Combustion, Explosion, and Shock Waves, Vol. 38, No. 4, pp.

463469, 2002

Performance of Emulsion Explosives

S. Cudzilo,1 P. Kohlicek,2 V. A. Trzcinski,1 and S. Zeman2
UDC 662.215

Translated from Fizika Goreniya i Vzryva, Vol. 38, No. 4, pp. 95102, JulyAugust, 2002. Original article submitted September 18, 2001.

Some performance of a number of emulsion explosives containing glass micro-baloons were studied experimentally and theoretically. For each of the explosives, detonation velocity was measured and calculated and ballistic mortar tests and cylinder expansion tests were carried out. The results obtained enables a comparison of the usefulness of both testing methods. The inuence of some metal nitrates contained in the emulsion matrix on the performance and detonation parameters of the explosives was examined. Key words: explosives, glass micro-balloons, nitrates of metals, detonation parameters, performance.

INTRODUCTION Emulsion explosives belong to commercial explosives. They were developed in the early 1960s [1, 2] and have become quite important blasting means because of their comparatively high detonation parameters and exceptionally good safety characteristics [36]. Emulsion explosives were prepared by agitation of a supersaturated aqueous solution of some oxidizers and a fuel doped with an emulsifying agent. The composition thus prepared is extremely insensitive to initiation, and, hence, it has to be sensitized by appropriate additives (usually, polymeric or glass micro-balloons). The basic oxidizer used in emulsion explosives is ammonium nitrate (AN), and sodium and calcium nitrates are frequently added to modify properties of the oxidizer solution. The fuel phase consists of various mineral oils, waxes, and (in some cases) polymers. A distinguishing feature of emulsion explosives is that in the aqueous solution, the oxidizer is present in the form of tiny droplets covered with a very thin fuel layer. Consequently, the interfacial surface of the emulsions is very large, as a result of which their detona1

tion behavior is almost ideal, unlike other ammonium nitrate based composite fuels. This is manifested, for example, in the fact that the experimental values of detonation parameters of emulsion explosives measured at large charge diameters nearly coincide with theoretical values obtained under the assumption of complete ammonium nitrate decomposition at the detonation front. In the work described here, we studied the detonation and performance properties of ve emulsion explosives containing glass micro-balloons. The emulsion matrix was prepared using aqueous solutions of pure ammonium nitrate or its mixture with sodium, calcium, nickel, and cobalt nitrates. The contents of other ingredients were changed insignicantly in order to maintain the oxygen balance within the range of 2%. For each explosive, the detonation velocity was measured and calculated, and ballistic mortar and cylinder expansion tests were carried out. The results obtained enabled a comparison of the eciency of both methods for testing explosive performance. They were also used to analyze the eect of metal nitrates on the performance of the explosives and to choose the formulations characterized by the best detonation and performance characteristics.

Department of Explosives and Physics of Explosion, Military Technological University, Warsaw, Poland; cudzilo@wul.wat.waw.pl. 2 Department of Theory and Technology of Explosives, University of Pardubice, Pardubice, Czech Republic. 0010-5082/02/3804-0463 $27.00 c 2002 Plenum Publishing Corporation

463

464 1. TESTED EXPLOSIVES The compositions of the emulsion matrices are given in Table 1. The emulsions were prepared using a simple facility consisting of a thermostat and a container equipped with a stirrer. The solution of oxidizers was heated to 120 C and then slowly added to the container, in which a preheated (95 C) mixture of fuels (oil and polybutadiene) with the emulsier was agitated with the stirrer at a speed of 900 rpm. After adding the entire amount of the oxidizer, the agitation was continued for about two minutes to obtain ne particles of the emulsion. The nal explosive mixtures were prepared by mixing the emulsion matrices with glass micro-spheres (produced by 3M; mean size 80 m). Mixing was performed carefully (using the same stirrer but at lower speed) until the distribution of the micro-spheres in the emulsion matrix became uniform. In all experiments, the mass fraction of micro-spheres was 3% (above 100%). The initial density of the explosives was determined from the weight and volume of samples in plastic or copper tubes used in detonation velocity measurements and in cylinder expansion tests.

