Korean J. Chem. Eng.

, 30(12), 2254-2258 (2013) pISSN: 0256-1115

DOI: 10.1007/s11814-013-0203-8 eISSN: 1975-7220
INVITED REVIEW PAPER INVITED REVIEW PAPER

Extinction effectiveness of pyrogenic condensed-aerosols extinguishing system

Kyungok Kwon† and Younggeun Kim

Department of Fire Safety Engineering, College of Engineering, Jeonju University, 45, Baengma-gil, Jeonju 560-759, Korea
(Received 3 May 2013 • accepted 7 October 2013)

Abstract−We studied the extinction effectiveness of pyrogenic condensed-aerosols in gaseous fire extinguishing sys-
tems through the ISO (International Organization for Standard) 15779. The thermal characteristics of solid aerosols
as an extinguishing agents were evaluated by using TG and DTA. The modified closed pressure vessel test (MCPVT)
and the conductivity of the solid aerosol extinguishant were also measured to ensure the safety of extinguishant. The
TG and DTA result showed that the resin added to the main component of Potassium Nitrate (PN) has the effectiveness
to mitigating the exothermic reaction of the pyrogenic condensed-aerosol extinguishant. The results of maximum height
test revealed the extinguishing capability of a pyrogenic condensed-aerosol extinguishing agent as a gaseous extinguish-
ing system.
Key words: Pyrogenic Condensed-aerosol Extinguishant, Halon 1301, Gaseous Extinguishing System, GWP

INTRODUCTION installation of the solid aerosol extinguishing systems within resi-

dential areas has yet to be considered. Recently, there has been a
The gaseous pyrogenic condensed-aerosol extinguishing system movement worldwide that HCFC and CFC gaseous fire extinguish-
has been under development as a new type of alternative Halon 1301 ing agents should be restricted as they are one of the fluorinated
(bromotrifluoromethane, CBrF3) gaseous fire extinguishing agent gaseous extinguishing agents that involve a high GWP. For the halon
as it is connected to depletion of the ozone layer [1-3]. Also, in ac- alternative extinguishing agents, a system containing a lower GWP
cordance with the development of construction technology, many is becoming an essential factor for selection [20-23].
high-rise buildings above fortieth floors are causing major difficul- In this study, the extinction effectiveness of pyrogenic condensed-
ties for fire departments in reaching these heights with ladders. The aerosols possessing the main component of potassium nitrate (PN)
most important advantage of gaseous pyrogenic condensed-aerosol in a gaseous fire extinguishing system was investigated according
extinguishing systems is their easy installation, which includes no to the maximum height test method of the ISO 15779 [26-28]. Also,
piping and only occupying a small space. For the alternative gaseous experiments on the thermal behaviors of the component of the solid
fire extinguishing systems of halon, there are dry chemicals, water aerosol extinguishing agents were conducted regarding the safety
sprays, carbon dioxide, Inergen, hydrochloroflurocarbons (HCFCs) use of the extinguishing agents.
and chloroflurocarbons (CFCs) within the fire extinguishing sys-
tems [4-9]. Among them, the fluorinated gaseous fire extinguish- EXPERIMENTAL
ing systems contain a problem in that they produce a great deal of
hydrogen fluoride (HF), which possess a high level of global warm- 1. Thermal Analysis
ing potential (GWP). None of the gas systems, including the dry The curves of DTA (Differential thermal analysis) and TG (Ther-
chemical and water spray systems, show weaknesses in their chem- mal gravity) were obtained by using MAC Science/9801FA2. The
ical residue after the fire suppression. An Inergen fire extinguishing DSC (Differential scanning calorimetry, DSC 1 Mettleer) was carried
system is safer from the viewpoint of no toxins being produced from out by placing 2 mg samples of PN into an aluminum cell with a
the inert gas, yet it requires a large quantity of extinguishing agents carrier gas of N2 at a flow rate of 50ml/mi at various heating rates
and a large space for its storage system, resulting in a higher expense from 10 to 50 K/min. An alumina was used as a reference sample.
[10-16]. The pyrogenic condensed-aerosol extinguishing system, 2. MCPVT (Modified Closed Pressure Vessel Test)
in which the GWP factor and ozone depletion are zero, respectively, The MCPVT was used to measure the pressure generated from
stands as the most suitable candidate for the next halon alternative the solid aerosol extinguishing system. As the MCPVT is a small
gaseous fire extinguishing system [17-19]. However, this system has pressure vessel test modified by the ISO 10156, the temperature
not been widely used, while the tests on how solid aerosol extin- and pressure of the inside chamber can also be determined [24].
guishing agents affect humans, the tests on its design concentration, 3. Extinguishing Performance Test (Maximum Height Test)
its reliability, and its toxicity have yet to be concluded; therefore, The test of the extinguishing efficiency of a solid aerosol extin-
guishing agent was conducted in a 100 m3 fire model in accordance
†
To whom correspondence should be addressed. with the ISO 15779 and the NFPA 2010 code [26-28].
E-mail: [email protected], [email protected] 4. Material
Copyright by The Korean Institute of Chemical Engineers. The PN used in the study was manufactured in Chile with a purity
2254
 Extinction effectiveness of pyrogenic condensed-aerosols extinguishing system 2255

