NFPA RecentDevelopments

1
Recent Developments in Clean

Fire Suppression Agents
Mark L. Robin, Ph.D.
DuPont Chemicals1 & Fluoroproducts
NFPA Conference & Expo

June 12, 2013
Chicago, IL
04/2009
-DuPont Confidential-
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Learning Objectives
1.
2.
3.
4.
What Are Clean Agents?

The History of Clean Agents
The Halon Clean Agents
2
Halon Replacements
Desired Properties
Current Commercial Clean Agents
5. DuPont Clean Agent Program
Total Flood Candidate
Streaming Candidates
04/2009
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I. Clean Agents: What are they?

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What is a Clean Agent?

NFPA 2001 Standard on Clean Agent Fire
Extinguishing Systems (2012 edition)
3.3.6 Clean Agent. Electrically
nonconducting, volatile, or gaseous fire
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extinguishing agent that does not leave a
residue upon evaporation
No residue
No cleanup
No downtime
04/2009
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Which Fire Extinguishing Agents

are NOT Clean?
Water
Foam
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Powder
Residue
Cleanup
Downtime
Non-fire damage to assets
04/2009
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Comparison Testing of Preaction

Sprinkler and FM-200 Systems
In-cabinet fire
Clean Agent System
FM-200 system designed and installed in
accordance with NFPA6 2001
Preaction Sprinkler System

Designed and installed in accordance with NFPA 13
Detection/Alarm Systems
Designed and installed in accordance with NFPA 72
04/2009
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Clean Agent vs Sprinklers
In-cabinet fire
NFPA Compliant FM-200 and pre-action sprinkler systems

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Before..
DuPont FM-200 Clean Agent System

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After..
DuPont FM-200 Clean Agent System

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Before..
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Automatic Sprinkler System

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After..
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After..
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Comparison of Sprinkler and Clean Agent Systems

Suppression agent
Sprinkler Systems
Clean Agent System
Water
Gas
Design Objective
Fire Control:
Confine fire
Control ceiling T
Protect structure
Activation
Sprinkler head 15
T 135 oF
Fire size at
activation
Can be 100's of kW
Design Objective
Total Flooding
Cleanliness
04/2009
No. Water not three

dimensional, will not fill
entire enclosure
No. Water damage,
smoke damage
Fire Extinguishment
Protect contents
Automatic activation
following detection (air
sampling, smoke detectors)
Low as 0.1 kW with air
aspirating detection system
Yes. Agent distributed
uniformly throughout
enclosure
Yes. No residues to clean up
following extinguishment
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Foam System Discharge
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Dry Chemical System Discharge
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II. History of Clean Agents

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The History of Clean Agent

Fire Suppression
Why should we look to the past in order to
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prepare for the future? Because there is
nowhere else to look.
James Burke
04/2009
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Halogenated Compounds as
1870 to 1910
04/2009
CCl4 extinguishers introduced

Handhelds
Fire Grenades20
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Late 1920s : Methyl Bromide (CH3Br)
More effective than CCl4

21 applications
British aircraft
WWII - German military aircraft, marine
Late 1930s: Bromochloromethane (CH2BrCl)
04/2009
German Luftwaffe
US Air Force in late 1940s
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Late 1940s
US Army sought agent as effective as
CH3Br or CH2BrCl, but with lower toxicity
Over 60 agents evaluated:
Purdue University
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Four selected for further study
Halon 1301
Halon 1211
Halon 1202
Halon 2402
04/2009
CF3Br
CF2BrCl
CF2Br2
BrCF2CF2Br
Br reacts chemically with

key flame species
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The Halon Era: 1960s to 1994

Halon 1301: CF3Br
Total flooding applications
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Prefer a
Gaseous Agent
04/2009
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The Halon Era: 1960s to 1994

Halon 1211: CF2BrCl
Portable applications
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Prefer a
Liquid Agent
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III. The Halons were near ideal

What Happened?
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IV. Halon to be Phased Out

- Now What?
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The Search for Son of Halon

mid-1980s to Present
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The Search for Halon Replacements:

Mid 1980s to today
Academia
NMERI / CGET
Government/Military
NIST
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Army, Navy, Air Force
FAA
Industrial
04/2009
DuPont
ICI
Great Lakes Chemical Corporation
3M
American Pacific
Ansul-DuPont Confidential-
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Search for Halon Replacements

Chemical Agents
Extinguish fire by interfering with the flame chemistry
React with and remove key flame species
Chain carriers H, O and HO radicals removed
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Very efficient
Physical Agents
Extinguish fire via physical mechanisms
Heat removal
O2 dilution
Separation of fuel and oxidant
04/2009
Fire Tetrahedron
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Chemical Agents
Bromine or iodine containing molecules
Great Lakes Chemical Corporation
FM-100TM ; CF2HBr
Performance = Halon 1301
ODP too high; toxicity too high
ICI
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CF3CHFBr Fluothane
Good performance
Inhalation Anesthetic, ODP too high
CF3I
04/2009
Purple Haze
Good performance
High toxicity
Chemically reactive, corrosive
High manufacturing cost
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Chemical Agents
Advanced Agent Working Group (AAWG)

