Combustion, Explosion, and Shock Waves, Vol. 41, No. 5, pp.

591598, 2005

Detonation Velocity of Emulsion Explosives Containing Cenospheres

A. G. Anshits,1 N. N. Anshits,1 A. A. Deribas,2 S. M. Karakhanov,2 N. S. Kasatkina,3 A. V. Plastinin,2 A. Yu. Reshetnyak,4 and V. V. Silvestrov2
UDC 622.216.1

Translated from Fizika Goreniya i Vzryva, Vol. 41, No. 5, pp. 119127, SeptemberOctober, 2005. Original article submitted December 28, 2004.

The detonation velocity of an emulsion explosive containing hollow alumosilicate microspheres (cenospheres) as the sensitizer is measured. The size of the microspheres is 50250 m. The relations between the detonation velocity and the charge density and diameter are compared for emulsion explosives containing cenospheres or glass microballoons as the sensitizer. It is shown that for a 55 mm diameter charge, the maximum detonation velocity of the composition with cenospheres of size 70100 m is 5.55.6 km/sec, as well as for 3M glass microballoons. The critical diameter for the emulsion explosive with cenosphere is 1.52 times larger than that for the emulsion explosive with glass microballoons and is 3540 mm. Key words: emulsion explosives, cenospheres, detonation velocity, critical diameter.

INTRODUCTION Emulsion explosives (EEs) were developed more than 40 years ago [1] and their characteristics have been studied extensively [211]. At present, abroad EEs rank rst among commercial high explosives (HE) because of a number of unquestionable advantages. Having a high detonation velocity (up to 56 km/sec), EEs are characterized by low toxicity of explosion products, high water resistance, low values of the critical diameter, high safety, and the possibility of mechanical loading. The main components of EEs are ammonium nitrate or its mixture with sodium or calcium nitrates, water, a combustible component (light petroleum), and an emulsier, which ensures a stable state of the emul1

sion base for the required time. Actually, emulsions are incapable of detonating without special sensitizers [4]. Usually, the sensitizers are gas microbubbles, which are added to the emulsion by chemical methods [8, 10], inclusion of porous perlite [8] or hollow glass [28] or polymer [9] microballoons. The goal of the present study was to measure the two basic characteristics, the detonation velocity D and critical diameter dcr , of an emulsion HE containing cenospheres hollow microballoons obtained from coal ash [12]. Their use as a sensitizer for EEs is of interest in blasting because of the potential cheapness of the starting material for picking cenospheres.

Institute of Chemistry and Chemical Engineering, Siberian Division, Russian Academy of Sciences, Krasnoyarsk 660049. 2 Lavrentev Institute of Hydrodynamics, Siberian Division, Russian Academy of Sciences, Novosibirsk 630090; silver@hydro.nsc.ru. 3 Boreskov Institute of Catalysis, Siberian Division Russian Academy of Sciences, Novosibirsk 630090. 4 Institute of Theoretical and Applied Mechanics, Siberian Division, Russian Academy of Sciences, Novosibirsk 630090.

EMULSION The weight percentage of the emulsion base is as follows: 76.9% ammonium nitrate, 6.9% I-20 industrial oil, 15.2% water, and 1% REM emulsier. The emulsion was prepared in a porcelain container on a boiling water bath in the laboratory. Ammonium nitrate was dissolved at a temperature of 86 C, and the solution was then heated to 9496 C. Industrial oil was mixed with the emulsier in another porcelain container, which was 591

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Fig. 1. Structure of the emulsion base.

Fig. 2. Ash particle size distribution for the ash concentrate (1) and 3M microballoons (2).

