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Review of alternative streaming agents for halon 1211
Kim, A. K.; Su, J. Z.
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https://nrc-publications.canada.ca/eng/view/object/?id=dfae076c-737c-4542-9e32-b6343b4f4286 https://publications-cnrc.canada.ca/fra/voir/objet/?id=dfae076c-737c-4542-9e32-b6343b4f4286
Andrew K. Kim and Joseph Z. Su
Fire Risk Management Program Institute for Research in Construction National Research Council of Canada Ottawa, Ontario, CANADA, K1A 0R6
(A version of this paper was published in the Proceedings of the Fire Suppression and Detection Application Symposium, February 2000)
INTRODUCTION
Since 1994, the National Research Council of Canada (NRC) and the Department of National Defence (DND) have established a research partnership under the Halon Alternatives Performance Evaluation (HAPE) program to respond to the production ban on ozone-depleting halons by the Montreal Protocol. Previous HAPE projects focused on Halon 1301 alternatives for total flooding fire suppression applications. It was recognized that there is a need for information on suitable alternative streaming agents to replace Halon 1211. A new project was initiated to review the information on alternative streaming agents. This involves the review of new technologies that are under development as well as the review of currently available halocarbon streaming agents.
This paper provides summary of the project findings on alternative streaming agents for Halon 1211. Compared to systematic and extensive work carried out on total flooding agents worldwide, performance evaluation of streaming agents is lacking.
RÉSUMÉ
FUTURE DEVELOPMENT IN ADVANCED STREAMING AGENTS
Although halon replacements with zero or reduced ozone depletion potentials now become commercially available as a result of many years’ development [1-4], most of them are global warmers. Recent research effort has been directed toward developing advanced agents with a short atmospheric lifetime and low global warming potential. Four groups of chemical compounds have been identified in laboratory screening for further assessment as potential substitutes to Halon 1211, including halogenated organosilicon compounds, metallic
compounds, phosphorus compounds, and tropodegradable halocarbons [5-8].
Many organic silicon compounds (such as silanes and siloxanes) are expected to have short atmospheric lifetimes and, therefore, low global warming potentials, compared to similar carbon compounds (such as alkanes and dialkyl ethers). Silanes are a class of silicon organic compounds that contain silicon-silicon (Si-Si) bonds. Siloxanes are a class of silicon organic compounds that contain silicon-oxygen-silicon (Si-O-Si) bonds. Because of their environmental
* For presentation at the Fire Suppression and Detection Research
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characteristics, these two classes of silicon compounds have received attention for development of halon alternatives [5, 9-11].
Metallic compounds are very effective fire extinguishants. Some of them, such as alkali metal salts (dry chemicals), have been used in fire extinguishment for many years. Because metallic compounds offer high effectiveness for flame extinguishment, there has been a lot of interest in this group of compounds [2, 5, 12, 13]. Further studies, however, are needed to better understand the inhibition chemistry involving iron and other metals, to investigate the influence of delivery system and technique on extinguishment effectiveness of these solid agents, and to assess the toxicological impact of interested metal compounds to humans and to the environment.
Many phosphorus compounds have been used as fire retardant or fire resistant
materials [2, 11]. A number of this type of compounds has also showed effectiveness for flame extinguishment [11, 14]. Phosphorous compounds have a large variability in toxicity and a possibility of cholinesterase inhibition, which is a concern. Although phosphorus compounds are unlikely to have unacceptable environmental properties, atmospheric chemistry involving phosphorus has not been fully studied [10].
Global environmental impact of a chemical is usually associated with its atmospheric time. The potential of an agent for ozone depletion and global warming generally decreases with decreasing atmospheric time. Some halocarbons have very short atmospheric times of a few days or a few weeks, and can be rapidly removed from the troposphere by physical and chemical processes. They are called tropodegradable halocarbons [5, 8, 15-20].
The advanced streaming agents are still in the initial development stage. Phosphorus compounds and tropodegradable halocarbons appear to be more promising. Many scientific and technical issues need to be resolved through further research and development before their commercialization.
Some of these potential compounds are not even tested in cup burner or bench-scale streaming apparatus because of difficulty in synthesis of these compounds. A major challenge is the syntheses of interested compounds. Their manufacturability is also a major uncertainty. The toxicity of many of these compounds is yet to be determined, including cardiac toxicity, acute inhalation toxicity and chronic and developmental toxicity, etc. Some environmental characteristics and key physical/thermodynamic properties have to be determined.