Roots in CF3I working group
Goal: Halon 1301 replacement
North Slope Operators, U.S. military, EPA, NASA,
Kidde International, Kidde-Fenwal Combustion
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Research, QinetiQ, UK MOD, American Pacific
Corporation, NMERI, NIST, 3M, Great Lakes, DuPont,
HARC
Bromine-containing alkenes, alcohols, ethers, amines,

carbonyl compounds, and aromatics
Selection: bromine-containing alkenes
04/2009
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Chemical Agents
Advanced Agent Working Group (AAWG)
Bromine-containing alkenes
CF2BrCH=CH2
CF2BrCF2CH=CH2
CF3CH=CHBr
CF3CBr=CH2
CF2BrCF2CH=CH2
CF3CF2CBr=CH2
All too toxic for total flooding

in occupied areas
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Tropodegradable short lifetime due to rxn with

hydroxyl radical
Too reactive = high toxicity
Short atmospheric lifetime = high toxicity
04/2009
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Physical Agents
Chlorine-containing Agents: Safety Hi-Tech
NAF-S-III: HCFC-22/HCFC-123/HCFC-124/d-limonene
Nonzero ODP; slated for phaseout
Perfluorocarbons: 3M
C3F8 PFC-2-1-8
n-C4F10 PFC-3-1-10 45
Extremely long atmospheric life, extremely high GWP
Permanent effect on climate change
Ethers
C-O linkage leads to more rapid rxn with HO
Only true for -OCH2-, -OCHF-, -OCH2F, -OCH3 groups
Amines
RfNH2, RfRfNH, RfRfRfN
Difficult synthesis; toxic
04/2009
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Physical Agents
Inert Gases: Ansul
Inergen: N2/Ar/CO2
Hydrofluorocarbons
Great Lakes: CF3CHFCF3 FM-200
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DuPont: CF3H (FE-13TM); CF3CF2H (FE-25TM)
Perfluoroketones: 3M
CF3CF2C(O)CF(CF3)2 NovecTM 1230 ; NovecTM 649
04/2009
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Why Fluorine?
-C-H
- C-F
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Volatility
Stability
Low Toxicity
Flame Suppression
04/2009
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100s of Researchers
1000s of Compounds Screened Later..
V. Halon Replacements
- Commercialized Agents
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Commercialized Halon
1301 Replacements
Hydrofluorocarbons (HFCs)
HFC-227ea:
HFC-125:
HFC-23:
DuPont FM-200
DuPont FE-25TM
DuPont FE-13TM
CF3CHFCF3
CF3CF2H
CF3H
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Hydrochlorofluorocarbons
(HCFCs)
HCFC Blend A: NAF-S-III
Subject
to Phase-out
HCFC-22/HCFC-123/HCFC-124/d-limonene
Inert Gases
IG-541:
IG-55:
InergenTM Ar/N2/CO2
ArgoniteTM Ar/N2
Perfluorinated Ketones
FK-5-1-12:
04/2009
NovecTM 1230
CF3CF2C(O)CF(CF3)2
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Commercialized Halon
1211 Replacements
Hydrofluorocarbons (HFCs)
HFC-236fa:
DuPont FE-36TM
CF3CH2CF3
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Hydrochlorofluorocarbons (HCFCs)
Halotron I: HCFC-123 + Ar + CF4
04/2009
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Comparison of Halon Replacements

X = provides desired property
Ideal Halon 1301 Replacement
Halon 1301
High weight efficiency

Gas at ambient temperature
Low chemical reactivity
Electrically nonconducting
Low toxicity
Lack of metabolism
Low agent cost
Low system cost
Low number agent cylinders
Low storage volume
Low system footprint
Low cylinder pressure rating
Low manifold pressure rating
Low negative pressures during discharge
Low positive pressures during discharge
Slow stratification
Zero ODP (ozone depletion potential)
Zero GWP (global warming potential)
VOC exempt (no contribution to smog)
XX
X
X
X
X
X
X
X
X
X
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X
X
X
X
X
X
HFCs
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Inert Gases
X
X
X
X
X
X
X
Perfluoroketones
X
X
X
X
X
X
X
X
X
X
X
HFCs offer the best overall combination

of the properties desirable in a Halon replacement
04/2009
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Worldwide Clean Agent Market

Number of Installed Systems
HFCs are the most widely employed
Halon 1301 alternatives
Other (10%)
HFCs (70%)
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Inert Gases (20%)

