The document discusses halon total flooding fire suppression agents, highlighting the advantages of halon 1301 and its replacements, such as hydrofluorocarbons (HFCs), hydrochlorofluorocarbons (HFCs), inert gases, and perfluorinated ketones. It outlines the configurations, performance metrics, and chemical properties of these agents, emphasizing the importance of low chemical reactivity for optimal effectiveness in fire suppression. Additionally, it addresses environmental impact, toxicity, and implications of chemical interactions of the various agents on performance and safety.

1. Halogenated Total Flooding FireHalogenated Total Flooding Fire
Suppression AgentsSuppression Agents

2. The Halon Era: 1960s to 1994
Halon 1301: CF3Br
 Total flooding applications
Halon 1211: CF2BrCl
 Portable, local applications
“Clean Agents”
No corrosive or abrasive residues left
following extinguishment
Water, foam, powder – secondary damage due
to agent can exceed damage due to fire

3. Clean Agents under NFPA 2001
 Safe for occupied areas protection
 No corrosive residues
No damage to sensitive/expensive assets
 No cleanup required after discharge
No business interruption
Source: Alinenan ROI Report, January 2004.

4. The Halon Era: 1960s to 1994
What made the Halons “Ideal Fire
Extinguishing Agents” ???
 Clean
 Efficient fire suppression
 Chemically inert
• Storage stable
• Non-reactive chemically
 Electrically non-conducting
 Low Toxicity
 Low Cost
A unique combination of properties

5. Source: U.S. EPA
Ozone Depletion

6. Properties of the Ideal Halon ReplacementProperties of the Ideal Halon Replacement
• Clean
• Efficient fire suppression
• Chemically inert
 Long term storage stability
 No chemical reactions with water, fuels, assets
• Electrically non-conducting
• Low toxicity
• Zero ODP
• Zero GWP
• Reasonable manufacturing cost
No replacement has been found which
satisfies ALL of the above requirements

7. Halon 1301 ReplacementsHalon 1301 Replacements
• Hydrofluorocarbons (HFCs)
 HFC-227ea: FM-200®
CF3CHFCF3
 HFC-125: FE-25TM
CF3CF2H
 HFC-23: FE-13TM
CF3H
• Hydrochlorofluorocarbons (HCFCs)
HCFC Blend A: NAF-S-III
• HCFC-22/HCFC-123/HCFC-124/d-limonene
• Inert Gases
 IG-541: InergenTM
Ar/N2/CO2
 IG-55: ProInertTM
, ArgoniteTM
Ar/N2
• Perfluorinated Ketones
 FK-5-1-12: NovecTM
1230 CF3CF2CCF(CF3)2
O

8. Halogenated Agents:
Extinguishing Mechanism
• Primarily via physical mechanism of
heat removal
 Reduces flame temperature below
that required to maintain
combustion
 Efficient mechanism – extinguishing
concentrations typically 4.2 to 12% v/v

9. Agent Quantity for Protection of 100 m3
Volume
Agent
Class A Hazard Class B Hazard a
Agent
required,
% v/v
Agent
required,
kg
Agent
required,
% v/v
Agent
required,
kg
HFC-227ea 7.0 54.8 8.7 69.4
IG-541 40.0 72.4 43.9 81.9
AGENT PERFORMANCE: Inert Gases & HFCsAGENT PERFORMANCE: Inert Gases & HFCs
a
Heptane

10. Agent Efficiency: Requirements for
Total Flooding Agents
 Low boiling point
• Desire gaseous agent to completely and rapidly flood
the protected enclosure, including obstructed areas
• Allows for larger area coverage, higher maximum ceiling height,
lower storage and operation temperatures
 Low mass of agent required for extinguishment
• Agent pricing is on a weight basis (kg), not volume
 Low vapor density of air/agent mixture
• Lower vapor density = longer hold times
 Low system cost

11. Halon 1301 Replacements:Halon 1301 Replacements:
Chemical/Physical PropertiesChemical/Physical Properties
Halon
1301 HFCs Inert Gases F-Ketones
Physical State a
Gas Gas Gas Liquid
Boiling point - 58 o
C
HFC-227ea -16 o
C
HFC-125 -48 o
C
HFC-23 -82 o
C
IG-541 -196 o
C
IG-55 -190 o
C
NovecTM
1230:
47 o
C
Chemical
Reactivity Very Low Very Low Very Low High
a
At room temperature (25 o
C)

12. Agent Quantity for Protection of 1000 m3
Volume
Agent
Class C Hazard Class B Hazard a
Agent
required,
% v/v
Agent
required,
kg
Agent
required,
% v/v
Agent
required,
kg
ECARO-25®
9.0 502 11.0 627
FM-200®
7.0 548 8.7 694
NovecTM
1230 4.7 687 5.9 872
AGENT PERFORMANCE/EFFICIENCYAGENT PERFORMANCE/EFFICIENCY
a
Heptane

