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SPRING 2011 EDITION

FIRE DETECTION
& SUPPRESSION
Special Edition for SUPDET 2011
Fire Protection Research Foundation
Supported by NFPA Mission
www.fs-world.com [ 26 ] Spring 2011 edition
Mark L. Robin, Ph.D., is a Senior Technical Services Consultant for DuPont Fluoroproducts.
Mr. Robin has been extensively involved in the development, testing and approval of
Halon alternatives, including HFC and inert gas clean extinguishing agents, and
participates on numerous fire suppression related technical committees
including NFPA 2001 and ISO 14520.
By Mark L. Robin
A SHORT HISTORY OF
INTRODUCTION
Clean fire suppression agents are characterized by a unique
combination of chemical and physical properties which
allow them to extinguish fires without creating a need for
cleanup or business interruption. This contrasts to traditional
fire extinguishing agents such as water, foam, and dry
powder where cleanup and business disruption are inev-
itable. In addition, the use of extinguishing agents such as
water, foam or dry powder oftentimes results in more
secondary damage due to the extinguishing agent than
due to the fire; for example, the use of water or foam to
combat fires in museums, libraries, or facilities containing
expensive, sensitive electronic equipment. In this paper
we will discuss the history of the clean fire suppression
agents: where they came from, their current status, and
what the future holds for clean agent fire suppression.
THE WONDER GASES: HALONS
Early mans response to fire likely involved the use of dirt,
sand, or water, all of which were thrown at a fire; if these
techniques failed early man most likely employed his feet
to run away from an out of control fire. With time man
improved his fire fighting techniques. By 200 BC Ctesibus
of Alexandria, Egypt developed a hand pump to deliver a
jet of water to a fire and records indicate the use of the
bucket brigade in ancient Rome. The primary concern
throughout most of history has been to extinguish fire,
with little concern over the mess that water or other
extinguishing agents made.
Near the close of the 19
th
century man began to realize
the advantage of clean agents which could be used to
extinguish a fire but caused little or no damage themselves.
The original clean agents were halogenated molecules.
CLEAN FIRE
SUPPRESSION AGENTS
www.fs-world.com [ 27 ] Spring 2011 edition
From the late 1800s to the 1920s
carbon tetrachloride (CCl
4
) was com-
monly employed in small thin-walled
glass containers to fight small fires
in the event of a fire these fire
grenades were simply thrown at the
fire. Handheld extinguishers containing
carbon tetrachloride were also intro-
duced in the early 1900s. In the late
1920s methyl bromide (CH
3
Br) was
found to be more effective than carbon
tetrachloride. It was widely employed
as a fire suppressant agent by the
British in the late 1930s in aircraft pro-
tection and by the German military
during World War II for aircraft and
marine applications. Suppression sys-
tems employing bromochloromethane
(CH
2
BrCl) were also developed in the
late 1930s and were employed by the
German Luftwaffe. Bromochl o-
romethane was evaluated in the United
States during the late 1930s to the late
1940s and was eventually employed
by the US Air Force.
Although extremely effective as fire
suppression agents, the relatively high
toxicities of carbon tetrachloride, me-
thyl bromi de, and bromochl o-
romethane prompted the US Army to
initiate a research program in 1947 to
develop an extinguishing agent which
retained the high fire suppression ef-
fectiveness of these agents but that
was less toxic. US Army sponsored
research at Purdue University evaluat-
ed over 60 candidate agents, most of
which were halogenated hydrocar-
bons, for both fire suppression effec-
tiveness and toxicity. As a result of
these studies, four agents were select-
ed for further evaluation:
Bromotrifluoromethane (Halon 1301)
Bromochlorodifluoromethane (Halon
1211)
Dibromodifluoromethane (Halon
1202)
1,2-Dibromotetrafluoroethane (Halon
2402)
These further evaluations ultimately
led to the widespread use of Halon
1301 in total flooding and small porta-
ble applications and the use of Halon
1211 in streaming applications (porta-
bles and local application).