also placed on a boiling water bath. After the heating of this mixture, a hot solution of ammonium nitrate was trickled in the mixture of industrial oil with the emulsier with simultaneous intense stirring for 35 min using an electrical mixer. The mixture gradually acquired the properties of an emulsion. On-line monitoring of the degree of mixing was performed with a special probe which was immersed in the emulsion and measured the electrical capacitance of the container with the emulsion. Immediately after the mixing of the components, it was 18002000 pF. The stirring was continued until the capacitance reduced to 750800 pF; at this time, the temperature of the emulsion was 9092 C. As a result, we obtained a water-in-oil emulsion, which was a dense low-uidity medium of light yellow to dark yellow color and density e = (1.35 0.002) g/cm3 . Microscopic analysis showed that the emulsion contained a discrete phase droplets of ammonium nitrate solution of size 550 m surrounded by a continuous phase oil with the emulsier (Fig. 1). Sensitizing inclusions were added to the hot (8590 C) emulsion over 100% and stirred at the least rate of rotation of the mixer to prevent failure of the microballoons. The volume concentration of the microspheres was vmb = 732% over the emulsion volume, and the weight concentration was mb = 118%. In each experiment, the EE density 0 was measured with an error of 0.003 g/cm3 . It varied in the range of 1.141.3 g/cm3 , depending on the quantity and bulk density of microspheres. We note that the preparation of the emulsion and the addition of microspheres to the EE inevitably leads to incorporation of atmospheric air into the EE, and the latter always contains air bubbles. The quantity of the admixed air cannot be controlled in practice. Therefore, the EE density was dif-

ferent even in the case of identical mixing compositions and regimes, and the dierence reached 0.006 g/cm3 . We note that the initiation of the EE based on the obtained emulsion requires a booster charge made of a more powerful HE. The EE containing 3M microspheres or cenospheres as sensitizers did not detonate when us ing a EDV-1 blasting cap alone. CENOSPHERES We used an ash concentrate of bulk density 0.380.4 g/cm3 (as-received ash waste material from the Novosibirsk Heat-Generation Plant No. 5), whose fractional weight composition is given in Fig. 2. In the ash weight particle size distribution, the maximum corresponds to the fraction of 150250 m. About 85% (by weight) of the particles in the ash concentrate have sizes of 100300 m, not more than 5% have sizes <100 m, and less than 10% sizes >300 m. Floatation of the ash concentrate in water showed that 0.5% of the ash particles have density over 1 g/cm3 . Most of the ash particles are spherical hollow formations, called cenospheres. The shape of unsieved cenospheres is nearly spherical but their size varies over a wide range from 50 to 450 m. For comparison, 3M hollow glass microspheres of K1 fraction are considered. They have a bulk density mb = 0.12 g/cm3 and a wall thickness 0.30.6 m. The size of as-received 3M microspheres is 10100 m with the size distribution maximum in the range of 3570 m (see Fig. 2). These microspheres are produced from low-melting glass by a complex technology and are the best sensitizers from the viewpoint of the values and stability of detonation characteristics of EEs but their cost (7 EUR per kilogram) is too high for most customers of EEs in Russia.

Detonation Velocity of Emulsion Explosives Containing Cenospheres TABLE 1

Characteristic of Cenospheres Fraction, m 5063 5063 6371 70100 70100 70100 100125 80180 125160 160180 dmb , m 57 57 67 86 86 86 113 130 143 170 mb , g/cm3 0.46 0.34 0.33 0.36 0.38 0.4 0.350.36 0.360.38 0.36 0.38 , g/cm3 2.44 2.44 2.44 2.42 2.45 2.45 2.44 2.45 2.44 2.45 , m 3.8 2.6 2.8 3.2 3.6 3.7 56.1 5.65.9 6.1 7.6 /dmb 0.067 0.046 0.042 0.038 0.042 0.044 0.0440.054 0.0430.045 0.043 0.045

593

In the present work, emphasis is on the use of cenospheres of narrow fractions as sensitizers for the EE. The separation of cenospheres from the ash concentrate was performed by a three-step procedure, which included magnetic separation, hydrodynamic separation according to density, and granulometric classication [12]. The cenospheres of the narrow fractions have an almost regular shape (Fig. 3a and b). The characteristics of the narrow fractions of cenospheres are given in Table 1. The bulk density of the cenospheres was measured by a volumetric-weight method (Russian State Standard No. 9758-86). The true density of the glass-crystalline phase of the shell of broken cenospheres was determined by a bottle method (Standard No. 2211-65 for Russia or Standard No. 5018-83 for International Organization for Standardization). The average thickness of the cenosphere shell was calculated by the formula = 0.25dmb 2 2.148mb ,

