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

463–469, 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. 95–102, July–August, 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 influence 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 [3–6]. 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 five 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 insignificantly 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 efficiency of both methods for testing explosive performance. They were also used to analyze the effect 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; 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


These values were large enough to enure a steady detonation and determination of the detonation velocity with an accuracy of ≈1%. 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 data of Fig. After adding the entire amount of the oxidizer. [AN]inert . and ng is the number of moles of gaseous detonation products). 1. In all experiments. The magnitude of the pendulum deflection was recorded and used to obtain (from a calibration curve) the relative performance defined as the ratio of the mass of the blasting charge of the tested explosive to the mass of dynamite that produces the same pendulum deflection. 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. Cudzilo. which also gives experimental values of density of (ρ0 ). The explosive charges were confined in plastic tubes 250 mm long with an inner diameter of 32 mm. The emulsions were prepared using a simple facility consisting of a thermostat and a container equipped with a stirrer. [AN]inert is the fraction of ammonium nitrate that remained inert in a detonation wave. and some calculated characteristic for the explosives (Dideal is the ideal detonation velocity. and the first sensor was at 90 mm from the booster. in which a preheated (95◦ C) mixture of fuels (oil and polybutadiene) with the emulsifier was agitated with the stirrer at a speed of 900 rpm. æ = 10. detonation velocity (Dexp ). The final explosive mixtures were prepared by mixing the emulsion matrices with glass micro-spheres (produced by 3M. and Zeman Fig. The detonation velocity was measured by ionization sensors. 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. 2. The solution of oxidizers was heated to 120◦ C and then slowly added to the container. These values were optimized using a very large product database and measured Chapman–Jouguet properties compiled by Hobbs and Baer [9]. From the results presented in the figure it follows that the use of calcium nitrate (AN–CaN) as an additional oxidizer deteriorates the parameters considered most insignificantly.5. The absence of correlation between . Theoretical calculations of detonation parameters (Dideal . 1 show how the introduction of metal nitrates into the emulsion matrices affects both the detonation and performance characteristics. Relative performance (R) versus the parameter ρ0 D2 . BALLISTIC MORTAR TESTS The relative performance of the explosives was measured by the procedure described in [7]. Trzcinski. the agitation was continued for about two minutes to obtain fine particles of the emulsion. the mass fraction of micro-spheres was 3% (above 100%). mean size ≈80 µm). 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. and ng ) were performed using the thermodynamic code CHEETAN [8] with the following coefficients of the BKW equation of state recommended in [9]: α = 0. In each charge there were measuring courses 50 mm long. 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. Kohlicek. This can be explained by the fact that these explosives generate smaller amounts of gaseous detonation products. β = 0. and θ = 6620.464 1.298. 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. TESTED EXPLOSIVES The compositions of the emulsion matrices are given in Table 1. Partial substitution of nickel nitrate (AN–NiN) or sodium nitrate (AN–NaN) for ammonium nitrate causes a substantial decrease in performance.5. Values of the relative performance obtained in this way are listed in Table 2.

m/sec 5100 4800 4410 4560 4740 Dideal .6 ng . it is possible to determine the expansion velocity of the shell and then the Gurney energy and detonation energy of the tested explosive [15.0 1.9 2. mole/kg 34. A notable feature of the quantity ng is that in cylinder expansion tests.2 47.0 — — — Ni(NO3 )2 · 6H2 O (NiN) — — — 15.8 33. % Explosive NH4 NO3 (AN) 84.0 12. which is manifested in nonideal detonation properties.24 29. A comparison of the data of Table 2 and 3 shows that the performance of the charge shell has a strong effect on detonation parameters. Expansion of the detonation products can be recorded by methods used to measure fast processes. Their experimental and calculated characteristics are shown in Table 3.0 65.3 67.3 3.5 0.0 13. more ammonium nitrate reacts in the detonation wave and there is better agreement between measured and theoretical detonation velocities.0 12. For example. In the present work.6 3.Performance of Emulsion Explosives TABLE 1 Composition of Emulsion Explosives Mass fraction of components.0 82. TABLE 2 Characteristics of Explosive in Ballistic Mortar Tests Explosive AN∗ AN–CaN AN–NiN AN–CoN AN–NaN Relative performance. One of these can stem from the fact that the relative performance and detonation velocity were measured for different samples and under different conditions.5 0. the cylinder expansion test was employed to obtain some quantitative energy parameters of the emulsion explosives.2 2. such as streak photography.0 — NaNO3 (NaN) — — — — — 15.0 2. m/sec 5924 5716 5712 5559 5575 [AN]inert . we conducted cylinder expansion tests to determine the performance of the explosive using some energy parameters obtained during these tests [10].3 0.3 0.4 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).0 Notes. However. the difference between . Therefore. % 25.43 31. Here the values of Dexp are much larger than those in Table 2.0 2.6 67.78 28. laser interferometry or flash radiography.0 12.0 2.4 3.7 H2 O Emulsifier Mineral oil 3.0 — — Co(NO3 )2 · 6H2 O (CoN) — — — — 15.3 65. % 74 73 65 72 67 ρ0 . compositions containing sodium and nickel nitrates yield a smaller amount of gaseous detonation products. Here and below AN∗ is the composition used only in ballistic mortar tests and AN∗∗ is the composition used only in cylinder expansion tests.32 31.7 Ca(NO3 )2 · 4H2 O (CaN) — — 15.6 3.0 465 AN∗ AN∗∗ AN–CaN AN–NiN AN–CoN AN–NaN 10. This indicates that in cylinder expansion tests.8 36.0 13.8 0. from the dependence of the radial displacement of the external tube wall on the axis coordinate. Moreover.04 the relative performance and the parameter ρ0 D2 indicates that there are other factors influencing these characteristics. cylinder test data can be used to determine some other important characteristics of explosives. 16]. kg/m3 1051 1073 1109 1063 1077 Dexp . Results of recording the acceleration process are commonly employed to derive a semi-empirical equation of state of detonation products [11–14].6 Polybutadiene 0.5 36. 3.