level of at least 99%. Resin was used as the laboratory reagent. Step 2: Formation of gaseous combustion products from a quick
combustion reaction
RESULTS AND DISCUSSION Step 3: Movement through a filter system which minimizes or
inhibits the emission of dust
The pyrogenic condensed-solid aerosol extinguishing system gen- Step 4: Movement through a cooling system, which cools down
erated the combustion of propellants in which K containing com- the high temperature of the combustible gas
pounds were able to terminate the chain reaction with H or OH rad- Step 5: Emission of a gaseous aerosol extinguishant on the out-
icals. Potassium nitrate (PN, KNO3) is one of the most effective side.
and useful materials among the pyrogenic condensed-solid aerosol The pyrogenic condensed-aerosol extinguishing agent needs to
fire extinguishing agents. The main mechanism for pyrogenic con- be adjusted to the temperature of the pyrogenic aerosol being dis-
densed-solid aerosol extinguishing agents focuses on the rapid sup- charged from the generator because PN decomposes and burns at a
pression of a fire by efficiently generating the extinguishing agents high temperature. The resin is required to be added to the pyro-
(solid aerosols) which include nitrogen, carbon dioxide, potassium genic aerosol extinguishant for reducing the temperature of pyro-
oxide, etc. [17-19]. genic aerosols which are exothermically produced and for assisting
In this pyrogenic condensed-aerosol extinguishing system, the to balance the thermal reaction of PN.
fire extinguishing agent is burned and discharged along the follow- Fig. 1 displays the TG and DTA curves of pure PN and resin,
ing steps: respectively. PN produces an exothermic reaction during its ther-
Step 1: Ignition of the solid extinguishing agent mal decomposition (Fig. 1(b)). It is necessary to reduce the heat
capacity at the same range regarding the exo-thermal heat of PN.
The curves of Fig. 1(b) reveal that within the same areas in which

Fig. 1. TG(a)/DTA(b) curves of PN and resin at a heating rate of Fig. 2. TG(a)/DTA(b) curves of a solid aerosol extinguishant at a
5 oC/min. heating rate of 5 oC/min.
Korean J. Chem. Eng.(Vol. 30, No. 12)
2256 K. Kwon and Y. Kim

