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August 2006 - Issue 5 - Clean Agent Fire Suppression Update


This issue of Emerging Trends is brought to you by DuPont
Letter from the Editor: Welcome to the August 2006 issue of Fire Protection Engineering
Emerging Trends, Fire Protection Engineering magazine's 8-time a year e-newsletter, that :: Issue 5 - Clean Agent
deploys on the off-months of the magazine. Each issue will highlight a new trend and/or Fire Suppression Update ::
innovation in the fire protection engineering industry. This issue will focus on clean agents.

Please enjoy the August issue and thank you for your continued support!

Sincerely,

Morgan J. Hurley, P.E.

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DuPont Fire Extinguishants

For over 200 years, DuPont has put science to work by creating sustainable solutions that are
essential to a better, safer, healthier life for people everywhere. DuPont is a leader in fire
protection and a driving force in the development of safe, clean agent alternatives that protect
assets and ensure business continuity. We pioneered much of the science that makes clean
agent fire extinguishants possible. Through the Science of Protection™, we are committed to
protecting what matters most.

Clean Agent Fire Suppression Update


By: Tom Wysocki

Background:

For over half a century from 1910 to the late 1960s, when a clean, dry, gaseous fire-
extinguishing agent was required, carbon dioxide was the choice, usually the only available
choice. In the late 1960s, the "halons" became commercially viable alternatives to carbon
dioxide for applications where the life safety risks posed by carbon dioxide were considered
unacceptable. In particular, halon 1301 became popular as a fire protection agent for total
flooding spaces where personnel might be present.

For nearly two decades, halon 1301 was the gaseous agent of choice for protection of areas
containing high-value electronic equipment. Halon 1301 also made inroads to the marine fire
protection market for total flooding machinery spaces where flammable liquids presented the
primary risk. Halon 1301 was also widely used in aerospace and military applications.

By the mid-1980s, a growing body of scientific data indicated that halons were contributing to
depletion of the stratospheric ozone layer. In 1987, the Montreal Protocol was adopted requiring
a phase-out of halon 1301 production in developed countries. The U.S. C lean Air Act
Amendments of 1990 banned new production and import of halons into the United Stated as of
1994. These regulatory actions triggered an accelerated search for gaseous fire extinguishing
agents to replace the popular halon 1301. In the U.S., existing halon systems are still permitted
and the use of recycled halon is allowed. However, in recent years, new installations have
become very rare.

Next year marks the 20th anniversary of the Montreal Protocol. During the last two decades, a
number of gases have gained acceptance as halon replacements --- "life-safe" alternatives to
traditional carbon dioxide fire protection for total flooding applications. NFPA 20011 covers the
use of "halon alternatives." The current Standard 2001 lists over a dozen "halon alternatives."

Some of the halocarbon agents currently included in NFPA 2001 are HFC 227ea (FM-200™, FE-
227™), HFC -125 (FE-25™), HFC -23 (FE-13™), and FK-5-1-12 (Novec 1230™) as well as a
number of "blends," that is, combinations of various chemical agents. The inert gases identified
in NFPA 2001 are nitrogen (IG-100) and argon (IG-01) and mixtures of 50 percent nitrogen and
50 percent argon (IG-55). There is also a mixture of nitrogen and argon with a small amount of
carbon dioxide (IG-541, trade name "Inergen™").

Choosing a Gaseous Agent

If the fire protection engineer determines that a space would best be protected by total flooding
with a gaseous agent, the choice of the many available agents should be given careful
consideration. The engineer may consider whether traditional carbon dioxide protection is a
desirable or viable option. If people will normally be present in a space, carbon dioxide should
generally be eliminated as an option. (There may exist specialized applications where people
are normally present that are best protected by total flooding carbon dioxide. NFPA 122 covers
the considerations for such hazards.)

When a clean agent is required, halocarbon and inert gas clean agents each have advantages

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4/20/2011 Fire Protection Engineering - The Offic…
When a clean agent is required, halocarbon and inert gas clean agents each have advantages
and disadvantages.