of analysis of the cenosphere shell thickness obtained by the volumetricweight method. Cenospheres of the fraction of 5063 m with mb = 0.34 g/cm3 have a thin (13 m) solid shell with a small amount of gas inclusions (Fig. 3c). Cenospheres of the same fraction with mb = 0.46 g/cm3 have a thicker (38 m) wall with a large number of gas inclusions (Fig. 3d). This fraction includes 510% plerospheres, in which the main hollow shell is lled with ner globules (of size 120 m). The largest fractions of 125160 and 160180 m (mb = 0.360.38 g/cm3 ) have shells with a thicker wall ( = 520 m) and high porosity. Thus, an increase in the size and bulk density of the cenospheres leads to an increase in the shell thickness and porosity. Unlike for cenospheres, the wall thickness of 3M glass microballoons decreases with an increase in their diameter and wall porosity is almost absent [8].

where dmb is the number average diameter of globules of the narrow fractions. The data of Table 1 show that the shell thickness increases with an increase in the cenosphere size and bulk density. For example, for the fractions of 5063 m for mb = 0.34 and 0.46 g/cm3 , the shell thicknesses are 2.6 and 3.8 m, respectively. As the cenosphere size increases to dmb = 160180 m for mb = 0.37 g/cm 3 , the average shell thickness reaches 7.6 m. In addition to the large thickness of the shell (5.65.9 m), the broad (80180 m) fraction of cenospheres has a broad maximum of the particle size distribution 110170 m. An analysis of scanning electron photomicrographs of previously broken cenospheres conrms the results

DEPENDENCE OF DETONATION VELOCITY ON DENSITY OF EMULSION EXPLOSIVE The relation between the detonation velocity and density of the EE and the type of microspheres was determined using cylindrical charges of diameter d = 55 mm in polyethylene tubes with a wall thickness of 1 mm. The length of the charges was 350 mm, and in control experiments, it was 700 mm. The critical diameter of detonation was determined for charges of smaller diameters in vinyl plastic or paper tubes with a wall thickness of 0.51 mm and a charge length of 1015 calibers. The charge was initiated by a 50/50 TNT/RDX booster of diameter d and height d/2 to reduce the transition length. The detonation velocity

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Fig. 3. Photomicrographs of intact (a and b) and broken (c and d) cenospheres with particle sizes of 7080 m (a), 70250 m (b), and 5063 m for mb = 0.34 (c) and 0.46 g/cm3 (d).

was measured on the last 120 mm of the EE charge using four contact probes. The pressure operating threshold of the probes was 1 kbar, and in the case of detonation failure, a damped shock wave was recorded in the EE. The time intervals were recorded by digital timers with a resolution of 10 nsec. The detonation velocity measurement error was <1%. For a 55 mm diameter charge (with 3M glass microballoons as the sensitizer), the relation D(0 ) was determined to control the quality of the emulsion used. Figure 4 shows the results of the present measurements and the data of [4] for d = 52.5 mm. The data of [4] were obtained for unsieved 3M microspheres with an average size of dmb 70 m and an emulsion close in composition to ours but containing oxidizer droplets of smaller size (15 m). Our data for charges containing 3M microspheres with 0 = 1.141.26 g/cm3 nearly coincide with the data of [4], indicating that in the range of 150 m, the maximum size of the oxidizer droplets has an insignicant eect on the detonation velocity

for EE charges of large diameter. The maximum detonation velocity is observed for m 1.181.22 g/cm3 (vmb = 1417% and mb 2.32.7%). Detonation failure is observed for 0 1.26 g/cm3 (vmb < 8% and mb < 1.3%). The critical density cr decreases by approximately 0.02 g/cm3 compared to [4]. This is likely due to the dierence in the degree of dispersion between the emulsion and the combustible component used for the manufacture of the EE. The relation D(0 ) was determined for three fractions of cenospheres. For the light narrow fraction of 70100 m (mb = 0.360.38 g/cm3 ), the maximum velocity is Dmax = 5.55.6 km/sec and is reached for m = 1.181.2 g/cm3 (vmb = 16.718% and mb 89%). Detonation failure is observed for 0 > 1.28 g/cm3 (vmb < 11% and mb < 5%). Our data on the detonation velocity almost coincide with the results of experiments using 3M glass microballoons of bulk density 0.12 g/cm3 . The maximum detonation velocity is higher than the maximum detonation velocity of EEs