04/2009
90% Inergen
10% Argonite
70% FM-200
20% FE-25TM
10% NovecTM 1230
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VI. Recent Developments in Clean Agents

DuPonts Clean53Agent Program
04/2009
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DuPont Clean Agent History
1947 Halon 1301 identified (U.S. Army Engineering Development

Research Lab, DuPont, and Purdue Research Foundation)
1960s Halon 1301 - manufactured and marketed by DuPont
1995
DuPont launches FE-13 (HFC-23)

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1997 DuPont launches FE-36 (HFC-236fa) for portable

extinguishers
2001
DuPont launches HFC-227ea as FE-227
2002
DuPont launches FE-25 (HFC-125)
2008
DuPont acquires FC business of GLCC

- FM-200 becomes DuPont trade name
04/2009
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DuPont Clean Agent Program

Goal: Discover and commercialize a range of new clean fire
extinguishing agents to extend our current portfolio and
satisfy the safety, environmental and performance
requirements of clean agent users around the world
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04/2009
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Clean Agent Development

Total Flooding Agents
High mass efficiency
Chemically inert
No reaction with water, common solvents
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Long term storage stability
High volatility
bp -70 to + 40 oC
Electrically non-conducting
Low toxicity
MDC < CS NOAEL
MDC < 4h LC50
Cost effective
04/2009
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Toxicological Requirements = BIG Challenge

Tox Requirements
4h LC50 > MDC
Cardiac NOAEL > 57MDC
Cardiac LOAEL > MDC
Much higher bar compared to refrigeration, foam

blowing, propellant, & solvent tox requirements
04/2009
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Toxicological Testing
No Qualitative Structure Activity Relationships
(QSAR) available for 4h LC50 or cardiac
sensitization tests
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Agent screening: 1h LC
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200 - 300 g material = $$
$10,0000
4 h LC50 and Cardiac Sensitization Tests

50 60 kg material = $$$$
$150,000 for tox tests
04/2009
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Fire Suppression Testing

Class B
Cup Burner Testing
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Total Flood Tests
Class A
Plastic Rod Test
Total Flood Tests
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Class B (liquid, gaseous) Fuels
Cup burner apparatus
Standardized apparatus (NFPA 2001/ISO 14520)
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Cup Burner: Assembled View

85 mm
heater/TC
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535 mm
235 mm
90 mm
air/agent inlet
04/2009
fuel inlet
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Class A (solid) Fuels
UL 2166 Full-scale Tests
95% of clean agent

applications
are Class A/Class C hazard
protection
Plastic Sheets (PMMA,

ABS, PP)
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Wood crib
100 m3 enclosure; 50 kg per single test run
04/2009
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Class A Performance
Lab Scale Method Developed
DuPont-developed rod tests
Modification of cup burner apparatus

Plastic rod special design
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Laboratory scale : 300
g requirement
Excellent agreement with UL 2166 results
FM-200, FE-25, Novec 1230
04/2009
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Small Scale Total Flooding Tests

0.6 m3 Lexan test enclosure
Class B pan fire tests
Class A tests 64
plastic pieces (PMMA, PP, ABS)
mini wood crib
04/2009
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Total Flooding Candidate

bp = 31 oC
Toxicology
4h LC50 > 231,000 ppm (> 23.1% v/v)
CS NOAEL = 100,000 ppm (10% v/v)
CS LOAEL = 125,000 ppm (12.5% v/v)
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Fire Suppression
Class A MDC = 5.6% v/v
Class B MDC = 6.9% v/v a
Class C MDC = 6.3% v/v
04/2009
n-heptane
95% of applications
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Stability
High thermal and chemical stability
Stable to water
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Material compatibility
Compatible with common metals, plastics,
elastomers
Environmental Properties
ODP = 0
GWP < 20 (estimate; determination in
progress)
04/2009
-DuPont
Confidential-
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Inert gas solubility
N2, Ar, CO2
Isotherms measured isotherms -10, 20, 50 oC
Henrys Law constants generated for -40 to 80 oC
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Thermodynamic and Transport Properties

PVT data
Fit to various equations of state
04/2009
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Current Activity
Process scale-up to produce 1000 kg
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Intermediate-scale
fire testing
Additional material of construction
testing
GWP determination in progress
04/2009
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Clean Agent Development

Streaming Agents
High mass efficiency
Chemically inert
No reaction with water, common solvents
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Long term storage stability
Liquid or high bp gas

bp -10 to + 40 oC
Electrically non-conducting
Toxicity
Equal to or better than Halon 1211 or HCFC-123
Cost effective
04/2009
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Portables Development
Complex interaction of variables affecting

performance
Fill density
Superpressure level
Application rate 70
Agent droplet size
Agent quality (% mass in vapor)
Valve, nozzle, horn design
Operator technique
Design of Experiment (DOE) not applicable