Halons 1301 and 1211 are character-
ized by high fire suppression efficiency,
low chemical reactivity, low toxicity,
and low electrical conductivity. They
produce no corrosive or abrasive res-
Compound bp (C) Ext. Conc.
a
ODP LC50
% v/v % v/v
b
CHFBr
2
65 1.8 < 0.2 -
CF
2
HBr -15.5 3.9 0.74 10.8 (4 h)
CF
3
CH
2
Br 26 3.5 - 11.7 (10 m)
CF
3
CHBr
2
73 1.9 < 0.1 1.2 (30 m)
CF
3
CHFBr 8.6 3.6 0.3-0.4 -
BrCF
2
CF
2
H 10.8 3.2 - 18.7 (30 m)
TABLE 1. PROPERTIES OF HYDROBROMOFLUOROCARBONS
a
n-heptane ;
b
Lethal concentration to kill 50% of exposed animals (rat)
TABLE 2. PROPERTIES OF BROMINATED OLEFINS
Compound AAWG Code bp (C) Ext. Conc. ODP Atmospheric Toxicity
Name % v/v Lifetime,
(n-heptane) Days
CF
3
CH=CHBr 707 40 4.3 0.0017-0.0079 2.4 - 4 Toxic at 1.5%
CH
2
=CHCF
2
Br 872 42 4.5 Toxic at 1%
CF
3
CBr=CH
2
873 35 4.7 0.0028-0.0037 3-4 NOAEL=0.5%
LOAEL = 1%
CH
2
=CHCF
2
CF
2
Br 903 65 5.0 0.0016 2 -7
CH
2
=CHCFClCF
2
Br 905 99 4.5
CH
2
=CBrCF
2
CF
3
1116 59 3.8 0.0019 3.5 - 4
CH
2
=CBrCF
2
CF
2
CF
3
1358 78.5 3.7 Toxic
CH
2
=CBrCF(CF
3
)
2
1359 78 3.3 Very toxic
CH
2
=CBr(OCF
3
)CFCF
3
1380 75 3.8 Very toxic
(CF
3
)
2
C=CHBr 1391 63 2.6 Toxic
NOAEL = no observed adverse effect level (cardiac sensitization)
LOAEL = lowest observed adverse effect level (cardiac sensitization)
www.fs-world.com [ 28 ] Spring 2011 edition
idues upon extinguishment and as a
result are ideally suited to protect areas
such as libraries and museums where
the use of water or solid extinguishing
agents could cause secondary dam-
age equal to or exceeding that caused
by direct fire damage. The electrically
non-conducting nature of Halon 1301
and 1211 allows their use to protect
electrical and electronic equipment
while their low toxicity allows the use
of the agents in areas where egress
of personnel may be undesirable or
impossible.
Due to their unique combination of
properties, Halon 1301 and 1211
served as near ideal fire suppression
agents for more than 30 years. How-
ever, due to their implication in the
destruction of stratospheric ozone,
the Montreal Protocol of 1987 identified
Halon 1301 and Halon 1211 as two
of a number of halogenated agents
requiring limitations of use and produc-
tion. An amendment to the original
Protocol resulted in the halting of pro-
duction of Halons 1301 and 1211 on
January 1, 1994.
THE SEARCH FOR SON
OF HALON
The ideal Halon replacement, in addi-
tion to possessing the desirable char-
acteristics of the Halons, needs to
have a much lessened environmental
impact with regard to its potential for
ozone depletion as well as with regard
to its potential contribution to climate
change. The ideal Halon replacement
would therefore be characterized by
the following properties:
Clean (no residues)
High fire extinguishment efficiency
Low chemical reactivity
- Long term storage stability
- Noncorrosive to metals
- High material compatibility (metals,
plastics)
Electrically non-conducting
Low toxicity
Zero ozone depletion potential (ODP)
Zero global warming potential (GWP)
Reasonable manufacturing cost
To date no replacement agent has
been found which satisfies all of the
above requirements; although replace-
ments have been found that match
many of the above criteria. Each class
of extinguishant has strengths and
weaknesses, yet agent selection must
be based on the criteria listed above
along with detailed knowledge of the
specific project requirements.
The various agents investigated as
possible Halon replacements are dis-
cussed below where they are divided
into the chemical class of compound
examined.
