extensively has been made in the predictive abilities of
used and applied to the simulation of the vertical FireFOAM when compared against flame spread
spread of fire between parallel panels at an inter- experiments in the parallel panel configuration
mediate scale [60, 93–97]. For this application, [97]. An example is shown in Fig. 36.29 where
model-specific properties were determined using the heat release rate of single-wall corrugated
the pyrolysis model included in FireFOAM cardboard collected during three separate parallel
[98, 99], a Large Eddy Simulation (LES) solver. panel tests (a schematic of the test is also shown in
The target data used for optimization were col- the figure, for more details refer to [93–97] as well
lected in the Fire Propagation Apparatus in inert as section “Fire Propagation”) is compared against
environments (i.e., 100 % nitrogen); this is a simulations. A considerably good agreement can
unique feature of the apparatus (see section be observed. This is an encouraging result which
“Flammability Apparatuses and Measurement confirms that the approach described in this sec-
Capabilities”) which allows for the decoupling tion for the characterization of material flamma-
of flame heat flux from the pyrolysis process. bility is promising and may lead to cost-effective
Following the recommendations of the previous modeling alternatives to large-scale testing.
section, the data consisted of mass loss rates and
surface temperatures over heat fluxes spanning the
20–110 kW/m2 range. The model-specific mate- Heat Release Rate
rial properties were shown to successfully predict,
at least qualitatively, flame propagating and The determination of heat release rate in fires has
non-propagating behavior of several materials been influenced by the principles and techniques
when used in the LES simulation [60]. used for controlled combustion in the heating and
Further experience with the application of the power industries. Heat in the flowing combustion
methodologies described herein has elucidated the products (convective heat) and thermal radiation
importance of properly characterizing boundary are used to generate steam, heat a furnace or
conditions in the FPA experiments and the relative space, produce mechanical power in internal
1182 M.M. Khan et al.

combustion engines or gas turbines, and so forth. incomplete combustion per unit mass of fuel
Heat is generated by injecting fuel (gas, liquid, or consumed is defined as the chemical heat of
solid) into a hot environment, where it undergoes combustion. In the heating and power industries,
evaporation, gasification, and thermal decompo- combustion efficiency is determined routinely
sition or pyrolysis. from the analysis of waste products (flue gas),
Fuel vapors react chemically with oxygen especially for CO, CO2, and O2, and from the
and produce heat and products, such as measurements of temperature in the combustion
carbon monoxide (CO), carbon dioxide (CO2), products-air mixture and thermal radiation. For
hydrocarbons, water (H2O), and soot and other higher combustion efficiency, mass fuel-to-air
particulates. The theoretical amount of air ratio relative to the stoichiometric fuel-to-air
required for complete combustion is estimated mass ratio or the equivalence ratio is controlled
from an empirical guide [100], which suggests by maintaining the desired primary and second-
that, for every 10.6 kJ of heat in the fuel burned, ary airflow.
3.4 g of air are required for complete combustion The net heat of complete combustion can be
[101]. Equivalently, the heat of combustion per measured in the oxygen bomb calorimeter [102]
unit mass of molecular oxygen consumed (ΔH0*) (see Chap. 27) and is calculated from the stan-
is 13.4 kJ/g. Using ΔH0* 13.4 kJ/g to deter- dard heats of formation of the materials, CO2,
mine the heat release rate in fires from the mass and H2O (the standard heat of formation of O2 in
consumption rate of oxygen is discussed in Refs. its standard state being zero).
[14, 21]. This technique forms the basis of oxy- In fires, complete combustion is rarely achieved
gen consumption (OC) calorimetry. and products of incomplete combustion, such as
A combustion process is characterized by its CO and smoke, are quite common. An example of
combustion efficiency, χ ch, defined as the fraction incomplete combustion is given in Table 36.9,
of heat of complete combustion released in the where chemical heat of combustion and combus-
chemical reactions, which is the ratio of the tion efficiency decrease as CO, carbon, and ethyl-
chemical heat of combustion to the net heat of ene are formed at the expense of CO2 and H2O
complete combustion. The calorific energy with reduced O2 consumption, a typical condition
generated in chemical reactions leading to found in ventilation-controlled fires [103].
complete combustion per unit mass of fuel, with The upper limit of the combustion efficiency is
water produced being in the vapor state, is 1.00, corresponding to complete combustion,
defined as the net heat of complete combustion. and the lower limit is 0.46, corresponding to unsta-
The calorific energy generated in chemical ble combustion leading to flame extinction for
reactions leading to varying degrees of combustion efficiency 0.40 [103, 104].

Table 36.9 Chemical heat of combustion and combustion efficiency of polymethylmethacrylate


Reaction stoichiometry ΔHch (kJ/g)a χch
C5H8O2 (g) + 6.0 O2 (g) ¼
5CO2 (g) + 4H2O (g) 24.9 1.00
C5H8O2 (g) + 5.5 O2 (g) ¼
4CO2 (g) + 4H2O (g) + CO (g) 22.1 0.89
C5H8O2 (g) + 4.5 O2 (g) ¼
3CO2 (g) + 4H2O (g) + CO (g) + C (s) 18.2 0.73
C5H8O2 (g) + 3.0 O2 (g) ¼
2CO2 (g) + 3H2O (g) + CO (g)
+ C (s) + 0.50 C2H4 (g) 11.5 0.46
a
Standard heat of formation in kJ/mol: PMMA (C5H8O2) (g) ¼ 442.7; O2 (g) ¼ 0; CO2(g) ¼ 393.5; H2O
(g) ¼ 241.8; CO (g) ¼ 110.5; C (s) ¼ 0; and C2H4 (g) ¼ +26.2, where g and s stand for gaseous and solid states,
respectively
36 Combustion Characteristics of Materials and Generation of Fire Products 1183

Chemical Heat Release Rate amounts of CO generated. The variations of 11 %


As described in section “Flammability and 18 % in the ΔH*CO2 and ΔHCO *
values, respec-
Apparatuses and Measurement Capabilities” of tively, would reduce significantly if values for
this chapter, chemical heat release rate in bench low molecular weight hydrocarbons with small
scale apparatuses such as the Fire Propagation amounts of O, N, and halogen were not used in
Apparatus and cone calorimeter can be deter- averaging. For the determination of the chemical
mined from CDG and OC calorimetries. heat release rate, generation rates of CO2 and CO
are measured and either the actual values
CDG Calorimetry The chemical heat release (if material composition is known) or the average
rate is determined from the following values of the net heat of complete combustion per
relationships [14, 28, 31, 43, 44, 103, 105]: unit mass of CO2 and CO generated are used. The
00 00 00 measurements for the generation rates of CO2 and
Q_ ch ¼ ΔH *CO2 G_ CO2 þ ΔH *CO G_ CO ð36:22Þ CO are described in section “Generation of Fire
Products and Smoke Yields” of this chapter.
ΔHT
ΔH *CO2 ¼ ð36:23Þ Care must be taken in the application of CDG
ψ CO2
calorimetry depending on the scenario of inter-
ΔHT  ΔHCO ψ CO est. For example, in fires where incomplete com-
ΔH*CO ¼ ð36:24Þ bustion is ubiquitous and copious amounts of
ψ CO2
unburned hydrocarbons, soot, and other
where particulates are generated, the equations above
00
will not yield an accurate measure of heat release
Q_ ¼ Chemical heat release rate (kW/m2)
ch
rate as corrections for the formation of these
ΔH *CO2 ¼ Net heat of complete combustion per
species have to be included (much like is done
unit mass of CO2 generated (kJ/g) above for CO). One more example is a scenario
ΔHCO *
¼ Net heat of complete combustion per where a fire is suppressed by water (i.e., a sprin-
unit mass of CO generated (kJ/g) kler) and a large amount water vapor is present in
ΔHT ¼ Net heat of complete combustion per unit the combustion-product-air mixture. Some cor-
mass of fuel consumed (kJ/g) rection procedures are available (e.g., [106]) to
ψ CO2 ¼ Stoichiometric yield for the maximum account for these effects.
conversion of fuel to CO2 (g/g)
ψ CO ¼ Stoichiometric yield for the maximum OC Calorimetry The chemical heat release rate
conversion of fuel to CO (g/g) is determined from the following relationships
00
G_
CO2 ¼ Generation rate of CO2 (g/m2/s) [13, 21–24, 28, 31, 43, 44, 103, 105, 107]:
00
ĠCO ¼ Generation rate of CO (g/m2/s) 00 00

The values for the net heats of complete com- Q_ ch ¼ ΔH *O C_ O ð36:25Þ


bustion per unit mass of fuel consumed and CO2 ΔH T
and CO generated are listed in Table A.38. The ΔH *O ¼ ð36:26Þ
ψO
values depend on the chemical structures of the
materials. With some exceptions, the values where
remain approximately constant within each ΔHO* ¼ Net heat of complete combustion per unit
generic group of fuels. The average values mass of oxygen consumed (kJ/g)
00
are also listed in the tables. From the ĊO ¼ Mass consumption rate of oxygen (g/m2/s)
average values, ΔH *CO2 ¼ 13.3
1.5 kJ/g and ψ O ¼ Stoichiometric oxygen-to-fuel mass ratio
ΔHCO
*
¼ 11.1
2 kJ/g. In CDG calorimetry, the (g/g)
CO correction (which accounts for the heat The values for the net heats of complete com-
generated for incomplete combustion) for well- bustion per unit mass of oxygen consumed are
ventilated fires is very small because of the small listed in Table A.38 along with the values for the
1184 M.M. Khan et al.

net heats of complete combustion per unit mass of Ta ¼ Ambient temperature (K)
fuel consumed and CO2 and CO generated. The Ẇ ¼ Total mass flow rate of the fire product-air
average values of the net heat of complete com- mixture (g/s)
bustion per unit mass of oxygen consumed are A ¼ Total exposed surface area of the material
also listed in the tables. The values depend on the (m2)
chemical structures of the materials. With some
exceptions, the values remain approximately con- Radiative Heat Release Rate The chemical
stant within each generic group of fuels. From the heat release rate consists of a convective and a
average values, ΔHO* ¼ 12.8
0.9 kJ/g. The ΔHO* radiative component [25]. Some fraction of the
value of 12.8 kJ/g is in good agreement with the chemical heat release rate may be lost as conduc-
value 13.1
0.7 kJ/g reported in Ref. [21]. tive heat. In systems where such conductive heat
The variation of
0.9 kJ/g (7 %) would reduce losses are negligibly small, the radiative heat
significantly if values for low molecular weight release rate can be obtained from the difference
hydrocarbons with small amounts of O, N, and between the chemical and convective heat
halogen were used in averaging. For the determi- release rates [14, 25, 28, 31, 44, 103]:
nation of chemical heat release rate, mass con- 00 00 00
sumption rate of oxygen is measured, and either Q_ rad ¼ Q_ ch  Q_ con ð36:28Þ
the actual values or the average values of the net 00
heats of complete combustion per unit mass of where Q_ rad is the radiative heat release rate
oxygen consumed are used. The measurement for (kW/m2).
the consumption rate of oxygen is described in
section “Generation of Fire Products and Smoke Energy Released in a Fire The total amount of
Yields” of this chapter. heat generated as a result of chemical reactions in
As discussed above for CDG calorimetry, in the combustion of a material is defined as chemi-
situations where incomplete combustion is prev- cal energy. The chemical energy has a convec-
alent, the equations above will have to be tive and a radiative component:
corrected for the formation of products such as
soot and unburned hydrocarbons [108, 109]. Ech ¼ Econ  Erad ð36:29Þ
Furthermore, for materials that have bound oxy-
gen in their chemical structures, oxygen may be where
released as a product of combustion which will Ech ¼ Chemical energy (kJ)
affect the OC methodology [110]. Thus, chemi- Econ ¼ Convective energy (kJ)
cal structure plays an important role in the deter- Erad ¼ Radiative energy (kJ)
mination of heat release rate [111]. The chemical energy and its convective and
radiative components are calculated by the time
Convective Heat Release Rate integration of the respective heat release rates,
The convective heat release rate is determined expressed here by a numerical summation:
from GTR calorimetry, where the following rela- X
n¼tex 00
tionship is used [1–3, 13, 14, 28, 31, 44, 103]: Ei ¼ A Q_ i ðtn ÞΔtn ð36:30Þ
  n¼tig
00 W_ cp T g  T a
Q_ con ¼ ð36:27Þ
A where
Ei ¼ Chemical, convective, or radiative energy
where (kJ)
00
Q_ ¼ Convective heat release rate (kW/m2)
con A ¼ Total surface area of the material burning
cP ¼ Specific heat of the combustion product-air (m2)
mixture at the gas temperature (kJ/g/K) tig ¼ Ignition time (s)
Tg ¼ Gas temperature (K) tex ¼ Flame extinction time (s)
36 Combustion Characteristics of Materials and Generation of Fire Products 1185

The total mass of the material lost during average chemical heat of combustion determined
combustion can be measured directly from the in the cone calorimeter is defined as the effective
initial and final mass or calculated by the time heat of combustion [22–24].
integration of the mass loss rate, expressed here
by a numerical summation: Heat Release Parameter (HRP) From
Equations 36.15 and 36.32 the amount of energy
X
n¼tex
00
Wf ¼ A m_ ðtn ÞΔtn ð36:31Þ generated per unit amount of energy absorbed
n¼tig can be expressed as:
 
where Wf is the total mass of the material lost 00 ΔH i  00 
Q_ i ¼
00 00 00

(g) in the combustion process. q_ e þ q_ f r þ q_ fc  q_ rr ð36:34Þ


ΔH g
Heat release rate can also be expressed as the
product of the mass loss rate and the heat of
where the ratio ΔHi/ΔHg is defined as the Heat
combustion of the material, if it is known a
Release Parameter (HRP) and, as the heat release
priori:
rate itself, has chemical, convective, and radia-
00
tive components (HRPch, HRPcon, and HRPrad,
Q_ i ¼ ΔH i m_
00
ð36:32Þ
respectively) [44]. The HRP values are charac-
where ΔHi is the chemical, convective, or radia- teristic fire properties of materials but depend on
tive heat of combustion (kJ/g). In turn, the aver- fire ventilation. The chemical HRP is indepen-
age chemical, convective, or radiative heats of dent of fire size.
combustion can be calculated from the calorime- Experimental data support Equation 36.34, as
try relationships based on Equations 36.22 shown in Figs. 36.30, 36.31, and 36.32, where
(or 36.25), 36.27, 36.28, and 36.30 so that: the average peak or steady-state chemical heat
release rates are plotted against the net heat flux. A
Ei clear linear relationship between the chemical
ΔH i ¼ ð36:33Þ
Wf heat release rate and net heat flux can be discerned.
00 00 00 00
For the condition q_ e >> q_ f r þ q_ fc  q_ rr , the
where ΔH i is the average chemical, convective,
or radiative heat of combustion (kJ/g). The average HRP value can be calculated from

Fig. 36.30 Average 2000


steady-state chemical heat
release rate versus net heat FMRC
flux for a polystyrene
1600 Cone
sample. Net heat flux is the
Average steady-state chemical

sum of the external and


heat release rate (kW/m2)

flame heat fluxes minus the


surface re-radiation
1200

800
(HRP)ch = 29

400

0
0 10 20 30 40 50 60 70 80
Net heat flux (kW/m2)
1186 M.M. Khan et al.