13. Agent Efficiency
Property FM-200®
ECARO-25®
(FE-25)
NovecTM
1230 a
Maximum Area
Coverage
256 m2
(2735 ft2
)
256 m2
(2735 ft2
)
95 m2
(1024 ft2
)
Maximum Ceiling
Height
4.9 m
(16 ft)
4.9 m
(16 ft)
4.3 m
(14 ft)
Container Storage
Temperature b
0 to 54 o
C
(32 to 130 o
F)
0 to 54 o
C
(32 to 130 o
F)
16 o
to 27 o
C
(60 to 80 o
F)
Vapor Density 7.15 kg/m3
4.98 kg/m3
11.6 kg/m3
Volume of Hazard
Protection
with 1 kg of agent
1.82 m3
(NFPA factor = 0.5483
@ 20 o
C
@ 7% design conc. )
2.0 m3
(NFPA factor = 0.4412
@ 20 o
C
@ 9% design conc.)
1.46 m3
(NFPA factor = 0.6101
@ 20 o
C
@ 4.7% design conc.)
a
Sapphire Design Manual, Ansul
b
Engineered system protecting multiple hazards

14. Agent Efficiency
Requirement FM-200®
ECARO-25®
NovecTM
1230
Gaseous agent √ √ Liquid; potential for liquid
discharge
Large nozzle area
coverage
√ √ 260 % less area coverage vs
FM-200TM
& ECARO-25TM
High maximum ceiling
height
√ √ Lower maximum ceiling height
Wide storage temperature √ √ Limited to 16 to 27 o
C
Low vapor density √ √ Higher vapor density
High efficiency on mass
basis
√ √ Up to 27% more agent by mass
vs ECARO-25
Up to 20% more agent by mass
vs FM-200
Low cost on mass basis √ √ Agent cost higher on mass
basis
Low system cost √ √ 20-30% higher

15. Halon Replacements:Halon Replacements:
Chemical/Physical PropertiesChemical/Physical Properties
Fundamental Differences
• Chemical Reactivity
 Halons/HCFCs/HFCs/Inert Gases: Chemically unreactive
 Perfluoroketones: Chemically reactive – water, alcohols
• Physical State
 Halons/HCFCs/HFCs/Inert Gases: Gases at room temperature
 C6 Perfluoroketone: Liquid at room temperature
These fundamental differences impact the characteristics
and performance of HFCs/Inert Gas Systems
compared to Perfluoroketone Systems

16. NovecTM
1230
CF3CHFCF3
+ CF3CF2C(O)OCH3
CF3CHFCF3 + CF3CF2COOH
CF3CHFCF3
+ CF3CF2C(O)OCH2CH3
CF3CHFCF3 + CF3CF2C(O)NH2
CF3CHFCF3
+ CF3CF2C(O)NR2
CF3CHFCF3
+ CF3CF2C(O)NHR
Chemistry of NovecChemistry of NovecTMTM
1230:1230:
Reactions with water, alcohols, aminesReactions with water, alcohols, amines
a. H2O; b. CH3OH; c. CH3CH2OH;
d. NH3; e. RNH2; f. NHR2
a
b
c
d
e
f
FM-200 as by product

17. No reaction
FM-200FM-200®®
: No reaction with: No reaction with
water, alcohols, amineswater, alcohols, amines
a. H2O; b. CH3OH; c. CH3CH2OH;
d. NH3; e. RNH2; f. NHR2
FM-200®
No reaction
No reaction
No reaction
No reaction
No reaction
a b
c
d
e
f
FE-25 ®

18. NovecNovecTMTM
1230 Chemistry:1230 Chemistry:
Reaction with Water: HydrolysisReaction with Water: Hydrolysis
CF3CF2C(O)CF(CF3)2 + H2O CF3CF2COOH + CF3CHFCF3
NovecTM
1230 F-Propionic acid HFC-227ea
● NovecTM
1230 reacts with water
- produces HFC-227ea (FM-200®
) and F-propionic acid a
● “The hydrolysis leaves a corrosive aqueous phase
that will act on metals” a
● Hydrolysis to F-propionic acid and HFC-227ea occurs when
NovecTM
1230 is absorbed across the lung-air interface b
a
3M: P.E. Tuma, 24th
IEEE 2008 SEMI-THERM Symposium Proceedings, p. 173
b
3M Technical Brief, Novec 1230 Fire Protection Fluid Safety Assessment, 2004