CURRENTLY ACCEPTABLE AND COMMERCIALIZED AGENTS
Although advanced streaming agents offer promises, they need time to be developed. Current commercially available halon replacements with zero or reduced ODPs are the result of many years’ research and development [1-4].
The acceptability of an agent by the regulatory authority is based mostly on the potential human health and environmental risks posed by the agent [21]. Table 1 lists the currently acceptable and already commercialized Halon 1211 replacement agents. The halocarbon streaming agents are restricted to non-residential uses.
HFC-227ea (1,1,1,2,3,3,3-heptafluoropropane, C3HF7) is produced by the Great Lakes
Chemicals Corporation with the trade name of FM-200. HFC-227ea has a zero ODP, moderate ALT and GWP. It is more volatile than Halon 1211, with a boiling point of -16oC. The cardiac
sensitization occurs at 10.5% HFC-227ea. The acute toxicity of HFC-227ea is low, with 4-hour LC50 equal to 80% agent concentration.
HFC-236fa (1,1,1,3,3,3-hexafluoropropane, C3H2F6) is produced by DuPont with the
trade name of FE-36. Like HFC-227ea, HFC-236fa has a zero ODP. The ALT and GWP of HFC-236fa, however, are longer and higher than those of HFC-227ea, respectively. It is as volatile as Halon 1211, with a boiling point of -1.5oC. The cardiac sensitization occurs at 15.0% agent concentration. The acute toxicity of HFC-236fa is reasonably low, with 4-hour LC50 equal
to 13.5% agent concentration.
FC-5-1-14 (perfluorohexane, C6F14) is produced by the 3M Company with the trade
name of CEA-614. Since FC-5-1-14 is a very stable chemical compound, it is basically non-toxic [22]. The 4-hour LC50 is greater than 30%. The cardiac sensitization did not occur, even
at 40% agent concentration. No adverse effects were observed at 5% concentration for 2-week inhalation tests. No toxic signs occurred at 0.5, 1.5 and 5.0% agent concentration for 90-day inhalation tests. Being very stable, however, it has an extremely long ALT, which renders high GWP. It may only be used where no other agent is technically feasible due to performance or safety requirement [21].
FIC-13I1 (trifluoroiodomethane, CF3I) is produced by the Newhouse International with
the trade name of Triodide. CF3I can be easily photolyzed by sunlight (UV radiation) and rapidly
removed from troposphere in days (ALT < 2 days). Since CF3I is so short lived, its ODP and
GWP become negligible. The cardiac lowest observed adverse effect level (LOAEL) is 0.4% CF3I and the no observed adverse effect level (NOAEL) is 0.2% CF3I. Ninety-day subchronic
tests of CF3I using live animals indicated no cancer precursors. Subchronic thyroid effects were
observed. Based on the evaluation of acute, reproductive, cardiac and genetic toxicity and exposure studies, the occupational exposure limit for CF3I was recommended to be 0.2% (2000
ppm) for fire fighting exposure [23-26]. (The chronic exposure limit for CF3I was recommended
to be 150 ppm.)
HCFC-123 (2,2-dichloro-1,1,1-trifluoroethane, C2HCl2F3) is produced by DuPont with the
trade name of FE-232. It has an ODP of 0.014, the lowest among hydrochlorofluorocarbons (HCFCs). A relatively large amount of toxicity data is available [27]. In vitro mutagenicity tests (Ames tests) are negative. Acute toxicity tests using rats indicated 4-hour LC50 equal to 3.2 to
3.5% HFC-123. Cardiac sensitization occurred at 0.2% HFC-123 for dogs. Test rats showed signs of central nerve system (CNS) depression at 0.5%. Test guinea pigs showed signs of hepatic lesions at 2% agent concentration. Subchronic toxicity showed changes of serum cholesterol, triglyceride and glucose in rats.
HCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane, C2HClF4) is another HCFC produced by
DuPont with the trade name of FE-241. It has a small ODP of 0.03. HCFC-124 is more volatile and less toxic than HCFC-123.