Fig. 36.31 Average 2000


steady-state chemical heat
release rate versus the net FMRC
heat flux for a high
1600 Cone
molecular weight

Average steady-state chemical


hydrocarbon liquid burning

heat release rate (kW/m2)


in a 100-mm-diameter dish.
The cone calorimeter data
were measured at the 1200
research laboratory of the
Dow-Corning Corporation,
Midland, Michigan. Net
800
heat flux is the sum of the (HRP)ch = 29
external and flame heat
fluxes minus the surface
re-radiation 400

0
0 10 20 30 40 50 60 70
Net heat flux (kW/m2)

Fig. 36.32 Peak chemical 1200


heat release rate versus the
external heat flux for a PVEST
PVEST—glass
100-mm  100-mm  1000
Epoxy
3-mm to 11-mm-thick slab Epoxy—glass
of polyvinyl ester
release rate (kW/m2)

Wood
Peak chemical heat

800
(PVEST), PVEST/
fiberglass, epoxy, epoxy/
fiberglass, and wood 600
(hemlock). Data measured
in the cone calorimeter are
shown [32] 400

200

0
0 20 40 60 80 100
External heat flux (kW/m2)

the summation of the heat release rate and the combustion are less than the heat release rate
external heat flux: for complete combustion or the net heat of com-
plete combustion, respectively. The ratio of the
X
n¼tex 00
Q_ i ðtn ÞΔtn chemical heat release rate to the heat release
Ei n¼tig rate for complete combustion or the ratio of the
HRP i ¼ ð ¼ n¼tex ð36:35Þ
00 X 00 chemical heat of combustion to net heat of com-
A q_ e dt q_ e ðtn ÞΔtn plete combustion is defined as combustion effi-
n¼tig ciency [13, 14, 28, 31, 44, 102]:
00
Q_ ch m_ ΔH ch ΔH ch
Incompleteness of Combustion In fires, 00

combustion is never complete. Thus, the chemi- χ ch ¼ 00 ¼ 00 ¼ ð36:36Þ


Q_ m_ ΔH T ΔH T
cal heat release rate or the chemical heat of T
36 Combustion Characteristics of Materials and Generation of Fire Products 1187

where χ ch is the combustion efficiency and heptane, the literature values are and χ ch ¼ 0.93,
00
Q_ T is the heat release rate for complete χ con ¼ 0.59, and χ rad ¼ 0.34. The net heat of
combustion (kW/m2). The convective and complete combustion for heptane reported in
radiative components of the combustion the literature is 44.6 kJ/g. Calculate the chemical
efficiency are defined in a similar fashion heat release rate and show that it is consistent
[13, 14, 28, 31, 44, 103]: with the rate based on the literature value of the
combustion efficiency. Also calculate the con-
00
Q_
00
m_ ΔH con ΔHcon vective and radiative heat release rates.
χ con ¼ con00 ¼ 00 ¼ ð36:37Þ
Q_ m_ ΔH T ΔH T
T Solution From Table A.38, for heptane, the net
00 heat of complete combustion per unit mass of
Q_ rad m_ ΔH rad ΔH rad
00

χ rad ¼ oxygen consumed is 12.7 kJ/g; the net heat of


00 ¼ 00 ¼ ð36:38Þ
Q_ m_ ΔH T ΔH T complete combustion per unit mass of CO2
T
generated is 14.5 kJ/g; and the net heat of
where χcon is the convective component of the complete combustion per unit mass of CO
combustion efficiency and χrad is the radiative generated is 12.8 kJ/g. From CDG calorimetry
component of the combustion efficiency [25]. (Equation 36.22),
From the definitions,
00 00 00
Q_ ch ¼ ΔH *CO2 G_ CO2 þ ΔH *CO G_ CO
ΔH ch ¼ ΔH con þ ΔH rad ð36:39Þ    
00 kJ  g  kJ  g 
Q_ ch ¼ 14:5 181 2 þ 12:8 9 2
χ ch ¼ χ con þ χ rad ð36:40Þ g m s g m s
00 kW
The chemical, convective, and radiative Q_ ch ¼ 2740 2
heat release rates, heats of combustion, and com- m
bustion efficiencies depend on the chemical From OC calorimetry (Equation 36.25),
structures of the materials and fire ventilation. 00 00
The distribution of the chemical heat into con- Q_ ch ¼ ΔH *O C_ O
 
vective and radiative components changes with
_
00 kJ  g 
fire size. The larger the fire size, the larger Q ch ¼ 12:7 216 2
g ms
the fraction of the chemical heat distributed into 00 kW
the radiative component. Q_ ch ¼ 2743 2
m
Chemical, convective, and radiative heats
of combustion and HRP values for several The chemical heat release rate from the CDG and
materials under well-ventilated fire conditions OC calorimetries are in excellent agreement, the
are listed in Tables A.38 and A.39, respectively. average being 2742 kW/m2.
Comparisons between the limited data from the The chemical heat of combustion can be
OSU apparatus, Fire Propagation Apparatus, and obtained from Equation 36.36:
cone calorimeter are satisfactory. Data were
taken from Refs. [32, 112–117]. ΔHch
χ ch ¼
ΔH T
Example 9 Heptane was burned in a 2-m-diam- ΔH ch ¼ χ ch ΔH T
 
eter pan, and measurements were made for the kJ
mass loss rate, mass generation rates of CO and ΔH ch ¼ ð0:93Þ 44:6
g
CO2, and mass consumption rate of O2. The kJ
average values in g/m2/s for the mass loss rate, ΔH ch ¼ 41:5
g
mass generation rates of CO and CO2, and mass
consumption rate of O2 were 66, 9, 181, and The chemical heat release can now be
216, respectively. For large-scale fires of obtained from the product of the mass loss rate
1188 M.M. Khan et al.

and chemical heat of combustion, as in (2) polystyrene: 36  27.0 ¼ 972 kW/m2;


Equation 36.32: (3) polyvinylchloride: 16  5.7 ¼ 91 kW/m2;
00
and (4) Teflon: 7  4.1 ¼ 28 kW/m2.
Q_ ch ¼ ΔH ch m_
00

 
_
00 kJ  g  Example 11 Heat release rate is the product of
Q ch ¼ 41:5 66 2 the HRP and the net heat flux absorbed by the
g m s
material, as indicated in Equations 36.34 and
00 kW
Q_ ch ¼ 2739 2 36.35. This concept is used in various models to
m predict fire propagation and heat release rates,
Compare this result the averaged value whereas values for the HRP are taken from a
2742 kW/m2 from the CDG and OC handbook such as this handbook, and net heat
calorimetries. Thus, the chemical heat release flux is estimated through correlations. The lower
determined from the measurements is consistent the HRP value for a fixed value of net heat flux,
with the rate obtained from the literature values the lower the heat release rate.
of the combustion efficiency. The values for the surface re-radiation, flame
Finally, the convective heat release rate can heat flux for large-scale fires, and chemical HRP
be computed much in the same manner as above. are listed in Tables 36.6, 36.7, and 36.10, respec-
Here, for simplicity, Equations 36.32 and 36.36 tively. Calculate the chemical heat release rates
are combined to yield the convective heat release expected in large-scale fires of heptane, kero-
rate: sene, polyethylene, polypropylene, polystyrene,
polymethylmethacrylate, polyvinylchloride, and
00
Q_ con ¼ χ con ΔHT m_
00
Teflon.

00 kJ g 
Q_ con ¼ ð0:59Þ 44:6 66 Solution The chemical heat release rates are cal-
g m2 s
00 kW culated from Equation 36.34:
Q_ con ¼ 1737 2
m  
00 ΔHch  00 
Q_ ch ¼
00 00 00

In a similar fashion, the radiative heat release q_ e þ q_ f r þ q_ fc  q_ rr


ΔH g
rate is calculated to be 1001 kW/m2.
In this specific example, there is no external
Example 10 From the flame radiation scaling heat flux sources. Recognizing that (ΔHch/ΔHg)
technique, the asymptotic mass loss rate values ¼ HRPch, and setting the asymptotic flame heat
in g/m2/s expected in large-scale fires, as listed 00 00
flux values from 7 to the relationship q_ f r þ q_ fc
in Table 36.7, for polyethylene, polystyrene,
one obtains:
polyvinylchloride, and Teflon are 26, 36,
16, and 7, respectively. The chemical heats of 00  00 
Q_ ch ¼ HRPch q_ f , asy  q_ rr
00

combustion in kJ/g listed in Table A.38 for these


materials are 38.4, 27.0, 5.7, and 4.1, respec-
tively. Estimate the chemical heat release rates Therefore:
expected in large-scale fires of polyethylene, 1. heptane: (75)(37 – 1) ¼ 2700 kW/m2
polystyrene, polyvinylchloride, and Teflon. 2. kerosene: (47)(29 – 1) ¼ 1316 kW/m2
(In this chapter Teflon refers mainly to FEP, 3. polyethylene: (17)(61 – 15) ¼ 782 kW/m2
except in cases where it is identified otherwise.) 4. polypropylene: (19)(67 – 15) ¼ 988 kW/m2
5. polystyrene: (16)(75 – 13) ¼ 992 kW/m2
Solution The chemical heat release rate is calcu- 6. polymethylmethacrylate: (15)(57 – 11) ¼
lated from Equation 36.32. The chemical heat 690 kW/m2
release rates estimated in the large-scale fires 7. polyvinylchloride: (2)(50 – 15) ¼ 70 kW/m2
are (1) polyethylene: 26  38.4 ¼ 998 kW/m2; 8. Teflon: (2)(52 – 38) ¼ 28 kW/m2
36 Combustion Characteristics of Materials and Generation of Fire Products 1189

Table 36.10 Chemical and convective heat release parameters

Materials (HRP)ch (HRP)con


ASTM E2058 ASTM E2058
Fire Propagation ASTM Fire Propagation ASTM
Apparatus E1354a Calb Apparatus E906c Calb
Liquids and gases (hydrocarbons, alkanes)
Hexane – – 83 – – 56
Heptane – – 75 – – 50
Octane – – 68 – – 46
Nonane – – 64 – – 42
Decane – – 59 – – 39
Undecane – – 55 – – 36
Dodecane – – 52 – – 34
Tridecane – – 50 – – 32
Kerosene – – 47 – – 17
Hexadecane – – 44 – – 28
Solids (abbreviations/names in the nomenclature)
ABS – 14 – – – —
Acrylic sheet – 6 – – – –
Epoxy – 11 – – – –
IPST – 6 – – – –
Polyamide 21 – – – – –
Polypropylene 19 – – 11 – –
Polyethylene 17 21 – 12 – –
Polystyrene 16 19 – 6 – –
Polymethylmethacrylate 15 14 – 10 – –
Nylon 12 – – 7 – –
Polyamide-6 – 21 – – – –
Filled phenolic foam–50 % inert – 1 – – – –
Polycarbonate 9 – – – – –
Polyoxymethylene 6 – – 5 – –
Polyethylene/25 % CI 11 – – 5 – –
Plasticized-PVC-3, LOI 0.25 – 5 – – – –
Plasticized-PVC-4, LOI 0.30 – 5 – – – –
Plasticized-PVC-5, LOI 0.35 – 5 – – – –
Polyethylene/35 % CI 4 – – 2 – –
Rigid PVC-1, LOI 0.50 – 3 – – – –
Rigid PVC-2 2 3 – 1 – –
PVC panel 2 – – – – –
Polyethylene/48 % CI 2 – – – – –
PVEST – 13 – – – –
ETFE (Tefzel) 6 – – – – –
PFA (Teflon) 5 – – – – –
FEP (Teflon) 2 – – – – –
TFE (Teflon) 2 – – – – –
Wood (hemlock) – 1 – – – –
Wood (Douglas fir) 7 – – 5 – –
Wool – 5 – – – –
(continued)
1190 M.M. Khan et al.

Table 36.10 (continued)

Materials (HRP)ch (HRP)con


ASTM E2058 ASTM E2058
Fire Propagation ASTM Fire Propagation ASTM
Apparatus E1354a Calb Apparatus E906c Calb
Composites and fiberglass-reinforced materials (FGR) (abbreviations/names in the nomenclature)
Bismaleimide/graphite/ceramic – 1 – – – –
(CC)
Epoxy/FGR – 2 – – – –
Epoxy/graphite 2 – – – – –
Epoxy/graphite/CC 2 – – – – –
Epoxy/graphite/intumescent (IC) 2 – – – – –
IPST/FGR – 1 – – – –
PEEK/FGR – 3 – – – –
PES/FGR – 1 – – – –
PEST-1/FGR 3 – — – – –
PEST-2/FGR 8 – – – – –
PEST-3/FGR 10 – – – – –
PEST-4/FGR 3 – – – – –
PEST-5/FGR 3 – – – – –
PEST-6-FGR 3 – – – – –
Phenol/FGR – 1 – – – –
Phenolic/Kevlar 2 – – – – –
Phenol/graphite 1 – – – – –
PVEST-1/FGR 3 – – – – –
PVEST-1/FGR/CC 3 – – – – –
PVEST-1/FGR/IC 1 – – – – –
PVEST-2/FGR 7 – – – – –
PVEST-3/FGR 2 – – – – –
Aircraft panel materials
Epoxy fiberglass 4 4 – 2 1 –
Epoxy Kevlar 4 4 – 2 2 –
Phenolic Kevlar 5 4 – 2 – –
Phenolic graphite 4 3 – 1 – –
Phenolic fiberglass 4 3 – 2 1 –
Polycarbonate panel 9 – – – – –
Foams
Polystyrene
GM53 20 – – 6 – –
GM49 19 – – 8 – –
GM51 18 – – 9 – –
Flexible polyurethane
GM 21 7 – – 3 3 –
GM 23 9 – – 5 6 –
GM 25 14 – – 6 4 –
GM 27 9 – – 4 2 –
Phenolic – 1 – – – –
Electrical cables (abbreviations/names in the nomenclature)
PVC/PVC-1 (Group 3) 15 – – – – –
PE/PVC (Group 3) 19 – – – – –
(continued)
36 Combustion Characteristics of Materials and Generation of Fire Products 1191

Table 36.10 (continued)

Materials (HRP)ch (HRP)con


ASTM E2058 ASTM E2058
Fire Propagation ASTM Fire Propagation ASTM
Apparatus E1354a Calb Apparatus E906c Calb
PP, PEST/PVC (Group 3) 11 – – – – –
PVC/PVC-2 (Group 3) 14 – – – – –
Chlorinated PE (Group 2) 5 – – – – –
PVC/PVC-3 (Group 2) 4 – – – – –
EPR/PVC (Group 2) 6 – – – – –
PVC/EPR (Group 2) 4 – – – – –
XLPE/XLPE (Group 2) 6 – – – – –
EPR/hypalon-1 (Group 2) 6 – – – – –
EPR/hypalon-2 (Group 2) 4 – – – – –
EPR/hypalon-3 (Group 1) 3 – – – – –
EPR/hypalon-4 (Group 1) 3 – – – – –
EPR/EPR-1 (Group 1) 3 – – – – –
EPR/EPR-2 (Group 1) 3 – – – – –
EPR/EPR-3 (Group 1) 2 – – – – –
XLPE-EVA-1 (Group 1) 3 – – – – –
XLPE-EVA-2 (Group 1) 3 – – – – –
ETFA (Group 1) 3 – – – – –
PVC/PVF2 (Group 1) 1 – – – – –
FEP/FEP-1 (Group 1) 2 – – – – –
FEP/FEP-2 (Group 2) 2 – – – – –
a
Calculated from the data reported in Refs. [32, 113]
b
Calculated from the data in Refs. [112, 114]
c
From Ref. [115]

The example shows the importance of the loss rate, in addition to other factors. For
chemical HRP, flame heat flux, and surface ventilation-controlled fires, the effects of mass
re-radiation. flow rate of air and fuel mass loss rate are
characterized, most commonly, by the local
Heat Release Rate and Fire Ventilation For equivalence ratio:
the most part, fire hazards are due to fires occur-
00
ring in enclosed spaces. In early stages, a build- Sm_ A
Φ¼ ð36:41Þ
ing fire is well ventilated and is easy to control m_ air
and extinguish. However, if the fire is allowed to
grow, especially with limited enclosure ventila- where
tion and large material surface area, it becomes a Φ ¼ Equivalence ratio
ventilation-controlled fire and can lead to flash- S ¼ Stoichiometric air-to-fuel mass ratio (g/g)
over, a very dangerous condition. In ventilation- ṁ00 ¼ Mass loss rate (g/m2 · s)
controlled fires, the chemical reactions between A ¼ Exposed area of the burning material (m2)
oxygen from air and products of incomplete ṁair ¼ Mass flow rate of air (g/s)
combustion from the decomposed and gasified Generalized-state relationships between mass
material (e.g., smoke, CO, hydrocarbons, and fractions of major species (O2, fuel, CO2, H2O,
other intermediate products) remain incomplete CO, and H2) and temperature as functions of
and heat release rate decreases [103]. local equivalence ratios for hydrocarbon-air
In ventilation-controlled fires, heat release diffusion flames are available [118]. The
rate depends on the air supply rate and the mass relationships suggest that the generation
1192 M.M. Khan et al.

