Modeling The Energy Release Characteristics of THPP Based Initiators

46th AIAA/ASME/SAE/ASEE Joint Propulsion Conference & Exhibit AIAA 2010-7007
25 - 28 July 2010, Nashville, TN
Modeling the Energy Release Characteristics of THPP Based

Initiators
Branden L. Poulsen1 and Karl K. Rink2

University of Idaho, Moscow, Idaho, 83844-0902
Abstract
Bridge-wire initiators using titanium hydride potassium perchlorate (THPP) as pyrotechnic
are commonly found in the aerospace, defense, and automotive industries. In certain
automotive airbag applications, the fraction of initiator energy transferred to the
surrounding gaseous environment is of primary importance. In this research, analytical
methods describing the total energy provided by the pyrotechnic initiator and the fraction of
Downloaded by AUBURN UNIVERSITY on September 15, 2016 | http://arc.aiaa.org | DOI: 10.2514/6.2010-7007
initiator energy transferred to the gaseous surroundings are presented. Total energy content
is calculated for THPP with two different subhydride values. A value of 7.0 kJ/g for the
specific THPP formulation used in this work is determined. The total energy content is used
in an additional model developed to predict the transient pressures obtained by the
discharge of THPP initiators into spherical 100 cm3, 40 cm3 and 10 cm3 test fixtures filled
with argon gas ranging in initial pressure from 3.45 to 34.5 MPa. The transient pressure
model uses known THPP burn rate parameters to describe the rate of energy release in
conjunction with an extinction parameter approach to account for heat lost to the test vessel
walls. The extinction parameter is found empirically through a non-linear regression
approach using experimental data obtained in the 100 cm3 test vessel. The value for the
extinction parameter found using the 100 cm3 data is then used for model predictions in the
40 cm3 and 10 cm3 volumes. Theoretical predictions for pressure rise rate are compared to
experimental data over the entire range of initial pressures. Model predictions agree with
experimental data for all vessel sizes tested. Therefore, the extinction parameter approach
developed in this work offers potential as a method for predicting pyrotechnic initiator
output in test vessels having similar geometry but disparate volumes.
Nomenclature
νx = variable for stoichiometric balance
νy = variable for stoichiometric balance
xf = mass fraction of Titanium Hydride
Mwf = molecular weight of fuel (g/mol)
Mwo = molecular weight of oxidant (g/mol)
∆Hrxn = enthalpy of reaction (kJ/mol)
∆Hf = enthalpy of formation (kJ/mol)
νf = stoichiometric coefficient of fuel
Ec = Energy content of THPP (kJ/g)
Esys = energy of system (kJ)
Ethpp = energy of THPP as a function of time (kJ)
Ef = amount of remaining energy of THPP (kJ)
Eg = amount of energy transferred from THPP to surrounding gas (kJ)
Ei = energy of THPP into vacuum conditions (J)
t = time (ms)
dt = time step (ms)
a = burn rate frequency (ms-1)
b = extinction coefficient (MPa-1/cm)
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.
1
American Institute of Aeronautics and Astronautics
Copyright © 2010 by the American Institute of Aeronautics and Astronautics, Inc. All rights reserved.
A = burn rate parameter (cm/ms/MPan)
P = pressure inside test vessel (MPa)
n = burn rate exponent
L = characteristic length (cm)
R = universal gas constant (J/mol/K)
T = temperature inside reactor (K)
V = volume of test vessel (cm3)
NAr = mol of Argon
CpAr = constant pressure heat capacity of Argon (J/mol/K)
XAr = concentration of Argon
F = fraction of energy remaining (J)
ds = differential length (cm)
mthpp = mass of THPP (mg)
s = path length of 2/3 diameter of spherical test vessel (cm)
∆P
= average rise rate (MPa/ms)