19. NovecNovecTMTM
1230 Chemistry:1230 Chemistry:
Reaction with Water: HydrolysisReaction with Water: Hydrolysis
CF3CF2C(O)CF(CF3)2 + H2O CF3CF2COOH + CF3CHFCF3
NovecTM
1230 F-Propionic acid HFC-227ea
● Rapid hydrolysis: half life < 2.5 min @ pH 1-9 a
● Well-known reaction of perfluoroketones b
● Perfluoroketones react with many common chemicals
(water, alcohols, amines,…) c
● “Contact with water or solvents either polar or hydrocarbon
could render NovecTM
1230 fluid ineffective” d
a
NICNAS Std/1019, August 2002, 3M NovecTM Fire Protection Fluid 1230
b
Saloutina, et. al., Izv. Akad. Nauk SSSR (8),1893 (1982)
c
Gambarayan, et. Al., Angew. Chemie Int. Ed., 5(11), 947 (1966)
d
3M: Sapphire Installation Manual, 5/15/2003

20. Perfluoropropionic AcidPerfluoropropionic Acid
CF3CF2COOH
 Strong Acid/Extremely Corrosive
• Is a perfluorocarboxylic acid – among strongest acids known
• Attacks steel, forming iron salt [DuPont, 2004]
 Toxic [MSDS]
• Causes eye and skin burns
• May cause severe & permanent damage to digestive tract
• Causes gastrointestinal burns
• Causes chemical burns to respiratory tract
• PFCAs known tumor promoters [Env. Sci. Tech 2005, 39, 5517]
• PFCAs are known peroxisome proliferators [Ibid.]
 Liver damage

21. Halon Replacements andHalon Replacements and
Chemical ReactivityChemical Reactivity
Low Chemical Reactivity Required –
Chemical Reactivity Impacts:
Performance/Leakage
Handling
Human Exposure
Cleanliness
Environmental Impact

22. Potential Consequences ofPotential Consequences of
Chemical ReactivityChemical Reactivity
System Performance CompromisedSystem Performance Compromised
Agent reacted is not available for suppression
“Contact with water or solvents either polar or hydrocarbon
could render Novec 1230 fluid ineffective” a
Systems in place 10-20 years
● Systems must remain leak-free throughout this period
● Chemical reactions producing even small amounts of
corrosive products could lead to corrosion and eventual
leakage of agent, compromising the effectiveness and
safety of the system
a
Sapphire Installation Manual, 5/15/2003

23. • Special Handling ProceduresSpecial Handling Procedures
• Example: vent driers, nitrogen purges required to
prevent contact of NovecTM
1230 with moist air a
• Human Exposure ImplicationsHuman Exposure Implications
• NovecTM
1230 hydrolyzed when crossing lung-air
interface to produce HFC-227ea and F-propionic
acid b
Potential Consequences ofPotential Consequences of
Chemical ReactivityChemical Reactivity
a
3M: Sapphire Installation Manual, 5/15/2003
b
3M Technical Brief, Novec 1230 Fire Protection Fluid Safety Assessment, 2004

24. • Atmospheric Impact ImplicationsAtmospheric Impact Implications
• Example: Atmospheric hydrolysis of NovecTM
1230
not considered in evaluation of GWP
• The extent of atmospheric hydrolysis, e.g., on
atmospheric aerosols, could render GWP of
perfluoroketones similar to that of HFCs
• Cleanliness ImplicationsCleanliness Implications
• Detrimental chemical reaction with enclosure,
enclosure contents
Potential Consequences ofPotential Consequences of
Chemical ReactivityChemical Reactivity

25. NovecNovecTMTM
1230 Discharge on Plastic Cladding1230 Discharge on Plastic Cladding

26. Chemical Reactivity
Requirements FM-200®
/
ECARO-25®
NovecTM
1230
Low Chemical
Reactivity
√ Characterized by high
chemical reactivity
No reaction with
alcohols, amines √ Reacts with alcohols, amines
No reaction with
solvents √
Incompatible with polar or
hydrocarbon solvents
“Additional work is needed to assess the
reactivity of C6K [NovecTM
1230]…” a
Source: 3M: 24thIEEE SEMI-THERM Symposium, 2008, page 173.