efficiencies of CO, fuel vapors, water, CO2, and where ζch is the ratio of the combustion effi-
H and the consumption efficiency of O2 are in ciency for ventilation-controlled (vc) combustion
approximate thermodynamic equilibrium for to that for well-ventilated (wv) combustion;
well-ventilated combustion but deviate from similarly, ζ con is the ratio of the convective com-
equilibrium for ventilation-controlled combus- ponent of the combustion efficiency for
tion. This concept has been used for fires of ventilation-controlled combustion to that for
polymeric materials [103]. In the tests, chemical well-ventilated combustion. These ratios can be
and convective heat release rates, mass loss rate, represented by the ratio of the chemical or con-
and generation rates of fire products were vective heats of combustion for ventilation-
measured for various equivalence ratios in the controlled to well-ventilated combustion.
Fire Propagation Apparatus (Fig. 36.2) and in The experimental data for the ratios of the
the Fire Research Institute’s (FRI) 0.022 m3 chemical and convective heats of combustion
enclosure in Tokyo, Japan [103]. The combus- for ventilation-controlled to well-ventilated
tion efficiency and its convective component fires at various equivalence ratios are shown in
were found to decrease as fires become fuel Figs. 36.33 and 36.34. The data and measure-
rich, due to an increase in the equivalence ratio. ment details are described in Ref. [103].
The ratio of the combustion efficiency and its The data for the polymers indicated in the figures
convective component or chemical and convec- satisfy the following general empirical
tive heats of combustion for ventilation- correlations, regardless of their chemical
controlled to well-ventilated combustion is structures:
expressed as [103]
ðΔHch Þvc 0:97
¼1 "  # ð36:44Þ
ðχ Þ ðΔHch =ΔH T Þvc ðΔH ch Þvc ðΔH ch Þwv Φ 1:2
ζ ch ¼ ch vc ¼ ¼ exp
ðχ ch Þwv ðΔH ch =ΔH T Þwv ðΔH ch Þwv 2:15
ð36:42Þ
ðΔH con Þvc 1:0
ðχ Þ ðΔHcon =ΔH T Þvc ðΔHcon Þvc ¼1 " 2:8 # ð36:45Þ
ζ con ¼ con vc ¼ ¼ ðΔH con Þwv Φ
ðχ con Þwv ðΔH con =ΔHT Þwv ðΔH con Þwv exp
1:38
ð36:43Þ

Fig. 36.33 Ratio of 1.4


ventilation-controlled to
well-ventilated chemical ζch = 1 – 0.97 / exp(2.5φ–1.2) Wood
heat of combustion versus 1.2 PMMA
equivalence ratio (Data are Nylon
taken from Ref. [103]). PE
1.0
Subscript vc represents PP
(ΔHch)vc /(ΔHch)wv

ventilation-controlled fires, PS
and subscript wv represents 0.8
well-ventilated fires
0.6 Nonflaming

0.4

0.2

0.0
10–1 100 101 102
Equivalence ratio
36 Combustion Characteristics of Materials and Generation of Fire Products 1193

Fig. 36.34 Ratio of the 1.4


ventilation-controlled to
well-ventilated convective ζcon = 1 – 1.0 / exp(2.5φ–2.8) Wood
heat of combustion versus 1.2 PMMA
the equivalence ratio (Data Nylon
are taken from Ref. [103]). PE
1.0
Subscript vc represents PP

(ΔHcon)vc /(ΔHcon)wv
ventilation-controlled fires, PS
and subscript wv represents 0.8
well-ventilated fires
0.6 Nonflaming

0.4

0.2

0.0
10–1 100 101
Equivalence ratio

The effects of ventilation on the chemical and Example 12 Calculate the chemical heats of
convective heats of combustion are reflected by combustion at equivalence ratios of 1, 2, and
the magnitudes of the expressions within the 3 for red oak, polyethylene, polystyrene, and
parentheses on the right-hand sides of nylon using Equation 36.44 and data from
Equations 36.44 and 36.45. For a well-ventilated Table A.39 for well-ventilated fires.
fire, Φ 1.0, (ΔHch)vc ¼ (ΔHch)wv, and
(ΔHcon)vc ¼ (ΔHcon)wv. Solution
As a fire changes from well ventilated to
ventilation controlled, the equivalence ratio Chemical heats of combustion (kJ/g)
increases and the magnitudes of the expressions Material Φ 1.0 Φ ¼ 1.0 Φ ¼ 2.0 Φ ¼ 3.0
within the parentheses on the right-hand sides of Red oak 12.4 11.4 8.3 6.2
Equations 36.44 and 36.45 increase. Thus, with Polyethylene 38.4 35.3 25.9 19.3
increasing equivalence ratio, the chemical and Polystyrene 27.0 24.9 18.2 13.6
Nylon 27.1 24.9 18.2 13.6
convective heats of combustion decrease. The
decrease in the convective heat of combustion
is higher than that for the chemical heat of Generation of Fire Products
combustion because the coefficients for the and Smoke Yields
equivalence ratios are different. The correlation
suggests that a higher fraction of the chemical Chemical compounds (smoke, toxic, corrosive,
heat of combustion is expected to be converted to and odorous compounds) are the main
the radiative heat of combustion as fires change contributors to nonthermal hazards and, thus,
from well ventilated to ventilation controlled. the assessments of their chemical natures and
This is in general agreement with observations generation rates are of critical importance for
for ventilation-controlled fires in buildings. the protection of life and property.
Equations 36.44 and 36.45 can be used in In fires, compounds are generated as a result
models for the assessment of the ventilation- of gasification and decomposition of materials
controlled fire behavior of materials, using chem- involved in the fire and burning of the species
ical and convective heats of combustion for well- in the gas phase with air in the form of a diffusion
ventilated fires such as from Table A.39. flame. In general, generation of fire products and
1194 M.M. Khan et al.

00
G_ j ¼ y j m_
consumption of oxygen in diffusion flames occur 00
ð36:46Þ
in two zones [103].
00
1. Reduction zone. In this zone, the material where Ġj is the mass generation rate of product
melts, decomposes, gasifies, and/or generates j (g/m2/s), and yj is the yield of product j (g/g).
species that react to form smoke, CO, The total mass of the product generated is
hydrocarbons, and other intermediate obtained by the summation of the generation
products. Very little oxygen is consumed in rate:
this region. The extent of conversion of the
material to smoke, CO, hydrocarbons, and X
n¼t f
00

other products depends on the chemical nature Wj ¼ A G_ j ðtn ÞΔtn ð36:47Þ


n¼t0
of the material.
2. Oxidation zone. In this zone, the reduction where
zone products (smoke, CO, hydrocarbons, Wj ¼ Total mass of product j generated from the
and other intermediates) react with varying flaming and/or nonflaming processes involv-
degrees of efficiency with the oxygen from ing the material (g)
air and generate chemical heat and varying t0 ¼ Time when the sample is exposed to heat(s)
amounts of products of complete combustion, tf ¼ Time when there is no more product
such as CO2 and H2O. The lower the reaction formation
efficiency, the higher the amounts of reduc- From Equations 36.31, 36.46, and 36.47, the
tion zone products emitted from a fire. The average value of the yield of product j is
reaction efficiency of the reduction zone
products with oxygen depends on the Wj
yj ¼ ð36:48Þ
concentrations of the products relative to Wf
the oxygen concentration, temperature, and
Similarly, the mass consumption rate of oxygen
mixing of the products and air. For example,
is also directly proportional to the mass loss rate
in laminar diffusion flames, smoke is emitted
(e.g., [9, 112]):
when the temperature of the oxidation zone
falls below about 1300 K. 00
C_ O ¼ cO m_
00

The hot ceiling layer in a building fire may be ð36:49Þ


considered in terms of oxidation and reduction 00
Where ĊO is the mass consumption rate of oxy-
zone products. In building fires with plenty of
gen (g/m2/s), and cO is the mass of oxygen con-
ventilation, the concentrations of the reduction
sumed per unit mass of fuel (g/g).
zone products are higher in the central region of
In the bench-scale apparatuses described in
the ceiling layer, whereas the concentrations of
this chapter, the mass generation rates of fire
the oxidation zone products are higher closer to
products and mass consumption rate of oxygen
the room opening. As the air supply rate, or
are determined by measuring the volume
oxygen concentration available to the fire,
fractions of the products and oxygen and the
decreases due to restrictions in the ventilation,
total volumetric or mass flow rate of the fire
the ceiling layer expands and starts occupying a
products-air mixture (e.g., [10, 11, 28, 31]):
greater room volume accompanied with an
increase in the concentrations of reduction zone !
00 f j V_ ρ j ρj
products. Under these conditions, large amounts G_ j ¼ ¼ f j W_ ð36:50Þ
of reduction zone products are released within A ρg A
the building increasing the nonthermal hazard. !
The generation rate of a fire product is 00 f V_ ρ ρO
C_ O ¼ O O ¼ f O W_ ð36:51Þ
directly proportional to the mass loss rate, the A ρg A
proportionality constant being defined as the
yield of the product (e.g., [9, 112]): where
36 Combustion Characteristics of Materials and Generation of Fire Products 1195

EXHAUST SYSTEM
AIR VELOCITY PORT
VERTICAL ACROSS DUCT
736.0 457 413
300 304
76 GAS SAMPLE PORT
1.575 mm WALL, HORIZONTAL ACROSS
S.S. TUBING, 30
DUCT
152 mm O.D.
TEST
BLOWER
300

MIXING DUCT SECTION


DUCT
50
ORIFICE PLATE (1.6 mm THK, THERMOCOUPLE
91.5 mm ORIFICE DIA.) PORT LASER SMOKE
AT THIS POSITION MEASURING SYSTEM
260

INTAKE FUNNEL
610 40

INSTRUMENTATION
CART
IR HEATING
SYSTEM & 1451
SPECIMEN
AREA OF
FPA

MAIN VIEW
ALL DIMENSIONS IN MM UNLESS NOTED

Fig. 36.35 Schematic of the commercial version [119] of the Fire Propagation Apparatus showing locations where
measurements are made for product concentration, optical transmission, particulate concentration, and corrosion

fj ¼ Volume fraction of product j mixed, such as in the Fire Propagation Apparatuses


fO ¼ Volume fraction of oxygen (Figs. 36.2, 36.3, and 36.35) and in the cone calo-
V_ ¼ Total volumetric flow rate of the fire product- rimeter (Fig. 36.4). Figure 36.35 shows the mea-
air mixture (m3/s) surement locations in the sampling duct of a
Ẇ ¼ Total mass flow rate of the fire product-air commercial version [119] of the Fire Propagation
mixture (g/s) Apparatus. The volume fractions are measured by
ρj ¼ Density of product j at the temperature of various types of instruments; for example, in the
the fire product-air mixture (g/m3) Fire Propagation Apparatus, they are measured
ρg ¼ Density of the hot fire product-air mixture continuously by (1) commercial non-dispersive
(g/m3) infrared analyzers for CO and CO2; (2) a high-
ρO ¼ Density of oxygen at the temperature of the sensitivity commercial paramagnetic analyzer for
fire product-air mixture (g/m3) oxygen; (3) a commercial flame ionization ana-
A ¼ Total area of the material burning (m2) lyzer for the mixture of low molecular weight
For volume fraction measurements, sampling gaseous hydrocarbons; and (4) by a laser (wave-
ducts are used where fire products and air are well length: 0.6328 μm) smoke measuring system.
1196 M.M. Khan et al.

The optical density at the measurement loca- The average data for the yields of CO, CO2,
tion in the sampling duct is determined from the mixture of gaseous hydrocarbons, and smoke for
following equation: well-ventilated fires are listed in Table A.39.

lnðI 0 =I Þ Example 13 For a fiberglass-reinforced material,


D¼ ð36:52Þ
l the following data were measured for combus-
where, D is the optical density (m1) at a laser tion in normal air at an external heat flux value of
wavelength of 0.6328 μm; I/I0 is the fraction of 50 kW/m2:
monochromatic light transmitted through smoke; Total mass of the sample lost (g) 229
and l is the optical path length (m). The volume Total mass generated (g)
fraction of smoke fs is obtained from the follow- CO 0.478
ing expression [120]: CO2 290
Hydrocarbons 0.378
Dλ  106 Smoke 6.31
fs ¼ ð36:53Þ
Ω Total energy generated (kJ) 3221

where, λ is the wavelength of the light source


(μm) and Ω is the coefficient of smoke extinction Calculate the average yields of CO, CO2,
taken as 7 [120]. The mass generation rate hydrocarbons, and smoke and the average chem-
(kg/m2/s) of smoke is given by: ical heat of combustion.

  
00 f V_ ρ Dλ  106 ρs V_ Solution The average yields are calculated
G_ s ¼ s s ¼ ð36:54Þ from Equation 36.48, and the average chemical
A 7 A
heats of combustion are calculated from
Incorporating the value of smoke density, Equation 36.33.
ρs ¼ 1.1  106 g/m3, as determined in Ref.
Average yields (g/g)
[120] and the laser wavelength of 0.6328 μm in
CO 0.0021
Equation 36.54 then gives the following result: CO2 1.27
  Hydrocarbons 0.002
00
2 DV
_
_
G s ¼ 9:944  10 ð36:55Þ Smoke 0.028
A Average chemical heats of combustion (kJ/g) 14.1

Equation 36.55 can then be used along with Example 14 A circular sample of polystyrene,
Equations 36.31, 36.47, and 36.48 to calculate about 0.007 m2 in area and 25 mm in thickness,
the average smoke yield, ys , for a given material. was burned in normal air in the presence of
The average value of smoke yield, can also be external heat flux. In the test, measurements
obtained from the average mass-specific extinc- were made for the mass loss rate and light obscu-
tion area [24, 121], τ (m2/g), at the same laser ration by smoke in the sampling duct with an
wavelength of 0.6328 μm: optical path length of 0.149 m. The total volu-
ð metric flow rate of the mixture of fire products
1 Xf _
n¼t
1 _ and air through the sampling duct was
τ¼ VDdt ¼ V ðtn ÞDðtn ÞΔtn
Wf W f n¼t0 0.311 m3/s, and the wavelength of light source
ð36:56Þ used was 0.6328 μm. At the steady-state combus-
tion of polystyrene, the measured mass loss rate
The average smoke yield is, in this case, calcu- was 33 g/m2/s with smoke obscuring 83.5 % of
lated from the following expression: the light. Calculate the yield of smoke from the
data using a value of 1.1  106 g/m3 for the
ys ¼ 9:944  102 τ ð36:57Þ density of smoke.
36 Combustion Characteristics of Materials and Generation of Fire Products 1197

Solution The optical density from Equa- ΨO ¼ Stoichiometric oxygen-to-fuel mass ratio
tion 36.52 is for the maximum possible conversion of the
fuel monomer to products
lnðI 0 =I Þ lnð1=0:835Þ
D¼ ¼ ¼ 1:21 m1 MO ¼ Molecular weight of oxygen (32 g/mol)
l 0:149 Mf ¼ Molecular weight of the fuel monomer of
The smoke generation rate from Equa- the material (g/mol)
tion 36.55 is Mf is calculated from its elemental composition
  which may be determined from microanalyti-
00 g DV_ cal techniques.
G_ s ¼ 9:944  102 2
m A The stoichiometric yield for the maximum
2  3 possible conversion of the fuel monomer of the
1 m3
1:21 0:311
00 g6 m s 7 material to a product is expressed as
G_ s ¼ 9:944  102 2 6 7
m 4 0:007 m2 5 ν jM j
Ψj¼ ð36:60Þ
Mf
00 g
G_ s ¼ 5:35 2
m s where Ψj is the stoichiometric yield for the max-
imum possible conversion of the fuel monomer
The smoke yield from Equation 36.46 is
of the material to product j, and Mj is the molec-
00 ular weight of product (g/mol).
G_ s ¼ ys m_
00

The stoichiometric yields for some selected


00 g materials, calculated from the elemental compo-
G_ s 5:35m2 s
ys ¼ 00 ¼ g sition data from the flammability laboratory, are
m_ 33 2 listed in Table 36.11 for fuel monomer conver-
m s
sion to CO, CO2, hydrocarbons, smoke, HCl,
ys ¼ 0:162
and HF. The yields provide an insight into the
nature of products and the amounts of products
Efficiencies of Oxygen Mass Consumption expected to be generated in flaming and
and Mass Generation of Products nonflaming processes, when expressed as the
A chemical reaction between oxygen (air) and stoichiometric oxygen mass consumption rate
a fuel monomer of a material can be expressed as and stoichiometric mass generation rates of
X products:
F þ νO O2 þ νN N2 ¼ νN N2 þ ν ji J i
i 00
C_ stoich, O ¼ Ψ O m_
00

ð36:58Þ ð36:61Þ

where 00
G_ stoich, j ¼ Ψ j m_
00

F ¼ Fuel monomer of a material ð36:62Þ


νO ¼ Stoichiometric coefficient for oxygen 00 00

νN ¼ Stoichiometric coefficient for nitrogen where C_ stoich, O and G_ stoich, j are the stoichiometric
v ji ¼ Stoichiometric coefficients for the maxi- oxygen mass consumption rate and stoichiomet-
mum possible conversion of the fuel mono- ric mass generation rate of product j for the
mer to products Ji maximum possible conversion of the fuel mono-
The stoichiometric mass oxygen-to-fuel ratio mer to the product, respectively (g/m2/s).
for the maximum possible conversion of the fuel In fires, due to incompleteness of combustion
monomer is expressed as as discussed above, the actual oxygen mass con-
sumption rate and the mass generation rates of
νO M O
ΨO ¼ ð36:59Þ products may be significantly less than the stoi-
Mf chiometric rates. The ratio of the actual oxygen
mass consumption rate to stoichiometric rates is
where
1198 M.M. Khan et al.