Cudzilo, Kohlicek, Trzcinski, and Zeman

Fig. 1. Relative performance (R) versus the parameter 0 D2 .

2. BALLISTIC MORTAR TESTS The relative performance of the explosives was measured by the procedure described in [7]. Tengram samples placed in thin tubes of 24 mm diameter were detonated with a cap inside the explosive chamber (283 cm3 in volume) of the mortar. The magnitude of the pendulum deection was recorded and used to obtain (from a calibration curve) the relative performance dened as the ratio of the mass of the blasting charge of the tested explosive to the mass of dynamite that produces the same pendulum deection. Values of the relative performance obtained in this way are listed in Table 2, which also gives experimental values of density of (0 ), detonation velocity (Dexp ), and some calculated characteristic for the explosives (Dideal is the ideal detonation velocity, [AN]inert is the fraction of ammonium nitrate that remained inert in a detonation wave, and ng is the number of moles of gaseous detonation products). The detonation velocity was measured by ionization sensors. The explosive charges were conned in plastic tubes 250 mm long with an inner diameter of 32 mm. In each charge there were measuring courses 50 mm long, and the rst sensor was at 90 mm from the booster. These values were large enough to enure a steady detonation and determination of the detonation velocity with an accuracy of 1%.

Theoretical calculations of detonation parameters (Dideal , [AN]inert , and ng ) were performed using the thermodynamic code CHEETAN [8] with the following coecients of the BKW equation of state recommended in [9]: = 0.5, = 0.298, = 10.5, and = 6620. These values were optimized using a very large product database and measured ChapmanJouguet properties compiled by Hobbs and Baer [9]. The basis for determining the amount of ammonium nitrate that did not reacted in the detonation wave was the conformity of experimental and theoretical values of detonation velocity. An analysis of the data in Table 2 shows that the formulation containing only AN as the oxidizer has the highest performance and detonation parameters. Partial substitution of nickel nitrate (ANNiN) or sodium nitrate (ANNaN) for ammonium nitrate causes a substantial decrease in performance. This can be explained by the fact that these explosives generate smaller amounts of gaseous detonation products. The data of Fig. 1 show how the introduction of metal nitrates into the emulsion matrices aects both the detonation and performance characteristics. From the results presented in the gure it follows that the use of calcium nitrate (ANCaN) as an additional oxidizer deteriorates the parameters considered most insignicantly, whereas the addition of sodium nitrate (AN NaN) to the mixture gives an explosive with comparatively high detonation parameters but its performance is rather poor. The absence of correlation between

Performance of Emulsion Explosives TABLE 1

Composition of Emulsion Explosives Mass fraction of components, % Explosive NH4 NO3 (AN) 84.0 82.0 65.6 67.3 67.3 65.7 H2 O Emulsier Mineral oil 3.6 3.3 3.6 3.4 3.4 3.6 Polybutadiene 0.5 0.5 0.8 0.3 0.3 0.7 Ca(NO3 )2 4H2 O (CaN) 15.0 Ni(NO3 )2 6H2 O (NiN) 15.0 Co(NO3 )2 6H2 O (CoN) 15.0 NaNO3 (NaN) 15.0

465

AN AN ANCaN ANNiN ANCoN ANNaN

10.0 12.0 13.0 12.0 12.0 13.0

1.9 2.2 2.0 2.0 2.0 2.0

Notes. Here and below AN is the composition used only in ballistic mortar tests and AN is the composition used only in cylinder expansion tests.