Detonation Velocity of Emulsion Explosives Containing Cenospheres

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Fig. 4. Detonation velocity versus density of the EE: points 1 refer to the data of [4] for EE charges of diameter d = 52.5 mm with 3M microspheres; points 26 refer to the data of the present study for EE charges of d = 55 mm with 3M microspheres (2), cenospheres of sizes 70100 (3), 80180 (4), and 70250 m (5), and ash concentrate (6).

than that of a thin-walled 3M microballoon because of the thicker wall. Therefore, the needed number of cenospheres as hot spots (number of individual microballoons) is approximately 3 (46) 1.7 times larger. In addition, the higher (by a factor of three) bulk density of cenospheres increases the required weight concentration. Therefore, for the practical application of cenospheres as a sensitizer for EEs, it is necessary that their cost be at least approximately one-fth of the cost of 3M glass microballoons of K1 fraction per unit weight. The negative eect of the high bulk density of cenospheres (the eect of the thicker wall) is apparent from the result of experiments using cenospheres of size 70100 m with mb = 0.4 g/cm3 (the point marked by an arrow in Fig. 4). As the specic weight or the relative wall thickness /dmb of the cenospheres increases only by 10% (see Table 1), the maximum detonation velocity decreases by 0.5 km/sec. We note that with a twofold increase in the bulk density of 3M glass microballoons (K1 and K25 fractions), the detonation velocity also decreases, but only by 0.13 km/sec [8].

EFFECT OF CENOSPHERE SIZE with a gas-generating additive of sodium nitrite, which is Dmax 5 km/sec [10] for charges of 70 mm diameter made of P-1 poremit emulsion explosive (approximate composition: 67% ammonium nitrate, 14% sodium nitrate, 12% water, 5% industrial oil, and 2% emulsier). This result is inconsistent with the statement that the detonation velocity of EEs is 4501600 m/sec lower when using hollow solid inclusions than with gas sensitizers [10], but agrees with the results of [8], which show that the eect of gas inclusions on the detonation velocity is intermediate between the eects of perlite inclusions and hollow glass microballoons. For the broader fraction of 80180 m (mb = 0.360.38 g/cm3 ) in the range of m = 1.181.22 g/cm3 , the maximum detonation velocity Dmax = 4.84.9 km/sec is observed for vmb = 1828% and mb 914% (see Fig. 4). For EE density 0 1.29 g/cm3 (mb < 5.5%), detonation failure is observed. An increase in the number average size of the cenospheres to 200 m (the fraction of 70250 m with mb = 0.43 g/cm3 ) leads to a further decrease in the maximum velocity to 4.64.7 km/sec, which is achieved for 0 1.2 g/cm3 (vmb 25% and mb 15%). Thus, to ensure the maximum detonation velocity at a level of 4.65.7 km/sec for a EE charge of 55 mm diameter, one needs 46 times more (by weight) cenospheres than 3M microballoons of K1 fraction. Under initiation of detonation in a local EE volume, the efciency of separate cenosphere as a hot spot is lower The eect of the size of hollow glass or polymer microspheres on the detonation velocity is well known [2, 6, 9]: the larger the microballoon diameter, the lower the detonation velocity. It is assumed that this eect is due to the cooling of the hot spot by the rarefaction wave generated from the center of the hot spot during its explosion. These data were obtained for various emulsion compositions and various EE charge diameters but can be used for qualitative estimations of the eect of the average size of glass microballoons dmb and cenospheres on the detonation velocity. For 3M microballoons, as dmb varies from 153 to 35 m, the value of Dmax increases with decreasing inclusion size but a maximum is not reached (Fig. 5). To determine the optimum cenosphere size at which the detonation velocity reaches the maximum value with other conditions being equal, experiments were performed for cenospheres of number average size in the range of dmb = 57200 m at a volume concentration of the cenospheres vmb 17%. The EE density was 1.181.22 g/cm3 . The results for a 55 mm diameter charge are given in Fig. 5. As in the case of glass microballoons, the detonation velocity decreases by more than 1 km/sec as the average cenosphere size increases from 85 to 200 m. The maximum detonation velocity is reached for cenospheres of the fraction of 70100 m with a ratio of the wall thickness to the diameter /dmb 0.04.