Hydrobromofluorocarbons
(HBFCs)
The first compounds considered by
researchers for the replacement of the
Halons were the hydrobromofluorocar-
bons (HBFCs). The bromine atom is
known to provide high fire suppression
characteristics, and the fluorine atom
is known to impart stability and volatility.
Laboratory and large scale testing of
the leading candidates in this class,
CHBrF
2
(FM-100) and CF
3
CHBrF
demonstrated that these agents could
indeed provide fire suppression capa-
bilities essentially equal to that of the
Halons. However, it was found that
compounds in this class lacked the
desired property of low toxicity and
are hence unsuitable for use in normally
occupied areas. In addition, atmo-
spheric models predict that small
amounts of HBFCs would survive
transport into the stratosphere and
contribute to ozone destruction. The
HBFCs are classified as ozone deplet-
ing substances (ODSs), and like the
Halons, the HBFCs are banned under
the Montreal Protocol. Properties of a
selection of the HBFCs evaluated as
Compound bp (C) Ext. Conc.
a
ODP NOAEL LOAEL
% v/v % v/v % v/v
CF
2
HCl -40.7 11.6 0.05 2.5 5.0
CF
3
CHCl
2
28.7 6.3 0.02 1.0 2.0
CF
3
CHFCl -12 7.0 0.022 1.0 2.5
HCFC Blend A -38.3 11.6 - 10 10
TABLE 3. PROPERTIES OF HYDROCHLOROFLUOROCARBONS
a
n-heptane ;
b
NOAEL/LOAEL for cardiac sensitization
Compound bp (C) Ext. Conc.
a
NOAEL LOAEL LC
50
% v/v % v/v % v/v % v/v
CF
3
I -2.5 3.0 0.2 0.4 27.4 (15 m)
CF
3
CF
2
I 12 2.1 0.02 0.05 7.5 (1h)
(CF
3
)
2
CFI 40 3.2 - - 0.91 (1h)
CF
3
CF
2
CF
2
I 41 3.0 - - 3.3 (2h)
CF
3
CF
2
CF
2
CF
2
I 67 - - - > 0.5 (1h)
TABLE 4. PROPERTIES OF IODOFLUOROCARBONS
NOAEL/LOAEL for cardiac sensitization
Enquiry Card No. 409
www.fs-world.com [ 30 ] Spring 2011 edition
Halon replacements are shown in
Table 1.
Brominated Olefins
In response to the need for the replace-
ment of Halon 1301 in North Slope
applications, the Advanced Agent
Working Group (AAWG) - a consortium
of Halon manufacturers, academic
researchers and oil & gas industry
representatives - conducted extensive
research on the potential use of bro-
minated olefins and other classes of
chemicals in fire suppression applica-
tions. Because of the difficulty in syn-
thesizing members of this class of
compounds, relatively few brominated
olefins have been examined for flame
suppression. Atmospheric models pre-
dict that small amounts of brominated
olefins would survive transport into the
stratosphere and as a result the bro-
minated olefins are ozone depleting
substances. High toxicities and high
cost of manufacture also limit the prac-
tical use of the brominated olefins.
Properties of brominated olefins are
shown in Table 2.
Hydrochlorofluorocarbons
(HCFCs)
HCFCs have been extensively evalu-
ated as Halon replacements (see Table
3). However, their toxicological prop-
erties prevent them from being em-
ployed in total flooding applications in
normally occupied areas. HCFC-123
(CF
3
CHCl
2
) and to a lesser extent
HCFC-124 (CF
3
CHCl) have been
found useful in portable extinguisher
applications.
The HCFCs are characterized by non-
zero ODPs and as a result are classified
as ozone depleting substances; under
the provisions of the Montreal protocol
the HCFCs are slated for phase out
and hence the HCFCs can be regard-
ed as transitional agents only.