TABLE 2
Characteristics of Explosive in Ballistic Mortar Tests Explosive AN ANCaN ANNiN ANCoN ANNaN Relative performance, % 74 73 65 72 67 0 , kg/m3 1051 1073 1109 1063 1077 Dexp , m/sec 5100 4800 4410 4560 4740 Dideal , m/sec 5924 5716 5712 5559 5575 [AN]inert , % 25.8 33.2 47.5 36.8 36.6 ng , mole/kg 34.43 31.78 28.32 31.24 29.04

the relative performance and the parameter 0 D2 indicates that there are other factors inuencing these characteristics. One of these can stem from the fact that the relative performance and detonation velocity were measured for dierent samples and under dierent conditions. Therefore, we conducted cylinder expansion tests to determine the performance of the explosive using some energy parameters obtained during these tests [10]. 3. CYLINDER EXPANSION TEST The so-called cylinder expansion test consists of recording a chosen stage of acceleration of a shell driven by expanding products of detonation grazing along the internal surface of the shell (copper tube). Expansion of the detonation products can be recorded by methods used to measure fast processes, such as streak photography, laser interferometry or ash radiography. Results of recording the acceleration process are commonly employed to derive a semi-empirical equation of state of detonation products [1114]. Moreover, cylinder test data can be used to determine some other important

characteristics of explosives. For example, from the dependence of the radial displacement of the external tube wall on the axis coordinate, it is possible to determine the expansion velocity of the shell and then the Gurney energy and detonation energy of the tested explosive [15, 16]. In the present work, the cylinder expansion test was employed to obtain some quantitative energy parameters of the emulsion explosives. Their experimental and calculated characteristics are shown in Table 3. Here the values of Dexp are much larger than those in Table 2. This indicates that in cylinder expansion tests, more ammonium nitrate reacts in the detonation wave and there is better agreement between measured and theoretical detonation velocities. A comparison of the data of Table 2 and 3 shows that the performance of the charge shell has a strong eect on detonation parameters, which is manifested in nonideal detonation properties. A notable feature of the quantity ng is that in cylinder expansion tests, compositions containing sodium and nickel nitrates yield a smaller amount of gaseous detonation products. However, the dierence between

466 TABLE 3

Cudzilo, Kohlicek, Trzcinski, and Zeman

Experimental and Calculated Characteristics of Explosive Used in Cylinder Expansion Tests Explosive AN ANCaN ANNiN ANCoN ANNaN 0 , kg/m3 1062 1065 1146 1093 1079 Dexp , m/sec 5460 5095 5240 5200 5040 Dideal , m/sec 5973 5680 5872 5687 5584 [AN]inert , % 17.0 22.5 29.3 21.4 27.0 ng , mole/kg 37.47 34.78 33.54 35.58 31.62

3.1. Accelerating Ability of Detonation Products Gurney Energy One of the parameters that can characterize explosive performance is the accelerating ability of detonation products. Souers and Kury [17] proposed to evaluate this parameter using velocities of an accelerated copper tube under cylinder test conditions at volume expansion ratios of 2.2, 4.1, and 6.5. The accelerating ability can also be described as the Gurney energy EG , which is the sum of the kinetic energy of a driven liner and detonation products following it [18]. In the case of a cylindrical liner, the Gurney energy is given by the equation 1 u2 L , (1) EG = + 2 2 where is the ratio of tube mass to explosive mass and uL is the total velocity of the tube. Usually, in the literature one can nd nal values of the Gurney energy or Gurney velocity equal to the square root of the doubled Gurney energy. The parameters correspond to the velocity of a tube with radius for which integrity of the tube material is still preserved [18]. Trzcinski [15] showed that the accelerating ability of an explosive can be estimated using the dependence of Gurney energy [dened by relation (1)] on the relative volume of expanding detonation products. From Eq. (1) it follows that to obtain this dependence, it is necessary to know the total velocity of the tube (uL ) driven by detonation products. A detailed description of the procedure of determining tube velocity using the dependence of the position of the external surface of the tube on axial coordinate recorded in a cylinder test is given in [15]. The position of the central cylindrical surface (rm ) was rst determined. Under the assumption of incompressible tube material, the value of rm can be found from the relation 1 2 2 r ri2,0 , (2) rm = re 2 e,0

