47th AIAA/ASME/SAE/ASEE Joint Propulsion Conference & Exhibit AIAA 2011-5582

31 July - 03 August 2011, San Diego, California

Estimating Maximum Pressures and Dissociation of Nitrous

Oxide Induced by THPP Based Initiators

Branden L. Poulsen1 and Karl K. Rink2

University of Idaho, Moscow, Idaho, 83844-0902

Abstract
Experiments are performed in a 100 cm3 isochoric test vessel to investigate the extent of
nitrous oxide dissociation. The dissociation is induced by the discharge of titanium hydride
potassium perchlorate (THPP) based pyrotechnic initiators into gas mixtures composed of
20/70/10 nitrous oxide, argon and helium, respectively. A shell model originally developed to
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estimate the dissociation of nitrous oxide when heated by zirconium potassium perchlorate
(ZPP) based initiators is applied to this work. The original shell model incorporates a
modified transient pressure predictive model (MTPPM) in order to describe the amount and
rate of energy transferred from burning THPP particles to the nitrous oxide gas mixture.
Validity of the shell model is established through comparison of experimental data and
model predictions for maximum pressures and extent of nitrous dissociation over initial
densities ranging between 0.026 and 0.205 g/cm3. Further validation is also provided through
a comparison between model predictions and experimental data for the transient pressure
response of the gas mixture for the specific density cases: 0.026 g/cm3, 0.142 g/cm3 and 0.205
g/cm3. The shell model is shown to accurately predict the maximum pressures and extent of
nitrous dissociation over the initial densities of interest.

Nomenclature
P = pressure (MPa)
Po = initial pressure (MPa)
t = time (ms)
dt = time step (ms)
R = universal gas constant (J/mol/K)
T = temperature (K)
ωi = reaction rate of the ith species (mol/cm3/ms)
Xi = concentration of the ith species (mol/cm3)
Qɺ = heat transfer rate (J/ms)
V = internal volume of reactor (cm3)
hi = enthalpy of the ith species (J/mol)
No = total initial number of moles
Cpi = constant pressure heat capacity of the ith species (J/mol/K)
Cpmix = heat capacity of initial gas mixture (J/mol/K)
a = burn rate frequency (ms-1)
A = burn rate parameter (cm/ms/MPan)
n = burn rate exponent
L = characteristic web thickness (cm)
Es = energy transferred from THPP (J)
Ec = energy content of THPP (J/mg)
Ea = activation energy (kJ/mol)
Ar = pre-exponential factor (ms-1)
mthpp = mass of THPP (mg)
σ = Plank’s constant (J/ms/cm2)

1
Graduate Student, Department of Chemical Engineering, bpoulsen@vandals.uidaho.edu, Student Member AIAA.
2
Associate Professor, Department of Mechanical Engineering, karlrink@uidaho.edu, Associate Fellow AIAA.
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American Institute of Aeronautics and Astronautics

Copyright © 2011 by the American Institute of Aeronautics and Astronautics, Inc. All rights reserved.
 e = gas emittance
α = gas absorptance
Ls = binary term
Ns = number of reacting shells
Kf = forward rate constant for the dissociation of nitrous oxide (ms-1)
Co = proportionality constant (MPa-1)
Tr = reaction temperature (K)
As = surface area of a shell (cm2)
Twall = internal wall temperature (K)
Rs = radius of a shell (cm)
Vs = volume of a shell (cm3)