Table 36.11 Stoichiometric yields of major productsa


Material Formula ΨO Ψ CO2 ΨCO Ψs Ψhc ΨHCI ΨHF
Carbon-hydrogen atoms in the structure
PE CH2 3.43 3.14 2.00 0.857 1.00 0 0
PP CH2 3.43 3.14 2.00 0.857 1.00 0 0
PS CH 3.08 3.38 2.15 0.923 1.00 0 0
Expanded polystyrene
GM47 CH1.1 3.10 3.36 2.14 0.916 1.00 0 0
GM49 CH1.1 3.10 3.36 2.14 0.916 1.00 0 0
GM51 CH 3.08 3.38 2.15 0.923 1.00 0 0
GM53 CH1.1 3.10 3.36 2.14 0.916 1.00 0 0
Carbon-hydrogen-oxygen-nitrogen atoms in the structure
POM CH2O 1.07 1.47 0.933 0.400 0.467 0 0
PMMA CH1.6O0.40 1.92 2.20 1.40 0.600 0.680 0 0
Nylon CH1.8O0.17 N0.17 2.61 2.32 1.48 0.634 0.731 0 0
Wood (pine) CH1.7O0.83 1.21 1.67 1.06 0.444 0.506 0 0
Wood (oak) CH1.7O0.72 N0.001 1.35 1.74 1.11 0.476 0.543 0 0
Wood (Douglas fir) CH1.7O0.74 N0.002 1.32 1.72 1.10 0.469 0.536 0 0
Polyester CH1.4O0.22 2.35 2.60 1.65 0.709 0.792 0 0
Epoxy CH1.3O0.20 2.38 2.67 1.70 0.727 0.806 0 0
Polycarbonate CH0.88O0.19 2.26 2.76 1.76 0.754 0.872 0 0
PET CH0.80O0.40 1.67 2.29 1.46 0.625 0.667 0 0
Phenolic foam CH1.1O0.24 2.18 2.60 1.65 0.708 0.773 0 0
PAN CHN0.33 2.87 2.50 1.59 0.681 0.681 0 0
Flexible polyurethane foams
GM21 CH1.8O0.30 N0.05 2.24 2.28 1.45 0.622 0.715 0 0
GM23 CH1.8O0.35 N0.06 2.11 2.17 1.38 0.593 0.682 0 0
GM25 CH1.7O0.32 N0.07 2.16 2.22 1.41 0.606 0.692 0 0
GM27 CH1.7O0.30 N0.08 2.21 2.24 1.43 0.612 0.698 0 0
Rigid polyurethane foams
GM29 CH1.1O0.23 N0.10 2.22 2.42 1.54 0.660 0.721 0 0
GM31 CH1.2O0.22 N0.10 2.28 2.43 1.55 0.662 0.729 0 0
GM37 CH1.2O0.20 N0.08 2.34 2.51 1.60 0.685 0.753 0 0
Rigid polyisocyanurate foams
GM41 CH1.0O0.19 N0.11 2.30 2.50 1.59 0.683 0.740 0 0
GM43 CH0.93O0.20 N0.11 2.25 2.49 1.58 0.679 0.732 0 0
Carbon-hydrogen-oxygen-silicone atoms in the structure
Silicone-1b CH1.3O0.25Si0.18 1.98 1.97 1.25 0.537 0.595 0 0
Silicone-2c CH1.5O0.30Si0.26 1.86 1.72 1.09 0.469 0.528 0 0
Silicone-3d CH3O0.50Si0.50 1.73 1.19 0.757 0.324 0.405 0 0
Carbon-hydrogen-oxygen-chlorine-fluorine atoms in the structure
Fluoropolymers
PVF (Tedlar) CH1.5 F0.50 1.74 1.91 1.22 0.522 0.587 0 0.435
PVF2 (Kynar) CHF 1.00 1.38 0.875 0.375 0.406 0 0.594
ETFE (Tefzel) CH1.0 F0.99 1.01 1.38 0.880 0.377 0.409 0 0.622
E-CTFE (Halar) CHF0.75CI0.25 0.889 1.22 0.778 0.333 0.361 0.257 0.417
PFA (Teflon) CF1.7O0.01 0.716 1.00 0.630 0.270 0 0 0.765
FEP (Teflon) CF1.8 0.693 0.952 0.606 0.260 0 0 0.779
TFE (Teflon) CF2 0.640 0.880 0.560 0.240 0 0 0.800
CTFE (Kel-F) CF1.5CI0.50 0.552 0.759 0.483 0.207 0 0.310 0.517
(continued)
36 Combustion Characteristics of Materials and Generation of Fire Products 1199

Table 36.11 (continued)


Material Formula ΨO Ψ CO2 ΨCO Ψs Ψhc ΨHCI ΨHF
Chloropolymers
PE-25 % CI CH1.9CI0.13 2.56 2.38 1.52 0.650 0.753 0.254 0
PE-36 % CI CH1.8CI0.22 2.16 2.05 1.30 0.558 0.642 0.368 0
Neoprene CH1.25CI0.25 1.91 2.00 1.27 0.546 0.602 0.409 0
PE-42 % CI CH1.8CI0.29 1.94 1.84 1.17 0.501 0.576 0.424 0
PE-48 % CI CH1.7CI0.36 1.73 1.67 1.06 0.456 0.521 0.493 0
PVC CH1.5CI0.50 1.42 1.42 0.903 0.387 0.436 0.581 0
PVCI2 CHCI 0.833 0.917 0.583 0.250 0.271 0.750 0
a
Calculated from the data for the elemental compositions of the materials; subscript hc is total gaseous hydrocarbons;
s is soot
b
ηSiO2 ¼ 0.483
c
ηSiO2 ¼ 0.610
d
ηSiO2 ¼ 0.811

thus defined as the efficiency of oxygen mass ratio, stoichiometric air-to-fuel mass ratio, and
consumption or product mass generation stoichiometric yields for maximum possible con-
(e.g., [103]): version of the fuel monomer of the material to
CO, CO2, hydrocarbons, water, and smoke.
00
C_ actual, O Assume smoke to be pure carbon, and
00
cO m_ cO
ηO ¼ 00 ¼ 00 ¼ ð36:63Þ hydrocarbons as having the same carbon-atom-
C_ stoich, O Ψ O m_ ΨO
to-hydrogen-atom ratio as the original fuel
monomer.
00
C_ actual, j
00
y j m_ yj
ηj ¼ 00 ¼ 00 ¼ ð36:64Þ Solution
C_ stoich, j Ψ j m_ Ψj
1. For stoichiometric yields of CO2 and water
and the stoichiometric oxygen- and air-to-
Where ηO is the efficiency of oxygen mass con- fuel mass ratio for the maximum possible
sumption and ηj is the generation efficiency of conversion of the fuel monomer of the mate-
product j. rial to CO2 and H2O, the following expression
is used:
Example 15 A material is made up of carbon,
hydrogen, and oxygen. The weight of the mate- CH1:33 O0:56 þ 1:06 O2 ¼ CO2 þ 0:67 H2 O
rial is distributed as follows: 54 % as carbon, 6 % The molecular weight of the fuel monomer of
as hydrogen, and 40 % as oxygen. Calculate the the material is 1  12 + 1.33  1 + 0.56
chemical formula of the fuel monomer of the  16 ¼ 22.3 g/mol, the molecular weight of
material. oxygen is 32 g/mol, the molecular weight of
CO2 is 44 g/mol, and the molecular weight of
Solution From the atomic weights and the H2O is 18 g/mol. Thus, from Equation 36.59:
weight percent of the atoms, the numbers of
44
atoms are as follows: carbon (C): 54/12 ¼ 4.5; Ψ CO2 ¼ ¼ 1:97
hydrogen (H): 6/1 ¼ 6.0; and oxygen (O): 22:3
40/16 ¼ 2.5. Thus, the chemical formula of the 0:67  18
Ψ H2 O ¼ ¼ 0:54
fuel monomer of the material is C4.5H6.0O2.5 or, 22:3
dividing by 4.5, CH1.33O0.56. 1:06  32
ΨO ¼ ¼ 1:52
22:3
Example 16 For the material in Example 15, cal- The stoichiometric air-to-fuel mass ratio can
culate the stoichiometric oxygen-to-fuel mass be obtained by dividing ΨO by 0.233 (i.e., the
1200 M.M. Khan et al.

mass fraction of oxygen in air); that is, 1.52/ 3. Asymptotic values for the mass generation
0.233 ¼ 6.52. rates of products from Equation 36.46 and the
2. For stoichiometric yields of CO, above data:
hydrocarbons, and smoke for the maximum 00
G_ CO2 ¼ yCO2 m_ ¼ 1:77  30 ¼ 53 g=m2 =s
00
possible conversion of the fuel monomer of
the material to these products, different chem- 00
G_ CO ¼ yCO m_ ¼ 0:005  30 ¼ 0:159 g=m2 =s
00
ical reactions have to be written, as follows:
00
For CO,
G_ hc ¼ yhc m_ ¼ 0:001  30 ¼ 0:036 g=m2 =s
00

CH1:33 O0:56 þ z O2 ¼ CO þ xðHOÞ 00


G_ hc ¼ yhc m_ ¼ 0:019  30 ¼ 0:584 g=m2 =s
00

Ψ CO ¼ 28=22:3 ¼ 1:26

For hydrocarbons (same H/C ratio as fuel Generation Rates of Fire Products and Fire
monomer), Ventilation Effects
CH1:33 O0:56 þ z O2 ¼ CH1:33 þ xðHOÞ As discussed previously, the effects of decreasing
fire ventilation, as characterized by the increase in
Ψ hc ¼ 13:3=22:3 ¼ 0:60
the local equivalence ratio, are reflected by an
For smoke (i.e., pure carbon), increase in the generation rates of the reduction
zone products (smoke, CO, hydrocarbons, and
CH1:33 O0:56 þ z O2 ¼ C þ xðHOÞ others). For example, for flaming wood crib
Ψ s ¼ 12=22:3 ¼ 0:54 enclosure fires, as the equivalence ratio increases,
the combustion efficiency decreases, flames
become unstable, and the generation efficiency
Example 17 For the material in Examples of CO reaches its peak for the equivalence
15 and 16, the generation efficiencies of CO2, ratio between about 2.5 and 4.0 [103].
CO, hydrocarbons, and smoke are 0.90, 0.004, Ventilation-controlled building fires are gen-
0.002, and 0.036, respectively. The heat of gasi- erally characterized by two layers: (1) a vitiated
fication is 1.63 kJ/g, the surface re-radiation loss ceiling layer, identified as upper layer, and (2) an
is 11 kW/m2, and the predicted asymptotic flame uncontaminated layer below, identified as lower
heat flux value for large-scale fires is 60 kW/m2. layer. Incorporation of these two layers is the
Calculate the yields and asymptotic values for classical two-zone modeling of fires in enclosed
the generation rates of CO2, CO, hydrocarbons, spaces. Under many conditions, the depth of the
and smoke expected in large-scale fires. upper layer occupies a significant fraction of
the volume of the enclosed space. Eventually,
Solution the interface between the upper layer and the
1. Yields from Equations 36.63 and 36.64 and lower layer positions itself so that it is very
data from Example 16: close to the floor, very little oxygen is available
yCO2 ¼ ηCO2 Ψ CO2 ¼ 0:90  1:97 ¼ 1:77 g=g for combustion, and most of the fuel is converted
to the reduction zone products, that is, smoke,
yCO ¼ ηCO Ψ CO ¼ 0:004  1:26 ¼ 0:005 g=g
CO, hydrocarbons, and others.
yhc ¼ ηhc Ψ hc ¼ 0:002  0:60 ¼ 0:001 g=g Ventilation-controlled large- and small-
ys ¼ ηs Ψ s ¼ 0:036  0:54 ¼ 0:019 g=g enclosure and laboratory-scale fires and fires in
the vitiated upper layer under experimental
2. Asymptotic values for the mass loss rate from hoods have been studied in detail and reviewed
Equation 36.15: [103, 122–125]. The results from these types of
00 00 fires are very similar. Detailed studies [103]
00 q_ f , asy  q_ rr 60  11 g
m_ ¼ ¼ ¼ 30 2 performed for the generation rates of fire
ΔH g 1:63 m s products for various fire ventilation conditions
36 Combustion Characteristics of Materials and Generation of Fire Products 1201

Fig. 36.36 Ratio of the


mass of oxygen consumed ζσ = 1 – 0.97 / exp(2.5φ–1.2)
per unit mass of the fuel for Wood
PMMA
ventilation-controlled to 100
well-ventilated fires (Data Nylon
are taken from Ref. [103]). PE
Subscript vc represents PP
ventilation-controlled fires, PS

(co)vc /(co)wv
and subscript wv represents
well-ventilated fires Nonflaming

10–1

10–1 100 101 102


Equivalence ratio

in the Fire Propagation Apparatus and in the Fire where ζoxid is the oxidation zone product genera-
Research Institute’s (FRI) enclosure, show that tion efficiency ratio.
with an increase in the equivalence ratio (1) gen- Reduction zone products (smoke, carbon monoxide,
eration efficiencies of oxidation zone products, hydrocarbons, etc.)
such as CO2, and reactant consumption effi-    
 
ciency (i.e., oxygen) decrease, and (2) generation ηj vc yj =Ψ j yj
efficiencies of the reduction zone products, such ζ red ¼   ¼   vc ¼   vc ð36:67Þ
ηj wv yj =Ψ j yj
as smoke, CO, and hydrocarbons increase. wv wv
Generalized correlations have been esta-
blished between the generation efficiencies and where ζred is the reduction zone product genera-
the equivalence ratio for the oxidation and reduc- tion efficiency ratio.
tion zone products. The changes in the consump- The relationships between the ratios of the
tion or generation efficiencies of the products are mass of oxygen consumed per unit mass of fuel,
expressed as ratios of the efficiencies for the the yields of the products for the ventilation-
ventilation-controlled (vc) to well-ventilated controlled to well-ventilated fires, and the equiv-
(wv) fires: alence ratio are shown in Figs. 36.36, 36.37,
Reactants (oxygen) 36.38, 36.39, and 36.40. The ratios for oxygen
and CO2 (an oxidation zone product) do not
ðηO Þvc ðcO =ΨO Þvc ðcO Þvc depend on the chemical structures of the
ζO ¼ ¼ ¼ ð36:65Þ materials, whereas the ratios for the reduction
ðηO Þwv ðcO =ΨO Þwv ðcO Þwv
zone products do depend on the chemical
Oxidation zone products (carbon dioxide, structures of the materials.
water, etc.)
    Oxygen and CO2 The relationships for oxygen
 
ηj yj =Ψ j yj consumed and carbon dioxide generated are
ζ oxid ¼   vc ¼   vc ¼   vc
ηj wv yj =Ψ j yj shown in Figs. 36.36 and 36.37, respectively.
wv wv The relationships are very similar to the
ð36:66Þ relationships for the chemical and convective
1202 M.M. Khan et al.