Fig. 2. Radiograph of a copper tube driven by detonation products of the composition AN .

them and the other explosives is not as large as that in ballistic mortar tests (see Table 2). The expansion of a copper tube driven by detonation products was recorded by a SCANDIFLASH x-ray setup [10, 13]. The copper tube lled with the explosive tested was placed at a distance of 2.7 m from the x-ray source and at 0.5 m from the recording lm. The charge was xed vertically, and the line connecting the x-ray source and the lm was perpendicular to the charge axis. The copper tubes were 300 mm long, and their inner diameter and wall thickness were 25 mm and 2.5 mm, respectively. The sensor triggering the x-ray pulse was at 20 mm from the end of the charge. This allowed us to observe continuously the expansion of detonation products for 40 sec until the detonation wave reached the charge section in which the sensor was placed. Figure 2 gives a radiograph of a copper tube driven by detonation products of the composition AN , which was used only in cylinder expansion tests. From the photograph, the dependence of the outer radius of the tube on the axial coordinate was determined using computer processing. The examined range of the axial coordinate was limited to the value for which the volume of detonation products was 910 times larger than the initial volume. This dependence along with data on detonation velocity (see Table 3) was used to determine the explosive performance.

Performance of Emulsion Explosives

467

Fig. 3. Radial displacement of the central surface of the tube versus time: the points refer to the experiment and the curves refer to Eq. (3).

Fig. 4. Gurney energy versus relative volume of detonation products.

where re,0 and ri,0 are the initial radii of the external and internal surfaces and re and rm are the current radii of the external and central surfaces of the tube at a given distance x. Assuming that the motion of the detonation products and the tube is stationary (i.e., x = Dt, where D is the detonation velocity and t is time), we can replace the dependence rm (x) by the dependence rm (t). In [15], the position of the central surface of the tube in time is approximated by the function rm = rm,0 +
i

ai {bi (t t0 ) [1 exp(bi (t t0 ))]}, (3)

where rm,0 is the initial value of rm and ai , bi , and t0 are parameters. The thus obtained dependence rm (t) is shown in Fig. 3. Having determined the relations rm (t) and dierentiating Eq. (3), we can calculate the radial velocity of the tube drm um = ai bi [1 exp(bi (t t0 ))], (4) dt i and, then, the total velocity um uL = 2D sin , = arctan . (5) 2 D Using Eqs. (4) and (5) and the measured detonation velocities (see Table 3), we determined values of uL and then evaluated EG by Eq. (1). The calculated dependence of Gurney energy on the relative volume of detonation products (v/v0 ) is shown in Fig. 4.

An analysis of the curves in Fig. 4 shows that for v/v0 > 6, the Gurney energy of the composition AN practically does not increase, which is characteristic of strong explosives. Thus, the values of EG for emulsion explosives containing only ammonium nitrate are nearly ideal. If an explosive contains metal nitrates, the Gurney energy increases slowly but continuously even for v/v0 > 6. This shows that in this case, the energy release behind the detonation front is decelerated. The addition of nickel and sodium nitrates leads to the most considerable decrease in the detonation properties of the composition AN . Figure 5 shows a curve of EG (0 D2 ). For v/v0 = 2.5, it is close to that given in Fig. 1, and for v/v0 = 9, the data for all explosives lie on one line. This implies that there is a linear relationship between explosive performance and detonation parameters. The data of Figs. 4 and 5 also suggest that in charges with a strong connement, chemical reactions in expanding detonation products occur during a long period of time and the released additional energy is converted to the expansion work of detonation products.