I. Introduction
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D evelopment of alternative materials and new techniques for inflating supplemental restraints used in
automotive applications has led to many different types of airbag inflators.1-7 One specific type of reactive
gas inflator contains a relatively high pressure (approximately 29 MPa at 293 K) gas mixture containing nitrous
oxide, argon and helium in a 20/70/10 volume ratio, respectively.8-10 Although nitrous oxide based inflators can
conceivably make use of any pyrotechnic initiator, Zirconium Potassium Perchlorate (ZPP) and Titanium Hydride
Potassium Perchlorate (THPP) are advantageous.11 THPP is especially beneficial due to its high energy content
(approximately 7,000 J/g) and moderate burn rate characteristics. In practice, a number of design factors necessitate
the use of relatively small pyrotechnic loads (approximately 460 mg THPP) and high density gas mixtures (typically
0.442 g/cm3). Once these initiators are actuated, the energy transferred from burning pyrotechnic results in local
dissociation of the high density nitrous oxide mixture. However, a large fraction of un-dissociated nitrous oxide
(typically 70 %) discharges into the air bag. Earlier work by Poulsen and Rink12,13 describes the incomplete
dissociation of nitrous oxide induced by burning ZPP particles. The objective of this work is to predict the
incomplete dissociation of nitrous oxide induced by THPP based initiators.
To understand the extent of nitrous oxide dissociation in closed vessels, it is first necessary to characterize the
energy transferred from the initiator to the surrounding gas. In prior work,14,15 experimentally-derived values for the
amount of energy released by the discharge of 275 mg ZPP and 460 mg THPP initiator pyrotechnic formulations
into pure argon environments is discussed. In both cases, the total energy released is found to be a strong function of
the initial argon pressure.14,15 As the initial pressure increases progressively, more energy is transferred from the
burning pyrotechnic to the gas mixture instead of the test vessel wall.14,15 The total energy released by 275 mg of
ZPP is found to asymptotically approach a value of about 1500 J (5455 J/g) as the initial argon pressure approaches
approximately 20 MPa.14,15
Differential equations describing transient temperature and pressure responses of uniformly heated isochoric
reactive mixtures are known in the literature.16,17 However, the utility of these models is limited to low initial
densities and they have been shown to become inaccurate as the density of the reactive mixture is increased.12,13
More specifically, these equations predict no reaction will occur for sufficiently high initial density cases because
the energy provided by these initiators is inadequate to raise the entire gas mixture to the auto-ignition temperature.
Furthermore, these models assume uniform heating and do not account for localized heat sources, such as burning
pyrotechnic particles.
To address these deficiencies, a model developed by Poulsen sub-divides the reactor domain into equal volume
shells.12,13 This allows an estimation of the transient pressure and temperature inside each individual shell to account
for localized heating caused by burning pyrotechnic. Furthermore, the shell model is shown to accurately predict the
extent of dissociation and maximum pressures produced by ZPP discharged into isochoric nitrous oxide gas
mixtures over the densities of interest.12,13 The subject of this work is to apply the shell model to THPP based
initiators.
Application of the shell model to nitrous oxide heated by burning THPP particles requires an estimation of both
the amount and rate of energy transferred from burning pyrotechnic to the surrounding reactive gas mixture. A
model describing the amount and rate of energy transferred from burning THPP particles to an inert gas is found in
the prior work of Poulsen and Rink14 and is termed the modified transient pressure predictive model (MTPPM). In
order to predict the maximum pressures produced and extent of dissociation the shell model is used in conjunction
with the MTPPM.

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 A. Objectives
There are three main objectives of this work. First, experimental measurements of the extent of nitrous oxide
dissociation and transient pressures in closed vessels are obtained for the gas mixture N2O/Ar/He in the volume ratio
20/70/10, respectively. Measurements are made over ambient temperatures ranging from 233 K (-40 oC) to 263 K
(90 oC) and initial densities between 0.026 g/cm3 and 0.205 g/cm3. Second, the transient pressure response of the gas
mixture estimated by the shell model is compared to measured data for the following initial densities: 0.026 g/cm3,
0.0142 g/cm3 and 0.205 g/cm3. To illustrate the performance differences between nitrous oxide mixtures and inert
gases, predictions using the MTPPM for the transient response of argon heated by burning THPP particles are also
provided. Third, the shell model is combined with the MTPPM in order to predict the extent and maximum
pressures produced through the dissociation of nitrous oxide and model predictions are compared to experimental
data.

II. Experimental Apparatus and Methodology

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Specific details describing the mechanical design of the experimental test apparatus have been previously
disclosed.18-20 However, a few general design features are mentioned for clarity. The spherical 100 cm3 reactor is
designed for repetitive use and can withstand pressures in excess of 690 MPa and temperatures potentially generated
in closed volume testing of pyrotechnics and/or reactive gas mixtures. The reactor design features several
attachment locations for static and dynamic pressure transducers, pyrotechnic initiators, a fill valve, and
thermocouples.
Special attention is paid to fill the test vessel with the correct gas mass and composition prior to each test. Each
gas constituent is filled individually and its mass monitored using a Mettler Toledo® PR8002 electronic scale with
an accuracy of ± 0.001g. If the desired gas mass for one component is filled incorrectly the entire gas charge is
discarded and the fill process repeated.
Dynamic pressures produced during testing are recorded using Piezotronics® model 119B piezoelectric
pressure transducers. A Nicolet® MultiPro Transient Analyzer and Ectron® Model 765 Programmable Transducer
Conditioner Amplifiers are coupled with a desk top computer and record pressure transducer signals every 10 µs for
a total duration of 50 milliseconds. Furthermore, the experimental data is time averaged using a type SAE Class
1000 filter. After completion of a test the gas sample is transferred to a 1000 cm3 Tedlar® bag via the fill port and
analyzed using both a Nicolet® Model 560 FTIR and Hewlett Packard® Model 6890 gas chromatograph. This
process is completed in less than 15 minutes. The extent of nitrous dissociation is determined using initial gas fill
data in conjunction with measured mole fractions of gases collected from the Tedlar® bags. The experimentally
determined extent of dissociation is calculated from the equilibrium constituents in the Tedlar® bags.