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Fig. 5. Detonation velocity versus microballoon size: points 1 and 2 refer to the data of the present study for EE charges of diameter d = 55 mm with cenospheres (1) and 3M microballoons (2); points 3 and 4 refer to the data for EE charges with 3M microballoons from [6] for d = 30 mm (3) and from [7] for d = 23.6 mm (4).

Fig. 6. Detonation velocity versus charge diameter: points 13 refer to the data for 3M microballoons from the present study (1), from [4] (2), and from [11] (3); points 4 refer to data for gas inclusions (P-1 poremit) from [10]; points 57 refer to cenospheres of the fractions of 70100 (5), 80180 (6), and 70250 m (7); points 8 refer to ash concentrate.

In Fig. 5, point marked by an arrow refers to the result of experiments using heavy cenospheres of the fraction 5063 m (mb = 0.46 g/cm3 ) with a maximum ratio /dmb = 0.067. In this case, the detonation fails, i.e., the cenospheres failed to act as hot spots because of the presence of 510% plerospheres shells lled with ner globules. This experiment provided further evidence that the high bulk density of some fractions of cenospheres plays a negative role. If the main mechanism of hot-spot heating in the EE is the viscous heating of the emulsion due to internal friction upon collapse of hollow microspheres, the curve of D = f (dmb ) should have a maximum because the limiting diameter of micropore collapse d is limited by the volume of the broken shell material. The results of the experiment described above provides an estimate of the collapse diameter d dmb /3 at which eective hotspot heating occurs; in this case, the micropore surface area decreases by approximately a factor of 10. Another reason for the considerable eect of the size and bulk density of cenospheres on the maximum detonation velocity (see Fig. 5) may be the signicant eect of the size and bulk density of the microspheres (and the degree of dispersion of the emulsion) on critical detonation diameter of the EE.5 In this case, the detonation velocity reduction due to cenosphere size en5

largement is explained by an increase in the critical diameter of the EE since the data in Fig. 5 were obtained for a EE charge of xed diameter (this reason is qualitatively similar to that which explains the detonation velocity reduction due to an increase in the EE density, see Fig. 4 and an explanation of this eect below). From this it follows that the detonation velocity of the examined EE can considerably increase with increasing charge diameter even when using hollow microspheres of large size, over 100 m (unsieved cenospheres or ash concentrate). Thus, in the application of cenospheres as sensitizers for EEs, it is reasonable to use the lightest fractions with bulk density not higher than 0.4 g/cm3 and to eliminate the heavy ne fraction with dmb < 70 m in order to obtain the maximum detonation velocity. The maximum cenosphere size should be limited to the value of 200250 m. Under these conditions, the detonation velocity of the employed emulsion is not lower than 4.55.5 km/sec for charge diameters d 55 mm. CRITICAL DETONATION DIAMETER OF EMULSION EXPLOSIVE In the rst series of experiments, 3M microballoons were used as sensitizers and the critical diameter of the examined emulsion was in the range of 19 (failure) < dcr < 24 mm (explosion) for 0 1.191.20 g/cm3 (Fig. 6). For the same EE with emulsion droplet sizes of 15 m, the value of dcr was 14 mm [4]. Obviously, the dierence is due to the dierence between the de-

This explanation was proposed by the reviewer of this paper K. K. Shvedov, for which the authors express deep gratitude to him.