∆t
I. Introduction
B ridge-wire initiators are electrically actuated pyrotechnic devices used in the aerospace, defense and
automotive industries. One specific pyrotechnic composition commonly found in automotive airbag
initiators is titanium hydride potassium perchlorate (THPP). THPP is particularly useful in hybrid airbag inflators
with nitrous oxide as one of the gaseous constituents1. In these applications, both the stoichiometry of the THPP and
the total energy released by the initiator are important factors that influence system performance. The total amount
of energy transferred by the burning THPP is dependent on a number of factors including load, stoichiometry, and
physical design features. For example, significant amounts of energy may be lost to the surroundings if initiators are
discharged into small chambers with large surface area to volume ratios. Furthermore, depending upon the specific
application, THPP initiators may feature a wide range of fuel to oxidant ratios ranging from fuel lean to fuel rich,
which also affects energy content2-4.
The total energy released by pyrotechnic initiators when discharged into nitrous oxide-bearing mixtures in both
closed and vented test vessels controls (to a large degree) the extent of nitrous oxide dissociation5-7. Although the
fraction of energy released from a bridge-wire initiator into a surrounding high-pressure gaseous environment can be
measured experimentally, the experimental methods commonly employed suffer from various difficulties8. For
example, while the high-pressure experimental technique developed by Rink and various co-workers1-5 has been
shown to be accurate, it relies upon identification of the maximum pressure occurring within a very short time
period, usually between 1 to 5 milliseconds. However, identification of peak pressures is often difficult given the
oscillatory response of pressure transducers in pyrotechnic testing9-12. Furthermore, the accuracy of the entire data
acquisition system must be fully understood13. Therefore, it is of interest to develop a semi-analytical method that
may be used in conjunction with experimental techniques to verify total initiator energy content as well as the
fraction of energy deposited in a particular environment.
An analytical prediction of the energy content in pyrotechnic devices is inherently difficult. Although burn rate
parameters are known for many THPP based initiator pyrotechnic formulations, the complexities associated with
coupled heat transfer, fluid dynamics and chemical kinetics in actual devices makes energy release calculations
difficult. To model the dissociation of nitrous oxide-bearing mixtures induced by the discharge of zirconium
potassium perchlorate (ZPP) initiators, Poulsen5 developed a modified version of the closed vessel combustion
model of Turns14 which describes the rate of heat released by the initiator using global ZPP reaction rate kinetic
parameters. However, global reaction kinetic parameters for THPP combustion are scarce or currently not available.
Alternatively, a more detailed approach with a complete kinetic scheme for THPP combustion could be developed,
but this would necessitate complete knowledge of the chemical kinetic parameters for all chemical reactions of
interest. Regardless of the kinetic scheme chosen, a specific heat transfer mechanism must be included to make use
of the closed vessel combustion model presented in the literature14.
Models of pyrotechnic discharged into closed vessels also generally require description of the relevant heat
transfer mechanisms during the transient period of initiator function. Conductive, convective and/or radiative heat
transfer mechanisms are often added to model descriptions to account for energy lost to the surroundings with little
concern for their applicability over the time frames of device operation. Therefore, to simplify model formulation, it
2
is of interest to develop a semi-empirical technique to account for heat transfer in closed vessels without reliance
upon specific heat transfer correlations, thermal conductivities, emissivities, or other transport coefficient and
chemical kinetic information.
In this research, a model is first developed to predict the amount of energy released by THPP as a function of
fuel weight fraction. Simple kinetic mechanisms for fuel rich and fuel lean conditions are coupled with the First Law
of thermodynamics and thermo-chemical data as described in Section III. The output from the energy content model
is then used to develop a subsequent model which describes the rate of energy release from burning THPP particles
into closed vessels. A semi-empirical particle energy intensity approach is used to describe the remaining energy of
a burning particle as it traverses through a surrounding medium. The empirical extinction parameter is determined
using 100 cm3 test data and the energy release model using this parameter is shown to accurately replicate
experimental data in 40 cm3 and 10 cm3 test vessels.
II. Experimental Apparatus and Methodology

A detailed description of the experimental test vessels used in this work can be found in the literature15-17.
However, some general features are reviewed for clarity. The spherical test vessels have internal volumes of
approximately 100 cm3, 40 cm3 and 10 cm3. These vessels are intended for repetitive use and are designed to
withstand pressures in excess of 690 MPa and transient temperatures that are generated in closed volume testing of
pyrotechnic initiators. The test vessels feature several ports for pressure transducers (static and dynamic),
pyrotechnic initiators, a fill valve, and thermocouples.
Dynamic pressures are recorded using Piezotronics® model 119B piezoelectric pressure transducers. An
Agilent 54624A digital oscilloscope is coupled with a desk top computer to record 50 pressure transducer signals
every microsecond for a total duration of 50 milliseconds. The region of interest in this work occurs on the order of
a few milliseconds and therefore measurements are sampled at a rate greater than twice the Nyquist frequency13.
Since piezoelectric pressure transducers do not measure static pressures, initial pressure data is recorded using an
STI transducer, coupled with an inline amplifier and a desk top computer recording 200 signals every millisecond.
The THPP initiator used in this work is contained within a stainless steel cylindrical output can 0.75 cm in
diameter and 0.86 cm in length. The composition of THPP used in this work is approximately 34% TiH2 61%
KClO4 and 5% Viton B by weight. The THPP mass in each initiator is approximately 460 mg +/- 10 %. During
processing the THPP is pressed to 68% of the theoretical maximum density. Test vessels are loaded with industrial
grade argon gas (99.995 % purity) at pressures varying from 3.45 MPa to 34.5 MPa. Tests are performed in
increments of 3.45 MPa. Three test replicates are performed for each experimental condition. Test vessels are
cleaned prior to each test to remove residual solid combustion products that may influence the accuracy of the
experimental data.
III. THPP Energy Content Model