III. Shell Model

A shell model applicable to the dissociation of nitrous oxide induced by burning THPP particles is developed to
predict the performance of this reactive mixture and allow comparison to inert gases heated by identical pyrotechnic
initiators. Differential equations describing the transient pressure and temperature response for reactive mixtures
heated uniformly in isochoric vessels are used as a basis for the shell model:16

dP dT
= R ⋅ T ⋅ ∑ ωi + R ⋅ ∑ X i (1)
dt i i dt

Qɺ
+ R ⋅ T ⋅ ∑ ωi − ∑ ( h ⋅ ωi )
dT V i i i
= (2)
dt ∑ X i (Cpi − R )
i

These equations describe the transient temperature and pressure response of a uniformly heated mixture. Upon
discharge of the pyrotechnic energy is transferred from burning THPP particles into the reactive gas mixture in a
non-uniform manner. The shell model is used to approximate this spatially non-uniform energy transfer. In prior
work, a semi-empirical differential equation is derived to describe the transient temperature response of argon gas
receiving energy from burning THPP particles:14

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 dT a ⋅ Es ⋅ Exp[ − a ⋅ t ]
= (3)
dt N ( Cp − R)
o mix

In this prior work, Poulsen and Rink termed the parameter (a) in Equation (3) the burn frequency.14 In the original
shell model, in order to describe the discharge of ZPP into nitrous oxide bearing mixtures a value for the burn
frequency is estimated using known chemical kinetic parameters for ZPP.13 Following the prior work of Poulsen and
Rink,14 the expression for the burn frequency is formulated using the burn rate constants and characteristic web
thickness (L) for THPP:
n
A ( Po + 34.47 )
a= (4)
L
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The burn rate parameter (A) and burn rate exponent (n) for THPP particles are 2.41x10-3 cm/MPan/ms and 0.38,
respectively.21 The value for the characteristic web thickness of a typical THPP particle is taken as 4.5x10-3 cm.22 In
addition, the value 34.47 MPa appearing in Equation (4) is the minimum pressure required to burst the initiator
output can used to contain the pyrotechnic. This pressure is determined by both experimental and finite element
analysis for specific output can geometries.23
The parameter (Es) in Equation (3) is the amount of energy transferred to the surrounding gas mixture. Previous
work by Poulsen and Rink14 describes the energy transferred from burning THPP particles to surrounding argon gas
as a function of both the test vessel size and initial pressure:

Es = Ec ⋅ mthpp (1 − Exp[ −0.104 ⋅ Po ]) + 475 (5)

The energy content (Ec) and load of THPP used in this work is 7.0 J/mg and 460 ± 46 mg, respectively. Equation (2)
and Equation (3) are independent ordinary differential equations that describe the temperature rise of the system.
Recall that Equation (2) describes the temperature rise of a system due to a chemical reaction, while Equation (3)
describes the temperature rise of system due to energy transferred from burning pyrotechnic. Therefore, applying
the principle of superposition they can be combined to yield:

Qɺ
+ R ⋅ T ⋅ ∑ ωi − ∑ ( h ⋅ ω i )
dT V i i i a ⋅ Es ⋅ Exp[ − a ⋅ t ]
= + (6)
dt ∑ X i ( Cpi − R ) N o (Cp mix − R )
i

Thus, Equation (6) describes the temperature rise of a heterogeneous reactive system that receives energy from
burning pyrotechnic. These equations accurately describe the extent of nitrous oxide dissociation in isochoric
spherical reactors under low initial gas density cases for specific volumes of interest. However, as discussed in prior
work as nitrous oxide gas densities approach 0.0263 g/cm3 numerical predictions using this model are unable to
predict local dissociation of nitrous oxide.12,13 As explained in this prior work, as the initial gas density becomes
sufficiently high the energy transferred from burning pyrotechnic is insufficient to cause heating and complete
dissociation of the entire quantity of nitrous oxide.12,13 To address this deficiency in the model, the reactor domain is
sub-divided into 25 concentric shells.12,13 Using the model described by Equation (1) and Equation (6) and sub-
dividing the 100 cm3 reactor domain into 25 equal volume shells allows for an estimation of the transient
temperature and pressure response in separate concentric 4 cm3 volume shells. The choice of 25 shells is discussed
in this prior work.12,13
The shell model formulation is briefly reviewed for clarity. For a more detailed review the reader is referred to
the work of Poulsen.13 First, the energy transferred from THPP is delivered to a 4 cm3 sphere located in the center of
the reactor. The energy transferred from the pyrotechnic raises the temperature of the central shell to a value that
induces dissociation of nitrous oxide. The specific value for this temperature under the given test condition is
essential to this work and is discussed in greater detail in subsequent paragraphs. Any excess energy after heating
the centrally located sphere is transferred to the surrounding concentric shell. This scheme continues until the energy
from the pyrotechnic is transferred to the nitrous oxide gas mixture.
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 To develop an analytical description for the shell model, Equation (1) and Equation (6) are modified to describe
the transient temperature and pressure response of any arbitrary shell (j) and become:

ɺ
Q E
s,j s
+R ⋅ Ts,j ⋅ ∑ ωi - ∑ (h ⋅ ωi )s,j Ls , j ⋅ a ⋅ ⋅ Exp[ − at ]
dTs , j Vs i s, j i i Ns
= + (7)
dt ∑ X i (Cp i -R) s,j No ⋅ ( Cpmix − R)
i s,j s, j s, j

dPs , j dTs , j
= R ⋅ Ts , j ⋅ ∑ ω + R ⋅ ∑ Xi (8)
dt i is , j i s, j dt

The parameter (Ls,j) appearing in Equation (7) is a binary term that has a value of one for reacting shells and zero for
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non-reacting shells.12,13 More specifically, the binary term is used to analytically describe if a specific shell receives
energy from burning THPP.
Values for enthalpies (hi) and heat capacities (Cpi) of all species are found using the NIST chemical database.24
The reaction rates (ωi) describing the dissociation of nitrous oxide are found assuming the global kinetic mechanism:

1
N 2 O → N 2 + O2 (9)
2

Assuming a first order and irreversible reaction takes place the rates for nitrous oxide, nitrogen and oxygen can be
written as:
dX N O
2
ωN O = = −K f ⋅ X N O (10)
2 dt 2

dX N
2
ωN = = K f ⋅ XN O (11)
2 dt 2

dX O
2
ωO = = 0.5 K f ⋅ X N O (12)
2 dt 2

The forward rate constant (Kf) for any shell (j) is expressed as:

 Ea 
K f , j = Ar ⋅ Exp  −  ⋅ Co ⋅ Po (13)
 R ⋅ Ts , j 

The value of the pre-exponential factor (Ar), activation energy (Ea) and the proportionality constant (Co) are taken as
4.98x107 ms-1, 234.4 kJ/mol and 6.71 MPa-1, respectively.25
A weakness of the original shell model involves the necessity of assuming an initial temperature required for
the complete local dissociation of nitrous oxide within the reacting shells.12,13 This assumed temperature is based
upon prior work obtained in systems significantly different from the spatially non-uniform and heterogeneous
system studied herein.25 Specifically, the work of Yetter and Dreyer25 did not involve the rapid discharge of burning
pyrotechnic particles into high density gas mixtures. Therefore, a technique to estimate the temperature required to
initiate complete local dissociation within 4 cm3 volumes is necessary for this work.
Upon discharge of the pyrotechnic, the burning particles begin to transfer energy to the surrounding nitrous
oxide gas mixture. Therefore, a specific amount of transient energy released by burning pyrotechnic is transferred to
the surrounding gas mixture. This energy transfer will cause localized heating around the pyrotechnic raising the
temperature of the nitrous oxide. Since the reactor domain is approximated by 4 cm3 regions, it is assumed that a
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 fraction of total initiator energy is transferred from a specific amount of burning pyrotechnic into these volumes.
The fraction of energy deposited in each shell increases the temperature within that shell and the remaining energy is
transferred to subsequent shells. This process continues until the fraction of the total initiator energy transferred to
the outer shells is insufficient to induce dissociation. In reacting shells where both nitrous oxide dissociation and
pyrotechnic combustion are occurring simultaneously, the temperature termed the reaction temperature is generally
greater than that required for nitrous oxide dissociation.
The temperature of a reacting shell is estimated assuming burning pyrotechnic will cause local dissociation to
occur within the reacting shell. More specifically, it is assumed that 100% dissociation occurs within a reacting shell
before the pyrotechnic burns completely. Therefore, the reaction temperature can be estimated by equating the burn
frequency to the reaction rate and is illustrated in Equation (14).

Ea A( Po + 34.47)n
Co ⋅ Po ⋅ Ar ⋅ Exp [− ]= (14)
R ⋅ Tr L
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Although the use of the initial pressure is strictly invalid in finding the value of the reaction temperature, an order of
magnitude change in pressure only produces a 5 % difference in this value. For example, the initial pressures used in
this work range between 1.6 MPa and 11.63 MPa. By using the appropriate values for the remaining parameters and
using Equation (14), the estimated reaction temperature ranges between 1295 K and 1373 K.
Following earlier work, the number of reacting shells is found:12,13

Es
Ns = (15)
N o ⋅ (Cpmix − R )(Tr − To )