Detonation Velocity of Emulsion Explosives Containing Cenospheres grees of dispersion of the emulsions: as the maximum size of the emulsion droplets reduces from 10 to 3 m, the critical diameter of the EE decreases by a factor of approximately 1.7 [13]. For the fraction of cenospheres of 70100 m, the critical detonation diameter was 35 < dcr < 40 mm for 0 = 1.211.23 g/cm3 . For the larger fraction of cenospheres of 80180 m with 0 = 1.211.22 g/cm3 , the same result was obtained: 35 < dcr < 40 mm. For cenospheres of 100250 m and a EE density 0 = 1.21.21 g/cm3 , the critical detonation diameter is in the range of 30 < dcr < 35 mm. For the cenospheres, the detonation velocity near the critical diameter is Dcr = 3.74.1 km/sec, which is close to the detonation velocity near the critical density (see Fig. 4). This similarity is not incidental and indicates that the reason for detonation failure near the critical diameter and near the critical density is the same. Our study would be incomplete without data for unsieved cenospheres the cheapest of the sensitizers considered. To obtain these data, we measured the detonation velocity of a 55 mm diameter charge (mb 14% and 0 = 1.2 g/cm3 ) using as-received ash concentrate as the sensitizer. In two experiment, the value D = (4.24 0.04) km/sec was obtained (see Fig. 4). For this EE charge, the critical detonation diameter was 40 dcr < 45 mm: at dcr = 40 mm in both experiments, a decaying explosion process at a velocity of 3.33.45 to 2.93.3 km/sec on the last 150 mm of the charge of length 0.5 m (see Fig. 6) was recorded. Data representation as curves of D(d) shows again that the detonation velocity of EEs with cenospheres is intermediate between the detonation velocities of EEs with 3M microballoons and P-1 poremit an emulsion explosive with gas inclusions. For EEs with cenospheres, the average value of the critical detonation diameter is 3540 mm, which is 1.52 times larger than that for EEs with 3M microballoons. However, the use of a mixture of ammonium and sodium nitrates in the manufacture of emulsions provides a decrease in the critical detonation diameter of EEs [24] with cenospheres, which is necessary when using packaged EEs with cenospheres for charge diameters of 3035 mm.

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REASON FOR THE DECREASE IN THE DETONATION VELOCITY OF THE EMULSION EXPLOSIVE WITH INCREASING DENSITY Let us consider the issue of the decrease in the detonation velocity of EEs with increasing density after the attainment of the maximum detonation velocity (see

Fig. 4). Qualitatively, the reason for this eect is obvious.6 As the quantity of microspheres decreases, the EE porosity decreases and both its density and critical detonation diameter increase. This is well-known from experiments with glass microballoons [28, 13]. In experiments, the relation D = D(0 ) is determined for a constant diameter of the cylindrical charge d. As the EE porosity decreases (the density increases), the detonation velocity rst grows due to an increase in the specic energy of the explosive. With a further increase in the density as the values d and dcr approach each other, the detonation velocity begins to decrease and there comes the time when the ratio d dcr (cr ) is satised, i.e., the detonation fails. The density at this time is the critical density cr for the given charge diameter. Physically, this concept is meaningless since cr depends on the charge diameter [10]. In the range of m < 0 < cr , the detonation velocity decreases because the eect of lateral rarefaction is enhanced as the constant diameter of the HE charge and the critical diameter of the EE approach each other. This explanation implies that the relation D = D(0 ) with the extremum for the constant value of d is the eect of two-dimensionality, and this relation cannot be explained adequately without accounting for the eect of the charge diameter on the detonation velocity for a charge of nite diameter. As a rst approximation, the eect of the diameter can be taken into account using the simple Eyring model [14], for example, as D = Di (0 )(1 Ar (0 )/d), where Di (0 ) is the detonation velocity of the charge of innite diameter and Ar (0 ) is the reaction-zone width, which depends on the HE density. For EEs, the reaction-zone width should increase as its density becomes higher. This qualitative model explains not only the existence of the maximum on the curve of D = D(0 ), i.e., the decrease in D for > m , but also the increase in the values of max and cr with increasing HE charge diameter. Assuming that the reaction-zone width ar and, hence, the critical diameter dcr ar (the Khariton principle) increase as the detonation reaction rate decreases with increasing microballoon diameter dmb due to the rarefaction wave from the center of the microballoon, it is possible to understand why the detonation velocity becomes higher as the value of dmb decreases. All these eects are indeed observed in experiments [38]. In this connection, it is of interest to perform direct measurements of the reaction-zone width ar for 0 > max in the region where the reaction-zone width should be signicantly aected by the EE porosity, the value of dmb , and the specic weight of microballoons mb .
6

An idea that correctly explains the decrease in detonation velocity due to increasing density for composite commercial HEs was apparently rst proposed in [15].