"Clean Agent" Considerations

When floor space for the agent storage is limited, halocarbon clean agents often have an
advantage. If the clean agent storage must be located some distance from a protected space,
inert gases may sometimes have an advantage. When flammable liquid hazards are to be
protected with a clean agent, availability of data for inerting concentrations using the agent/fuel
combination must be considered. Availability of listings or approvals for specific hazards, such
as Marine hazards, can affect the choice of agent. Other considerations may include cost, local
availability of the agent for recharge, and operating temperature range.

Jurisdictions within the United States generally accept agents that are included in NFPA 2001. If
the system is to be installed outside the United States, the engineer should check local
regulations for possible restrictions on the use of the agent of choice.

"Class A" and "Class C"

If the fuel is electrical equipment, such as computer or telecommunications equipment, virtually


all of the clean agents in NFPA 2001 are listed and approved for such hazards when electric
power to the equipment is shut down upon discharge of the clean agent. All clean agents listed
by UL or approved by FM per NFPA 2001 guidelines have been tested to determine their "C lass
A" fire-extinguishing concentrations. The "C lass A" fire tests include not only the traditional
"wood crib" fire but also arrays of plastic materials simulating the fuels in computer and
telecommunications equipment.

Although the "C lass A" fire tests use fuels simulating those found in electrical equipment, they
are not representative of fire scenarios where electrical energy is continuously supplied to the

fuel array. Limited testing with clean agents on fuel arrays where electrical power is maintained
after application of the clean agent indicates that higher concentrations of clean agent than the
"C lass A" concentrations may be needed to extinguish the fire. As of this writing, the NFPA 2001
technical committee continues to study this issue. Electric power to the protected equipment
should be shut down upon discharge of a clean agent unless issues related to possible reflash
and continued agent decomposition (in the case of halocarbons) are adequately addressed.
Presently, the designer should seek advice from the system manufacturer for such hazards
where electrical power shutdown has untenable repercussions.

article continues below

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"Class B"

If the space to be protected contains quantities of flammable liquids and gases, the engineer
must select an agent for which the flame-extinguishing and possibly the inerting concentrations
for the specific flammable fuels have been determined. Alternatively, the engineer could
arrange for determination of the required concentration by laboratory testing.

A notable difference between the fire protection using carbon dioxide and the "clean agent"
alternatives to C O2 is the consideration of inerting versus flame-extinguishing. All total-flood
carbon dioxide systems designed with C O2 concentrations per NFPA 12 produce an "inert"
atmosphere --- precluding fire or explosion of even stochiometric mixtures of fuel and air with a
persistent ignition source for as long as the specified C O2 concentration remains.

NFPA 2001 recognizes two levels of protection for flammable liquids and gases --- flame-
extinguishment and inerting. NFPA 2001 requires inerting concentrations to be used for hazards
involving C lass B fuels if "conditions for subsequent reflash or explosion could exist." 1 Annex A
of NFPA 2001 describes such "conditions."

Practically speaking, nearly all hazards where flammable liquids are the primary fuel load would
best be protected by systems employing an inerting concentration.

Going Forward

Although many alternatives have been developed, no single alternative has emerged with all of
the desirable characteristics of halon 1301. There are, however, some fine alternatives that
provide excellent fire protection. "C lean agent" development is now focusing on developing
design criteria for hazards involving electrical equipment where equipment cannot be de-
energized, standardizing the cup burner test used to determine flame-extinguishing
concentrations for C lass B fuels, refining requirements for room pressure venting during clean
agent discharges, and expanding the database of inerting concentrations.

Tom Wysocki is with Guardian Services, Inc.

1
NFPA 2001, C lean Agent Fire Extinguishing Systems, National Fire Protection Association,
Quincy, MA, 2004.
2
NFPA 12, Standard on C arbon Dioxide Extinguishing Systems, National Fire Protection
Association, Quincy, MA, 2005.
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Position Available: Fire Engineering/Code Consulting

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Fire Engineering/C ode C onsulting

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fpemag.com/archives/enewsletter.asp… 2/3
4/20/2011 Fire Protection Engineering - The Offic…
registration in Fire Protection Engineering or related field is also desired.

We offer competitive salaries and benefits.