Several HCFC blend streaming agents are commercially available. HCFC Blend B contains primarily HCFC-123, produced by the American Pacific Corporation with the trade name of Halotron I. HCFC Blends C, D and E are mixtures of HCFC-123 and/or HCFC-124 with additives, produced by the North American Fire Guardian with the trade names of NAF P-III, Blitz III and NAF P-IV, respectively. HCFC Blend C is a mixture of HCFC-123, HCFC-124, HFC-134a and proprietary additive. HCFC Blend D is a mixture of HCFC-123 and proprietary additive. HCFC Blend E is a mixture of an HCFC (primary constituent currently listed as acceptable for use in non-residential streaming applications), an HFC (secondary constituent
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listed acceptable as a flooding agent subject to application conditions) and an additive. HCFC Blend E has been proposed as an acceptable Halon 1211 substitute for use in non-residential applications; final acceptance is pending [21].
EVALUATION OF CURRENT HALOCARBON STREAMING AGENTS
There have been a few studies of currently acceptable and already commercialized streaming agents as Halon 1211 replacement for fire suppression applications. HFC-227ea, HFC-236fa, FC-5-1-14, CF3I, HFC-123, HCFC-124, HCFC Blend B and HCFC Blend C were
evaluated for streaming applications in small-scale tests to study the effect of agent quantity, nozzle type, flow rate and fire size on fire extinguishment time and to determine minimum flow rate versus fire size [28]. These bench-scale tests provided insight for design of larger field tests and for design or modification of portable extinguishers (such as minimum flow rate, appropriate nozzle selection, etc.).
HFC-227ea and HFC-236fa
Evaluation of HFC-227ea and HFC-236fa were conducted using handheld extinguishers for potential application on aircraft and in vehicle crew compartment [28-30]. For onboard aircraft fire scenarios, as long as the quantity of the agent was scaled based on the cup burner extinguishing concentration, fire extinguishment results were comparable to Halon 1211 [30]. A weight penalty and a volume penalty have to be paid [30]. Portable extinguishers (1.13-kg or 2.5-lb CO2 extinguishers) filled with HFC-227ea and HFC-236fa were tested at ambient, hot
(60oC) and cold (-48oC) temperatures to extinguish different test fires (0.46 m2 or 5 ft2, 1.1 m2 or 12 ft2, and 2.3 m2 or 25 ft2 pans with Jet A-1 fuel, equivalent to JP-8 fuel) [28, 29]. The fill densities, pressurization, flow rates, discharge patterns with various nozzles and fire fighting technique required to extinguish the test fires were determined [28, 29]. Nozzle design is important to achieve appropriate agent flow rate and pattern. A 70 to 75% fill was found to be optimum (974 to 1043 kg/m3 or 60.8 to 65.1 lb/ft3 for HFC-227ea; 960 to 1027 kg/m3 or
59.9 to 64.1 lb/ft3 for HFC-236fa). Higher fill densities leave less volume for the pressurization gas, resulting in quicker decrease of pressure and flow rate during discharge. This flow rate problem would be amplified at lower temperatures. At elevated temperatures, high fill densities can lead to increase in the internal pressure, causing a safety concern. Fire fighting technique is also an important factor. Proper technique includes attacking the front edge of the pan, spraying in side-to-side sweeping motion, and keeping the angle of attack at 70o. For the 0.46 m2 (5 ft2) pan fire, average agent quantities required to extinguish the fire were 0.73 kg (1.6 lb) for HFC-227ea and 0.91 kg (2 lb) for HFC-236fa, respectively.
Tests were also conducted in an 18-m3 enclosure using a 0.2 m2 (2.25 ft2) pan with Jet A-1 fuel to determine thermal decomposition products (TDPs) during suppression [28]. TDP quantity was dependent on fire extinguishment time and agent quantity used. HFC-227ea produced more HF and much more COF2 than HFC-236fa did.
FC-5-1-14
FC-5-1-14 was tested for onboard aircraft, airport or airbase fire fighting. A 9.07-kg (20-lb) Halon 1211 handheld extinguisher charged with FC-5-1-14 was used to fight spill/pool fires (up to 6.7 m2 or 72 ft2), engine fires and small 3-dimensional running fuel fires [31-33]. A 68-kg (150-lb) Halon 1211 flightline fire extinguisher (30A 240B:C) was charged with FC-5-1-14 (with a change of elastomer material used in stem seal and collar O-ring and a change of nozzle tip) to extinguish unique flightline test fires [34, 35]. JP-4 spill/pool fires (23.2, 37.2, 74.3 m2 (250, 400,
800 ft2)), 3-D flowing JP-4 engine fuel fires, inclined-plane running JP-4 fuel fires and wheel well/tire fires involving hydraulic fluid were the flightline test fires. The agent was evaluated in terms of the extinguishment time and the quantity of agent required to extinguish the test fires for both extinguishers. FC-5-1-14 had a longer throw range and greater cooling effect than Halon 1211. The mass of FC-5-1-14 required to extinguish the fires was generally twice that of Halon 1211. The most severe engine nacelle fires with the 3-D flowing JP-4 fuel could not be extinguished by perfluorohexane since the 68-kg (150-lb) extinguisher was not optimized for perfluorohexane. For the onboard aircraft fire scenarios, a weight penalty and a volume penalty have to be paid in order to get extinguishment results comparable to Halon 1211 [30].