The original shell model assumes that all the energy from burning pyrotechnic is transferred to a system, for all
initial densities. However, if all the energy from THPP is assumed to be delivered to the nitrous oxide gas mixture
the maximum pressures would be over-predicted for all initial density cases. It is shown by Poulsen and Rink14,15
that a fraction of initiator energy is transferred to the reactor wall and this must be incorporated into the shell model
used in this work. As discussed in the work of Poulsen and Rink, the intent of the MTPPM is to account for the
affect of energy lost to the reactor walls on measured initiator performance.14,15 The fraction of initiator energy lost
to the surrounding wall is critical in estimating the number of reacting shells. The original shell model does not
account for energy transferred to the reactor walls from the pyrotechnic. Therefore, the MTPPM is incorporated into
the original shell model to account for this affect.
Combining Equation (15) with Equation (5) yields a convenient expression for the number of reacting shells:

( [
Ec ⋅ mthpp 1 − Exp −0.104 ⋅ Po + 475 ])
Ns = (16)
No ⋅ (Cpmix − R)(Tr − To)

All that remains in the concentric shell model formulation is to correct an oversight in the original shell model
involving the transfer of heat among shells by radiation. Recall that Equation (7) and Equation (8) represent
differential equations describing the transient temperature and pressure response of an arbitrary shell (j) that contains
a specific quantity of the nitrous oxide gas mixture. The heat transfer term (Qs,j) appearing in Equation (7) is used to
couple the transient temperature differential equations. Assuming negligible conductive and convective heat transfer
allows (Qs,j) to be represented by radiative heat transfer for the gas mixture only. Using the conductive heat transfer
method outlined by Poulsen it can be shown that radiative heat transfer is the only mechanism applicable over the
time domain of interest.13 To correctly account for thermal radiative transfer between concentric shells as opposed to
radiative transfer between spheres the following equation is recommended:

j −1   4
Qɺ s , j = σ * ∑  α * As ,i  T −T

i =1 
4
 s ,i s , j


 Ns  4 4
  − e * σ * As , j *  ∑  T −T
 k = j +1  s , j s ,k

( 4 4
 + T − Twall
 s , j )  (17)

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 In this work Kirchhoff’s law is assumed valid and the absorptance is equivalent to the emittance for all shells.25
Literature values for the emittance of nitrous oxide at elevated temperatures have not been found. Furthermore, the
emittance for reacting and non-reacting shells is different and therefore a procedure for their estimation is presented.
The nitrous oxide within a reacting shell is assumed to dissociate before a specific quantity of pyrotechnic
completely burns. Therefore, it is assumed that reacting shells contain nitrogen, oxygen, argon and helium at
approximately 1350 K and after a sufficient period of time the temperature of the reacting shell will decrease to 298
K. Nitrogen and oxygen emit at a 45 micron wavelength and the emittance is estimated to be 0.002 using an average
temperature of 675 K.25 Non-reacting shells contain nitrous oxide at an initial temperature of 298 K and it is
assumed that the temperature of these shells will be raised to the reaction temperature and then cool to 298 K after a
sufficient period of time. Nitrous oxide emits at a 4.5 micron wavelength and with an average temperature of 450 K
the non-reacting shell emittance is approximately 0.25.25 Although the assumption using an average temperature is
not strictly valid it provides an estimate for the emittance of reacting and non-reacting shells.
The temperature of the wall (Twall) is assumed to remain at 298 K even though it is in contact with the last shell.
This is a reasonable assumption since conduction through the reactor wall will begin to occur as the wall
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temperature increases. Furthermore, an estimation of the wall temperature is only used in the thermal radiative
mechanism and an exact value is unnecessary since the temperature of the wall becomes negligible as the shells are
heated.
The surface area for any arbitrary shell (j) is calculated once the radius is known:

1/3
 3Vs , j 3
Rs , j = + Rs , j −1  _∀_ j >1 (18)
 4π 
 

2
As , j = 4π Rs , j (19)

The concentric shell model comprises Equations (7-19) and describes the transient temperature, pressure and extent
of dissociation that occur as energy is transferred from burning THPP particles to the nitrous oxide gas mixture. In
summary, the shell model developed in this work uses discrete spatial domains to predict the dissociation of nitrous
oxide due to localized heat transfer from burning pyrotechnic. The validity of the model is established through
comparison between model predictions and experimentally determined values for the maximum pressures and the
extent of nitrous dissociation.

IV. Results and Discussion

A shell model developed in Section III is capable of predicting the transient temperature and pressure response
of a gas mixture containing Nitrous Oxide/Argon/Helium in the volume ratio 20/70/10 respectively and heated using
a THPP based initiator. Model predictions for the extent
of dissociation and maximum pressure are compared to
experimentally determined values over all initial
densities tested. Predictions for the transient pressure
response are compared to experimental data for three
specific densities: 0.026 g/cm3, 0.142 g/cm3 and 0.205
g/cm3. Predictions and experimental data are compared
for initial temperatures of 293 K (20 oC). The effect of
temperature is encompassed within the shell model and
results for other initial temperatures will be reported in a
future publication.
The influence of gas mixture density on the
transient pressure response is illustrated in Figures 1-3.
It is clear that the shell model predicts the transient
pressure response of the nitrous oxide gas mixture
between 0-15 percent of the experimental data from 0 to
50 milliseconds. This time frame is chosen because it Figure 1. Comparisons between the shell model, MTPPM and
encompasses the maximum pressure while retaining experimental data for initial density 0.026 g/cm3.