A value for the energy content of THPP is required in order to develop the energy release model that describes
the transient pressure response during the THPP combustion process. Therefore, a model that describes the energy
content of THPP as a function of fuel weight fraction is developed. The energy content model is used to validate the
THPP formulation in this work through comparison of analytical predictions with experimental data. Furthermore,
for comparative purposes, the energy content model can be used to estimate the energy content of THPP
formulations reported by previous workers.
The energy content model is developed using simplified kinetic mechanisms based upon the ratio of oxidant to
fuel. Simplified kinetic mechanisms describing the combustion of THPP with subhydride values ranging from 0.67
to 2 are reported for fuel lean, stoichiometric and fuel rich conditions2.
Fuel lean conditions:
2TiHν + (1 + 0.25ν x + ν y ) KClO4 → 2TiO2 + (1 + 0.25ν x + ν y ) KCl + ν x H 2 O + 2ν y O2 (1)

x
Stoichiometric conditions:
2TiHν + (1 + 0.25ν x ) KClO4 → 2TiO2 + (1 + 0.25ν x ) KCl + ν x H 2 O (2)

x
3
Fuel rich conditions: Table 1. Species and formation enthalpies
2TiHν +ν + (1 + 0.25ν x ) KClO4 → 2TiO2 + (1 + 0.25ν x ) KCl + ν x H 2 O + ν y H 2 (3) Species ∆Hf (kJ/mol)
x y
TiH2 solid -144.35
KClO4 solid -430.12
The THPP formulation used in this research contains titanium hydride and
TiO2 solid -938.72
therefore the variable (νx) in Equation (1) and Equation (2) must have a
KCl solid -436.68
value of two. Furthermore, the variables νx and νy in Equation (3) must
H2O liquid -285.83
sum to a value of two. To develop an equation describing the energy
content of THPP as a function of fuel weight fraction, the mol fraction of TiH1.65 -116.73
fuel must first be known. It is assumed that Viton B has a negligible effect
on the energy content of THPP and is therefore neglected in the mol fraction calculation.
For fuel lean conditions:

2
yf = (4)
3.5 + ν y
For fuel rich conditions:

2
yf = (5)
2 + (1 + 0.25ν x )
Since the fuel is titanium hydride, the mol and mass fractions for a stoichiometric condition are 57% and 32.3%
respectively, which are values quoted in literature2. Using a First Law analysis, the energy of THPP is calculated
as18:
xf ∆H rxn
Ec = (6)
Mw f vf
The heats of formation for the assumed products and the known reactants are found using the NIST chemical
database19 and are shown in Table 1. To solve Equation (6) as a function of fuel weight fraction the following
equation is used for fuel lean conditions:
∆H rxn = (571.66 + 436.68(1.5 + ν y ) + 1877.44) − (288.7 + 430.12(1.5 + ν y )) (7)
The stoichiometric coefficient (νy) in Equation (7) is

found by solving Equation (4) in terms of the mol
fraction of titanium hydride:
0.5(4 − 7 y f )
νy = (8)
yf
The mol fraction of fuel is related to the mass fraction

using the molecular weights of fuel and oxidant20:
xf
Mw f
yf = (9)
xf (1 − x f )
+
Mw f Mwo
Figure 1. Energy content of Titanium Hydride as a function of
fuel weight fraction.
4
Thus, knowing the stoichiometry of the THPP and assuming products for a fuel lean reaction, the energy content of
THPP can be found solving Equations (6-9). A similar method is used to solve Equation (6) for fuel rich conditions:
∆H rxn = (285.83ν x + 436.68(1 + 0.25ν x ) + 1877.44) − (288.7 + 430.12(1 + 0.25ν x )) (10)
Since the sum of stoichiometric coefficients νx and νy must equal two for the THPP formulation used in this work,
νy can be found from Equation (5) as:
8
ν y = 14 − (11)
yf
and, similarly, νx is found as:

ν x = 2 −ν y (12)
Solving Equations (4-12) the energy content of THPP as a function of fuel weight fraction is found. Results from
this analysis are illustrated in Figure 1. The fuel rich and fuel lean lines shown in Figure 1 converge at the
stoichiometric fuel weight fraction of 0.323 and indicate a maximum energy content of approximately 7.1 kJ/g.
The validity of the energy content model can be
verified through comparison of numerical predictions to
experimental values for energy content reported by
previous researchers. An energy content value of
approximately 6.6 kJ/g was previously reported for the
discharge of a specific THPP formulation into high
pressure helium environments1. Using the energy
content model developed above, the fuel weight fraction
corresponding to this energy content is found to be
approximately 0.30, which agrees with manufacturer
data. In a separate study, the energy content for THPP
with a subhydride value and fuel weight fraction of 1.65
and 0.33, respectively, is approximately 6.75 kJ/g as
reported 4. The energy content model using a subhydride
value of 1.65 agrees within 2% of this measured THPP
energy content as illustrated in Figure 2. Therefore, it is
reasonable to assume that the energy content model Figure 2. Energy content of Titanium Subhydride ν x=1.65 as a
developed in this work is accurate for subhydride values function of fuel weight fraction.
between 0.67 and 2.
The energy content for the THPP based initiator used in this work is approximately 7.0 kJ/g. This value
provides a basis for a subsequent model developed to describe the transient temperature and pressure response
resulting from discharge of burning THPP particles into argon gas. For convenience the burn rate of THPP is
described using the burn rate parameters found in literature21 as discussed in Section IV.
IV. Transient Pressure Predictive Model

In the transient pressure predictive model (TPPM), the burning THPP particles transfer energy to the
surrounding argon gas. In the TPPM, argon gas is defined as the system and burning THPP particles transfer energy
to this system:
dEsys dEthpp
=− (13)
dt dt
The kinetics of pyrotechnic combustion can be expressed in terms of an exponential function22. Therefore, it is
assumed that the chemical energy released from burning THPP particles can be represented by an exponential decay
function:
5
dEthpp
= − aEthpp (14)
dt
where, the parameter (a) is defined as the burn rate frequency. To introduce the burn rate exponent (n) and
temperature dependence factor (A) the classical linear burn rate expression of Vieille is used22:
n
r = AP (15)
Equation (15) is divided by a characteristic length (L) and defines the burn frequency (a):
n
AP
a= (16)
L
Substituting Equation (16) into Equation (14) and explicitly noting that pressure is a function of time yields:
dEthpp n
AP (t )
= Ethpp (17)
dt L
separating variables and integrating yields:
dEthpp n
AP (t )
∫E =∫
L
dt (18)
thpp
The burn rate parameter (A) and the burn rate exponent (n) for THPP have been reported for experiments
conducted in helium environments21. It is assumed that the burn rate parameters found in helium are approximately
the same as the burn rate parameters for argon. This assumption is based upon argon and helium having equivalent
values for their respective heat capacities19. Furthermore, the transfer of energy from burning THPP to the
surrounding gas mixture is proportional to the heat capacity value22.
Solution of Equation (18) is difficult since an explicit function of pressure with respect to time must be known.
Since a primary objective of this work is to develop a semi-analytical model to describe the rate of pressure increase
in closed vessel combustion, an alternative method for solving Equation (18) based upon the Mean Value Theorem
is developed23. Using the Mean Value Theorem, Equation (18) can be modified to incorporate an average value of
pressure over the time domain of interest to yield:
dEthpp n
AP
∫E =
L
∫ dt (19)
thpp
where, P represents an average pressure over the time

domain and is assumed to be equivalent to P t .A more
detailed discussion for this assumption is presented in
subsequent paragraphs. In addition, the ramifications of
this assumption on the accuracy of the model for short
transient time periods are discussed in Section V.
Solution of Equation (19) yields:
n
APt
Ethpp = E exp[ − t] (20) Figure 3. Error associated with Equation (21) for the TPPM
g
L 100 cm3 vessel and initial pressure of 24.1 MPa.
6
Using a Fist Law analysis the change in temperature of
the system due to energy transfer from THPP to the
surrounding argon gas is expressed as:
dE sys
dT dt
= (21)
dt 0.001 N Ar ( Cp Ar − R )
Combining Equations (14-20) provides a differential