27. Toxicological ConcernsToxicological Concerns
• Perfluoroketones
• Relatively little toxicological information for perfluoroketones
• Toxicology of perfluoroacetone well-studied
 Highly toxic
• NovecTM
1230
 Hydrolyzes when crossing the lung-air interface to form HFC-
227ea and perfluoropropionic acid

28. Toxicological Profiles: HFCs and PerfluoroketonesToxicological Profiles: HFCs and Perfluoroketones
FM-200®
NovecTM
1230
Inhalation LC50
(4h, rat)
> 80% >10%
Cardiac
Sensitization NOAEL 9.0% 10%
Cardiac
Sensitization LOAEL > 10.5% >10%
PBPK Safe Level 10.5% PBPK data unavailable
Repeated dose
inhalation
(28 day, rat)
NOAEL > 10.5 % a
LOAEL = 0.0997 % b
Peroxisome proliferation in liver
Increased lung and liver weights
Metabolism Negligible Hydrolyzes to F-Propionic acid
a
90 day, rat
b
NICNAS Std/1019, August 2002, 3M NovecTM
Fire Protection Fluid 1230
NOAEL = no observed adverse effect level; LOAEL = lowest observed adverse effect level

29. • NovecTM
1230
 Class A = 4.5
 NOAEL = 10%
 “Safety margin” 10/4.5 = 2.23
• FM-200®
 Class A = 6.7%
 NOAEL = 9%
“Safety margin” 9/6.7 = 1.35
““Safety Margin”Safety Margin”
Problem: NOAEL/LOAEL method so conservative that
Halon 1301 would not be allowed despite its long history
with an excellent safety record! a

30. Observations During CardiacObservations During Cardiac
Sensitization Testing of NovecSensitization Testing of NovecTMTM
12301230
Source: Novec 1230 Premanufacture Notice; US EPA Premanufacture Notice,
EPA case no. TS-120546, 2000.
“The severity of the clinical response prevented exposure above 15.48%”
NovecTM
1230 Conc.,
% v/v
Response
1.01 Agitation, pawing at mask, eyes half closed
1.98 Agitation, deep slow breathing, eyes half closed, muscle tremors, pawing at
mask
5.04 Agitation, eyes half closed, muscle tremors, pawing at mask
9.97 Eyes closed, shallow breathing, muscle tremors, pawing at mask
15.48 Rapid breathing, excessive struggling, staggering, loss of bladder control,
trembling, partial collapse, muscle tremors

31. Exposure Considerations
FM-200®
NovecTM
1230
Not metabolized
Approved for use in MDI
to deliver medicaments
orally
Hydrolyzes when crossing
lung-air interface to
produce HFC-227ea and
F-Propionic acid

32. Environmental PropertiesEnvironmental Properties
Halon 1301 FM-200® ECARO-25®
FE-25®
NAF-S-III Fike
ProInert
IG-55
NovecTM
1230
Composition CF3Br CF3CHFCF3 CF3CHFCF3
HCFC-22
HCFC-123
HCFC-124
d-limonene
N2
Ar CF3CF2C(O)CF(CF
3)2
ODP 10 0 0 > 0 0 0
GWP (100 y
ITH)
6900 2900 2800 1700
(HCFC-22)
0 1 a
Atmospheric
Lifetime (y)
65 36.5 32.6 12
(HCFC-22)
n/a 0.014
Scheduled for
Phaseout
PHASED
OUT
NO NO YES NO NO
a
neglects atmospheric hydrolysis

33. Environmental RegulationsEnvironmental Regulations
• Montreal Protocol
• Related to ozone depleting substances
HFCs all zero ODP, so not subject to Montreal Protocol
• Kyoto Protocol
 Related to greenhouse gases (GHGs)
 HFCs are one type of GHG
 Kyoto Protocol concerned with emission reductions
• No limits or banning of HFCs in fire suppression applications
• F-Gas Regulations
 Similar to Kyoto Protocol
 No limits or banning of HFCs in fire suppression applications

34. Impact of Emissions of HFCs from FireImpact of Emissions of HFCs from Fire
Suppression ApplicationsSuppression Applications
• Impact of all HFC emissions
< 3% of total impact of all GHG emissions
• Impact of HFC emissions from fire fighting
< 1% of total impact of all HFC emissions, hence….
• Impact of HFC emissions from fire fighting
< 0.03% of total impact of all GHG emissions
Fire suppression systems regarded as
essentially non-emissive

36. Desired Property FM-200®
NovecTM
1230
Ease of Gasification √ Liquid, bp 47 o
C
Efficient on mass basis
√ Systems require higher mass of
agent vs FM-200®
Slow stratification
√ More rapid stratification due to
increased vapor density
Low chemical reactivity √
High chemical reactivity – reacts
with water, amines, alcohols,
solvents
Not Metabolized in Body
√ Hydrolyzes to HFC-227ea and
F-propionic acid
Low agent cost √ Agent cost per kg higher vs FM-200
Low system cost √ System cost higher vs FM-200
Low Impact on Climate Change <0.03% impact GWP =1 (neglects hydrolysis)
Agent Comparison

37. Overall Comparison of Halon ReplacementsOverall Comparison of Halon Replacements