Fig. 36.37 Ratio of the


mass of carbon dioxide ζco2 = 1 – 1.0 / exp(2.5φ–1.2)
generated per unit mass of Wood
PMMA
the fuel for ventilation- 100
controlled to well- Nylon
PE
ventilated fires (Data are
PP
taken from Ref. [103]).
PS

(yco2)vc /(yco2)wv
Subscript vc represents
ventilation-controlled fires,
and subscript wv represents Nonflaming
well-ventilated fires

10–1

10–1 100 101 102


Equivalence ratio

Fig. 36.38 Ratio of the 102


mass of carbon monoxide
generated per unit mass of
Wood
the fuel for ventilation- PMMA
controlled to well- Nylon
ventilated fires (Data are PE
taken from Ref. [103]). PP
Subscript vc represents PS
(yco)vc /(yco)wv

ventilation-controlled fires,
and subscript wv represents
well-ventilated fires 101

Nonflaming

100
100 101 102
Equivalence ratio

heats of combustion ratios (Equations 36.44 and Carbon Monoxide The relationship between
36.45), as expected: the ratio of the CO yields for ventilation-
controlled to well-ventilated fires and the equiv-
ðcO Þvc 0:97
¼1 h  i ð36:68Þ alence ratio is shown in Fig. 36.38. The data
ðcO Þwv exp Φ
1:2
suggest the following relationship [103]:
2:14

 

yCO2
 vc ¼ 1 
0:97
h  i ð yCO Þvc α
ð36:69Þ ¼1þ   ð36:70Þ
yCO2 Φ 1:2 ð yCO Þwv exp 2:5Φξ
wv exp 2:15
36 Combustion Characteristics of Materials and Generation of Fire Products 1203

Fig. 36.39 Ratio of the 103


mass of hydrocarbons
generated per unit mass of Wood
the fuel for ventilation- PMMA
controlled to well- Nylon
ventilated fires (Data are PE
taken from Ref. [103]). PP
Subscript vc represents 102
PS

(yhc)vc /(yhc)wv
ventilation-controlled fires,
and subscript wv represents
well-ventilated fires
Nonflaming
101

100
100 101
Equivalence ratio

Fig. 36.40 Ratio of the 3.0


mass of smoke generated
per unit mass of the fuel for 2.8 Wood
ventilation-controlled to PMMA
well-ventilated fires (Data 2.6 Nylon
are taken from Ref. [103]). PE
Subscript vc represents 2.4 PP
ventilation-controlled fires, PS
2.2
(ys)vc /(ys)wv

and subscript wv represents


well-ventilated fires 2.0

1.8 Nonflaming

1.6

1.4

1.2

1.0
100 101
Equivalence ratio

where α and ξ are the correlation coefficients, the following order for the preferential conver-
which depend on the chemical structures of sion: wood (C-H-O aliphatic structure) >
the materials. The values for the correlation PMMA (C-H-O aliphatic structure) > nylon
coefficients for CO are listed in Table 36.12. (C-H-O-N aliphatic structure) > PE (C-H ali-
The increase in the ratio of the carbon mon- phatic linear unsaturated structure) > PP (C-H
oxide yields for the ventilation-controlled to aliphatic branched unsaturated structure) > PS
well-ventilated fires with the equivalence ratio (C-H aromatic structure). A similar trend is
is due to the preferential conversion of the fuel found for the liquid and gaseous fuels, such as
carbon atoms to CO. The experimental data show shown in Table 36.13 [103]. The presence of O
1204 M.M. Khan et al.

and N atoms in the fuels with aliphatic C-H to hydrocarbons than to CO, as the equivalence
structure appears to enhance preferential fuel ratio increases. The order for the preferential fuel
carbon atom conversion to CO. conversion to hydrocarbons is very similar to
CO, except for wood; that is, PMMA > nylon >
Hydrocarbons The relationship between the PE ¼ PP > wood > PS. The exception for
ratio of the hydrocarbon yields for ventilation- wood may be due to the char-forming tendency
controlled to well-ventilated fires and the equiv- of the fuel, which lowers the C-to-H ratio in the
alence ratio is shown in Fig. 36.39. The data gas phase.
suggest the following relationship [103]:
Smoke The relationship between the ratio of the
ð yhc Þvc α
¼1þ   ð36:71Þ smoke yields for ventilation-controlled to well-
ð yhc Þwv exp 5:0Φξ ventilated fires and the equivalence ratio is
shown in Fig. 36.40. The data suggest the follow-
The correlation coefficient values for
ing relationship: [103]
hydrocarbons are listed in Table 36.12. The
numerator in the second term on the right-hand ð ys Þvc α
¼1þ   ð36:72Þ
side of Equation 36.71 is 10–40 times that of CO, ð ys Þwv exp 2:5Φξ
whereas the denominator is twice that for
CO. This relationship suggests that there is a The correlation coefficient values for smoke
significantly higher preferential fuel conversion are listed in Table 36.12. The values of the cor-
relation coefficients in the second term on the
Table 36.12 Correlation coefficients to account for the right-hand side of Equation 36.72 suggest that,
effects of ventilation on the generation rates of CO, with increasing equivalence ratio, the preferen-
hydrocarbons, and smoke
tial fuel conversion to smoke is lower than it is to
CO Hydrocarbons Smoke hydrocarbons and CO. Also, the order for the
Material α β ξ α β ξ α β ξ preferential conversion of the fuel carbon atom
PS 2 1.44 2.5 25 2.45 1.8 2.8 2.02 1.3 to smoke is opposite to the order for the conver-
PP 10 1.39 2.8 220 1.90 2.5 2.2 2.50 1.0 sion to CO and hydrocarbons, except for wood.
PE 26 1.39 2.8 220 1.90 2.5 2.2 2.50 1.0 The order is PS > wood > PE ¼ PP > nylon
Nylon 36 1.36 3.0 1200 1.65 3.2 1.7 3.14 0.8 > PMMA, suggesting that the order is probably
PMMA 43 1.33 3.2 1800 1.58 3.5 1.6 4.61 0.6 due to a decrease in the preference for the
Wood 44 1.30 3.5 200 2.33 1.9 2.5 2.15 1.2 reactions between OH and CO compared to the
PVC 7 0.42 8.0 25 0.42 1.8 0.38 2.02 8.0
reactions between OH and soot.

Table 36.13 Carbon monoxide generation efficiency for ventilation-controlled and well-ventilated combustiona

Ventilation-controlled (vc)
Well-ventilated (wv)b Φ 4.0
Fuel Φ < 0.05 Beyler [123] Beyler [124] (yCO)vc/(yCO)wv
Methane 0.001 0.10 – 100
Propane 0.001 – 0.12 120
Propylene 0.004 0.10 – 25
Hexane 0.002 0.10 0.52c 50 (260c)
Methanol 0.001 0.27 1.00c 270 (1000c)
Ethanol 0.001 0.18 0.66c 180 (660c)
Isopropanol 0.002 0.21 – 105
Acetone 0.002 0.21 0.63c 105 (315c)
a
Table taken from Ref. [103]
b
Data taken in the Fire Propagation Apparatus
c
Nonflaming
36 Combustion Characteristics of Materials and Generation of Fire Products 1205

Other Reduction Zone Products Since the fuels with C-H structures are converted mainly to
sum of the generation efficiencies of all the CO, smoke, and hydrocarbons, rather than to
products for a material cannot exceed unity, the other products, whereas fuels with C-H-O and
generation efficiency of products other than CO, C-H-O-N structures are converted mainly to
CO2, hydrocarbons, and smoke is products other than CO, CO2, smoke, and
  hydrocarbons. Some of the products include
ηother ¼ 1  ηCO þ ηCO2 þ ηhc þ ηs ð36:73Þ formaldehyde (HCHO) and hydrogen cyanide
(HCN) [103].
where ηother is the generation efficiency of
products other than CO, CO2, hydrocarbons, Generation Efficiencies of Formaldehyde,
and smoke. The generation efficiency of other Hydrogen Cyanide, and Nitrogen Dioxide The
products can be calculated from Equations 36.68, experimental data for the generation efficiencies
36.69, 36.70, 36.71 and 36.72 using correlation of formaldehyde, hydrogen cyanide, and nitro-
coefficients from Table 36.12. The generation gen dioxide versus the equivalence ratio are
efficiency values for other products calculated shown in Figs. 36.42 and 36.43.
in this fashion for various equivalence ratios are Formaldehyde is generated in the pyrolysis of
shown in Fig. 36.41. The figure shows that, for wood (C-H-O structure). It is attacked rapidly by
equivalence ratios greater than 4, where fires are oxygen (O) and hydroxyl (OH) radicals in
nonflaming, about 10–60% of fuel carbon is the flame, if unlimited supply of oxygen is avail-
converted to products other than CO, CO2, soot, able. Thus, only traces of formaldehyde are
and hydrocarbons. found in well-ventilated fires. The generation
The order for the preferential conversion of efficiency of formaldehyde, however, increases
fuel carbon to other products in the nonflaming with the equivalence ratio, indicating reduced
zone is PS (C-H aromatic structure) < PE & PP concentrations of O and OH radicals and gas
(C-H aliphatic structure) < wood (C-H-O ali- temperature due to lack of oxygen available for
phatic structure) < nylon (C-H-O-N aliphatic combustion.
structure) < PMMA (C-H-O aliphatic structure). In fires, hydrogen cyanide is formed in the
It thus appears that, in nonflaming environments, reduction zone from materials with hydrogen

Fig. 36.41 Generation 0.8


efficiency of products other
than CO, CO2, Nonflaming
Generation efficiency of other products

hydrocarbons, and smoke


versus the equivalence ratio
0.6 PMMA
Nylon

Wood
0.4

PE & PP
0.2

PS

0.0
100–2 10–1 100 101 102
Equivalence ratio
1206 M.M. Khan et al.

Fig. 36.42 Generation


efficiency of formaldehyde
Nonflaming
generated from wood

Generation efficiency of formaldehyde


versus the equivalence ratio
10–3

10–4

100 101
Equivalence ratio

Fig. 36.43 Generation 10–1


efficiencies of hydrogen
cyanide and nitrogen Nonflaming
dioxide generated from
nylon versus the
equivalence ratio
10–2
Generation efficiency

10–3

HCN
NO2
10–4

100 101
Equivalence ratio

and nitrogen atoms in the structure, such as nylon the generation efficiency of hydrogen cyanide in
(C-H-O-N structure). Nitrogen dioxide (NO2), on nonflaming environments suggests a decrease in
the other hand, is formed in the oxidation zone, the fuel mass transfer rate.
as a result of the oxidation of hydrogen cyanide.
The data in Fig. 36.40 show that the generation Relationship Between the Generation Effi-
efficiency of hydrogen cyanide increases and the ciencies of CO2 and CO The relationship
generation efficiency of NO2 decreases with the between the generation efficiencies of CO2 and
equivalence ratio. This observation supports that CO is shown in Fig. 36.44, where the data are
O and OH radical concentrations decrease with taken from Ref. [103]. CO is generated in the
increase in the equivalence ratio. The decrease in reduction zone of the flame as a result of the
36 Combustion Characteristics of Materials and Generation of Fire Products 1207

Fig. 36.44 Relationship 0.30


between the generation
efficiencies of CO2 and CO Methanol Chemical structure
(Data taken from

CH4, C3H6, C3H8, C6H14


Ref. [103]) Fuel

CO generation efficiency
0.20 Ethanol PMMA
Wood
Nylon

PP
0.10
PE

PS

Air
0.00
0.0 0.2 0.4 0.6 0.8 1.0
CO2 generation efficiency

oxidative pyrolysis of the fuel, and is oxidized to above the upper flammability limit; however,
CO2 in the oxidation zone of the flame. The nonflaming processes may continue. The shaded
generation efficiency of CO2 is independent of region marked chemical structure and drawn to
the chemical structure of the fuel (Fig. 36.37), the right of the methanol curve is an imaginary
whereas the generation efficiency of CO depends region as it is not expected to exist, because there
on the chemical structure of the fuel (Fig. 36.38). are no stable carbon-containing fuel structures
In Fig. 36.44, the curves represent approximate below the formaldehyde with a structure of
predictions based on the correlation coefficients HCHO. For the stable fuels with C-H-O
from Table 36.12 and Equations 36.69 and 36.70. structures, formaldehyde (HCHO) and methanol
The relationship between the generation (CH3OH) have the lowest molecular weights
efficiencies of CO2 and CO is quite complex. (30 and 32, respectively). Thus, data for HCHO
The boundary of the shaded region marked air and CH3OH probably would be comparable.
in Fig. 36.44 is drawn using the data for the well- The curves in Fig. 36.44 show that, in flaming
ventilated combustion for equivalence ratios less combustion, with increase in the equivalence
than 0.05. The boundary of the air region may be ratio, the preference for fuel carbon atom conver-
considered as equivalent to the lower flammabil- sion to CO, relative to the conversion to CO2,
ity limit. No flaming combustion is expected to follows this order: methanol (C-H-O structure)
occur in this region, as the fuel-air mixture is > ethanol (C-H-O structure) > wood (C-H-O
below the lower flammability limit; however, structure) > PMMA (C-H-O structure) > nylon
nonflaming processes, generally identified as (C-H-O-N structure) > PP (C-H aliphatic unsat-
smoldering, may continue. The boundary of the urated branched structure)  (CH4, C3H6, C3H8,
shaded region marked fuel is drawn using the C6H14)  PE (C-H aliphatic unsaturated linear
data for the ventilation-controlled combustion structure) > PS (C-H aromatic unsaturated
for equivalence ratio of 4.0, and may be consid- structure). Thus, for fires in enclosed spaces,
ered as equivalent to the upper flammability generation of higher amounts of CO relative to
limit. In the fuel region, no flaming combustion CO2 at high local equivalence ratios is expected
is expected to occur, as the fuel-air mixture is for fuels with C-H-O structures compared to the
1208 M.M. Khan et al.

fuels with C-H structures. The reason for higher In Fig. 36.45, the order for the preference
amounts of CO relative to CO2 for fuels with for fuel carbon atom conversion to smoke rela-
C-H-O structures is that CO is easily generated tive to conversion to CO is wood (C-H-O struc-
in fuel pyrolysis, but is oxidized only partially to ture) < PMMA (C-H-O structure) < nylon
CO2 due to limited amounts of oxidant available. (C-H-O-N structure) < PP (C-H aliphatic
unsaturated branched structure) PE (C-H ali-
Relationship Between the Generation phatic unsaturated linear structure) < PS (C-H
Efficiencies of CO and Smoke The relationship aromatic structure). The generation efficiency
between the generation efficiencies of CO and of smoke for PS, which is a polymer with
smoke is shown in Fig. 36.45, where data are aromatic C-H structure, is the highest. The
taken from Ref. [103]. CO and smoke are both generation efficiency of smoke for wood,
generated in the reduction zone of the flame as a which is a polymer with aliphatic C-H-O struc-
result of the oxidative pyrolysis of the fuel, and ture, is the lowest.
their generation efficiencies depend on the chem-
ical structure of the fuel (Figs. 36.38 and 36.40).
In Fig. 36.45, the curves represent approximate Generalized Relationships to Calculate
predictions based on the correlation coefficients Chemical, Convective, and Radiative
from Table 36.11 and Equations 36.70 and 36.72. Heats of Combustion and Yields
The relationship in Fig. 36.45 is quite compli- of Products at Various Equivalence
cated. The boundary of the shaded region marked Ratios
air is drawn using the data for the well-ventilated
combustion for equivalence ratios less than 0.05. Equations 36.44, 36.45, and 36.68, 36.69,
The boundary of the shaded region marked fuel 36.70, 36.71, and 36.72 can be generalized as
is drawn using the data for the ventilation- follows:
controlled combustion for equivalence ratio of 9
8
4.0. The boundary for the region marked air >
> >
>
< α =
may be considered as equivalent to the lower
fp ¼ fp1 1 þ   ð36:74Þ
flammability limit, and the boundary for the > ξ >
>
: exp Φβ >
;
region marked fuel may be considered as equiva-
lent to the upper flammability limit.