equation for the transient temperature response of the
argon gas as the THPP burns:
n n
APt APt
E g exp[ − t]
dT L L Figure 4. Comparison between the TPPM and experimental
− =0 (22) data for 100 cm3 vessel at an initial pressure of 24.1 MPa.
dt 0.001N Ar ( Cp Ar − R )
where,
E g = mthpp Ec (23)
The ideal gas law has been shown to be appropriate throughout the range of experimental tests5 and is used to derive
a differential equation for the transient pressure response:
dP dT
= X Ar R (24)
dt dt
At each discrete time step, the mean value of pressure within that time step is assumed to approximate the pressure
evaluated throughout that incremental time period. This approximated value for average pressure is used to calculate
the rate of change in pressure and temperature by simultaneous solution of Equation (22) and Equation (24).
Furthermore, as time progresses, the mean value of pressure used in each successive time step increases. Therefore,
a representation of the time rate of change of temperature and pressure in isochoric test vessels can be estimated.
The transient pressure response expressed by Equation (24) is a homogeneous differential equation solved
numerically using Mathematica® 6.0. Although details of the solution method are beyond the scope of this paper,
Mathematica® solves Equation (22) and Equation (24)
simultaneously for P (t) and T (t). The accuracy of the
mean value assumption can be validated by checking
Equation (22) for homogeneity. The results of this
analysis for the case of 100 cm3 test vessel volume and
an initial pressure of 24.1 MPa are shown in Figure 3.
The pressure trace for this experimental condition is
shown in Figure 4. This particular test case is chosen for
convenience since the TPPM is shown to be most
accurate at relatively high pressures (in excess of 18
MPa) and large volumes (100 cm3) as discussed below.
In this analysis the error in the transient temperature
(Equation (22)) is expressed as a percent deviation from
homogeneity. Figure 3 illustrates that Equation (22) is
valid over the time period of interest except for a short
period of time between 1 to 2 milliseconds. Thus the
validity of the mean value pressure assumption is Figure 5. Comparison of average rise rate between the TPPM
verified. Furthermore, assuming a constant value for and experimental data for 100 cm3 vessel.
7
pressure in Equation (24) yields the trivial solution.
Therefore, as expected, the pressure must vary with
time. In summary, the mean value for pressure used to
solve Equation (22) does not assume constant pressure
over all times. Instead, it assumes a constant average
pressure evaluated at discrete increments of time used to
approximate the pressure within each incremental time
step.
The characteristic length (L) appearing in Equation
(22) representing the burn length warrants discussion. In
this research, the THPP particles are assumed to be
spherical with an average particle diameter of
approximately 90 µm and an effective burn length
equivalent to the radius, 45 µm. This assumed particle
size is deemed appropriate based upon published

literature4. Thus, sufficient information exists to solve Figure 6. Comparison of average rise rate between the TPPM
Equation (22) and Equation (24). Comparison of the and experimental data for 40 cm3 vessel.
TPPM to experimental data for the test condition of 24.1
MPa and 100 cm3 is shown in Figure 4. Results obtained from the TPPM are within experimental error and
accurately represents the experimental trace given the inherent oscillations in the pressure16. (Note the experimental
pressure shown in Figure 4 is unfiltered data.) In addition, since particle size directly influences rise rate, Figure 4
provides some justification for the assumed particle diameter since the predicted maximum pressure occurs at
approximately 1.5 ms. Ramifications of the assumed particle diameter on rise rate predictions are discussed more
thoroughly in Section V.
For comparison purposes it is convenient to define an average rise rate. In closed vessel testing of THPP based
pyrotechnic initiators it is generally found that peak pressures are generally achieved within approximately 1.5 ms1.
Therefore, the average rise rate is arbitrarily defined as:
∆P P t =1.5 − P t = 0
= (25)
∆t 1.5
The average rise rate is useful since it can be plotted as a function of initial pressure for the various volumes tested
to compare the TPPM results against experimental data. Results of this comparative analysis for the 100, 40 and 10
cm3 volumes are shown in Figures (5-7), respectively. The average rise rate is predicted reasonably well by the
TPPM at the highest pressure tested (34.5 MPa) for all test vessels. In general the TPPM is most accurate for the 100
cm3 test vessel. However, experimental data and the TPPM predictions begin to deviate at initial pressures less than
approximately 18 MPa as illustrated in Figure 5. Results
for the 40 cm3 test vessel are shown in Figure 6. The
TPPM and experimental data agree at high pressures but
deviate significantly at initial pressures less than 22
MPa. Furthermore, the deviation between the TPPM and
the experimental data in the 40 cm3 vessel exceeds the
deviation observed in the 100 cm3 vessel. This trend
continues for the 10 cm3 vessel where the average rise
rate is predicted reasonably well at the highest pressure
tested, but is over-predicted at lower initial pressures.
The disagreement between the TPPM and
experimental data at low initial pressures and small test
vessel volumes can be attributed to heat transfer effects.
Intuitively, burning THPP particles would be expected
to transfer energy to test vessel walls as the volume and
initial density of the surrounding argon gas decreases1.
In the TPPM the entire energy content of THPP is Figure 7.
5. Comparison of average rise rate between the TPPM
33
assumed to be transferred to the argon gas as defined in and experimental data for 10
100cm
cm vessel.
vessel.
8
Equation (23). In reality, a fraction of energy liberated
by THPP combustion is transferred to the test vessel
walls and therefore does not contribute to an increase in
temperature and pressure of the gas. This affect will be
greatest for small volumes in conjunction with low
initial pressures. Therefore, to enhance the accuracy of
the TPPM a modification is introduced to account for
heat lost to the vessel walls. This modification is
developed in Section V.
Section V. Modified TPPM