Iodine-Based Halon
Replacements
Iodofluorocarbons are extremely effi-
Designation IG-01 IG-100 IG-55 IG-541
Trade name Argotec: Minimax N100: Argonite: Ginge-Kerr Inergen: Ansul
GmbH Koatsu
Formula Ar N
2
50% N
2
52% N
2
50% Ar 40% Ar
8% CO
2
Molecular Weight 39.9 28.02 33.95 34.0
Boling point (C) -185.9 -195.8 -196 -196
Freezing point (C) -189.4 -210 -189 -78.5
Specific Volume 0.602 0.858 0.708 0.697
superheated vapor
at 1 bar, 20C
ODP 0 0 0 0
GWP 0 0 0 0
Class A design 41.3 40.2 40.0 40.0
conc., % v/v
Heptane design 53.0 43.7 49.1 41.2
conc., % v/v
TABLE 5. PROPERTIES OF THE INERT GAS AGENTS
www.fs-world.com [ 31 ] Spring 2011 edition
cient fire suppression agents; however,
due to their inherent instability, they are
characterized by high toxicity (see Table
4). One of the least toxic iodofluorocar-
bons, CF
3
I, has been shown to be an
extremely potent cardiosensitizer, re-
sulting in death to test animals at con-
centrations as low as 0.4 % v/v. As a
result, its use in occupied areas is
prohibited. Storage stability problems,
high manufacturing costs, and a non-
zero ODP all present significant hurdles
to the practical use of the iodofluoro-
carbon agents.
Zero ODP Halon
Replacements
The ideal Halon replacement would
be characterized by an ODP of zero;
as seen from the above discussion,
bromi ne, chl ori ne, and i odi ne-
containing molecules fail to satisfy this
key criteria. Four classes of com-
pounds have been evaluated which
are characterized by a zero ODP: inert
gases, hydrofluorocarbons (HFCs),
perfluorocarbons (PFCs), and perflu-
orinated ketones (PFKs).
Inert gases such as nitrogen, argon,
Agent Design Conc., % v/v Agent, kg Number of Cylinders
HFC-227ea 7.0% 548 2
IG-541 40.0 724 22
TABLE 6. HALOCARBON VS INERT GAS SYSTEM: 1000 M
3
ENCLOSURE, CLASS A HAZARD
Compound bp (C) Ext. Conc
a
NOAEL
b
LOAEL
b
% v/v % v/v % v/v
CF
3
H -82.2 12.6
d
30 50
CF
3
CF
2
H -48.5 9.3
d
7.5 10.0
CF
3
CH
2
CF
3
-0.7 6.5
d
10 15
CF
3
CHFCF
3
-16.4 6.7
d
9.0 > 10.5
CF
3
CF
2
CF
3
-36.7 6.3 - -
CF
3
CF
2
CF
2
CF
3
-2.2 5.3 - -
CF
3
CF
2
CF
2
CF
2
CF
2
CF
3
58 4.4 - -
TABLE 7. PROPERTIES OF HYDROFLUOROCARBONS AND PERFLUOROCARBONS
and inert gas mixtures are character-
ized by a zero ODP and zero GWP;
Table 5 compares the inert gas agents.
The inert gas agents extinguish fire by
reducing the oxygen content of the
atmosphere from 21% to the 12-15%
range. At or below this range most
ordinary combustibles will not burn.
The inert gas agents are clean (no
corrosive residues formed following
extinguishment), electrically non-
conductive, chemically non-reactive,
have low toxicity, and do not contribute
to ozone depletion or climate change.
The inert gas agents cannot be com-
pressed to liquids and hence can only
be stored as high pressure gases. As
a result, inert gas extinguishing sys-
tems require the use of high pressure
storage cylinders and high pressure
piping.
This element leads to increased system
costs though. In addition, inert gas
systems require a much larger number
of cylinders and therefore require much
more storage space for system cylin-
ders compared to the other clean
agents - further adding to the cost of
inert gas systems. Table 6 compares
the cylinder requirements for a 1000
m
3
Class A hazard with a typical HFC
(HFC-227ea) and a typical inert gas
(IG-541) system.
The HFC clean agents are gases at
room temperature and extinguish fire
predominantly via heat absorption.
Figure 1. Worldwide Clean Agent Market
www.fs-world.com [ 32 ] Spring 2011 edition
They remove enough heat from the fire
that the fire can no longer sustain itself
and is subsequently extinguished. HFC
clean agents are clean, electrically non-
conductive, and characterized by low
chemical reactivity as well as low tox-
icity. The HFC clean agents can be
stored as liquefied compressed gases
allowing HFC systems to require fewer
cylinders and less storage space com-
pared to the inert gas agents.