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 desired data resolution. Upon inspection of Figures 1-3,
it is clear the model becomes more accurate as the initial
density increases. This result is attributed to the transient
behavior of the chemical kinetics utilized in the shell
model.
The transient pressure characteristics within the gas
mixture are attributable to two parts. The pressure rise in
the first 1-2 milliseconds is due to energy transferred
from burning pyrotechnic into the gas mixture.
Simultaneously, a pressure rise occurs due to the
dissociation of nitrous oxide. The model predicts this
phenomena assuming that a certain number of reacting
shells are heated from burning pyrotechnic and these
shells transfer heat through radiative means to
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surrounding non-reacting shells. Therefore, at low initial

densities sufficient energy is transferred by thermal Figure 2. Comparisons between the shell model, MTPPM and
radiation to heat the initially non-reacting shells to cause experimental data for initial density 0.142 g/cm3.
complete dissociation. The plateau observed in Figure 1
between approximately 2-10 milliseconds is attributed to an induction period required for nitrous oxide dissociation
to proceed to completion within the initially non-reacting shells. As density is increased, a greater fraction of
initiator chemical energy is transferred to the gas mixture; however, there are progressively fewer reacting shells.
Furthermore, the energy transferred from reacting shells is insufficient to cause dissociation in initially non-reacting
shells. The decrease in the extent of nitrous dissociation due to increasing initial density is expected. In the limit, as
the initial density increases the amount of energy required for dissociation also increases, whereas the energy
liberated by a discrete pyrotechnic source remains constant. Therefore, at extremely high initial densities only a
small amount of nitrous dissociation will occur within close proximity to the initiator. In summary, once the density
is sufficiently high the shell model predicts that the dissociation of nitrous oxide is solely due to energy transferred
from burning pyrotechnic. Therefore, the accuracy of the model increases since no induction period is predicted at
sufficiently high initial densities.
A question encountered in the practical application of nitrous oxide bearing mixtures concerns the performance
differences between the reactive mixture and an inert gas. Following the discussion above, if sufficient energy is
supplied to cause dissociation within the reactive mixture, an increase in pressure results due to an increase molar
output and the release of stored chemical energy. Conversely, in an inert gas the pressure increase is solely attributed
to the energy transferred from the initiator. To illustrate this effect, the predicted pressure response (using the
MTPPM)14 for THPP discharged into pure argon of identical initial pressure is also presented in Figures 1-3. In
general, the maximum pressures produced in the nitrous oxide bearing mixtures are greater than those obtained in
pure argon environments. Furthermore, the percent increase in the maximum pressure of the nitrous mixtures
compared to the argon mixtures decreases as a function
of initial density. For example, Figure 1 shows that the
maximum pressure achieved in the nitrous oxide mixture
is approximately 50 % higher than that achieved in pure
argon. However as shown in Figures 2 and 3 as the
density is increased to 0.142 g/cm3 and 0.205 g/cm3, the
percent increase in maximum pressure reduces to 30 %
and 20 %, respectively. As discussed previously, this
reduction is because the amount of energy supplied by
the initiator becomes insufficient to induce complete
dissociation of nitrous oxide as the initial density
progressively increases. Therefore, at extremely high
densities the percent increase in the maximum pressure
between the inert gas and reactive mixture will be
identical.
The extent of dissociation as a function of initial
density is illustrated in Figure 4. At low initial densities Figure 3. Comparisons between the shell model, MTPPM and
the extent of nitrous oxide dissociation is nearly experimental data for initial density 0.205 g/cm3.
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 complete, while at an initial density of 0.205 g/cm3 the
experimentally determined extent of dissociation
decreases to approximately 34 %. A notable feature of
Figure 4 is the abrupt reduction in the extent of
dissociation as density exceeds 0.114 g/cm3. For the 460
mg THPP load, the shell model predicts complete
nitrous oxide dissociation for the four lowest initial
densities tested. Sufficient energy is transferred from
burning THPP to raise the mixture temperature to the
dissociation temperature in 20 and 12 reacting shells for
the 0.026 g/cm3 and 0.114 g/cm3 density cases,
respectively. As density is increased further, the shell
model predicts that energy transferred from burning
THPP is sufficient to dissociate the central shell and
Downloaded by UNIV OF CALIFORNIA SAN DIEGO on April 15, 2016 | http://arc.aiaa.org | DOI: 10.2514/6.2011-5582

