CLOSED VESSEL TEST: INFLUENCE OF THE IGNITION METHOD ON THE COMBUSTION RATE. Laurence Jeunieau1, Michel H.

Lefebvre1, Alexandre Papy2, Marc C. Pirlot2, Pierre Guillaume3, Christiane Reynaud4

1

Laboratory for Energetic Materials, Royal Military Academy Av. de la Renaissance 30, 1000 Brussels, Belgium Fax: +32(0)2 7376352 E-mail: laurence.jeunieau@rma.ac.be

Department of Weapon Systems and Ballistics, Royal Military Academy

3

PB Clermont s.a.

Rue de Clermont 176, 4480 Engis/ Belgium.

4

Centre de Recherches du Bouchet, SNPE,

Rue Lavoisier 9, 91710 Vert-le-Petit/ France Abstract A method of homogeneous ignition of deterred spherical particles has been proposed. The ignition mixture 0.05 MPa CH4-0.075 MPa O2 permits to discriminate the combustion properties of the two parts of the particles. This ignition method does not introduce additional influence on the combustion rate compared to the classical ignition by black powder. 1. Introduction The ballistic performance guns can be improved by the use of less degressive burning propellants. For this purpose, deterred propellants can be used especially in small arms. In deterred propellants, the concentration of deterrent in the surface layer is larger than that in the core of the propellant particles.

In ballistic models, factors characterising the burning rate of the propellant must be introduced. These factors are usually obtained in closed vessel experiments. These ones must be different for the two parts of the propellant particles. No difference between them can be observed if black powder is used as ignition system. The aim of this work is to investigate closed vessel tests, which permit to see clearly the difference between the two parts of the particles. For this purpose, an homogeneous ignition system is required. This study focuses on the influence of the ignition phase on the final experimental output (i.e. burning rate) of these tests. In order to have a homogeneous ignition of the propellant particles, gaseous ignition systems are investigated. These ignition systems are not comparable to the ones used in the actual combustion chamber of guns where ignition is done either by hot particles or by hot gases. In fact, the ballistic properties depend on the igniter [1]. Therefore, ballistic models must take into account the nature of the igniter and the more or less homogeneous ignition of the propellant. For this purpose, the following scheme of investigation is followed in this paper. Different ignition mixtures of methane and oxygen are investigated. These ignition systems are compared with the commonly used ignition by black powder. The possible influence of the ignition system on the combustion rate is investigated. At this state, an ignition system is selected. This ignition system is tested on propellants with different penetration depths of the deterrent to confirm that the two combustion processes correspond to the two chemical formulations of the particles. 2. Experimental Propellants used The different ignition systems have been tested on a spherical deterred propellant with an average diameter of 0.77mm. The selected ignition system has been tested on different spherical propellants with different types of coating. The characteristics of these propellants are shown in Table 1 (the percentage in

weight of deterrent in the particle is given). For propellants A and B all the dibutylphthalate is in the deterred portion of the particles. For the propellants C and D, some of the dibutylphthalate is in the inner part of the particle. Diameter (mm) Propellant A Propellant B Propellant C Propellant D 1.00 1.01 1.02 0.96 % dibutylphthalate in the powder 7% 7.4% 8.5% 7.9% % dibutylphthalate in the inner part 2% 1.8%

Table 1: Characteristics of the different investigated propellants.

Ignition system used The compositions of the different ignition systems are shown in Table 2. The gaseous ignition systems are characterized by their partial pressures. Igniter I Igniter II Igniter III Igniter IV Igniter V Igniter VI Composition 0.1 MPa CH4-0.2 MPa O2 0.1 MPa CH4-0.14 MPa O2 0.05 MPa CH4-0.075 MPa O2 0.1 MPa CH4-0.1 MPa O2 0.05 MPa CH4-0.05 MPa O2 Black powder (loading density: 0.007g/cm3)

Table 2: Characteristics of the different investigated ignition systems.

Closed vessel experiments Closed vessel experiments were carried out in a vessel of 140cm3 using a piezo-electric pressure transducer (Kistler 6201B4) to record the pressure. The output voltage of the pressure gauge was transferred to a data acquisition system (Nicolet Multipro, resolution 12 bit, sampling frequency 250KHz). The propellant loading density is 0.20g/cm3. The ignition system consists of two electrodes, which are connected with a nickeline hot wire, and a valve to introduce a CH4/O2 ignition mixture. The partial pressures of these mixtures are measured with a piezo-electric pressure transducer (Kistler 4070). When black powder is used as ignition method, 1g of powder is used. The combustion rate is calculated according to Stanag 4115 [2].