4. % 17. Radiograph of a copper tube driven by detonation products of the composition AN∗∗ . 2. The copper tubes were 300 mm long.5 m from the recording film. (1) EG = µ + 2 2 where µ is the ratio of tube mass to explosive mass and uL is the total velocity of the tube.0 22.5. mole/kg 37. The examined range of the axial coordinate was limited to the value for which the volume of detonation products was 9–10 times larger than the initial volume. Usually. This dependence along with data on detonation velocity (see Table 3) was used to determine the explosive performance. which is the sum of the kinetic energy of a driven liner and detonation products following it [18].4 27.3 21. Kohlicek. The expansion of a copper tube driven by detonation products was recorded by a SCANDIFLASH x-ray setup [10. them and the other explosives is not as large as that in ballistic mortar tests (see Table 2).62 3. In the case of a cylindrical liner. m/sec 5460 5095 5240 5200 5040 Dideal . m/sec 5973 5680 5872 5687 5584 [AN]inert . The sensor triggering the x-ray pulse was at 20 mm from the end of the charge. 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 2.5 mm.1. (2) rm = re 2 e. and the line connecting the x-ray source and the film was perpendicular to the charge axis. Under the assumption of incompressible tube material. and their inner diameter and wall thickness were 25 mm and 2.78 33. in the literature one can find final values of the Gurney energy or Gurney velocity equal to the square root of the doubled Gurney energy.0 . The position of the central cylindrical surface (rm ) was first determined. Trzcinski. Trzcinski [15] showed that the accelerating ability of an explosive can be estimated using the dependence of Gurney energy [defined by relation (1)] on the relative volume of expanding detonation products. The charge was fixed vertically. This allowed us to observe continuously the expansion of detonation products for ≈40 µsec until the detonation wave reached the charge section in which the sensor was placed.7 m from the x-ray source and at Fig. 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 value of rm can be found from the relation 1 2 2− r − ri2.54 35. 13].58 31. From Eq. . From the photograph.47 34.0 ng . which was used only in cylinder expansion tests. The copper tube filled with the explosive tested was placed at a distance of 2. kg/m3 1062 1065 1146 1093 1079 Dexp . (1) it follows that to obtain this dependence. the dependence of the outer radius of the tube on the axial coordinate was determined using computer processing. The parameters correspond to the velocity of a tube with radius for which integrity of the tube material is still preserved [18]. respectively. The accelerating ability can also be described as the Gurney energy EG . and Zeman Experimental and Calculated Characteristics of Explosive Used in Cylinder Expansion Tests Explosive AN∗∗ AN–CaN AN–NiN AN–CoN AN–NaN ρ0 . Figure 2 gives a radiograph of a copper tube driven by detonation products of the composition AN∗∗ .466 TABLE 3 Cudzilo. Accelerating Ability of Detonation Products — Gurney Energy One of the parameters that can characterize explosive performance is the accelerating ability of detonation products.5 29. and 6. the Gurney energy is given by the equation 1 u2 L . it is necessary to know the total velocity of the tube (uL ) driven by detonation products.