Fig. 36.45 Relationship


between the generation PS
efficiencies of CO and Air Fuel
PP
smoke (Data taken
Nylon & PE
Smoke generation efficiency

from Ref. [103])


10–1 PMMA
Wood

10–2

10–3
10–3 10–2 10–1 100
CO generation efficiency
36 Combustion Characteristics of Materials and Generation of Fire Products 1209

where Chemical Heat of Combustion Versus Equiv-


fp ¼ Fire property alence Ratio for Halogenated Polymers
α, β, and ξ ¼ Correlation coefficients character- (PVC) The effect of ventilation on the burning
istic of the chemical structures of the of halogenated materials is dramatically different
polymers from that shown in Equation 36.75,
subscript 1 ¼ Infinite amount of air (i.e., well 8 9
ventilated conditions) < 0:30 =
It is noted that this relationship is applicable ΔH ch ¼ ΔH ch, 1 1  h  i
: exp Φ
11 ;
under turbulent flame conditions where a given 0:53
fire property remains constant (i.e., it is not a func- ð36:76Þ
tion of flow conditions). Fire properties to consider
include heat of combustion (or combustion effi- As can be noted from the terms inside the
ciency) and yields (or generation efficiencies) of brackets in Equations 36.75 and 36.76, the effect
products. Three conditions can be identified: of ventilation on the chemical heat of combustion
(1) for Φ β, fp ¼ fp1(1 + α); (2) for Φ β, is much stronger for PVC than it is for nonhalo-
fp ¼ fp1; and (3) Φ β, fp fp1(1 + α/2.7). genated materials. The effect for PVC occurs at
Thus, the parameter α is associated primarily Φ  0.4, which is significantly lower than
with the magnitude of the fire properties in Φ  2.0 found for nonhalogenated compounds
nonflaming processes (high Φ values). The [103, 126]. For PVC homopolymer, flaming
parameter β is associated with the fire properties combustion changes transitions to nonflaming
in the transition region between fires with an infi- for Φ  0.70, which is also significantly lower
nite amount of air and fires with a very restricted than Φ  4.0 found for nonhalogenated
amount of air. The parameter ξ is associated with materials. This attribute is consistent with the
the range of Φ values for the transition region. A highly halogenated nature of PVC and its mode
high value of α is indicative of a strong effect of of decomposition. The decomposition of PVC is
ventilation on the fire and its properties and vice characterized by the release of HCl, which is
versa. High values of β and ξ are indicative of rapid initiated at temperatures as low as about
change from flaming to nonflaming conditions by 100  C. At temperatures of up to between
a small change in the equivalence ratio, such as for 200  C and 220  C, HCl is the major effluent.
the highly fire-retarded or halogenated materials The presence of oxygen in the air enhances HCl
for which flaming combustion in normal air itself release. The generation of HCl from PVC leads
is unstable. to the formation of double bonds and release of
various aromatic/unsaturated hydrocarbons (ben-
Chemical Heat of Combustion Versus Equiv- zene, ethylene, propylene, butylene, etc.).
alence Ratio for Nonhalogenated Com-
pounds From Equation 36.74, Convective Heats of Combustion Versus
8 9 Equivalence Ratio for Nonhalogenated
< 0:97 = Compounds From Equation 36.74,
ΔH ch ¼ ΔH ch, 1 1  h  i 8 9
: Φ 1:2 ;
exp 2:15 < 1:0 =
ΔH con ¼ ΔHcon, 1 1  h  i
ð36:75Þ : exp Φ 2, 8 ;
1:38

This equations stems from Equation 36.44. As ð36:77Þ


stated above, this relationship is found to hold for
a variety of compounds regardless of their chem- Similar to the chemical heat of combustion this
ical structure (Fig. 36.33). The values of ΔHch,1 equation stems from Equation 36.45 and is appli-
can be found in Table A.39. cable to a large number of materials, regardless of
1210 M.M. Khan et al.

their chemical structure (Fig. 36.34). Values for ventilation on the yield of CO2 for PVC than for
ΔHcon,1 are listed in Table A.39. nonhalogenated compounds can be noted. yCO2 , 1
values are listed in Table A.39.
Radiative Heats of Combustion Versus Equiv-
alence Ratio Radiative heats of combustion are Yields of Carbon Monoxide, Hydrocarbons,
obtained from the difference between the chemi- and Smoke for Selected Nonhalogenated
cal and the convective heats of combustion: Materials As discussed above and shown in
ΔH rad ¼ ΔH ch  ΔH con ð36:78Þ Figs. 36.38, 36.39, and 36.40, yields of CO,
hydrocarbons, and smoke are affected by the
chemical structure the given material involved
Consumption of Oxygen for Nonhalogenated
in the fire. In this case the generalized correla-
Compounds As shown in Fig. 36.36 and simi-
tion, Equation 36.74, will take different values
larly to the findings for chemical and convective
for the parameters α, β, and ξ depending on the
heat release rates, ventilation effects on oxygen
specific material considered, Parameters for
consumption are similar regardless of chemical
polystyrene, polypropylene, polyethylene,
structure. Therefore in generalized form. Equa-
nylon, PMMA, wood, and PVC are given in
tion 36.68 becomes:
Table 36.12; these are to be used in Equa-
8 9
< 0:97 = tion 36.74 along with the well ventilated values
cO ¼ c O , 1 1  h  i ð36:79Þ (i.e., fp1) for yields of CO, hydrocarbons, and
: exp Φ
1:2 ;
2:14 soot listed in Table A.39 for the materials in
Table 36.12.
Yield of Carbon Dioxide for Nonhalogenated For PVC, the relationships indicate that
Compounds The generation of CO2 follows for 0.40  Φ  1.0, the maximum CO and
similar trends with respect to equivalence ratio, smoke yields reach about 60 % of the stoichio-
as discussed above (see Fig. 36.37). Therefore, metric yields, listed in Table 36.11. For the non-
the generalized form of Equation 36.69 is: halogenated materials, the maximum CO and
8 9 smoke yields reach 30 % of the stoichiometric
< 1:0 = yields for Φ  2.0. Polystyrene is the only poly-
yCO2 ¼ yCO2 , 1 1  h  i ð36:80Þ mer, within the above group of polymers, for which
: exp Φ
1:2 ;
2:15 the smoke yield exceeds that of PVC. These trends
suggest that CO and smoke are generated much
yCO2 , 1 values for well ventilated fires are listed in more readily from PVC than from the nonhaloge-
nated materials, possibly due to the formation
Table A.39. of double bonds, as HCl is eliminated at
temperatures as low as 100  C from the PVC
Yield of Carbon Dioxide for Halogenated structure, and formation of various compounds
Polymers (PVC) Lastly, as indicated above occurs with aromatic/unsaturated bonds.
for the chemical heat of combustion of PVC, For the nonhalogenated materials considered
ventilation effects are markedly different for with Φ  4.0, the CO yield is lowest and the
halogenated materials compared to their nonha- smoke yield is highest for polystyrene, an aro-
logenated counterparts. In this case the matic ring-containing polymer; whereas, for
generalized equation for CO2 yield is: polymethylmethacrylate, an aliphatic carbon-
8 9
< 0:30 = hydrogen-oxygen-atom-containing polymer, the
yCO2 ¼ yCO2 , 1 1  h  i ð36:81Þ CO yield is highest and smoke yield is lowest.
: exp Φ
11 ;
This result suggests that aromatic ring structure
0:53
promotes smoke formation, whereas the strong
From the terms inside the brackets in C-O bond in the structure remains intact as ven-
Equations 36.80 and 36.81, a stronger effect of tilation is reduced.
36 Combustion Characteristics of Materials and Generation of Fire Products 1211

Example 18 Following Example 12, calculate The integer n can vary from one in a gas, such as
the yields of CO and smoke at equivalence ratios methane, to several thousands in solid polymers,
of 1, 2, and 3 for polystyrene, polyethylene, such as polyethylene. In cyclic aliphatic fuels,
wood, and nylon using Equation 36.74 and the carbon atoms are also arranged as rings. Dienes
data in Tables A.39 and 36.12. are classified as (1) conjugated—double bonds
alternate with single bonds, (2) isolated—double
Solution bonds separated by more than one single bond,

Yield (g/g)
Φ 1.0 (Table A.39) Φ ¼ 1.0 Φ ¼ 2.0 Φ ¼ 3.0
Material CO Smoke CO Smoke CO Smoke CO Smoke
Polystyrene 0.060 0.164 0.070 0.202 0.137 0.331 0.162 0.417
Polyethylene 0.024 0.060 0.074 0.071 0.459 0.098 0.580 0.117
Wood 0.004 0.015 0.018 0.018 0.145 0.028 0.171 0.034
Nylon 0.038 0.075 0.149 0.086 1.040 0.105 1.280 0.120

Smoke Point and (3) allenes—double bonds with no separa-


tion. Conjugated dienes are more stable than
Smoke emission characteristics of fuels have other dienes.
been expressed for decades by smoke point, Solid carbonaceous particles present in smoke
defined as a minimum laminar axisymmetric dif- are defined as soot [129, 134]. Soot is generally
fusion flame height (or fuel volumetric or mass formed in the fuel-rich regions of the flame and
flow rate) at which smoke just escapes from the grows in size through gas-solid reactions,
flame tip [112, 114, 127–145]. More recently, the followed by oxidation (burnout) to produce gas-
smoke point concept has been applied to develop eous products, such as CO and CO2. Flame resi-
subgrid soot formation, oxidation, and radiation dence time available for soot formation is on the
models for CFD simulations [146, 147]. Smoke- order of a few milliseconds. Soot particle incep-
point values have been measured for numerous tion occurs from the fuel molecule via oxidation
gases, liquids, and solids [112, 114, 127–145]. and/or pyrolysis products, which typically
Almost all the knowledge on smoke forma- include unsaturated hydrocarbons, especially
tion, oxidation, and emission from diffusion acetylene, polyacetylenes, and polycyclic aro-
flames is based on the combustion of fuels matic hydrocarbons (PAH). Acetylene,
containing carbon and hydrogen atoms polyacetylenes, and PAH are relatively stable
(hydrocarbons) [128, 129, 134, 136, 141]. On with respect to decomposition. Acetylene and
the basis of the chemical structure, hydrocarbons PAH are often considered the most likely
are divided into two main classes: (1) aliphatic precursors for soot formation in flames. PAH
and (2) aromatic. Fuels containing both aliphatic have the same role in diffusion flames for both
and aromatic units are known as arenes. Ali- aliphatic and aromatic fuels. In all flames,
phatic fuels have open-chain structure, and aro- regardless of the fuel, initial detection of soot
matic fuel structures consist of benzene rings. particles takes place on the centerline when a
Aliphatic hydrocarbons are divided into three temperature of approximately 1400 K [134] is
families: (1) alkanes (CnH2n+2) where n is an encountered. Thus, even though the extent of
integer—the suffix ane indicates a single bond; conversion of a fuel into soot may significantly
(2) alkenes (CnH2n)—the suffix ene indicates a change from fuel to fuel, a common mechanism
double bond, and diene, two double bonds of soot formation is suggested.
between carbon-carbon atoms; and (3) alkynes Soot production in the flame depends on the
(CnH2n-2)—the suffix yne indicates a triple bond. chemical structure, concentration, and
1212 M.M. Khan et al.

temperature of the fuel and flame temperature, Smoke-point values have been correlated with
pressure, and oxygen concentration [128, 129, flame radiation, combustion efficiency and its
134, 136, 141]. The diffusion-controlled flame convective and radiative components, and gener-
ends when fuel and oxidant are in stoichiometric ation efficiencies of products [112, 114, 127,
ratio on the flame axis. The flame is followed by 133–135, 140, 143]. Figures 36.46, 36.47, and
a soot after-burning zone, which is partially 36.48 show the relationships between the smoke
chemically controlled. The soot oxidation zone point and the combustion efficiency and its con-
increases from about 10–50 % of the visible vective and radiative components, and genera-
flame length as the soot concentration increases. tion efficiencies of CO and smoke. The data
Flame luminosity and smoke emission in the were measured in the Fire Propagation Apparatus
plume depend on overall soot production and (Fig. 36.2) and reported in Refs. [112, 114].
oxidation. Flames emit soot when soot tempera- Smoke-point data measured for a number of
ture in the oxidation zone falls below 1300 K polymers, as well as wood, are listed in
[134]. The soot temperature decreases down- Table 36.14. The following relationships can be
stream because of radiation losses and diffusion discerned from the data [112, 114]:
of fresh cold air, both of which quench soot
oxidation. At high soot concentrations, flame χ ch ¼ 1:15L0:10
sp ð36:82Þ
emissivity approaches unity, and flame luminos-
where χ ch is the combustion efficiency (), and
ity becomes independent of the amount of soot.
Lsp is the smoke point (m) as measured in the Fire
Smoke point, carbon-to-hydrogen ratio, aro-
Propagation Apparatus [112, 114].
maticity, and flame temperature have been
suggested as useful parameters to assess relative χ rad ¼ 0:41  0:85Ls p ð36:83Þ
smoke emission characteristics of fuels in lami-
nar diffusion flames [112, 114, 127, 133–135, where χ rad is the radiative component of the
140, 143]. The soot-forming tendency of fuels combustion efficiency (). This correlation is
is inversely proportional to smoke point. General very similar to the one reported by Markstein
trends observed for smoke points for hydrocar- [135]. The convective component of the combus-
bon fuels in laminar diffusion flames are tion efficiency, χ con, can now be obtained using
aromatics < alkynes < alkenes < alkanes. Equation 36.40:

Fig. 36.46 Relationships 1.4


between combustion χch
efficiency, its convective χcon
1.2 PMMA
and radiative components, PP χrad
and the smoke point (Data
Combustion efficiency

were measured in the Fire 1.0


PS
Propagation Apparatus
and reported in Refs. Ethanol
0.8 Pentane
[112, 114])

0.6

0.4

0.2

0.0
0.00 0.05 0.10 0.15 0.20 0.25
Smoke point (m)
36 Combustion Characteristics of Materials and Generation of Fire Products 1213

Fig. 36.47 Relationships 0.050


between CO generation
efficiency and smoke point ηco = – [0.0086 In (Ls) + 0.0131]
(Data were measured in the 0.040
Fire Propagation Apparatus

CO generation efficiency
Toluene
and reported in Refs. PS
[112, 114])
0.030

0.020

0.010
Ethanol
PP

0.000
10–3 10–2 10–1 100
Smoke point (m)

Fig. 36.48 Relationships 0.30


between the smoke
generation efficiency and ηs = – [0.0515 In (Ls) + 0.0700]
the smoke point (Data were 0.25
Smoke generation efficiency

measured in the Fire Toluene


PS
Propagation Apparatus
and reported in Refs. 0.20
[112, 114])
0.15

0.10

0.05 Ethanol
PP

0.00
10–3 10–2 10–1 100
Smoke point (m)

χ con ¼ χ ch  χ rad for the materials listed in Table 36.14 using


ð36:84Þ properties (i.e., chemical combustion efficiency,
χ con ¼ 1:15L0:10
sp þ 0:85Ls p  0:41
smoke yield, etc.) measured in the Fire Propaga-
For the generation efficiency of CO (ηCO) tion Apparatus and listed in Table A.39; in gen-
  eral, good agreement is observed. It is noted that
0:218 the highest value of Lsp that has been measured is
ηCO ¼ 0:0086ln ð36:85Þ
Ls p 0.24 m for ethane. Although methane and meth-
anol would be expected to have smoke points
For the generation efficiency of smoke (ηs)
higher than 0.24 m, they have not been measured
  experimentally. Since combustion efficiency
0:257
ηs ¼ 0:0515ln ð36:86Þ cannot exceed unity and the generation
Ls p
efficiencies of CO and smoke cannot be negative,
Smoke points were estimated using the relationships in Equations 36.82, 36.83,
Equations 36.82, 36.83, 36.84, 36.85 and 36.86 36.84, 36.85 and 36.86 are valid for
1214 M.M. Khan et al.

Table 36.14 Smoke point dataa

Smoke point (m)


Polymer Measured Estimatedb
Wood (oak) 0.080 0.085
Wood (fir) 0.080 0.085
Polyoxymethylene (POM) NM 0.225
Polymethylmethacrylate (PMMA) 0.105 0.139
Polyethylene (PE) 0.045 0.046
Polypropylene (PP) 0.050 0.057
Polystyrene (PS) 0.015 0.012
Polyester NM 0.009
Nylon 0.120 0.070
GM21 NM 0.013
GM23 NM 0.022
GM25 NM 0.011
GM27 NM 0.013
GM29 NM 0.008
GM31 NM 0.008
GM35 NM 0.009
GM41 NM 0.009
GM43 NM 0.009
GM47 NM 0.009
GM49 NM 0.010
GM51 NM 0.011
GM53 NM 0.011
PE +25 % Chlorine (Cl) NM 0.013
PE +36 % Cl NM 0.004
PE +48 % Cl NM 0.003
PVC NM 0.015
Polyethylene-tetrafluoroethylene (ETFE, Tefzel®) NM 0.121
Polytetrafluoroethylene-perfluoro ether (PFA, Teflon®) NM 0.120
Fluorinated ethylene propylene (FEP, Teflon®) NM 0.110
Polytetrafluoroethylene (PTFE, Teflon®) NM 0.110
NM not measured
a
Data taken from Refs. [112, 114]
b
Estimated from the polymer properties measured in the Fire Propagation Apparatus and their relationships with smoke
point