CF3I
CF3I proved to be as effective as Halon 1211 in tests simulating a handheld extinguisher
for onboard aircraft fire scenarios [30]. CF3I had very small weight penalty but no volume
penalty [30].
An exposure study was conducted in different size rooms using handheld extinguishers during 8 separate cold-shots (without fire), discharging 1.1 kg CF3I into a 26-m3 room; 1.1 and
2.3 kg CF3I into a 108-m3 room; 2.3, 4.1 and 5.9 kg CF3I into a 145-m3 room. Agent
concentration depended on agent quantity, room size and ventilation as well as position, height and time. Being heavier than air, CF3I quickly settled to the ground. The air samples in the
potential firefighter breathing zone contained CF3I below the cardiac LOAEL value during the
initial 30 s [23, 24]. HCFC Blend B
HCFC Blend B has been tested using a 68-kg (150-lb) Halon 1211 flightline fire extinguisher (30A 240B:C) [34, 35]. The extinguisher was first modified by changing the elastomer material used in stem seal and collar O-ring and changing the nozzle tip. The agent was evaluated in terms of extinguishment time and quantity of agent required to extinguish unique flightline test fires. Test fires included JP-4 spill/pool fires (23.2, 37.2, 74.3 m2 (250, 400, 800 ft2)), 3-D flowing JP-4 engine fuel fires, inclined-plane running JP-4 fuel fires and wheel well/tire fires involving hydraulic fluid. The optimum charge was 59 kg (130 lb) HCFC Blend B at 1756 kPa (240 psig), which gave a 37 s discharge. The extinguisher was later optimized to enhance the performance of HCFC Blend B by adding a booster cylinder to maintain a constant extinguisher operating pressure during discharge. Agent quantity (by weight) required for HCFC Blend B was 1.5 times that for Halon 1211 to achieve the same performance. HCFC Blend B was slightly more effective than perfluorohexane in the tests (twice as effective as
perfluorohexane in extinguishing the inclined-plane running fuel fires; 33% more effective in extinguishing the wheel-well hydraulic fluid fires; equal performance in the spill/pool fires and engine nacelle running fuel fires).
SUMMARY
Advanced streaming agents offer promise, however, they are still in the initial
development stage. Phosphorus compounds and tropodegradable halocarbons appear to be more promising. A major challenge is the syntheses of interested compounds, which is often a difficult task. Some compounds of interest are not even tested in cup burner or bench-scale apparatus because of this difficulty. Many scientific and technical issues need to be resolved through further research and development before advanced streaming agents reach the marketplace.
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Current commercially available halon replacements with zero or reduced ODPs are the result of many years’ research and development. Fully commercialized halocarbon fire
extinguishers now include FE-36 (Cleanguard) extinguishers, Halotron I extinguishers, FM-200 extinguishers and CF3I extinguishers. FE-36 and Halotron I extinguishers have obtained the
Underwriters Laboratories' certification.
Previous fire tests of halocarbon agents were conducted to determine the agent quantity, fill densities, pressurization, flow rates, discharge patterns and fire fighting technique required to extinguish the test fires. The primary experimental result was whether or not the fire was
extinguished. Limited tests were conducted to compare relative TDP production from one agent to another but not necessarily related to the actual exposures one would expect in suppressing a typical fire. There is little study on the potential level of human exposure to suppression agents and TDPs produced during fire suppression.
The evaluation for streaming agents is more complex than for total flooding agents because agent performance in a streaming application depends not only on the inherent flame suppressing ability but also on a number of other variables. These include fire hazard variables (fuel type, ambient temperature and wind conditions), extinguisher hardware variables (cylinder fill ratio and pressure, valve, nozzle size and flow rate) and human variables (fire fighting technique and application pattern). Exposure risk of the agents and toxic by-products to firefighters and other personnel also need careful examination.
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