Table 1. The Tpeak of pure PN (upper) and with resin (lower) for Table 2. The activation energy of pure PN and PN with resin in
DSC curves under various heating rates an extinguishing agent
Heat rate Φ Activation
Tpeak (oC) Tm (K) 1/Tm103 Materials Curve
(K/mim) energy (J/mol)
10 126.59 314.52 399.74 672.89 2.501 1.486 Pure PN 138.05 Y= − 16.605x 42.837 (R2 =0.96)
15 125.50 316.75 398.65 671.8 2.508 1.489 PN with resin 172.07 Y= − 20.696x 52.425 (R2 =0.98)
20 126.36 316.10 399.51 672.66 2.503 1.487
25 127.50 318.75 400.65 673.8 2.495 1.484
logarithm of the Arrhenius equation is as follows:
Heat rate Φ o 3
Tpeak ( C) Tm (K) 1/Tm10 ln(k)=− Ea/R×1/T+Ln(A) (2)
(K/mim)
10 129.64 307.88 402.79 581.03 2.484 1.721 Therefore, when a reaction has a rate constant, a plot of ln(k) versus
15 130.49 305.85 403.64 579.00 2.478 1.727 T−1 produces a straight line, whose gradient and intercept can be
20 132.01 309.03 405.16 582.18 2.469 1.718 used to determine the Ea and A [25,29].
25 132.52 - 405.67 - 2.466 - The activation energy of PN increases from 138.05 J/mol to 172.07
J/mol in the sample containing resin. The resin in the solid aerosol
extinguishing system produces an effect to increase the activation
PN is an exothermic reaction and the resin is an endothermic reac- energy of potassium nitrate, resulting in slowing the progress of the
tion, respectively, the temperatures are at around 400 oC to 600 oC. reaction of potassium nitrate. As the heating rate increases in the
It is expected that the additional resin mixed with PN deters the exo- pyrogenic condensed-aerosol extinguishment system, the combus-
thermic reaction of PN during decomposition. tion time of the solid aerosol by-products filling the generator is
Fig. 2 shows the curves of TG and DTA for the composition of reduced, speeding up the discharge rate. If the solid aerosol extin-
a pyrogenic aerosol extinguishant with 80% PN and 20%. The peak guishing agent burns too quickly, the pressure of the generator in-
at around 250 oC in Fig. 2(a) is of resin decomposition while the creases rapidly. If the pressure increases according to the reaction
PN decomposes at 450 oC. From the PN exothermic reaction, the dynamic theory, the reaction rate increases as well. In terms of the
temperature of the pyrogenic solid aerosols being discharged from reaction cycle, as the burning rate increases, the pressure increases.
the generating system is higher than 450 oC. A cooling element is As the heating rate increases, the pressure increases. For safety pur-
needed for the high temperature of the discharged pyrogenic aero- poses, the gas vent in the generator, which is used in the pyrogenic
sols as well as for the generator system regarding the resistance of condensed-aerosol extinguishment system, needs to be strongly pro-
the high pressure. From 300 oC to 500 oC, the resin reacts endot- moted. Installing the pyrogenic condensed-aerosol extinguishing sys-
hermically, leading to the lowering of the decomposition tempera- tem in buildings, etc., fire safety should be guaranteed at lower tem-
ture of PN in Fig. 2(b). By adding resin to PN, the resin inhibits the peratures below 300 oC. In Table 3, the MCPVT results are described
exothermically decomposed reaction of a solid aerosol extinguishant, of a pyrogenic condensed-aerosol extinguishant a change in pres-
resulting in a reduced temperature for the aerosols being discharged sure, resulting in increased temperatures.
from the generator. The rise in pressure of the gas produced by solid aerosols was
By the Kissinger method, the activation energy of PN was deter- measured using the MCPVT. Through mini-pressure vessels, the
mined to investigate the effects of resin on PN. Table 1 contains MCPVT can accurately measure the temperature and pressure in
the temperature of Tpeak of pure PN regarding a DSC analysis with the inner sections of the vessel. The MCPVT, the transformed ver-
various heating rates of 10, 15, 20, and 25 oC/min. The Tpeak of PN sion of the large scale DTA system, can measure the temperature
at 314.52 oC shifts to a higher temperature as the heating rate in- and pressure of the ISO. The sample weighed 1.1 g and applied heat
creases. at an increased increment rate of 10 K/min. The pressure rise of
The Arrhenius Equation explains the dependence of the rate con- the aerosol emitted from the aerosol extinguishing system should
stant k of chemical reactions on temperature T and the activation be guaranteed safe at temperatures below 300 oC. Table 3 shows
energy Ea in the following Eq. (1): that there were no significant pressure increases in the area from
room temperature to 300 oC. These results confirmed that the pyro-
k=A×e−(Ea/RT) (1)
genic condensed-aerosol extinguishing system in regards to the dis-
In this equation A is the pre-exponential factor and K is the ab- charging extinguishant would be safe in a normal environmental
solute temperature in Kelvin, while R is the universal gas constant condition.
(8.314 J/mol-K), and Ea is the activation energy. The units of the The extinction effectiveness of the pyrogenic condensed-aerosol
pre-exponential factor A are identical to those of the rate constant extinguishing system was conducted in accordance with the maxi-
and will vary depending on the order of the reaction. When the ac- mum height test method of ISO 15779 (Fig. 3(a)). The test can
tivation energy decreases, the rate of the reaction increases. The natural was placed on the floor and attached to the ceiling, each placed within