(4) dt i and. 3. which is characteristic of strong explosives. 1. This shows that in this case.0 and ri. (4) and (5) and the measured detonation velocities (see Table 3). and for v/v0 = 9. 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. and t0 are parameters. the Gurney energy of the composition AN∗∗ practically does not increase. we determined values of uL and then evaluated EG by Eq. 3. Figure 5 shows a curve of EG (ρ0 D2 ). Θ = arctan . This implies that there is a linear relationship between explosive performance and detonation parameters. The addition of nickel and sodium nitrates leads to the most considerable decrease in the detonation properties of the composition AN∗∗ . (3). If an explosive contains metal nitrates.e. bi . The calculated dependence of Gurney energy on the relative volume of detonation products (v/v0 ) is shown in Fig. then. 4 shows that for v/v0 > 6.2. The data of Figs. (3). the total velocity Θ um uL = 2D sin . Assuming that the motion of the detonation products and the tube is stationary (i. For v/v0 = 2. 4. (1). 20]). Expansion Work of Detonation Products In the literature (see. Radial displacement of the central surface of the tube versus time: the points refer to the experiment and the curves refer to Eq. where D is the detonation velocity and t is time). the energy release behind the detonation front is decelerated. [19. The thus obtained dependence rm (t) is shown in Fig. 3. (5) 2 D Using Eqs. 4. An analysis of the curves in Fig. Thus.Performance of Emulsion Explosives 467 Fig. Gurney energy versus relative volume of detonation products. for example. the values of EG for emulsion explosives containing only ammonium nitrate are nearly ideal. In [15]. the data for all explosives lie on one line. (3) where rm.5.0 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.0 is the initial value of rm and ai . Fig. the Gurney energy increases slowly but continuously even for v/v0 > 6.0 + i ai {bi (t − t0 ) −[1 − exp(−bi (t − t0 ))]}. where re. 4 and 5 also suggest that in charges with a strong confinement. the expansion work of detonation products w is defined as the work of the products expanding from volume at the Chapman–Jouguet point (vCJ ) to a volume v minus the energy of compression of the explosive: . x = Dt. we can calculate the radial velocity of the tube drm um ≡ = ai bi [1 − exp(−bi (t − t0 ))].. we can replace the dependence rm (x) by the dependence rm (t). the position of the central surface of the tube in time is approximated by the function rm = rm. it is close to that given in Fig. Having determined the relations rm (t) and differentiating Eq.

a value γ is chosen that ensures best agreement between the calculated and experimental profiles of the tube. from Eq. The figure also shows the interval of volume of detonation products corresponding to the pressure range for rock blasting [22]. and weak rock [22]. for different explosives there is some difference in results obtained by different methods. As a result. . Most often it is the so-called effective exponent of isentrope. As might be expected. and 20 can be used to compare the efficiency of explosion in hard.84 2.86 2. it is necessary to know values of two detonation parameters. Gurney energy versus the parameter ρ0 D2 . 6. To determine constants in Eq. the composition containing only ammonium nitrate performed the greatest expansion work (among the tested explosives). v w(v ) = −ec + vCJ p dv. This result is obtained with the usage of both experimental methods. After integration using relation (7). The dependence of the expansion work calculated by relation (8) on the relative volume of detonation products is given in Fig. In this method. and Zeman TABLE 4 Effective Poisson Adiabatic Exponent Explosive AN∗∗ AN–CaN AN–NiN AN–CoN AN–NaN γ 2. (7) v where γ is the adiabatic exponent. an experimental profile of a copper tube is compared with that obtained by numerical modeling of the expansion process. (6) To evaluate the expansion work. its value can be determined from results of a cylinder expansion test. 5. it is assumed that the values of expansion for v/v0 = 10. However.85 2.468 Cudzilo. Kohlicek. The first of these is usually experimental detonation velocity and the second is the exponent of isentrope of detonation products. taking into account that the sample mass was larger in cylinder tests and the duration of expansion in this case was also much longer. cracks form and detonation products penetrate into then. The state of detonation products is described by Poisson’s adiabat (7). Trzcinski. It is difficult to reliably determine which of them is more accurate because the difference is rather insignificant. which is not determined from the real isentrope in a certain range of volume of detonation products rather than from parameters at the Chapman–Jouguet point.83 Fig. thus weakening the destructive effect of the explosive. Expansion work of detonation products calculated using the Poisson adiabat.80 2. Therefore. (7). it is necessary to know the isentrope of expansion of detonation products. it is concluded that the data of these experiments are more exact in comparing the blasting performance of explosives. According to the procedure proposed in [13. As soon as rock begins to fracture. (6) we obtain the following expression for the expansion work: vCJ γ −1 pCJ vCJ γ + 1 − . However. 15. The effective exponent of isentrope of detonation products for the tested explosives are given in Table 4. A simple isentrope is the Poisson adiabat vCJ γ p = pCJ . 21]. (8) w= γ −1 2γ v Fig. 6. strong.

10. R. Weinheim. Trebinski and W. S. 16. “Comparison of cylinder data and code calculations for homogeneous explosives. “Detonation behavior of emulsion explosives. “Method of determination of the effective exponent of isentrope for the detonation products of condensed explosives (in Polish). Trebinski and W. 85. K. M. E. A. Explos.503 (1965). Massachusetts. In this connection. F.” in: Proc. A. 23–31 (1986). VCH Publ. Iida. A. UCRL-MA-117541 (1996). Albuquerque. Baer. the most realistic values of performance can be obtained in cylinder tests rather than in ballistic mortar tests. Fried and P. Explos. A. 9. Phys. Phys. 11..” J. S. Person and R. No. . 18.” in: 8th Symp. M. 469 Detonation Symp.. The addition of metal nitrates to emulsion compositions deteriorates the detonation properties of explosives containing only ammonium nitrate.. 8. Cudzilo and W.” Propellants. 18. et al. 11. Pyrotech.. Trzcinski. W. A. 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