Received: 12 February 2018 Revised: 9 July 2018 Accepted: 2 August 2018

DOI: 10.1002/fam.2671

RESEARCH ARTICLE

A novel hot aerosol extinguishing agent with high efficiency for

Class B fires
Ye Yan1,2 | Zhiming Du1 | Zhiyue Han1

1
State Key Laboratory of Explosion Science
and Technology, Beijing Institute of
Technology, Beijing, China
2
China Shipbuilding Information Center,
Beijing, China
Correspondence
Zhiyue Han, State Key Laboratory of
Explosion Science and Technology, Beijing
Institute of Technology, Beijing, China.
Email: hanzhiyue@bit.edu.cn
Funding information
Fundamental Research Funds for the Central
Universities, Grant/Award Number:
G20012017001
Summary
A novel hot aerosol extinguishing agent (HAEA), which is the combination of pyro-
technics and flame retardant technology, was found to have great efficiency in
extinguishing Class B fires. A mixture of P and P3N5, referred to as P90x, was chosen
as the reductant, and phase stabilized ammonium nitrate was chosen as the oxidant.
This paper describes a study of the effectiveness of this agent in extinguishing
n‐heptane fires (ie, Class B fires). We determined that the best efficiency was
15 g/m3 for extinguishing n‐heptane fires, four times more efficient than a traditional
agent. The efficiency increases as the mass fraction of P90x rises. We also identified
the key difference between the novel extinguishing agent and the traditional agent.
The former consists of an inorganic phosphorus compound, while the latter is mainly
comprised of KOH. Consequently, their extinguishing mechanisms are different. The
phosphorus oxide of the novel HAEAs is the leading component to extinguish fire,
which is more effective than alkali salts.

KEY W ORDS

extinguishing efficiency, hot aerosol extinguishing agent, phosphorus‐containing compound, PSAN

1 | I N T RO D U CT I O N and polytetrafluoroethylene, dibutyl‐phthalate, or dioctyl sebacate

Hot aerosol extinguishing technology based on pyrotechnics has been
invented for more than 50 years.1 Compared with the Halon, which
2
would lead to ozone depletion, hot aerosol extinguishing agents
(HAEAs) do not contribute to global warming and ozone depletion.
For this reason, it was suggested in 1992 as one of the substitutes
for Halon.3
Hot aerosol extinguishing agent is made up of superfine aerosol
particles produced in the combustion of an aerosol forming agent
(hereafter referred to as AFA), which is a solid material containing
oxidizers, reducers, binders, and additives. This new agent does not
require storage in a pressurized vessel, can be installed easily without
piping, and occupies a small space, which are major advantages of
HAEAs over other agents.
For decades, a large number of AFA formulations have been
reported in the literature and patented. In Canada, KNO3 has been
used as an oxidant; C has been used as a reductant.4 In the United
States, nitrates of sodium or potassium have been used as oxidants,
have been used as reductants.5 In China, potassium nitrate and stron-
tium nitrate have been used as oxidants, sucrose and magnesium or
aluminum powder have been used as reductants.6 To sum it up, most
oxidants are Group IA element salts, and reductants are organic or
inorganic combustibles. Therefore, these traditional HAEAs rely on
the same extinguish mechanism, in which alkali salts recombine with
fire supporting radicals such as OH· and H·.7 Although there are some
variations in the properties of these traditional HAEAs, the
extinguishing efficiency has not been improved significantly for
decades since the extinguishing mechanism of these HAEAs has not
changed since they were first developed.
Fortunately, it has been reported that phosphorus and halogen,
applied to flame retardant technology generally, could recombine with
the fire supporting radicals too, as an alternative to alkali salts.8,9 As
halogens can harm the ozone layer, phosphorus‐containing com-
pounds (PPCs) were the main object of the present study to improve
the extinguishing efficiency of HAEAs. A mixture of P and P3N5,
referred to as P90x, was chosen as the reductant. It is combustible,