only a few surrounding shells (as determined by

Equation 15). In these high initial density cases radiative
Figure 4. Comparison between shell model and experimental
heat transfer is insufficient to cause dissociation within predictions for the dissociation of nitrous oxide.
the surrounding non-reacting shells. As a consequence,
the experimentally determined reduction in the extent of
dissociation at high initial densities is predicted by the
shell model.
The effect of initial density on maximum pressure is
illustrated in Figure 5. Correlation between shell model
predictions and experimental data is within error
tolerance over the entire range of initial densities tested.
Maximum pressures are seen to progressively increase
as a function of initial density from 0.026 g/cm3 to 0.111
g/cm3. As density is further increased a 6 MPa reduction
in the maximum pressure is observed between the initial
densities 0.111g/cm3 and 0.142 g/cm3. As discussed
previously, this is the critical density range where the
radiative heat transfer from reacting shells is insufficient
to cause dissociation in the remaining non-reacting
shells. As the density is increased beyond 0.142 g/cm3
the maximum pressure is observed to increase. Although Figure 5. Comparison between shell model and experimental
somewhat counterintuitive, this increase in the predictions for maximum pressures.
maximum pressure can be explained by basic
thermodynamics and nitrous oxide dissociation. For example, at high initial densities the amount of energy
transferred from the initiator to the mixture approaches a constant value and a limited amount of dissociation (20%-
30%) occurs within the reactive mixture. Since both the energy transferred from the initiator and the extent of
dissociation is approximately constant, as the initial density is raised to values greater than 0.142 g/cm3 the
maximum pressure must also increase.

V. Conclusions
A shell model is developed to predict the pressures and extent of nitrous oxide dissociation occurring within
isochoric reactors containing N2O/Ar/He mixtures in a 20/70/10 volume ratio heated by burning THPP particles.
The model is shown to accurately predict the maximum pressures and extent of nitrous dissociation over a wide
range of initial densities. The shell model is also shown to accurately predict the transient pressure response of the
system for the specific densities 0.026 g/cm3, 0.142 g/cm3 and 0.205 g/cm3. In addition, a comparison between the
transient pressure response for the reactive nitrous oxide mixture and an inert gas is presented. For all initial
densities of interest the nitrous oxide mixture is observed to have a higher maximum pressure compared to the inert
gas. In summary, the shell model provides an accurate description of the transient pressure behavior for the nitrous
oxide mixture used in this work when heated by burning THPP particles.

9
American Institute of Aeronautics and Astronautics
 References
1
Air Bag Development and Performance New Perspectives from Industry, Government and Academia, R. Kent (ed).,
Society of Automotive Engineers, Warrendale, Pennsylvania, 2003.
2
Faerber, E., “Benefits of Fitting Airbags to Passenger Cars,” Proceedings of the 2nd International Symposium on
Sophisticated Car Occupant Safety Systems: Air Bag 2000 Conference, Fraunhofer-Institut fur Chemische Technologie,
November 29-30, Karlsruhe, Germany, 1994.
3
Deppert, T. M., Barnes, M. W., Mendenhall, I. V., Taylor, R. D., and J. A. Leonard, “Development of Gas Generators for
Passive Automobile Restraint Systems,” Proceedings of the 2nd International Symposium on Sophisticated Car Occupant Safety
Systems: Air Bag 2000 Conference, Fraunhofer-Institut fur Chemische Technologie, November 29-30, Karlsruhe, Germany,
1994.
4
Berger, J. M. and P. B. Butler, “Equilibrium Analysis of Three Classes of Automotive Airbag Inflator Propellants,”
Combustion Science and Technology, Vol. 104, No. 1-3, 1995, pp. 93-114.
5
Ulas, A., Risha, G. A., and K. K. Kuo, “Ballistic Properties and Burning Behavior of An Ammonium
Perchlorate/Guanidine Nitrate/Sodium Nitrate Airbag Solid Propellant Gas Generator,” Fuel, Vol. 85, 2006, pp. 1979-1986.
6
Khandhadia, P., Klosinski, R., and J. Vitek, “Advanced Inflator Technology for Automotive Airbag,” Proceedings of the
Downloaded by UNIV OF CALIFORNIA SAN DIEGO on April 15, 2016 | http://arc.aiaa.org | DOI: 10.2514/6.2011-5582