Development of an analytical model to describe the rate
of energy transferred from burning THPP particles to a
surrounding gas mixture is inherently difficult. This
difficulty is due to the coupling between heat transfer, Figure 8. Error associated with Differential Equation (21) for
fluid mechanics and chemical kinetics. Therefore, the modified TPPM in 100 cm3 vessel and initial pressure of
instead of attempting the derivation of a fully analytical 6.89 MPa.
model, an approximate approach based upon an analogy
describing the radiation intensity of un-collided particles24 is presented.
A differential energy balance of burning THPP particles over a differential length (∆S) yields:
Ef − Ef
( )
F ∆s =
s s +∆s
(26)
Ef
s
where, F (∆s) represents the fraction of energy that remains within the burning THPP as it travels a differential
length (∆s). Thus, F (∆s) represents energy that has not been transferred to the surrounding argon gas. Dividing by
the differential length and taking the limit as ∆S approaches zero, Equation (26) becomes:
dE f ( s ) 1
F (s) = − (27)
ds E f (s)
The fraction of energy released by burning THPP in a closed vessel is shown to be proportional to the initial
pressure of the surrounding medium1. Therefore, the fraction of total THPP energy (Ef) remaining as the pyrotechnic
burns can be expressed as:
− dE f ( s ) 1
F (s) = = bPo
ds E f (s)
or,
dE f
= −bPo E f (28)
ds
where the proportionality constant (b) is defined as the

extinction coefficient. The extinction coefficient is found
empirically as discussed below. The solution to Equation
(28) is:
E f = mthpp Ec exp[ −bPo s ] (29) Figure 9. Comparison of energy content for THPP between the
modified TPPM, experimental data and theoretical prediction
for the 100 cm3 vessel.
9
Equation (29) represents the total remaining energy of
burning THPP not delivered to the argon gas.
Conversely, the amount of energy transferred from the
burning THPP particles to the argon gas is:
( [
E g = E c mthpp 1 − exp − bPo s ]) (30)
Equation (30) describes the amount of energy argon