0 < Lsp  0.24 m. The correlations show that respectively, and an increase of 14 % in the radi-
emissions of CO and smoke are very sensitive to ative component of the combustion efficiency;
changes in the smoke point values compared to however, the generation efficiencies of CO and
combustion efficiency and its convective and smoke increase by 89 % and 67 %, respectively.
radiative components. This condition is expected Equations 36.82, 36.83, 36.84, 36.85 and
from the understanding of the relationship 36.86 can be used to estimate the fire properties
between the smoke point and chemical structures of gases, liquids, and solids from their smoke
of fuels. For example, a decrease of 33 % in the point values. The smoke point values, however,
smoke-point value from 0.15 to 0.10 m produces depend strongly on the apparatus used and cannot
a decrease of 4 % and 12 % in the combustion be used as reported. One of the approaches is to
efficiency and its convective component, establish correlations between the smoke-point
36 Combustion Characteristics of Materials and Generation of Fire Products 1215

values measured in different apparatuses and a mi


ΔH i ¼ hi þ ð36:87Þ
single apparatus for which relationships such as M
those given in Equations 36.82, 36.83, 36.84, bj
36.85 and 36.86 are available. This type of yj ¼ a j þ ð36:88Þ
M
approach has been described in Refs. [112,
114] for the Fire Propagation Apparatus, where where
smoke-point values for 165 fuels, reported in the ΔHi ¼ Net heat of complete combustion or
literature, were scaled based on measurements chemical, convective, or radiative heat of
performed in the FPA for 16 common fuels. Fire combustion (kJ/g)
properties (chemical, convective, and radiative yj ¼ Yield of product j (g/g)
heats of combustion and yields of CO and M ¼ Molecular weight of fuel monomer (g/mol)
smoke) were then estimated, using the scaled hi ¼ Mass coefficient for the heat of combustion
smoke-point-data, from Equations 36.82, (kJ/g)
36.83, 36.84, 36.85 and 36.86, and are listed in mi ¼ Molar coefficient for the heat of combus-
Table A.40. In the table, molecular formula and tion (kJ/mol)
weight, stoichiometric air-to-fuel mass ratio, aj ¼ Mass coefficient for the product yield (g/g)
and net heat of complete combustion have also bj ¼ Molar coefficient for the product yield
been tabulated. The estimated data in the table (g/mol)
have been validated by direct measurements in The reader is referred to [114] for listings of hi,
small- and large-scale fires using several mi, aj, and bj for each fuel class. The coefficients
fuels [112, 114]. depend on the chemical structures of the fuel; mi
Smoke point decreases with increasing and bj become negative with the introduction of
molecular weight for a given molecular sub- oxygen, nitrogen, and sulfur atoms into the
group. The smoke point values for monomers chemical structure [114]. Relationships in
and polymers, however, show different types of Equations 36.87 and 36.88 support the suggestion
dependencies [112]: (1) the smoke-point values [128] that generally smaller molecules offer
for ethylene and polyethylene are 0.106 and greater resistance to smoke formation and emis-
0.045 m, respectively; (2) the smoke point sion. The relationships also indicate that for
values for propylene and polypropylene are gases, liquids, and solids gasifying as high molec-
0.029 and 0.050 m, respectively; and (3) the ular weight fuels, ΔHi hi and yj aj. The
smoke point values for styrene and polystyrene variations of chemical, convective, and radiative
are 0.006 and 0.015 m, respectively. The smoke- heats of combustion as well as yields of CO and
point data for polymers support the accepted smoke with the chemical structures of the fuels
vaporization mechanisms of polymers [148]; are similar to the smoke point variations.
that is, polyethylene, polypropylene, and poly-
styrene vaporize as higher molecular weight Example 19 The following smoke point values
oligomers rather than as monomers, and thus, have been reported in Ref. [112]:
their smoke point values are different than the
Polymer PE PP PMMA PS
values for the monomers. The smoke point
Smoke point (m) 0.045 0.050 0.105 0.015
values suggest that polyethylene is expected to
have higher smoke emission than ethylene, For well-ventilated conditions, estimate
whereas polypropylene and polystyrene are (1) the chemical, convective, and radiative heats
expected to have lower smoke emissions than of combustion using Equations 36.82, 36.83, and
propylene and styrene. 36.84 and data for the net heat of complete com-
The data in Table A.40 exhibit linear bustion from Table A.39; and (2) yields of CO
dependencies of the different fire properties on and smoke using Equations 36.64, 36.85,
the molecular weight of the fuel monomer within and 36.86 and stoichiometric yields from
each group [114]: Table 36.10.
1216 M.M. Khan et al.

Solution In turn, the Thermal Response Parameter


1. From Equations 36.82, 36.83, and 36.84 and (TRP) is defined in Equation 36.2, and its rela-
ΔHT from Table A.39, tionship to fire propagation in Equations 36.12
and 36.13. The relationships between time to
Polymer PE PP PMMA PS ignition, fire propagation rate, Fire Propagation
ΔHT (kJ/g) 43.6 43.4 25.2 39.2 Index (FPI), and TRP (Equations 36.2, 36.12,
ΔHch (kJ/g) 36.8 37.0 23.1 29.6
and 36.13) show that the time to ignition is
ΔHcon (kJ/g) 20.6 21.1 15.0 14.0
directly proportional to the square of the TRP
ΔHrad (kJ/g) 16.2 15.9 8.1 15.6
value and the fire propagation rate and FPI are
inversely proportional to the TRP value to the
2. From Equations 36.64, 36.85, and 36.87 and power 2 and 1, respectively. Thus, the higher
Table 36.11, the TRP value, the longer the time to ignition,
Polymer PE PP PMMA PS the slower the fire propagation rate, and the lower
ΨCO 2.00 2.00 1.40 2.15 the FPI value. For high TRP values with rela-
Ψs 0.857 0.857 0.600 0.923 tively low FPI values, there is empirical evidence
yCO (g/g) 0.027 0.025 0.009 0.050 [28, 31, 43–46] that no fire propagation beyond
ys (g/g) 0.077 0.072 0.028 0.135 the ignition zone will occur, defined as the
nonfire-propagating behavior. Also, for materials
with high CHF values, higher heat flux exposure
is required to initiate a fire.
Ignition Resistance The CHF and TRP values can be increased by
modifying the pertinent parameters, such as an
Ignition resistance is provided by (1) modifying increase in the chemical bond dissociation
the chemical structures of the materials for high energy and a decrease in thermal diffusion (com-
resistance to ignition and fire propagation, (2) bination of the density, specific heat, and ther-
incorporating fire retardants within the materials, mal conductivity). Figures 36.49 and 36.50 show
(3) coating and wrapping the surfaces, (4) the CHF and TRP values for a tri-wall
separating materials by inert fire barriers, (5) corrugated paper sheet containing various
modifying configuration and arrangement of amounts of a passive fire protection agent
materials, and so forth. In the context of the (identified as agent “A” here); the data were
concepts introduced and discussed in this chapter, obtained from ignition experiments in the Fire
ignition resistance may be interpreted as follows: Propagation Apparatus. Similarly, Fig. 36.51
shows the TRP value for a single-wall corrugated
Increasing the Resistance to Ignition paper sheet containing various amounts of the
and Fire Propagation by Increasing passive fire protection agent A. The CHF and
the Critical Heat Flux (CHF) and Thermal TRP values increase with increasing amount of
Response Parameter (TRP) Values agent; thus, the passive fire protection agent
As discussed in section “Ignition (Fire Initia- would complement active fire protection agents.
tion)” of this chapter, the critical heat flux Corrugated paper boxes treated with higher
(CHF) can be expressed as amounts of the passive fire protection agent are
expected to require reduced amounts of active
 
CHF σ T ig 4  T 0 4 ð36:89Þ fire protection agents for fire control, suppres-
sion, or extinguishment compared to the amounts
where of active fire protection agents required for the
σ ¼ Stefan-Boltzmann constant untreated boxes [149]. The passive fire protec-
(56.7  1012 kW/m2K4) tion requirements for various materials can be
Tig ¼ Ignition temperature (K) assessed from the data for CHF and TRP listed
Ta ¼ Ambient temperature (K) in Table A.35.
36 Combustion Characteristics of Materials and Generation of Fire Products 1217

Fig. 36.49 Critical heat 30


flux for untreated and
Untreated
treated tri-wall corrugated
paper sheet. The amount of 25 Treated—1
passive fire protection Treated—2

Critical heat flux (kW/m2)


agent is increasing from
20 Treated—3
Treated 1–4. Data obtained
from ignition experiments Treated—4 19
in the Fire Propagation
15 17
Apparatus. Numbers 16
indicated on top of each bar
are the critical heat flux 13
10
values 10

Fig. 36.50 Thermal 4000


response parameter for
Untreated
Thermal response parameter (kW·s/m2)

untreated and treated


tri-wall corrugated paper Treated—1
3333
sheet. The amount of 3000 Treated—2
passive fire protection Treated—3
agent is increasing from
Treated 1–4. Data obtained Treated—4
from ignition experiments 2000
in the Fire Propagation 2000
Apparatus. Numbers
indicated on top of each bar
are the TRP values 1000
1000
769
370
0

Fig. 36.51 Thermal 500


response parameter for
Untreated
Thermal response parameter (kW·s/m2)

untreated and treated


single-wall corrugated Treated—1
400 417
paper sheet. The amount of Treated—2
passive fire protection
agent is increasing from
Treated 1–2. Data obtained 300
from ignition experiments
in the Fire Propagation
Apparatus. Numbers 200
indicated on top of each bar
179
are the TRP values
100
99

0
1218 M.M. Khan et al.

100
Treated—1
Treated—2
80

Percent reduction in chemical


Treated—3 81
73

heat release rate


60

40
43

20

Fig. 36.52 Percent reduction in the chemical heat 1–3. Data from combustion experiments in the Fire
release rate of untreated tri-wall corrugated paper sheet Propagation Apparatus. Numbers indicated on top of
by a passive fire protection agent. The amount of the each bar are the percent reductions in the chemical heat
passive fire protection agent is increasing from Treated release rate

Decreasing the Values of the Heat Release Figure 36.52 shows the reduction in the chem-
Parameter (HRP) and the Flame Heat Flux ical heat release rate as a result of an increase in
Heat release rate is equal to the heat release charring of a tri-wall corrugated paper sheet by
parameter (HRP) times the net heat flux (Equa- the passive fire protection agent A; the data were
tion 36.34). HRP is the ratio of the heat of com- obtained from combustion experiments in the
bustion to heat of gasification, and thus the HRP Fire Propagation Apparatus. The amount of
value can be decreased by decreasing the heat of agent A increases from Treated 1 to 3 in
combustion and/or increasing the heat of gasifi- Fig. 36.52. There is a very significant decrease
cation by various chemical and physical means. in the chemical heat release rate of the tri-wall
An examination of data in Table A.39 for heats corrugated paper sheet by the passive fire protec-
of combustion shows that introduction of oxy- tion agent A, which will complement active fire
gen, nitrogen, sulfur, halogen, and other atoms protection agents. Corrugated paper boxes
into the chemical structures of the materials treated with higher amounts of passive fire pro-
reduces the heat of combustion. For example, tection agent are expected to require reduced
the heat of combustion decreases when hydrogen amounts of active fire protection agents for fire
atoms attached to carbon atoms in polyethylene control, suppression, or extinguishment com-
are replaced by halogen atoms, such as by fluo- pared to the one required for the untreated boxes.
rine in Teflon. The chemical heat of combustion The effect on flame heat flux by passive fire
decreases from 38.4 kJ/g to 4.2 kJ/g (Table A. protection is determined by using the radiation
39), and the chemical HRP value decreases from scaling technique ([44], described in section
17 to 2 (Table 36.10). “Flaming and Nonflaming Phenomena” of this
HRP values can also be reduced by increasing chapter), where combustion experiments are
the heat of gasification and decreasing the heat of performed in environments with oxygen concen-
combustion by retaining the major fraction of the tration levels higher than the ambient values.
carbon atoms in the solid phase, a process Very little is known about this subject. Table 36.7
defined as charring. Several passive fire protec- lists some of the flame heat flux values derived
tion agents are available commercially to from the radiation scaling technique, but no sys-
enhance the charring characteristics of materials. tematic study has been performed for the
36 Combustion Characteristics of Materials and Generation of Fire Products 1219

effectiveness of passive fire protection. From the where


00
discussion in section “Flaming and Nonflaming q_ fc ¼ Convective flame heat flux from the flame
Phenomena” of this chapter, materials that to the surface as the extinction condition is
vaporize as species of low molecular weight reached (kW/m2)
tend to yield lower flame heat fluxes. Therefore, ϕ ¼ Maximum fraction of combustion energy
passive fire protection agents that can reduce the that the flame reactions may lose to the sample
molecular weight of the vaporized materials surface by convection without flame extinc-
would be effective in reducing the flame heat tion and is defined as the kinetic parameter for
flux and complement the active fire protection flame extinction
agents. ΔHT ¼ Net heat of complete combustion (kJ/g)
00
ṁcr ¼ Critical mass loss rate for flame extinction
Changing the Nature of Fire Products (g/m2/s)
Nonhalogenated passive fire protection agents or The kinetic parameter is defined as [150, 152]
agents that reduce or eliminate the release of
halogenated and highly aromatic products and ΔH g, con
φ¼ ð36:91Þ
enhance release of aliphatic products, rich in ΔHT
hydrogen and oxygen atoms but poor in carbon
where ΔHg,con is the flame convective energy trans-
atoms, are effective in reducing the nonthermal
fer to the fuel per unit mass of fuel gasified (kJ/g).
damage due to smoke and corrosion. Some of the
The kinetic parameter is expected to be higher for
passive fire protection agents, available commer-
fast-burning material vapors and lower for slower-
cially, interact with the materials in the solid as
burning material vapors, such as materials
well as in the gas phase during pyrolysis and
containing halogens, sulfur, and nitrogen. It is
combustion.
suggested that, at flame extinction, combustion is
The critical parameter that needs to be exam-
controlled primarily by convective heat transfer,
ined in the presence and absence of the passive
and thus the critical mass loss rate would follow
fire protection agents is the ratio of the genera-
Spalding’s mass transfer number theory [152]:
tion rate of products (such as for smoke, CO,
corrosive products [HCl], and others) to heat 00 h
release rate. The effectiveness of the passive m_ cr ¼ lnðBcr þ 1Þ ð36:92Þ
cp
fire protection agent is reflected in the small
values of the ratios at fire control, suppression, where
and/or extinguishment stages. h ¼ Convective heat transfer coefficient
(kW/m2/K)
cP ¼ Specific heat of air (kJ/g/K)
Flame Extinction Bcr ¼ Critical mass transfer number
The critical mass transfer number is defined as
Flame extinction is achieved by applying
agents to the flame and/or to the surface of the Y O ΔH *O  c p ðT s  T a Þ
Bcr ¼ ð36:93Þ
burning material. Fire control, suppression, and ΔH g, con
extinguishment have been described by the
firepoint concept [150, 151]. According to the where
firepoint theory, the convective heat flux from YO ¼ Oxygen mass fraction
the flame to the burning surface as the flame ΔH*O ¼ Net heat of complete combustion per unit
extinction condition is reached is expressed as mass of oxygen consumed (kJ/g), which is
[150, 151]. approximately constant
Ts ¼ Surface temperature (K)
00 00
q_ fc ¼ ΦΔH T m_ cr ð36:90Þ Ta ¼ Ambient temperature (K)
1220 M.M. Khan et al.

Table 36.15 Critical mass loss rate for ignition and kinetic parameter for flame extinction

Critical mass loss rate (g/m2/s) Kinetic parameter


Material Ref. [14]a Ref. [155]b Ref. [14]a Ref. [155]b
Polyoxymethylene 4.5 1.7 0.43 1.05
Polymethylmethacrylate 3.2 1.9 0.28 0.53
Polyethylene 2.5 1.3 0.27 –
Polypropylene 2.7 1.1 0.24 0.50
Polyethylene foams
1 2.6 – 0.24 –
2 2.6 – 0.25 –
3 2.5 – 0.25 –
4 2.6 – 0.25 –
Chlorinated polyethylenes
25 % chlorine 6.6 – 0.15 –
36 % chlorine 7.5 – 0.09 –
48 % chlorine 7.6 – 0.08 –
Polystyrene 4.0 0.80 0.21 0.78
Polystyrene foams
GM47 6.3 – 0.11 –
GM49 4.9 – 0.14 –
GM51 6.3 – 0.10 –
GM53 5.7 – 0.11 –
Polyurethane foams (flexible)
GM21 5.6 – 0.16 –
GM23 5.3 – 0.17 –
GM25 5.7 – 0.15 –
GM27 6.5 – 0.12 –
1/CaCO3 7.2 – 0.19 –
Polyurethane foams (rigid)
GM29 7.9 – 0.10 –
GM31 8.4 – 0.09 –
GM35 6.9 – 0.11 –
Polyisocyanurate foams (rigid)
GM41 6.8 – 0.12 –
GM43 5.5 – 0.15 –
Phenolic foam 5.5 – 0.17 –
a
Ignition data measured in the Fire Propagation Apparatus
b
Ignition data measured at the University of Edinburgh, U.K.