nd
2 International Symposium on Sophisticated Car Occupant Safety Systems: Air Bag 2000 Conference, Fraunhofer-Institut fur
Chemische Technologie, November 29-30, Karlsruhe, Germany, 1994.
7
Ericsson, D., Sanden, R., and R. Tryman, “A Comparative Study of Some Energetic Air-Bag Compositions Concerning
Toxic Products,” Proceedings of the 2nd International Symposium on Sophisticated Car Occupant Safety Systems: Air Bag 2000
Conference, Fraunhofer-Institut fur Chemische Technologie, November 29-30, Karlsruhe, Germany, 1994.
8
Rink, K. K. and M. S. Johnson, “Nitrous Oxide Inflator Technology,” 5th International Symposium and Exhibition on
Sophisticated Car Occupant Safety Systems: Airbag 2000+, Karlsruhe, Germany, December 4-6, 2000.
9
K. K. Rink, Airbag Inflation Gas Generation via a Decomposing Material, U.S. Patent 5,669,629 September 23, 1997.
10
Rink, K. K., and Johnson, M. S., “Nitrous Oxide Inflator Technology,” 5th International Symposium and Exhibition on
Sophisticated Car Occupant Safety Systems, Airbag 2000+, Karlsruhe, Germany, December 4-6, 2000.
11
Green, D.J., Johnson, M. S., Richardson, W. B., and Rink, K. K., “An Experimental Apparatus for the Determination of
the Energy Release During Combustion of Pyrotechnic Initiators Used for Automotive Airbag Applications,” 2002 Spring
Meeting of the Western States Section of the Combustion Institute, San Diego, CA, March 25-26, 2002.
12
Poulsen, B. L., Rink, K. K., “Modeling the Pyrotechnically-Induced Dissociation of Nitrous Oxide in Closed Vessels,” 48th
AIAA Aerospace Sciences Meeting Including the New Horizons Forum and Aerospace Exposition, Orlando, FL, Jan 4-7, 2010.
13
Poulsen, B. L., “The Development of a Mathematical Model to Estimate the Non-Equilibrium Thermodynamic and
Kinetic Behavior of Pyrotechnically-Induced Nitrous Oxide Dissociation,” Master’s Thesis, Chemical Engineering Department,
University of Idaho, 2009.
14
Poulsen, B. L., Rink, K. K., “Modeling the Energy Release Characteristics of THPP Based Initiators,” 46th
AIAA/ASME/SAE/ASEE Joint Propulsion Conference and Exhibit, Nashville, TN, July 25-28, 2010.
15
Poulsen, B. L., Rink, K. K., “Modeling the Energy Release Characteristics of ZPP Based Initiators,” 49th AIAA Aerospace
Sciences Meeting Including the New Horizons Forum and Aerospace Exposition, Orlando, FL, Jan 4-7, 2010.
16
Turns, R. S., “An Introduction to Combustion Concepts and Applications,” 2nd ed., McGraw-Hill, New York, NY, 2000.
17
S. H. Fogler, “Elements of Chemical Reaction Engineering,” 4th ed., Upper Saddle River, New Jersey, 2006.
18
Gunter, D. V., and Rink, K. K., “Design, Instrumentation, and Testing of a Ballistic Test Fixture for Bridge-Wire
Initiators,” Proceedings of the Western States Section of the Combustion Institute 2003 Fall meeting, Los Angeles, CA, October
11-12, 2003.
19
Gunter, D. V., DuBuisson, A. C., and Rink, K. K., “Design and Specification of Ballistic Test Fixtures and a Data
Acquisition System for Analysis of Bridge-Wire Initiators,” 43rd AIAA Aerospace Sciences Meeting and Exhibit, AIAA-2005-
0276, Reno, NV, January 10-15, 2005.
20
DuBuisson, A. C., and Rink, K. K., “Testing and Verification of a Ballistic Test Fixture and Data Acquisition System for
Experimental Analysis of Bridge-Wire Initiators,” 44th AIAA Aerospace Sciences Meeting and Exhibit, AIAA-2006-0282, Reno,
NV, January 9-12, 2006.
21
Holly, J. A., “Pressure Dependent Burn Rates of TiHx/KClO4,” Proceedings of the 11th International Pyrotechnics
Seminar, Vail, CO, July 7th-11th, 1988, pp. 327-344.
22
Massis, T. M., “The Processing, Properties and Use of the Pyrotechnic Mixture-Titanium Subhydride/Potassium
Perchlorate,” 32nd AIAA/ASME/SAE/ASEE Joint Propulsion Conference, Lake Buena Vista, FL, July 1-3, 1996.
23
Private communication
24
NIST chemical web book, http://webbook.nist.gov/chemistry/, July 6, 2011.
25
Allen, M. T., Yetter, R. A., and F. L. Dryer, “The Decomposition of Nitrous Oxide at 1.5 ≤ P ≤ 10.5 Atm and 1103 ≤ T ≤
1173 K,” International Journal of Chemical Kinetics, Vol. 27, 1995, pp. 883-909.
25
Siegel, R., and Howell, J., “Thermal Radiation Heat Transfer,” 4th ed., Taylor and Francis, New York, NY, 2002.

10
American Institute of Aeronautics and Astronautics