Table 3. The pressure variation according to an increasing temperature

Temperature (oC) 30 50 100 150 200 250 300
Pressure (MPa) 0.01208 0.01812 0.03019 0.04227 0.06039 0.10266 0.19324

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 Extinction effectiveness of pyrogenic condensed-aerosols extinguishing system 2257

Fig. 4. Infrared (a), (c) and general (b), (d) photos for the maxi-
mum protected height limitation test in 100 m3 units.

Fig. 3. Plan view (a) and photos (b), (c) of the instrumentation place-
ment for the maximum height test of ISO 15779.

Fig. 5. The temperature change of the fire on the can during the
50 mm away from the corner of the unit, according to the enclo- maximum protected height limitation test in 100 m3 units.
sure arrangement model in Fig. 3(c). Each test can was placed 300
mm behind the center of the floor, and 300 mm away from the upper was viewed more clearly with the use of an infrared camera (Fig.
and lower sections. Fig. 3(b) illustrates the nozzle installation which 4(a) and (c)). Fig. 5 illustrates the temperature change of the fire on
is on the center of the wall in the test room. The test begins by igniting the can during the maximum protected height limitation test. The
the cans; then, the nozzle discharges the solid aerosol extinguishant temperature rise at around 700 oC but the temperature falls sharply
toward the baffle in the direction placed in the middle of the enclosure after the discharge. The graph indicates that the fire in the can was
(NFPA 2010, ISO 15779). successfully suppressed.
Fig. 4(a), (c) displays the infrared pictures of fire on the can. When K compounds discharged from the solid aerosol extinguishing
the solid aerosol gaseous extinguishing agents are discharged from agent, combined with O, H, and OH radicals, extinguished the fire
the extinguishing system, the color of the atmosphere in the test under a chemical chain reaction without consuming any air. The other
room turns from blue to green. The pyrolyzed aerosol heats the test discharged products, including the inert gases of carbon dioxide and
room and flows internal within the atmosphere because of the dis- nitrogen, extinguished the fire as a result of physical extinguishing
charged pressure and the difference in the specific gravity. After reaction. Through the mechanisms of physical fire suppression of
releasing the solid aerosols of the extinguishant from the generator, an inert gas and the chemical fire suppression of radicals of potas-
the protected area is rapidly filled, which was recorded by using a sium oxide, the solid aerosol extinguishing system produced a very
general camera (Fig. 4(b) and (d)); however, the change of the flame effective gaseous fire suppression system compared to Halon 1301
Korean J. Chem. Eng.(Vol. 30, No. 12)
2258 K. Kwon and Y. Kim

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