Fire and Materials. 2018;1–8. wileyonlinelibrary.com/journal/fam © 2018 John Wiley & Sons, Ltd. 1
2 YAN ET AL.

has low humidity, and is stable at normal temperature. Phase‐

stabilized ammonium nitrate (PSAN) was chosen as the oxidant. The
results show that novel HAEAs containing phosphorus exhibit great
extinguishing efficiency for Class B fires. The most effective HAEA
identified in the present study required a minimum concentration of
15 g/m3 to extinguish an n‐heptane fire, which is a factor of four
lower than for traditional HAEAs.

2 | EXPERIMENTAL METHODS

2.1 | Experiment chamber FIGURE 2 Test fire [Colour figure can be viewed at wileyonlinelibrary.
3
com]
A 1 m chamber with dimensions of 700 mm (W) × 1200 mm
(L) × 1200 mm (H) was used to test the extinguishing efficiency of lowest thermocouple was 5 cm, as was the distance between each of
novel HAEAs. The initial temperature was (20 ± 5)°C in the test cham- the consecutive thermocouples.
ber. In the side wall, there was a pressure relief hole, 30 mm diameter,
at 0.5 × L, 0.9 × H. The extinguishing agent generator, 71 mm 2.2 | Test procedure
(D) × 110 mm (H), was located 0.5 m away from the test fire and The test procedure was as follows:
ignited by electric heater as shown in Figure 1.
Figure 2 shows the square burn pan, 32 cm in length and width • Ignite the fuel and let it burn for 30 seconds with the box door
and 6 cm in height. The pan contains a layer of water and is placed open;
20 cm above the bottom of the chamber. A total of 100 mL of • Close the door and ignite the AFA to generate the HAEA;
n‐heptane was used as the fuel, which was consumed in about
• Open the door to find out whether the fire has been extinguished
150 seconds. There were four type K thermocouples, 1 mm diameter,
after 10 seconds;
fixed vertically above the pan. The distance between the pan and the
• Increase 5 g of the AFA for the next test if extinguishment has not
been achieved;
• Repeat experiments until three successful extinguishments have
been achieved.

All experiments on a specific AFA were completed within 1 day to

avoid the influence of changing temperature, humidity, and air
pressure.

2.3 | Simulation
The combustion of the AFAs were simulated by HSC Chemistry, a
thermochemical software package that can be used to calculate
equilibria for various chemical reactions based on Gibbs free energy.10
The program was based on the feature that all 14 calculation options
automatically utilized the same extensive thermochemical database
that contained enthalpy (H), entropy (S), and heat capacity (C) data
for more than 17 000 chemical compounds. HSC Chemistry offered
powerful calculation methods for studying the effects of different
variables on the chemical system at equilibrium. For example, if the
user gives the raw materials, amounts, and other conditions of almost
any chemical process, the program would give the amounts of the
product as a result.

3 | RESULTS AND DISCUSSION

3.1 | Formula design

FIGURE 1 Test chamber [Colour figure can be viewed at Aerosol forming agents include a combination of oxidants, reducers,
wileyonlinelibrary.com] and additives.11 In pyrotechnics, ammonium nitrate is a common
YAN ET AL. 3

oxidant, which can produce large amounts of nitrogen in aid of extin- TABLE 2 Novel aerosol forming agent formulations tested
guishment. Phase‐stabilized ammonium nitrate has been widely Formula PSAN: P90x (by mass) k
applied in the formulation of propellants because it is relatively safe
1# 70:10 2.33
and has low hygroscopicity.12,13 Phase‐stabilized ammonium nitrate
2# 60:20 1
was therefore chosen as the oxidant in the present study.
3# 50:30 0.56
The reductant was P90x. It is common and effective in flame
4# 40:40 0.33
retardancy. The production of PCCs via combustion can isolate
5# 30:50 0.20
oxygen by covering the surface of the burning substance.14
Additives are also important to stabilize the combustion process Abbreviation: PSAN, phase‐stabilized ammonium nitrate.