3. Results 3.1 Preliminary observations Figure 1 shows different combustion rates obtained with ignition by different gas mixtures and with black powder. Three types of combustion rate vs. pressure have been observed. (1) The largest combustion rate is obtained when using igniter I. In this case, important oscillations of the pressure are noticed. (2) For the igniters II and III, intermediate combustion rates are obtained. (3) When less energetic ignition mixtures are used (igniters IV and V) combustion rates similar to the one obtained with the black powder are observed. The important oscillations of the pressure which are noticed for the igniters I and II may be due to shock waves stemming from the detonating gas mixtures.

35 30
Combustion rate (cm/s) .

25 20 15 10 5 0 0 50 100 150 Pressure (MPa)

(I)

(II) (III)

(IV)

(V)

(VI)

200

Figure 1: Combustion rate of the deterred propellant obtained with different ignition systems. (I) Igniter I , (II) Igniter II, (III) Igniter III, (IV) Igniter IV, (V) Igniter V and (VI) Igniter VI .

Figure 2 shows some of the pressure derivative vs. time. The pressure derivative permits to distinguish clearly two phases in the combustion process when igniter I, II or III is used as ignition system. In fact, two different positive slopes can be observed in the pressure derivative vs. time. In the other cases, the variation of the derivative vs. time is more regular and the combustion process can no more be divided in two parts. The lack of discontinuity could stem from the inhomogeneous ignition of the propellant by the black powder. When ignition is inhomogeneous, the deterred layers of all the particles do not burn simultaneously. When one particle has its deterred layer burnt and Thus the observed combustion rate is 2
(I)

therefore its combustion rate increased the other particles may have their deterred layer not completely burnt. 1 more or less a smooth average of the overall combustion rate.
200 180 160 200 180 160

dP/dt (MPa/ms)

140 120 100 80 60 40 20

dP/dt (MPa/ms)
3 4 -5 -4 -3 -2

(III)

140 120 100 80 60 40 20 0

-5

-4

-3

-2

0 -1 0 1 time (ms)

-1 0 1 time (ms)

Figure 2: Derivative of the pressure vs. time for different ignition systems. 1 (I) Igniter I, (III) Igniter III. 2 Igniter VI.

The fact that the observed discontinuity in the derivative curve corresponds to the burning of the deterred layer has to be confirmed. If it does, the thickness of this layer can be calculated. This will be a first test to check whether the discontinuity corresponds to the end of the combustion of the deterred layer. If this is the case, the obtained thickness of the deterred layer should be the same for different loading densities and for different ignition

systems. To obtain the burnt thickness, the discontinuity in the derivative curve is associated with a time and from these with a pressure. From the pressure, the burnt mass fraction (zbreak) can be calculated using equation (1) where , , Pmax, Pmin, Pbreak, are the loading density, the propellant density, the maximum experimental pressure, the pressure resulting from the igniting gaseous mixture, the pressure corresponding to the discontinuity in the derivative curve and the covolume, respectively.
1 1 # $ ! K Pmax 1 Pmin 1 1 # + "#" + Pbreak ! Pbreak ! Pbreak 1 1 # $ ! Pmax # Pmin 1 1 # Pbreak + " Pbreak # " Pmax + Pmin $ ! ! Pmin

z break =

Pmax # Pmin $

(1)

K#

This equation permits to take into account the pressure coming from the ignition system (Pmin). As this pressure is not identical for all the ignition systems, it has to be taken into account in order to obtain comparable results. As the burnt mass fraction is defined by equation (2) where V is the propellant volume and V0 its initial value, the thickness of the deterred layer can be easily calculated from the propellant volume. The obtained values are given in Table 2.

z = 1!
Igniter Igniter I Loading density (g/cm3) 0.1 0.15 0.20 0.25 0.20 0.10 0.15 0.20

V V0

(2)

Igniter II Igniter III

Thickness of the deterred layer (mm) 0.042 0.048 0.049 0.046 0.047 0.044 0.041 0.041

Table 2: Thickness of the deterred layer for different ignition systems and for different loading densities.

These different values show that the discontinuities in the derivative curves are related neither to the ignition composition nor to the initial pressure.

At this stage, it must be checked that the ignition system does not influence the combustion rate of the propellant. For this purpose, the properties of the ignition systems have been studied thoroughly and the influence of the ignition system on the chemical reaction products has been investigated. 3.2 Comparative study of the ignition methods 3.2.1 Study of the ignition systems In order to characterize the different ignition systems, closed vessel experiments of the gas mixtures alone and of the black powder have been performed. Different pressure-time curves are shown in Figure 3. Thermodynamic calculations have been done with the ICT code [3]. For these calculations the presence of air in the closed vessel has been taken into account. Table 3 resumes different characteristics of the igniters.
8 7 6 (I) (II)

Pressure (MPa)

5 4 (III) 3 2 1 0 -5 -3 -1 1 3 time (ms) 5 7 (V) ( (IV) (VI)

Figure 3: Pressure vs. time curves of the different ignition systems. (I) Igniter I, (II) Igniter II, (III) Igniter III, (IV) Igniter IV, (V) Igniter V and (VI) Igniter VI.