For ambient conditions, YOΔHT cp (Ts – Ta). critical mass loss rate for ignition and flame
From Equations 36.91, 36.92 and 36.93, extinction and the kinetic parameter for flame
extinction are listed in Table 36.15. The values
Y O ΔH *O
Φ¼ h c 00  i ð36:94Þ for the critical mass loss rate for ignition from the
p
ΔHT exp m_ cr  1 Fire Propagation Apparatus [14] were measured
h
at the time period where the sustained flame is
Firepoint theory [150, 151] and experimental just being established and, thus, are higher than
data show that the critical mass loss rate for flame the values from Ref. [155] which were probably
extinction is similar to the critical mass loss rate measured just before the establishment of a
for ignition [14, 122, 153–155] The data for the sustained flame. For polymethylmethacrylate,
36 Combustion Characteristics of Materials and Generation of Fire Products 1221

the critical mass loss rate for ignition from Ref, (Equation 36.66) of the oxidation zone products
[14] agrees with the critical mass loss rate for (such as CO2), and (3) increased values of the
flame extinction from Ref. [154]. generation efficiencies (Equation 36.67) of the
The data in Table 36.15 show that the values reduction zone products (such as smoke, CO,
of the kinetic parameter are higher for the ali- and hydrocarbons).
phatic materials than the values for the aromatic Flame extinction can also be expressed in
and chlorinated materials, which is opposite to terms of the critical heat release rate:
the trend for the heat of combustion (Table A.39). 00
Q_ cr, i ¼ ΔH i m_ cr
00
The data suggest that the materials can be arranged ð36:95Þ
in the following decreasing order of the kinetic 00

parameter values (using data from Ref. [14]): where Q_ cr, i is the critical heat release rate (chem-
polyoxymethylene (ϕ ¼ 0.43) > polymethyl- ical, convective, or radiative in kW/m2), and ΔHI
methacrylate (ϕ ¼ 0.28) > polyethylene, polypro- is the heat of combustion (chemical, convective,
pylene, and polyethylene foams (ϕ ¼ 0.27 to and radiative in kJ/g). Table 36.16 lists the criti-
0.25) > polystyrene (ϕ ¼ 0.21) > polyurethane, cal chemical, convective, and radiative heat
polystyrene, and polyisocyanurate foams and release rates for flame extinction, where critical
chlorinated polyethylenes (ϕ ¼ 0.09 to 0.19). As mass loss rate values are taken from Table 36.15
expected from the firepoint theory [150, 151], the and heats of combustion from Table A.39.
reactivity of the vapors in the gas phase follows the The data in Table 36.16 suggest that the criti-
kinetic parameter. cal heat release rate for flame extinction is
The combustion efficiency and product weakly dependent on the chemical nature of the
generation efficiencies follow the reactivity of material, contrary to the critical mass loss rate.
the vapors in the gas phase, such as shown The critical heat release rates thus can be
in Fig. 36.53 for the combustion efficiency. The averaged, which are 100
7, 53
9, and
lower the value of the kinetic parameter 47
10 kW/m2 for the chemical, convective,
(Equation 36.94), the lower the reactivity of the and radiative heat release rates, respectively.
material vapors, which is reflected in the For materials with highly reactive vapors, such
(1) reduced values of the combustion efficiency as polyethylene, large amounts of extinguishing
(Equations 36.36, 36.37 and 36.38), (2) reduced agent are needed to reduce the heat release rate to
values of the generation efficiencies the critical value. For materials with highly

Fig. 36.53 Combustion 1.0


efficiency versus kinetic
parameter for flame
extinction versus. Data
were measured in the Fire 0.8
Combustion efficiency

Propagation Apparatus

0.6

0.4

0.0
0.0 0.1 0.2 0.3 0.4 0.5
Kinetic parameter
1222 M.M. Khan et al.

Table 36.16 Critical chemical, convective, and radiative heat release rates for flame extinction

Critical heat release rate (kW/m2)


Material Chemical Convective Radiative
Polyoxymethylene (65) 50 (14)
Polymethylmethacrylate 77 53 24
Polyethylene 96 55 42
Polypropylene 104 61 43
Polyethylene foams 88 51 38
Chlorinated polyethylenes 95 48 47
Polystyrenes 108 44 64
Polyurethane foams (flexible) 101 48 53
Polyurethane foams (rigid) 102 44 58
Average 96
10 51
6 46
12
Note: Critical mass loss rates from Table 36.15, and heats of combustion from Table A.39

nonreactive vapors, such as Teflon, it is difficult the local equivalence ratio is predominantly a
to reach the critical heat release rate values gas-phase process and, thus, is different from
unless high external heat flux is applied. the process of flame extinction by water, which
The energy balance at the surface as the occurs predominantly in the solid phase at the
flame extinction condition is reached can be surface of the material. The kinetic parameter for
represented by modifying Equations 36.15 and flame extinction defined in Equation 36.94, how-
36.34 [156] ever, is still applicable [156]:

00 00 00 00
ΦΔH T m_ cr þ q_ e  q_ rr  q_ agent 1 þ Δc p ðT ad  T a Þ þ ΔH D
m_ ¼
00
ð36:96Þ Φ0  κY j, ex
ΔH g Y O ΔH *O
Φ¼
1  Y j, ex
00 ΔHi   ð36:98Þ
Q_ i ¼
00 00 00 00
ΦΔH T m_ cr þ q_ e  q_ rr  q_ agent
ΔH g
where
ð36:97Þ
ϕ ¼ Kinetic parameter in the presence of the
where extinguishing agent
00 ϕ0 ¼ Kinetic parameter in the absence of the
q_ e ¼ External heat flux (kW/m2)
00 extinguishing agent
q_ rr ¼ Surface re-radiation loss (kW/m2) κ ¼ Ratio between the kinetic parameters at the
00
q_ agent ¼ Heat flux removed from the surface or flame temperature and at the adiabatic flame
from the flame by the agent as the flame temperature
extinction condition is reached (kW/m2) Yj,ex ¼ Mass fraction of the extinguishing agent
ΔHi ¼ Chemical, convective, or radiative heat Δcp ¼ Difference between the heat capacities of
of combustion (kJ/g) the extinguishing agent and the fire products
ΔHg ¼ Heat of gasification (kJ/g) (kJ/g/K)
ΔHi/ΔHg is defined as the heat release param- Tad ¼ Adiabatic flame temperature at the stoi-
eter (HRP) (see section “Heat Release Rate” of chiometric limit (K)
this chapter). Ta ¼ Initial temperature of the reactants (K)
ΔHD ¼ Heat of dissociation (kJ/g)
Flame Extinction by the Processes Equation 36.98 shows that the addition of
in the Gas Phase an extinguishing agent reduces the kinetic
The process of flame extinction by gaseous, pow- parameter from its normal value and includes
dered, and foaming agents and by an increase in the effects of four flame extinction mechanisms
36 Combustion Characteristics of Materials and Generation of Fire Products 1223

[156]: (1) dilution, effects are included in the Flame Extinction by Reduced Mass
κYj,ex term; (2) added thermal capacity, effects Fraction of Oxygen
are included in Δcp; (3) chemical inhibition, Flame extinction by reduced mass fraction of
effects are included through Tad; and (4) kinetic oxygen can be the result of (1) dilution and heat
chain breaking and endothermic dissociation capacity effects due to the addition of inert gases,
through ΔcP and ΔHD terms. such as N2 and CO2; and (2) chemical effects due
From Equation 36.96, in the presence of an to the retardation of chemical reactions and
extinguishing agent that works in the gas phase, reduction in the flame heat flux to the surface,
00 00 00
especially the radiative component.
00 φΔH T m_ cr þ q_ e  q_ rr Theoretical and experimental analyses have
m_ ¼ ð36:99Þ
ΔH g been performed for flame extinction by reduced
oxygen mass fractions. For example, for
For fixed values of external heat flux, the polymethylmethacrylate (PMMA), an oxygen
addition of an extinguishing agent reduces the mass fraction value of 0.180 is predicted for
normal value of the kinetic parameter by one or flame extinction [157] compared to the experi-
more of the four mechanisms expressed by Equa- mental values of 0.181 for a 70-mm-wide,
tion 36.98; the mass loss rate decreases and 190-mm-high, and 19-mm-thick vertical PMMA
approaches the critical value at which the flame slab [158] and 0.178 for a 100-mm-wide, 25-mm-
is extinguished. Increasing the external heat flux thick, and 300- and 610-mm-high vertical slabs of
would increase the mass loss rate, and further PMMA, and 25-mm-diameter and 610-mm-high
addition of the extinguishing agent would be vertical cylinder of PMMA [31]. The critical
needed to reduce the mass loss to its critical values of the chemical, convective, and radiative
value and to reestablish the flame extinction con- heat release for PMMA are 106, 73, and
dition. Continued increases in the extinguishing 33 kW/m2 [31], respectively, showing a trend
agent for increasing external heat flux will result similar to one reported in Table 36.16. At oxygen
in the denominator of Equation 36.98 to mass fractions equal to or less than 0.201, flames
approach zero, at which point it would represent are unstable and faint blue in color [31].
a nonflaming condition. The effect external heat flux on flame extinc-
For a fixed airflow rate, as is generally the tion due to reduced oxygen mass fraction has
case in enclosure fires where the extinguishing been examined for buoyant turbulent diffusion
agent working in the gas phase is used, an flames [159]. For example, for rectangular and
increase in the mass loss rate due to increasing circular horizontal PMMA slabs, 0.06–0.10 m2 in
external heat flux results in an increase in the area and 0.03–0.05 m in thickness, exposed
equivalence ratio, defined in Equation 36.41. As to external heat flux values of 0, 40, 60, and
the equivalence ratio increases and approaches 65 kW/m2, flame extinction is found at oxygen
values of 4.0 and higher, the combustion effi- mass fractions of 0.178, 0.145, 0.134, and 0.128,
ciency approaches values less than or equal to respectively [6]. The data support Equation 36.99
0.40 (see Fig. 36.33), flames are extinguished, and show that, for buoyant turbulent diffusion
and nonflaming conditions become important flames, flaming can occur up to relatively low
[103, 104]. Thus, the upper limit for the appli- oxygen mass fraction values. The only condition
cation of the extinguishing agent working in the is that, in the gas phase, the reactant-oxidizer
gas phase is dictated by the equivalence ratio mixture is within the flammability limit.
 4.0 and/or the combustion efficiency  0.40. The effect of reduced oxygen mass fraction
Under nonflaming conditions, an increase in the on flame extinction of materials in a three-
external heat flux increases the generation rate dimensional arrangement, where flame heat flux
of the fuel vapors and the reduction-zone is enhanced, has been examined. Figure 36.54
products. shows an example where chemical heat release
1224 M.M. Khan et al.

15

Chemical heat release rate (kW)


0.233
12

9
0.190

0.167
3

0
0 50 100 150 200 250 300
Time (s)

Fig. 36.54 Chemical heat release rate versus time for separated by about 12 mm). Measurements were made in
50-mm empty corrugated paper boxes in a 2  2  2 the Fire Propagation Apparatus with no external heat flux
arrangement (two boxes along the length  two boxes under co-flow conditions and at various oxygen mass
along the width  two layers, for a total of eight boxes fractions, which are indicated in the figure

rates at oxygen mass fractions of 0.233, 0.190, Definitions


and 0.167 versus time are shown for the combus-
Chemical heat calorific energy generated in
tion of 50-mm cubes of empty corrugated paper
of combustion chemical reactions leading to
boxes in a 2  2  2 arrangement. The weight
varying degrees of incomplete
of each box is about 13 g (839 g/m2). The
combustion per unit fuel mass
measurements were taken in the Fire Propagation
consumed
Apparatus.
Convective calorific energy carried away
In Fig. 36.54, at an oxygen mass fraction of
heat of combu- from the flame by the fire
0.167, the flame is close to the extinction condi-
stion products-air mixture per unit
tion, only 10.5 % of the initial weight of the
fuel mass consumed
boxes is consumed, which is equivalent to con-
Heat of gasi- energy absorbed to vaporize a
sumption of a single box with a surface area of
fication unit mass of fuel originally at
about 0.0155 m2. The peak chemical heat release
ambient temperature
rate close to flame extinction, in Fig. 36.54, is
Heat release par- calorific energy generated per
about 1.5 kW or 97 kW/m2, using a surface area
ameter unit amount of calorific energy
of 0.0155 m2. This value is in excellent agree-
by the fuel
ment with the average value in Table 36.16,
Kinetic maximum fraction of combus-
derived from the critical mass loss rates for igni-
parameter tion energy that the flame
tion. The data in Fig. 36.54 for the three-
for flame ext- reactions may lose to the sam-
dimensional arrangement of the corrugated
inction ple surface by convection
boxes thus support the firepoint theory [150,
without flame extinction
151], independent of the critical heat release
Net heat of com- calorific energy generated in
rate for flame extinction from the geometrical
plete combu- chemical complete reactions
arrangement and surface areas of the materials,
stion leading to combustion, with
and Equations 36.98 and 36.99 as originally
water as a gas, per unit fuel
formulated in Ref. [156].
mass consumed
36 Combustion Characteristics of Materials and Generation of Fire Products 1225

Radiative heat calorific energy emitted as ΔHT net heat of complete combustion per
of combustion thermal radiation from the unit of fuel vaporized (kJ/g)
flame per unit fuel mass ΔHv heat of vaporization at the vaporiza-
consumed tion temperature (kJ/g)
ΔH*CO net heat of complete combustion per
unit mass of CO generated (kJ/g)
ΔH *CO2 net heat of complete combustion per
Nomenclature unit mass of CO2 generated (kJ/g)
ΔHO
*
net heat of complete combustion per
A total exposed surface area of the mate- unit mass of oxygen consumed (kJ/g)
rial (m2) HRP heat release parameter
aj mass coefficient for the product yield hi mass coefficient for the heat of com-
(g/g) bustion (kJ/g)
bj molar coefficient for the product yield I/I0 fraction of light transmitted through
(g/mol) smoke
Bcr critical mass transfer number j fire product
CHF critical heat flux (kW/m2) k thermal conductivity (kW/m/K)
00
ĊO mass consumption rate of oxygen Lsp smoke point (m)
(g/m2/s) l optical path length (m)
00
Ċstoich,O stoichiometric mass consumption rate ṁ00 mass loss rate (g/m2/s)
of oxygen (g/m2/s) M molecular weight (g/mol)
cO mass of oxygen consumed per unit mi molar coefficient for the heat of com-
mass of fuel (g/g) bustion (kJ/mol)
cP specific heat (kJ/g/K) ṁair mass flow rate of air (g/s)
00
ΔcP difference between the heat capacities q_ e external heat flux (kW/m2)
of the extinguishing agent and the fire 00
q_ f flame heat flux (kW/m2)
products (kJ/g/K) 00
D optical density (1/m) Q_ i heat release rate per unit sample sur-
Ei total amount of heat generated in the 0
face area (kW/m2)
combustion of a material (kJ) Q_ i heat release rate per unit sample width
fj volume fraction of a product (kW/m)
fp fire property S stoichiometric mass air-to-fuel ratio
FPI Fire Propagation Index (g/g)
FSPc convective flame spread parameter t time (s)
00
Ġj mass generation rate of product tf time at which there is no more vapor
j (g/m2/s) formation (s)
00
Ġstoich,j stoichiometric mass generation rate of t0 time at which the sample is exposed to
product j (g/m2/s) heat (s)
ΔHi heat of combustion per unit mass of T temperature (K)
fuel vaporized (kJ/g) ΔTig ignition temperature above ambient
ΔHD heat of dissociation (kJ/g) (K)
ΔHg heat of gasification at ambient temper- TRP thermal response parameter (kWs1/2/
ature (kJ/g) m2)
ΔHg,con flame convective energy transfer to u fire propagation rate (mm/s or m/s)
the fuel per unit mass of fuel gasified V_ total volumetric flow rate of fire
(kJ/g) product-air mixture (m3/s)
ΔHm heat of melting at the melting temper- Ẇ total mass flow rate of the fire product-
ature (kJ/g) air mixture (g/s)
1226 M.M. Khan et al.

Wf total mass of the material lost in the Subscripts


flaming and nonflaming process (g)
Wj total mass of product j generated a air or ambient
in the flaming and nonflaming ad adiabatic
process (g) asy asymptotic
Xf flame height (m or mm) ch chemical
Xp pyrolysis front (m or mm) con convective
Xt total length available for fire propaga- cr critical
tion (m or mm) e external
yj yield of product j ex extinguishment
Yj,ex mass fraction of extinguishing agent f flame or fuel
YO mass fraction of oxygen fc flame convective
fr flame radiative
Greek Letters g gas
g,con flame convective energy for fuel
α correlation coefficient (nonflaming fire) gasification
β correlation coefficient (transition region) i chemical, convective, radiative
ϕ kinetic parameter for flame extinction ig ignition
ξ correlation coefficient (transition region) j fire product
Φ equivalence ratio n net
χ ch combustion efficiency 0 initial
χ con convective component of the combustion oxid oxidation zone of a flame
efficiency rad radiation
χ rad radiative component of the combustion red reduction zone of a flame
efficiency stoich stoichiometric for the maximum possi-
ηj generation efficiency ble conversion of fuel monomer to a
κ ratio between the kinetic parameters product
for the flame temperature and adiabatic rr surface re-radiation
flame temperature s surface, smoke
λ wavelength of light (μm) vc ventilation-controlled fire
σ Stefan-Boltzmann constant wv well-ventilated fire
(56.7  1012 kW/m2/K4) 1 infinite amount of air
τ average specific extinction area (m2/g)
ρ density (g/m3) Superscripts
νj stoichiometric coefficient of product j
νO stoichiometric coefficient of oxygen . per unit time (s1)
Ψj stoichiometric yield for the maximum 0
per unit width (m1)
conversion of fuel to product j 00
per unit area (m2)
ΨO stoichiometric mass oxygen-to-fuel
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