and extend the storage life. As the compounds of PSAN and P90x
chamber and the test procedure15 were consistent with the ones
have high reaction rates and pose an explosion hazard, 4MgCO3·Mg
required in GA499.1‐2010.
(OH)2·5H2O was selected as the burning rate inhibitor with a mass
Oxygen concentration was measured inside the test enclosure
fraction of 15%. A phenolic resin was selected as a binder to shape
during each testing. Figure 3 shows how the oxygen concentration
the AFA into a firm and hard solid. The mass fraction of binder pheno-
changed in the process of testing one of the successful tests with
lic resin is 5%. Consequently, PSAN and P90x combined account for
formulation 1#. At 30 seconds, the start of extinguishment, the
80% of the mass of each AFA formulation. The compositions of the
oxygen concentration was 20.8 vol%. The minimal amount of oxygen
AFAs are given in Table 1.
within the enclosure was 19.9 vol% during the test. The oxygen
The proportion of PSAN to P90x in the formulation can be used
concentration met the requirements referenced in GA499.1‐2010,
to calculate the oxygen balance coefficient, k.
NFPA 2010, and ISO 15779. At the time of actuation of the system,
the amount of oxygen within the enclosure shall not be more than
A=a
k¼ ; (1) 0.5 vol% lower than the normal atmospheric oxygen concentration.
B=b
During the test, the oxygen concentration shall not change more than
where A is the mass ratio of oxidant in formulation (%), B is the mass 1.5 vol% due to fire products. Oxygen concentration during other
fraction of reductant in formula (%), a is the mass of oxidant releasing tests in this paper also met the requirements.
1‐g O2 (g), and b is the mass of reductant consuming 1‐g O2 (g). The experimental process was captured by a digital camera.
The formula is oxygen deficient when k < 1, the formula is in oxy- Figure 4 shows a series of pictures taken during one of the successful
gen neutral when k = 1, and the oxidant has excess oxygen,11 when tests with formulation 1#.
k > 1. Thus, when k = 1, the mass ratio of PSAN and P90x is 60:20.
From experiments, we learned that the AFA does not react
completely when the PSAN: P90x ratio is above 75:5, or below
25:55. Consequently, for the single formulation with k > 1, a ratio
was chosen of PSAN: P90x = 70:10. Six AFA formulations were
tested in the present study. The first five formulation, referred to as
#1 to #5, contained P90x and PSAN in different mass ratios. The sixth
formulation, referred to as #6, was a typical traditional AFA consisting
of KNO3 (75% by mass), C2H4N4 (22% by mass), 4MgCO3·Mg
(OH)2·5H2O (3% by mass), and phenolic resin (5% by mass)4 as the
control group. Details for the six AFAs are provided in Table 2.
The AFAs were prepared by thoroughly mixing all components with
the particle size below 60 meshes.

3.2 | The results of fire extinguishing experiment

This bench‐scale testing described above was based on the required FIGURE 3 Oxygen concentration of extinguishing process with
extinguishing tests referenced in GA499.1‐2010. The experiment formulation 1#

TABLE 1 The fundamental state of ingredients

Molecular The Mass of Releasing
Ingredient Function Weight 1‐g O2 (g) Grade Source

PSAN Oxidizer 80 2 Analytical reagent Beijing Chemical Works

P90x Reductant 71 −0.78 Analytical reagent Guangdong Wengjiang Chemical
Regent Co, Ltd
C7H6O2 Binder 122 −0.42 Analytical reagent Sinopharm Chemical Regent Co, Ltd
4MgCO3·Mg (OH)2·5H2O Burning rate inhibitor 486 0 Analytical reagent Beijing Chemical Works

Abbreviation: PSAN, phase‐stabilized ammonium nitrate.