receives from burning THPP particles as a function of
both the initial pressure of the gas as well as the path
length the particles traverse. In the limit of high initial
pressure and/or sufficiently large path length, Equation
(30) indicates that all the energy from burning THPP
will be transferred to the surrounding medium. Figure 10. Comparison between the modified TPPM and
Conversely, Equation (30) indicates that if the initial experimental data for 100 cm3 vessel at an initial pressure of
pressure is a vacuum and/or path length is very short, all 6.89 MPa with varying THPP particle diameter.
the energy from THPP will be transferred to the vessel
wall. The path length (s) is found assuming the THPP particles are distributed from the initiator into the gas in a
cone shaped pattern. This assumption allows the path length (s) to be approximated by the geometric mean path
length, which for a sphere is equal to 2/3 the diameter25.
The prediction of zero energy transfer for a vacuum condition is not physically true since THPP is self oxidized
and produces a relatively small, but measureable, pressure increase when burning in a vacuum environment.
Therefore Equation (29) is modified to account for this effect:
( [
E g = E c mthpp 1 − exp − bPo s ]) + Ei (31)
The initial energy (Ei) deposited by THPP into a test vessel initially at a vacuum condition is found from a best fit to
the experimental data extrapolated to an initial pressure of zero. Using this technique Ei is found to be 0.69 kJ, 0.36
kJ, and 0.3 kJ for the 100 cm3, 40 cm3 and 10 cm3 test vessels, respectively. These values are necessary to accurately
predict the transient temperature and pressure response using Equations (22, 24, and 31).
The extinction coefficient (b) is found using a nonlinear regression curve fit to the experimental data. To
validate the model, the 100 cm3 test data is used to find a value for the extinction coefficient (b) equivalent to 0.027
MPa-1/cm. This value of (b) is then used to predict the transient pressure response in the 40 cm3 and 10 cm3 fixtures.
The choice of using the 100 cm3 data is arbitrary since (b) can also be found using the 40 cm3 or 10 cm3 data. In
summary, once the extinction coefficient (b) is determined for a specific spherical volume it can be incorporated into
the modified TPPM and used to accurately predict the
transient pressure response for a spherical volume of any
size, as discussed in Section VI.
VI. Discussion
Prediction of the energy content for the THPP
initiator discharged into 100 cm3 vessel using the
modified TPPM compared to experimental data is shown
in Figure 9. The model predictions are within
experimental error over the entire range of initial
pressures tested. The experimental error of 0.683 kJ/g in
the dependent variable shown in Figure 9 is calculated
using the root sum square method incorporating the 10
% uncertainty in the mass of THPP and the error
associated with the PCB dynamic pressure transducer13.
Thus, the modified TPPM accurately predicts the energy Figure 11. Comparison of average rise rate between the
content as determined by experiment throughout the modified TPPM and experimental data for 100 cm3 vessel.
10
range of initial pressures tested. This implies that the
heat transferred to the test vessel walls at low pressures
(energy transfer that is difficult to predict analytically
using specific heat transfer mechanisms) can instead be
modeled using the extinction parameter approach.
The extinction coefficient technique of the modified
TPPM improves predictions of system performance at
low initial pressures compared to the TPPM. For
example, a prediction of the transient pressure response
using the modified TPPM for a 100 cm3 vessel at an
initial pressure of 6.89 MPa is shown in Figure 10. The
predicted pressure lies within experimental error over
the entire time domain. Furthermore, the accuracy of the
predicted pressure implies the choice of THPP particle
size is reasonable. For comparison, the transient pressure
predicted for two different particle sizes, 9 µm and 900 Figure 12. Comparison of average rise rate between the
µm, are also shown in Figure 10. This change in particle modified TPPM and experimental data for 40 cm3 vessel.
size, one order of magnitude greater than and one order
of magnitude less than the assumed particle size, results in over-prediction and under-prediction, respectively, of the
experimentally observed rise rate. Therefore, the choice of an average particle size of 90 µm is justified.
Further justification for the applicability of the extinction parameter approach is provided by predictions of the
average pressure rise rate in the various test vessels. The average rise rate as a function of initial pressure for the 100
cm3, 40 cm3 and 10 cm3 vessels are illustrated in Figures 11-13, respectively. The model predictions are within
experimental error for all initial pressures in all volumes tested.
The improved accuracy of the modified TPPM in comparison to the TPPM for all test vessels and initial
pressures is expected from theory. The modified TPPM is derived assuming a specific amount of energy from
burning THPP is released to the surrounding medium as a function of the test vessel size. In addition, the extinction
coefficient (b) is a constant value independent of pressure and test vessel volume as formulated in Equation (30).
Furthermore, initial pressure and test vessel volume are also accounted for as input parameters in the modified
TPPM formulation. Therefore, it is expected that the extinction coefficient (b) found from experimental data
obtained from one specific spherical volume will be applicable to any other arbitrary spherical volume. In summary,
the improved accuracy of the modified TPPM in comparison to the TPPM is apparent in Figures 9-13.
Prediction of energy release rate using the extinction parameter approach has important ramifications on
pyrotechnic testing in closed vessels. Specifically, the output of a pyrotechnic device as measured in one specific
volume may be used to accurately predict the output of an identical device in other volumes of similar design. The
extinction parameter approach can potentially be used in vessels of different geometry. However, to do so the
characteristic length (L) for the particular vessel geometry must be determined and the energy content of the
pyrotechnic must be known. Thus, identification and
inclusion of specific modes of heat transfer to an
analytical formulation describing the heat losses to the
vessel wall are unnecessary.
VII. Conclusions
A model describing the energy content of THPP as
a function of weight fraction is presented in this work.
The model predicts an energy content of 7.0 kJ/g for the
THPP formulation used in this work. This value closely
agrees with the experimentally determined value for
THPP energy content obtained at high initial pressures.
The total energy content is used as a basis to develop the
transient pressure predictive model (TPPM) that
describes the transient pressure response of argon gas in Figure 13. Comparison of average rise rate between the
closed spherical vessels during initiator actuation. modified TPPM and experimental data for 10 cm3 vessel.
11
Predictions using the TPPM are found to deviate from experimental data as the test vessel volume and initial
pressure decrease. The deviation between numerical predictions and experimental data are attributed to heat transfer
effects at low initial pressures and/or small test vessel volumes.
The TPPM model is modified to account for heat transfer effects by using an approach analogous to the
radiation intensity of un-collided particles. The modified TPPM model describes the rate of energy transfer from
burning THPP particles to the surrounding argon gas as a function of a characteristic path length found to be 2/3 of
the vessel diameter. The modified TPPM uses a proportionality constant termed the extinction parameter which is
found empirically using test vessel data. In this work, the extinction parameter determined from non-linear
regression using 100 cm3 test vessel data is approximately 0.027 MPa-1/cm. The extinction parameter found using
100 cm3 data is the used to predict transient pressure response in 40 cm3 and 10 cm3 test vessels. The modified
TPPM is shown to accurately predict unfiltered transient pressure data within experimental error. In addition, the
modified TPPM agrees with experimentally determined average pressure rise rates for all initial pressures in all
vessels tested.
References
1
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.
2
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International Pyrotechnics Seminar, Vail, CO, July 1988, pp. 915-930.
3
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4
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University of Idaho, 2009.
6
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Helium Mixtures in a Closed Vessel,” Proceedings of the 19th International Colloquium on the Dynamics of Explosions and
Reactive Systems, Hakone, Japan, July 27-August 1, 2003.
7
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Sophisticated Car Occupant Safety Systems, Airbag 2000+, Karlsruhe, Germany, December 4-6, 2000.
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10
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at the 40th AIAA/ASME/SAE/ASE Joint Propulsion Conference and Exhibit, Fort Lauderdale, FL, July 11th-14th, 2004.
11
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Variations on Measurements in Pyrotechnic Test Apparatus,” American Institute of Aeronautics and Astronautics, 2009.
12
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International Pyrotechnic Seminar, Vail, CO, July 7-11, 1986.
13
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15
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0276, Reno, NV, January 10-15, 2005.
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13