3.2. Expansion Work of Detonation Products In the literature (see, for example, [19, 20]), the expansion work of detonation products w is dened as the work of the products expanding from volume at the ChapmanJouguet point (vCJ ) to a volume v minus the energy of compression of the explosive:

468

Cudzilo, Kohlicek, Trzcinski, and Zeman TABLE 4

Eective Poisson Adiabatic Exponent Explosive AN ANCaN ANNiN ANCoN ANNaN 2.86 2.85 2.80 2.84 2.83

Fig. 5. Gurney energy versus the parameter 0 D2 .

v

w(v ) = ec +
vCJ

p dv.

(6)

To evaluate the expansion work, it is necessary to know the isentrope of expansion of detonation products. A simple isentrope is the Poisson adiabat vCJ p = pCJ , (7) v where is the adiabatic exponent. To determine constants in Eq. (7), it is necessary to know values of two detonation parameters. The rst of these is usually experimental detonation velocity and the second is the exponent of isentrope of detonation products. Most often it is the so-called eective exponent of isentrope, which is not determined from the real isentrope in a certain range of volume of detonation products rather than from parameters at the ChapmanJouguet point. According to the procedure proposed in [13, 21], its value can be determined from results of a cylinder expansion test. In this method, an experimental prole of a copper tube is compared with that obtained by numerical modeling of the expansion process. The state of detonation products is described by Poissons adiabat (7). As a result, a value is chosen that ensures best agreement between the calculated and experimental proles of the tube. The eective exponent of isentrope of detonation products for the tested explosives are given in Table 4. After integration using relation (7), from Eq. (6) we obtain the following expression for the expansion work: vCJ 1 pCJ vCJ + 1 . (8) w= 1 2 v

Fig. 6. Expansion work of detonation products calculated using the Poisson adiabat.

The dependence of the expansion work calculated by relation (8) on the relative volume of detonation products is given in Fig. 6. The gure also shows the interval of volume of detonation products corresponding to the pressure range for rock blasting [22]. As soon as rock begins to fracture, cracks form and detonation products penetrate into then, thus weakening the destructive eect of the explosive. Therefore, it is assumed that the values of expansion for v/v0 = 10, 15, and 20 can be used to compare the eciency of explosion in hard, strong, and weak rock [22]. As might be expected, the composition containing only ammonium nitrate performed the greatest expansion work (among the tested explosives). This result is obtained with the usage of both experimental methods. However, for dierent explosives there is some dierence in results obtained by dierent methods. It is dicult to reliably determine which of them is more accurate because the dierence is rather insignicant. However, taking into account that the sample mass was larger in cylinder tests and the duration of expansion in this case was also much longer, it is concluded that the data of these experiments are more exact in comparing the blasting performance of explosives.

Performance of Emulsion Explosives CONCLUSIONS The results of the experiments described here show that the cylinder test can be used with advantage for quantitative determination of explosive performance. Gurney energy is easy to determine from radiographs of the motion of the copper tube wall. Results of these experiments together with data of numerical modeling of the process allow one to obtain the equation of state for detonation products and, hence, to estimate their eective expansion work. The addition of metal nitrates to emulsion compositions deteriorates the detonation properties of explosives containing only ammonium nitrate, which is manifested in a decrease in both detonation parameters and performance. The decrease in performance is most considerable in the initial stage of expansion of detonation products. With increase in the volume of detonation products, these discrepancies decrease. This implies that chemical reactions also proceed in expanding detonation products and additional energy released in these reactions is converted to mechanical work. For this reason, detonation parameters and performance characteristics determined in the initial stage of expansion depend strongly on charge diameter and type shell type. In this connection, the most realistic values of performance can be obtained in cylinder tests rather than in ballistic mortar tests. The authors are grateful to Jiri Tesitel (The Research Institute of Industrial Chemistry, Pardubice, Czech Republic) for his help in some of experiments and to Professor Andrzej Maranda (Military University of Technology, Warsaw, Poland) for many discussions and helpful suggestions.
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