4 YAN ET AL.

(A) (B) (C)

(D) (E) (F)

FIGURE 4 Fire extinguishing experiment process [Colour figure can be viewed at wileyonlinelibrary.com]

Pictures (C) and (D) show the steady flame was initially enhanced
with the application of the extinguishing agent. The HAEA, generated
via combustion, when ejected into the chamber, enhanced the com-
bustion process by stimulating the flow of the air, which temporarily
facilitated the reaction of oxygen and fuel.
The minimum effective extinguishing mass (MEEM) is an index
that provides a quantitative measure of the extinguishing effect of
HAEAs as shown in Table 3.
All formulations #1 to #6 were capable of extinguishing the
n‐heptane fire. The MEEM for formulations #1 to #5 decreases with
increasing P90x content. The MEEM of formulation #1 had the
highest value (190 g/m3), while formulation #5 had the lowest
(15 g/m3). The control group formulation #6 could extinguish the
n‐heptane fire at 80 g/m3. The formulas from the reference have
been tested through the methodology of this article. And the testing
results were listed in Table 3 too. The formula of S1 is as follows:
K2CO3 (50% by mass), epoxy resin power (10% by mass), KNO3
(15% by mass), and NH4HCO3 (25% by mass). The formula of S2 is
as follows: KNO3 (75% by mass), epoxy resin power (23% by mass),
and Mg (2% by mass). The formula of S3 is as follows: KNO3 (77%
by mass), epoxy resin power (18% by mass), K2CO3 (4% by mass),
and Mg (1% by mass).16
The diffusion flame temperature of 100 mL n‐heptane is shown in
Figure 5, 100 mL of n‐heptane burnt for more than 150 seconds. The
HAEAs reduced the burning duration to about 100 seconds as shown

TABLE 3 The minimum effective extinguishing mass

Formula Mass of the AFA, g Releasing Time, s

1# 190 42
2# 100 38
3# 50 36
4# 30 32
5# 15 30
6# 80 44
S1 90 43
S2 85 21
S3 60 45
FIGURE 5 Temperature of combustion process with 100 mL of n‐
Abbreviation: AFA, aerosol forming agent. heptane [Colour figure can be viewed at wileyonlinelibrary.com]
YAN ET AL. 5

FIGURE 6 Temperature of extinguishing process [Colour figure can be viewed at wileyonlinelibrary.com]

FIGURE 7 Comparison of the time between the temperature variation and experimental procedure [Colour figure can be viewed at
wileyonlinelibrary.com]
6 YAN ET AL.

in Figure 6. Consequently, 100 mL of n‐heptane was sufficient to

evaluate the AFAs.
It is apparent that there are three distinct phases in the tempera-
ture graphs in Figure 6. The first phase is the ignition period, from 0 to
about 15 seconds, during which the temperature increased. The
second phase was approximately from 15 to 60 seconds, when the
n‐heptane was burning freely and HAEAs were discharged. During
the second phase, the temperature reached its peak point but
continued to fluctuating around it. Then in the last phase, at about

FIGURE 8 Continued.

TABLE 4 The main products of 6 formulas at 1000°C

CO2, N2, H2O, Mg3(PO4)2, P4O10, KOH,
Formula mol mol mol mol mol mol
1# 0.144 0.127 0.144 0.020 0.041 …
2# 0.144 0.140 0.122 0.020 0.048 …
3# 0.144 0.100 0.115 0.020 0.057 …
4# 0.144 0.080 0.113 0.020 0.063 …
5# 0.144 0.060 0.110 0.020 0.084 …
FIGURE 8 The simulation products [Colour figure can be viewed at
6# 0.225 0.179 0.0939 … … 0.297
wileyonlinelibrary.com]
YAN ET AL. 7

FIGURE 9 The main products of

combustion for the six formulations at 1000°C
[Colour figure can be viewed at
wileyonlinelibrary.com]