Additionally, their use does not require
high pressure cylinders or piping. The
HFCs are also characterized by a zero
ODP and minimal impact on climate
change. The US EPA has employed
its Vintaging Model [1] to estimate the
emissions of GHGs from various sourc-
es and based on their results the im-
pact of HFC emissions from fire sup-
pression applications represents
0.0098% of the total impact of all
GHGs. In other words, the impact of
HFC emissions from fire protection
applications represents less than
0.01% of the impact of all greenhouse
Designation Chemical Formula Trade Name Manufacturer
HFCs HFC-227ea CF
3
CHFCF
3
FM-200 DuPont
HFC-125 CF
3
CF
2
H FE-25 DuPont
HFC-23 CF
3
H FE-13 DuPont
HFC-236fa
a
CF
3
CH
2
CF
3
FE-36 DuPont
HCFCs HCFC Blend A CF
2
HCl (82%), NAF-S-III Safety Hi-Tech
CF
3
CHCl
2
(4.75%)
CF
3
CHFCl (9.5%)
d-limonene (3.75%)
HCFC Blend B
a
CF
3
CHCl
2
, CF
4
, Ar Halotron I American Pacific
Inert Gases IG-541 N
2
(52%) Inergen Ansul
Ar (40%)
CO
2
(8%)
IG-55 N
2
(50%), Ar (50%) Argonite Ginge-Kerr
Proinert Fike Corp.
IG-01 Ar Argotec Minimax
IG-100 N
2
N-100 Koatsu
Perfluorinated FK-5-1-12 CF
3
CF
2
C(O)CF(CF
3
)
2
Novec-1230 3M
Ketones
TABLE 8. COMMERCIALLY AVAILABLE HALON REPLACEMENTS
a
Streaming applications (Halon 1211 replacements)
gas (GHG) emissions. Recent results
from the HFC Emissions Estimating
Program (HEEP), which also estimates
the emissions of HFCs from fire sup-
pression, are in good agreement with
the results of EPA's vintaging model
[2]. Table 7 compares the properties
of the PFC and HFC agents.
Perfluorocarbons (PFCs) and perfluori-
nated ketones (PFKs) are molecules
in which all of the hydrogen atoms in
the hydrocarbon analog have been
replaced with the fluorine atom. PFCs
are characterized by low toxicity and
are effective suppression agents. How-
ever, the PFCs have been found to
have a large impact on climate change
and as a result their use in fire sup-
pressi on appl i cati ons has been
banned. Perfluorinated ketones are
characterized by zero ODP and mini-
mal impact on climate change. Yet,
the perfluorinated ketones differ from
the Halons, inert gases, HFCs, and
HCFCs in that they are characterized
by high chemical reactivity and are
liquids at room temperature.
COMMERCIALLY AVAILABLE
HALON REPLACEMENTS
Out of the thousand of compounds
evaluated as replacements for the
www.fs-world.com [ 33 ] Spring 2011 edition
Ideal Halon Replacement Halon 1301 HFCs HCFCs Inert Gases F-ketones
Zero ODP
High Weight Efficiency
Cleanliness
Low Chemical Reactivity
Electrically Non-conducting
Low Toxicity
Low Metabolism
Low Agent Cost
Low System Cost
Ease of Gasification
Low Storage Volume
Low No. Cylinders
Low Storage Footprint
Low Cylinder Pressure Rating
Low Manifold Pressure Rating
Slow Stratification
Low Enclosure Pressures
Zero GWP
TABLE 9. OVERALL COMPARISON OF HALON REPLACEMENTS
Halons, less than a dozen compounds
have seen commercialization. Four
classes of compounds have emerged
as commercially available Halon re-
pl acements: hydrofl uorocarbons
(HFCs), hydrochlorofluorocarbons
(HCFCs), inert gases, and a perfluori-
nated ketone; the HCFCs, however,
are slated for phaseout due to their
non-zero ODPs and are transitional
replacement agents only. Examples of
fire extinguishing agents from each of
these chemical classes are shown in
Table 8.