Brute force empirical approach to
optimization
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Portable Fire Extinguisher Design
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Source: NFPA 12B (1990)

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Portable Fire Extinguisher Design

Fill Density
Fill density = kg agent per volume of unit
As the fill density increases, a more rapid
decrease in the application rate and throw
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distance during discharge occurs
As the fill density decreases, the application
rate and throw remain more constant
throughout the discharge
Low fill densities not economical; balance between
economics and performance required
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Portables Development
No reliable small-scale test available
Pan fire tests according to UL 711
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Wood crib tests according
to UL 711
04/2009
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Flow Visualization : PLIF

Concentration, temperature, and velocity maps
Qualitative droplet size info
Discharge shape
Discharge throw
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Small droplet size:

150 psig
61 lb/ft3
1530 nozzle
2 kg
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atomizing nozzle
Droplets too
small and light
buoyed away from
flame
04/2009
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Large droplet size

150 psig
23 lb/ft3
2 kg
H nozzle
Droplets too big
- Poor fire
performance
04/2009
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04/2009
Sweet spot:
150 psig
43 lb/ft3
H nozzle
2 kg
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Streaming Candidate 1
bp = 31 oC
Toxicology
4h LC50 > 102,900 ppm (> 10.3% v/v)
CS NOAEL = 12,500 ppm (1.25 % v/v)
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CS LOAEL = 25,000
ppm (2.5% v/v)
Fire Suppression
Class A MEC = 4.7% v/v
Class B MEC = 5.3% v/v a
a
04/2009
n-heptane
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Streaming Candidate 2
bp = 18 oC
Toxicology
4h LC50 = 120,000 ppm (12% v/v)
CS LOAEL = 25,000 ppm (2.5% v/v)
Fire Suppression
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Class A MEC = 3.7% v/v

Class B MEC = 4.8 % v/v a
04/2009
Efficiency on mass
basis ~ Halon 1301
n-heptane
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Agents: Summary
Total flooding: occupied areas
Development of a promising candidate based on
toxicological testing and small-scale fire testing
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Suitable for use in normally occupied areas

Zero ODP
Low GWP
Further evaluation in progress
04/2009
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Agents: Summary
Streaming or Non-occupied Areas
Development of several promising candidates
based on toxicological85testing and small-scale
fire testing
High mass efficiency; Candidate #2 close to Halon 1301 in

mass efficiency
Zero ODP
Low GWP
04/2009
Further evaluation
in progress

NFPA RecentDevelopments

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1

Recent Developments in Clean

NFPA Conference & Expo

What Are Clean Agents?

I. Clean Agents: What are they?

What is a Clean Agent?

Which Fire Extinguishing Agents

Comparison Testing of Preaction

Preaction Sprinkler System

Clean Agent vs Sprinklers

NFPA Compliant FM-200 and pre-action sprinkler systems

DuPont FM-200 Clean Agent System

DuPont FM-200 Clean Agent System

Automatic Sprinkler System

Automatic Sprinkler System

Automatic Sprinkler System

Automatic Sprinkler System

Automatic Sprinkler System

Comparison of Sprinkler and Clean Agent Systems

Clean Agent System

No. Water not three

Foam System Discharge

Dry Chemical System Discharge

II. History of Clean Agents

The History of Clean Agent

CCl4 extinguishers introduced

More effective than CCl4

Late 1930s: Bromochloromethane (CH2BrCl)

Br reacts chemically with

The Halon Era: 1960s to 1994

The Halon Era: 1960s to 1994

III. The Halons were near ideal

IV. Halon to be Phased Out

The Search for Son of Halon

The Search for Halon Replacements:

Search for Halon Replacements

Advanced Agent Working Group (AAWG)

Bromine-containing alkenes, alcohols, ethers, amines,

All too toxic for total flooding

Tropodegradable short lifetime due to rxn with

Only true for -OCH2-, -OCHF-, -OCH2F, -OCH3 groups

HCFC Blend A: NAF-S-III

Comparison of Halon Replacements

High weight efficiency

HFCs offer the best overall combination

Worldwide Clean Agent Market

Inert Gases (20%)

VI. Recent Developments in Clean Agents

DuPont Clean Agent History

1947 Halon 1301 identified (U.S. Army Engineering Development

1960s Halon 1301 - manufactured and marketed by DuPont

DuPont launches FE-13 (HFC-23)

1997 DuPont launches FE-36 (HFC-236fa) for portable

DuPont launches HFC-227ea as FE-227

DuPont launches FE-25 (HFC-125)

DuPont acquires FC business of GLCC

DuPont Clean Agent Program

Clean Agent Development

Toxicological Requirements = BIG Challenge

Much higher bar compared to refrigeration, foam

4 h LC50 and Cardiac Sensitization Tests

Fire Suppression Testing

Total Flooding Agents