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Position Available: New Creative Chair in Structures and Fire at Edinburgh


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The C hair is being prime funded by The Ove Arup Foundation charity (www.arup.com) and by
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Position Available: Fire Protection Engineer

SmithGroup, a national Architecture, Engineering and Planning firm needs an experienced FPE.
We offer competitive compensation and excellent benefits including 15 Fridays off.

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3 Technical Brief

Novec 1230 ™

Fire Protection Fluid


Environmental properties of
Novec 1230 Fluid
3M™ Novec™ 1230 Fire Protection Fluid was developed as an environmentally responsible
extinguishing agent. This total flooding clean agent is the first halogenated halon alternative
to address not only the concerns of stratospheric ozone depletion but also those related to
climate change (i.e., global warming).

Definitions
When speaking of halogenated compounds, several terms relating to their environmental
impact are commonly used. The following provides a brief explanation of what these
terms mean.
Ozone Depletion Potential (ODP)—An index that provides a relative measure of the effect
a compound has on the stratospheric ozone layer. The halogens bromine and chlorine are
known to cause depletion of the ozone layer. Each atom of these halogens can react with
thousands of ozone molecules, collectively contributing to a thinning of the ozone layer. The
halogen fluorine, however, has been shown to have no effect on the ozone layer. Novec 1230
fluid is a highly fluorinated ketone containing no chlorine or bromine. As a result, the ODP
for Novec 1230 fluid is zero, meaning it has no effect on stratospheric ozone.
Global Warming Potential (GWP)— A parameter that provides a relative measure of the
possible climate impact due to the presence in the atmosphere of a compound that acts as a
greenhouse gas. The two primary characteristics that determine whether a compound will
act as a greenhouse gas are absorption of infrared energy and persistence in the atmosphere.
All organic compounds absorb infrared energy. Compounds that contain carbon-fluorine
bonds typically exhibit strong infrared absorption. If these compounds are also atmospheri-
cally long-lived, the material will have a high GWP. What sets Novec 1230 fluid apart from
the first generation of halogenated halon alternatives is its extremely short atmospheric life-
time.
The previous halon replacements are long-lived in the atmosphere–taking tens, hundreds or
even thousands of years to degrade after they are emitted. In contrast, Novec 1230 fluid
degrades very rapidly when released to the atmosphere. Exposure to natural sunlight causes
this material to break up in a matter of several days. However, this unique material remains
stable in normal storage conditions as a component of a fire protection system.
How Global The GWP of a compound, as defined by the Intergovernmental Panel on Climate Change
Warming (IPCC) [1], is calculated as the integrated radiative forcing due to the release of 1 kilogram
Potential is of that compound relative to the warming due to 1 kilogram of CO2 over a specified period
of time (the integration time horizon (ITH)):
Calculated

F is the radiative forcing per unit mass of a compound (the change in the flux of radiation
through the atmosphere due to the IR absorbance of that compound), C is the atmospheric
concentration of a compound, τ is the atmospheric lifetime of a compound, t is time and x is
the compound of interest [1].
The commonly accepted ITH used for comparative purposes is 100 years, representing a
compromise between short-term effects (20 years) and longer-term effects (500 years or
longer). The concentration of an organic compound, x, in the atmosphere is assumed to fol-
low pseudo first order kinetics (i.e., exponential decay). The concentration of CO2 over that
same time interval incorporates a more complex model for the exchange and removal of
CO2 from the atmosphere (the Bern carbon cycle model).