A summary comparing the qualitative
differences between the extinguishant
classes relative to Halon 1301 is found
in Table 9. As seen from the table, no
agent satisfies all of the requirements
of the ideal Halon replacement. How-
ever, it can be seen from the table that
the HFCs, followed by the inert gas
agents, provide the best overall com-
bination of the desired properties. As
TABLE 10. DOWNTIME IMPACT PER MINUTE FOR VARIOUS
BUSINESS APPLICATIONS
Business Application Estimated Outage Cost
per Minute
Supply Chain Management $11,000
Electronic Commerce $10,000
Customer Service Center $3,700
ATM $3,500
Financial Management $1,500
Messaging $1,000
Infrastructure $700
can be seen in Figure 1, this is reflected
in the Halon replacement market. HFC
systems dominate the global clean
agent market accounting for approx-
imately 70% of all installed clean agent
systems; inert gas systems account
for approximately 20% of the total
market; and other agents represent
approximately 10% of the total installed
clean agent systems.
Applications of the clean agents in-
clude the classic Halon 1301 applica-
tions: telecommunication facilities,
computer rooms, data centers, muse-
ums, libraries, hospitals, medical facil-
ities, medical equipment, clean rooms,
engine compartments, engine nacelles,
petrochemical facilities, grain elevators,
oil rig platforms, floating roof tanks,
and aircraft. In addition to the advan-
tage of requiring no clean up, a further
advantage of the use of clean agents
is there is no need for business inter-
ruption following their use. This allows
for business continuity, i.e., no inter-
ruption of the services a business
www.fs-world.com [ 34 ] Spring 2011 edition
supplies is required following the dis-
charge of a clean agent system. The
financial impact of service disruptions
can be significant, especially in tele-
communications facilities and in data
processing centers. The estimated
downtime impact per minute for var-
ious business applications is shown
in Table 10. The downtime impact for
a typical computing infrastructure is
American Museum of Natural History US EPA Supercomputing Center
Smithsonian Institute Caesars Palace, Las Vegas
Library of Congress Harrahs Casino
Eiffel Tower MGM Casino
Alexandria Library, Egypt Cox Communications
National Museum of Prehistory, Taiwan F/A-18 E/F Aircraft
Field Museum, Chicago Abrams tank
Aristoteles Univ Rare Book Collection, Greece US Navy ground and naval vessels
Royal Thai Silk Museum, Thailand Madrid International Airport
North American DEW Line Radar Installation Charles DeGaulle Airport
Dusseldorf Airport Newark International Airport
San Francisco Airport New Bangkok International Airport
TABLE 11. SELECT APPLICATIONS OF CLEAN AGENTS
estimated at $42,000 per hour. Down-
time impacts for companies relying
entirely on telecommunications tech-
nology, such as online brokerages or
e-commerce sites, can reach $1 million
per hour or more. Table 11 lists a num-
ber of facilities worldwide which employ
clean agent systems.
CONCLUSION
Clean agents are ideally suited for the
1. US EPA, Inventory of Greenhouse Gas Emissions: 1990-2007, US EPA 2009
2. Report of the HFC Emissions Estimating Program (HEEP), April 2010
References
protection of sensitive, expensive,
and mission-critical assets. They are
employed to protect billions of dollars
worth of assets worldwide. With the
demise of the Halons, extensive ef-
forts have been undertaken in the
past 25 years to develop Son of
Halon involving the screening and
evaluation of thousands of candi-
dates. However, to date no replace-
ment has been found which meets
all of the criteria of the ideal Halon
replacement. As a result, agent selec-
tion must be based with consideration
to all the key criteria of a Halon re-
placement along with detailed knowl-
edge of the specific project require-
ments. The HFC cl ean agents,
followed by the inert gas agents, have
been proven to provide the best over-
all combination of the properties de-
sired in a clean agent replacement
for the Halons: high effectiveness,
cleanliness, low chemical reactivity,
low toxicity, minimal environmental
impact, and competitive system cost.
With the expected future reliance of
business and homes on expensive,
sensitive, and mission-critical equip-
ment such as computers and elec-
tronic equipment, the need for clean
agent fire protection is also expected
to experience vigorous growth.