Igniter I Igniter II Igniter III Igniter IV Igniter V Igniter VI

Detonationa Yes Yes Yes No No -

Instabilitiesb Yes Yes No No No No

rp/rpVIc Highest Higher Higher Similar Similar -

Pmaxd (MPa) 5.38 4.68 2.52 3.60 1.87 2.64

Pmaxe (MPa) 5.48 4.90 2.87 4.24 2.56 3.10

Texplosion, (K) 3581 3555 3377 3254 3227 2002

Energyf (J) 3252 2841 1632 2308 1400 2186

Table 3: Different characteristics of the igniters. (a) The detonation limits are not known in the used experimental setting. The used detonation limits (0.105-0.98 PCH4 / PO2 ) are obtained in a tube with a diameter of 1 cm [4]. (b) The combustion instabilities refer whether or not important oscillations are observed in the experiments. (c) Comparison of the obtained burning rate with the one obtained with the black powder (igniter VI). (d) Experimental maximum pressure. (e) Theoretical maximum pressure. (f) The energy has been obtained by E= Cv * T*migniter

The important oscillations observed for igniter I and II in the closed vessel test experiments with and without propellant may be due to the detonation of the gas mixture. The composition of igniter III is also in the detonation limit. But these limits are for methane mixed with pure oxygen. In fact, the critical energy for direct initiation of detonation increases significantly when the percentage of diluant increases [5]. The maximum pressure is relatively important for igniter I, II and IV. The maximum pressure of igniter III and VI are in the same order. The explosion temperature is far lower for the igniter VI than for the gaseous ignition systems. The energy produces by the igniter is important for igniter I, II and IV. It is also in the same order for igniter III and VI. The slope of the pressure-time curve (Fig.3) is lower for igniter VI and is more important for igniter I and II. From these results, the only factor that can be related to the change of combustion rate as a function of the igniter is the slope of the pressure-time curve. In fact, the gaseous ignition systems, which have a similar combustion

rate than the black powder, have also the slowest increase in pressure. This factor can be related to a more or less homogeneous ignition of the propellant. The more the combustion of the igniter is rapid the more the ignition must be homogeneous. 3.2.2 Effect of the ignition system on the chemical composition A required important characteristic for an experimental ignition system is that it must not affect the determination of the combustion rate. In fact, it is considered that the first part of the pressure-time curve is somehow influenced by the ignition system and consequently for the determination of the combustion rate only the range between 30%-70% of the maximum pressure is used [2]. Table 4 shows the influence of the ignition system on the combustion of the propellant. Two factors have been considered: first, the ratio between the molar percentage of CO2 and H2O (rich oxygen species) vs. the percentage of CO and H2 (poor oxygen species) and secondly, the percentage difference of the explosion temperature. The amount of rich oxygen species increases by adding the igniter. The increases are more important for the igniter I and VI. The explosion temperature increases when the ignition system is gaseous and decreases when black powder is used. The increase due to igniter I is important.

%CO 2 + %H 2 O () %CO + %H 2
Propellant +Igniter I +Igniter II +Igniter III +Igniter IV +Igniter V +Igniter VI 0.418 0.444 (5.80%) 0.432 (3.35%) 0.429 (2.63%) 0.424 (1.44%) 0.424 (1.44%) 0.436 (4.28%)

%Texplosion 2.61 0.90 0.95 0.61 0.46 -0.71

Table 4: Influence of the ignition system on the propellant. The percentages used in the calculations are the percentages in mole. The figures between brackets are the percentages of increase of the ratio due to the igniter.

At this point, an ignition system must be selected. Igniter I and II must be excluded, important oscillations in the pressure-time curves are observed and the maximum pressure of the igniter alone in the closed vessel is high. Igniter IV has also a high maximum pressure and produces a lot of energy. It must therefore also been excluded. The increase of rich oxygen specie due to igniter III is important, but the increase due to igniter VI is larger. As the igniter III permits to see a difference between the two parts of the particles, it is selected. 3.3 Study of propellants with different deterrent penetration depths Now that an ignition system has been selected, one must check whether or not the discontinuity in the curves is actually due to change in chemical composition. 1. As at the end of the coating, almost all the deterrent is in the particles, the penetration depth must follow the same sequence than the percentage of deterrent. Figure 4 shows the obtained combustion rate with the Igniter III and with the igniter VI. The difference between the different propellants is noticeable when the gas ignition mixture is used. A great difference is observed between the propellants with and without dibutylphthalate in their inner core. A difference of combustion rate is observed between propellants A and B. The increase of combustion rate appears further in the case of propellant B than for propellant A. This is to be related to the higher percentage of deterrent in propellant A resulting in a larger coating layer. A small difference is also observed between propellant C and D. When black powder is used, a slight difference is observed between the propellants, whit and without dibuthylphtalate in their inner core. For this purpose, spherical propellants with different concentrations in deterrent are used. These propellants are described in Table

1
20 18 16 14 12 10 8 6 4 2 0 0 50 100 Pressure (MPa) 150 (d) (c)

2
20 18

Combustion rate (cm/s).