100 seconds, the temperature decreased sharply and returned to For formulations #1 to #5, the extinguishing efficiency improved
ambient temperature. with increasing generation of phosphorus oxide. The results of the
Figure 7 shows the temperature evolution during the experi- experiments suggest that the inorganic phosphorus play a role in
ments. After ignition, the fuel was left to burn freely for 30 seconds, the gas phase by the radical trap mechanism proposed for halogen
during which the temperature continued to increase for about compounds.19
15 seconds before reaching the peak value, and then continued to H3 PO4 →HPO2 þ HPO þ PO
fluctuate around the peak. After 30 seconds, the door was closed H þ PO→HPO
and the AFA was ignited to generate the HAEA. The temperature H þ HPO→H2 þ PO
did not drop but stayed around the peak. The release time of the OH þ PO→HPO þ H2
HAEA was about 30 to 45 seconds, after which the AFA was OH þ H2 þ PO→HPO þ H2 O

completely consumed and the concentration of the HAEA in the test

In summary, the phosphorus oxide of the novel HAEAs is the
chamber reached a maximum. If the concentration of the HAEA was
leading component to extinguish the fire and is more efficient than
sufficient, the fire was extinguished and the temperature started to
alkali salts.
decrease. The release time is an important factor, which could affect
the extinguishing process.
4 | CO NC LUSIO NS

3.3 | Component analysis of the new type HAEAs A novel HAEA, which is the combination of pyrotechnics and flame
retardant technology, was found to be very efficient in extinguishing
The components of HAEAs were simulated via HSC Chemistry.
Class B fires. This study described in this paper was designed to eval-
Figure 8 shows that the components change with temperature and
uate the efficiency in extinguishing n‐heptane fires (ie, Class B fires). It
depend on the AFA that was used in the test. The actual combustion
was determined that the best‐performing agent required a minimum
temperature of all six formulations was also measured and deter-
concentration of 15 g/m3 to extinguish the n‐heptane fire. This is four
mined to be between 800°C and 1000°C. The main products at
times more efficient than traditional HAEA‐generating AFAs. The
1000°C of all the formulas are shown in Table 4 and Figure 9. The
efficiency improved as the mass fraction of P90x increased.
main gaseous products of all six formulations were CO2, H2O, and
The interaction of the HAEAs with the heptane combustion
N2. There were no differences in the generation of CO2 and H2O
reactions was simulated with the HSC Chemistry software package.
in the tests with formulations #1 to #5, while N2 decreased slightly.
The simulations identified some key difference between the new
Mg3(PO4)2 remained as a residue in the amount of approximately
extinguishing agents and the traditional agents. The former consists
0.200 mol.
of inorganic phosphorus compound such as P2O5 and P4O10, while
The HAEAs produced by the combustion of formulations #1 to #5
the latter primarily consisted of KOH. Phosphorus oxides were
consist of inorganic phosphorus compounds such as P2O5 and P4O10.
identified as the leading components of the novel HAEAs to extin-
KOH, which has good efficiency in gas phase,17 was the main compo-
guish fire and were found to be more efficient than alkali salts.
nent of the HAEA for formulation #6. The extinguishing mechanism
for formulation #6 can be described as follows18: ACKNOWLEDGEMENTS
This work has been supported by the Fundamental Research Funds for
þH þOH
KOHƒ!Kƒƒ!KOH the Central Universities, the 111 Project No. G20012017001, and the
KOHƒ!þH Kƒ
ƒ!þO2 KO2 ƒƒ
ƒ!þH2 O KOH Key Laboratory of Firefighting and Rescue Technology, the Ministry of
KOHƒƒ!þOH KOƒ!H2 O KOH Public Security.
8 YAN
ORCID
Zhiyue Han http://orcid.org/0000-0002-8517-5760
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How to cite this article: Yan Y, Du Z, Han Z. A novel hot
aerosol extinguishing agent with high efficiency for Class B
fires. Fire and Materials. 2018;1‐8. https://doi.org/10.1002/
fam.2671