Atmospheric A study conducted by Taniguchi and colleagues [2] examined the atmospheric loss mecha-
Lifetime of nisms for C2F5C(O)CF(CF3)2 commercially known as 3M™ Novec™ 1230 Fire Protection
Fluid. The authors of this study determined that this compound does not react with hydroxyl
Novec 1230 radical (OH) but that substantial decay occurs when exposed to UV radiation. The authors
Fluid measured the UV cross-section for Novec 1230 fluid, finding a maximum wavelength of
absorbance at 306 nm. Because this compound shows significant absorbance at wave-
lengths above 300 nm, a wavelength higher than that required for UV light to reach the
ground, photolysis in the lower atmosphere will be a significant removal mechanism or sink
for this compound.
The rate of photolysis under atmospheric conditions and the mechanism of decomposition
of this compound were investigated by Taniguchi, et al. The rate of photolysis of Novec
1230 fluid was measured relative to that of Acetaldehyde (CH3CHO), which has a known
atmospheric lifetime by photolysis of 3 to 4 days. The photolysis rate of the Novec 1230
fluid leads to an atmospheric lifetime of 4.5 to 15 days or “approximately 1-2 weeks”. The
authors of this study have concluded that their work is consistent with a previous study con-
ducted by 3M, which found the atmospheric lifetime of Novec 1230 fluid to be on the order
of 5 days or about one week [3].
Impact on The potential for 3M™ Novec™ 1230 fluid to have an impact on the radiative balance in the
Climate Change atmosphere (i.e., climate change) is limited by its very short atmospheric lifetime and low
global warming potential. The quantitative IR cross-section of Novec 1230 fluid was meas-
ured in accordance with section 4.6 of the U.S. EPA FTIR Protocol [4]. The IR measure-
ments were made with a 0.5 cm-1 spectral resolution at 293K on a MIDAC (Model I2001)
FTIR spectrometer, which employs a mercury-cadmium-telluride infrared detector main-
tained at 77 K. The experimental setup used a nominal 4 m path length, which was calibrat-
ed using certified ethylene gas standards.
Using the measured IR cross-section and the method of Pinnock et al. [5] the instantaneous
radiative forcing for Novec 1230 fluid is calculated to be 0.50 Wm-2ppbv-1. This radiative
forcing value and a one-week atmospheric lifetime results in GWP values as shown below
using the IPCC 2001 method [1]. The most commonly cited GWP value is that calculated
using a 100-year integration time horizon.

Compound Atmospheric Radiative 20 year 100 year 500 year


lifetime Forcing ITH ITH ITH
(years) (Wm-2ppbv-1)
C2F5C(O)CF(CF3)2 0.014 0.50 4 1 0
Novec 1230 fluid

This GWP calculation and the method of Pinnock et al. use the assumption that the com-
pound emitted to the atmosphere will be well mixed throughout the troposphere. A material
as short lived as Novec 1230 fluid cannot reasonably meet this condition due to its rapid
removal from the atmosphere. As a result, this calculation overestimates the GWP for this
compound. For this reason, Taniguchi et al. have concluded that “with an atmospheric life-
time of 1-2 weeks, CF3CF2C(O)CF(CF3)2 will have a global warming potential that, for all
practical purposes, is negligible.”

Direct vs. The GWP calculated thus far is the direct GWP, which accounts for the potential warming
Indirect Global effects due to the parent compound released to the atmosphere. In some cases, it is possible
to calculate an indirect GWP in an attempt to account for the potential warming effects due
Warming to the atmospheric degradation products from that compound. While IPCC has indicated
Potential that these indirect GWPs are much less certain [1], it is possible to estimate an indirect
GWP for Novec 1230 fluid since its atmospheric chemistry is well understood.
The decomposition mechanism determined by Taniguchi et al. indicates Novec 1230 fluid
produces fluorinated degradation products, which are atmospherically short-lived [6],
resulting in negligible GWP. However, this decomposition mechanism indicates that one
mole of Novec 1230 fluid will produce 4 moles of CO2. Since the direct GWPs are calculat-
ed on a mass basis, the indirect GWPs need to be calculated on this basis as well. Therefore,
release of 1 kg of Novec 1230 fluid to the atmosphere will produce 0.56 kg of CO2.

1000 g Novec 1230 fluid/(316 g/mol)(4 mols CO2/mol Novec 1230 fluid)(44 g/mol) = 556 g CO2

This results in an indirect GWP of 0.56, regardless of the time horizon chosen. Therefore,
both the direct and indirect GWP for Novec 1230 fluid are less than one. Clearly, com-
pounds with such low GWP are not of concern with respect to potential climate change.
Comparison to Highly fluorinated compounds typically have a GWP of 1000 or more, meaning that 1 kg of
other Halocarbons that compound has the same climate effect as one ton or more of CO2. For example, the
GWPs of HFC-227ea, HFC-125 and HFC-23, all first generation halon replacements, are
3500, 3400 and 12,000, respectively. Due to the exceptionally short atmospheric lifetime of
Novec 1230 fluid, its GWP is extremely low – only one, the equivalent to that of CO2. Such
a low GWP is virtually unprecedented for a fluorochemical, making Novec 1230 fluid a unique
and sustainable alternative technology to halon and the first generation of replacements.