(b)

Combustion rate (cm/s).

(a)

16 14 12 10 8 6 4 2 0 0 50 100 Pressure (MPa) 150 (c),(d) (a),(b)

Figure 4: Combustion rates of (a) Propellant A, (b) Propellant B, (c) Propellant C, (d) Propellant D.1 Igniter III 2 Igniter VI

Figure 5 shows the derivative of the pressure vs. time. If the gas mixture is used as ignition system, a difference can be easily observed between the different propellants (Fig. 5-1). The discontinuity occurs first for propellant A, followed by propellant B. This is the variation expected from the different percentages in deterrent. Propellant C and D have a more gradual increase of their derivative curve. This comes from the deterrent in the inner core of the particles. Therefore the difference between the two chemical compositions of the particles is less important. It can be seen that the discontinuity occurs first for propellant C than for propellant D, this stems from the higher deterrent concentration of propellant C. If the black powder is used as ignition system, a difference can be observed only between the propellants with and without dibutylphthalate in their inner core.

1
120 100
(b) (a)

2
120 100
(b) (a) (c)

(d)

80 60 40
(c)

dP/dt (MPa/ms).

dP/dt (MPa/ms)

(d)

80 60 40 20

20 0 -1 1 time (ms)

-5

-3

-5

-3

0 -1 1 time (ms)

Figure 5: Derivative curves (a) Propellant A, (b) Propellant B, (c) Propellant C, (d) Propellant D. To clarify the graphs, the curves of propellant B and D are in gray. 1. Igniter III 2. Igniter VI.

Table 5 shows the penetration depth of the propellants obtained as previously explained for the propellants ignited by the gas mixture. expected, the penetration depth increases with the deterrent concentration. Propellant A Propellant B Propellant C Propellant D Penetration depth (mm) 0.076 0.095 0.102 0.098 As

Table 5: Penetration depths corresponding to the discontinuities in the derivative curves (see Equation (1) for calculation procedure).

4 Conclusions This study demonstrates the possibility to observe in closed vessel experiment the difference between the two chemical compositions of a deterred propellant. First, different gaseous ignition systems have been tested. It has been clearly observed that the ignition system has a significant influence on the combustion rate. Three of the tested ignition systems permit to see a

discontinuity in the measured combustion rate as a function of the pressure. These discontinuities are emphasized in their pressure-time derivative curves. Secondly, attention has been taken on the possible perturbation of the combustion rate by the ignition systems. It has been concluded that the gaseous ignition system 0.05 MPa CH4-0.075 MPa O2 has little influence on the combustion rate. In fact, the difference observed for the combustion rate must be due to a more homogeneous ignition. Finally, gaseous ignition mixtures and black powder as benchmark have been used to ignite propellant with different deterrent penetration depths. It has been observed that the ignition system 0.05 MPa CH4-0.075 MPa O2 emphasizes the difference between the two parts of the propellants and between the different propellants. Research is being done for characterizing more deeply this ignition system. This includes the measurement of the dibutylphthalate penetration This will permit to correlate the calculated depth by infra-red microscopy.

penetration depth to the experimental one. Tests in an interrupted closed bomb are also in progress. This will provide a real insight on the homogeneity of the ignition. References [1] A. Steinmann, B. Vogelsanger, U. Schaedeli, E. Rochat, G. Giusti, Influence of different ignition systems on the interior ballistics of an EI-propellant, 19th International Symposium of Ballistics, 7-11 May 2001, Interlaken, Switzerland, p123. [2] Stanag 4115, Definition and determination of ballistic properties of gun propellants. North Atlantic Council, 1997. [3] Bathelts H. and Volk F., ICT-thermodynamic code Fraunhofer-Institut fr Chemsiche Technologie, 1988. [4] A. Van Tiggelen, Oxydations et combustions, Publications de lInstitut Franais du Ptrole, 1968. [5] D.C. bull, J.E. Elsworth, G. Hooper and C.P. Quinn, A Study of spherical detonation in mixtures of methane and oxygen diluted by nitrogen, J. Phys D., vol 9, 1976, p1991