Modeling The Energy Release Characteristics of THPP Based Initiators

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46th AIAA/ASME/SAE/ASEE Joint Propulsion Conference & Exhibit AIAA 2010-7007

25 - 28 July 2010, Nashville, TN

Modeling the Energy Release Characteristics of THPP Based

Branden L. Poulsen1 and Karl K. Rink2

= average rise rate (MPa/ms)

II. Experimental Apparatus and Methodology

III. THPP Energy Content Model

Fuel lean conditions:

2TiHν + (1 + 0.25ν x + ν y ) KClO4 → 2TiO2 + (1 + 0.25ν x + ν y ) KCl + ν x H 2 O + 2ν y O2 (1)

2TiHν + (1 + 0.25ν x ) KClO4 → 2TiO2 + (1 + 0.25ν x ) KCl + ν x H 2 O (2)

For fuel lean conditions:

For fuel rich conditions:

∆H rxn = (571.66 + 436.68(1.5 + ν y ) + 1877.44) − (288.7 + 430.12(1.5 + ν y )) (7)

The stoichiometric coefficient (νy) in Equation (7) is

The mol fraction of fuel is related to the mass fraction

∆H rxn = (285.83ν x + 436.68(1 + 0.25ν x ) + 1877.44) − (288.7 + 430.12(1 + 0.25ν x )) (10)

and, similarly, νx is found as:

IV. Transient Pressure Predictive Model

separating variables and integrating yields:

where, P represents an average pressure over the time

Combining Equations (14-20) provides a differential

size is deemed appropriate based upon published

Section V. Modified TPPM

where the proportionality constant (b) is defined as the

Equation (30) describes the amount of energy argon

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