References 1. IPCC (Intergovernmental Panel on Climate Change), Climate Change 2001: The
Scientific Basis, edited by J. T. Houghton, et al., Cambridge University Press, Cambridge,
U.K., 2001.
2. Taniguchi, N., Wallington, T.J., Hurley, M.D., Guschin, A.G., Molina, L.T., Molina, M.J.,
Journal of Physical Chemistry A, 107(15), 2674-2679, 2003.
3. Plummer, G., “Laboratory measurements and calculations related to the photo-disassoci-
ation of L-15566 in the Earth’s lower atmosphere,” 3M Environmental Laboratory Report
Number E01-0549, 2001.
4. Addendum to Method 320 – Protocol for the Use of Extractive Fourier Transform
Infrared (FTIR) Spectrometry for the Analyses of Gaseous Emissions from Stationary
Sources (40 CFR Part 63).
5. Pinnock, S., Hurley, M.D., Shine, K.P., Wallington, T.J., Smyth, T.J., J. Geophys. Res.,
100, 23227, 1995.
6. Wallington, T.J., Schneider, W.F., Worsnop, D.R., Nielsen, O.J., Sehested, J., Debruyn,
W.J., Shorter, J.A., Environ. Sci. Technol., 28, 320, 1994.

United States Europe Canada Japan Asia Pacific and


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Materials Division Materials Electronics Markets 33-1, Tamagawadai 2-chome Call (U.S.) 651 736 7123
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800 810 8513 B-2070 Zwijndrecht London, Ontario 813 3709 8250
800 810 8514 (Fax) 32 3 250 7826 N6A 4T1
800 364 3577

Product Use: All statements, technical information and recommendations contained in this document are based on tests
or experience that 3M believes are reliable. However, many factors beyond 3M’s control can affect the use and performance
of a 3M product in a particular application, including conditions under which the product is used and the time and environ-
mental conditions in which the product is expected to perform. Since these factors are uniquely within the user’s knowledge
and control, it is essential that the user evaluate the 3M product to determine whether it is fit for a particular purpose and
suitable for the user’s method of application.
Warranty and Limited Remedy: Unless stated otherwise in 3M’s product literature, packaging inserts or product packaging
for individual products, 3M warrants that each 3M product meets the applicable specifications at the time 3M ships the prod-
uct. Individual products may have additional or different warranties as stated on product literature, package inserts or prod-
uct packages. 3M MAKES NO OTHER WARRANTIES, EXPRESS OR IMPLIED, INCLUDING BUT NOT LIMITED TO, ANY
IMPLIED WARRANTIES OF MERCHANTABILITY OR FITNESS FOR A PARTICULAR PURPOSE OR ANY IMPLIED WAR-
RANTY ARISING OUT OF A COURSE OF DEALING, CUSTOM OR USAGE OF TRADE. User is responsible for determin-
ing whether the 3M product is fit for a particular purpose and suitable for user’s application. If the 3M product is shown to be
nonconforming within the warranty period,your exclusive remedy and 3M’s sole obligation will be, at 3M’s option, to replace
the product or refund the purchase price.
Limitation of Liability: Except where prohibited by law, 3M will not be liable for any loss or damage arising from the 3M
product, whether direct, indirect, special, incidental, or consequential regardless of the legal theory asserted, including
warranty, contract, negligence or strict liability.

3
Electronics Markets Materials Division
3M Center, Building 224-3N-11
3M and Novec are trademarks of 3M Company.

St. Paul, MN 55144-1000


Used under license by 3M subsidiaries and affiliates.

www.3m.com/novec1230fluid
4916(HB)
Issued: 11/04 © 2004 3M 60-5002-0067-4