598 CONCLUSIONS It was shown that cenospheres obtained from coal ash can be used as sensitizers in emulsion HE. The maximum detonation velocity is reached when using the narrow fraction of cenospheres of 70100 m with a bulk density of 0.36 g/cm3 and an EE density of 1.181.2 g/cm3 ; for a charge diameter of 55 mm, it is 5.55.6 km/sec. The required volume concentration of cenospheres is 1720%, and their weight concentration is 810%. For the examined EE based on ammonium nitrate with cenospheres, the critical diameter is about 3540 mm. An increase in the number average size of the cenospheres to 200 m results in a decrease in the maximum detonation velocity by 11.3 km/sec. The use of as-received ash concentrate provides a detonation velocity of 4.2 km/sec and a critical diameter of up to 45 mm. In blasting, cenospheres as sensitizers for EEs can compete with glass microballoons or gaseous inclusions if the EE charge diameter is not less than 4050 mm. However, their competitive advantage over other sensitizers will be determined by their cost. The application of EEs based on a mixture of ammonium and sodium (or calcium) nitrates will make it possible to obtain smaller values of the critical diameter and to develop EEs sensitive to detonation initiation using a blasting cap alone. We are grateful to A. S. Yunoshev for assistance in the experiments. We also thank the Moscow Oce of the 3M company for the free supply of glass microballoons. This work was supported by the integration project of the Siberian Division of the Russian Academy of Sciences No. 118, the Foundation of the President of the Russian Federation (number NSh-2073.2003.1), the Russian Foundation of Basic Research (Grant No. 0403-33187) and KKFN (12F0059C).

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3. H. Yoshida, M. Iida, K. Tanaka, et al., Detonation behavior of emulsion explosives containing glass microballoons, in: Proc. of the 8th Int. Symp. on Detonation (1985), pp. 171177. 4. J. Lee, F. W. Sandstrom, B. G. Craig, and P.-A. Persson, Detonation and shock initiation properties of emulsion explosives, in: Proc. of the 9th Int. Symp. on Detonation (1989), pp. 263271. 5. J. Cooper and G. Leiper, Void size dependence of the steady detonation properties of emulsion explosives, J. Energ. Mater., 7, 405417 (1989). 6. J. Lee and P.-A. Person, Detonation behavior of emulsion explosive, Propell., Explos., Pyrotech., 15, 208 216 (1990). 7. M. M. Chaudhri, L.-A. Almgren, and A. Persson, Detonation behavior of a water-in-oil type emulsion explosive containing glass microballoons of selected sizes, in: Proc. 10th Int. Symp. on Detonation (1993), pp. 741 748. 8. B Holcomb, The role of glass bubble in emulsion explosives, in: Proc. China Soc. of Engineering Blasting Conf. (1997). 9. Y. Hirosaki, K. Murata, Y. Kato, and S. Itoh, Detonation characteristics of emulsion explosive as function of void size and volume, in: Proc. of the 12th Int. Symp. on Detonation (2002), pp. 263271. 10. V. A. Sosnin and E. V. Kolganov, Detonation in commercial emulsion explosives, in: Vth Khariton Scientic Readings, Proc. Int Conf. (March 1721, 2003), Inst. Exp. Phys., Sarov (2003), pp. 288297. 11. K. K. Shvedov and V. V. Lavrov, Detonation parameters of emulsion explosives, in: Blasting Problems (collected scientic papers) [in Russian], No. 1, Moscow State Mining University, Moscow (2002), pp. 9099. 12. T. A. Vereshchagina, N. N. Anshits, et al., Producing cenospheres from power energetic ashes of stabilized composition and their properties, Khim. Interes. Ustoich. Razv., 9, 379391 (2001). 13. J. Cooper, G. A. Leiper, and G. W. Neilson, Molecular and microscopic structural eects in the detonation of uid explosives, in: Proc. of the 12th Int. Symp. on Detonation (2002). 14. H. Eyring, R. E. Powell, G. H. Duey, and R. B. Parlin, The stability of detonation, Chem. Rev., 45, 69 (1949). 15. A. N. Dremin, K. K. Shvedov, A. L. Krivchenko, et al., Detonation of commercial HEs. Detonation characteristics of 6ZhV ammonite, Fiz. Tekh. Probl. Razrab. Polezn. Iskop., No. 1, 4651 (1971).

REFERENCES
1. R. S. Egly and A. E. Neckar, Water-resistant sensitizers for blasting agents, U.S. Patent No. 31, 615, 51 (1964). 2. K. Hattori, Y. Fukatsu, and H. Sakaim, Eect of the size of glass microballoons on the detonation velocity of emulsion explosives, J. Ind. Explos. Soc. Jpn., 43, 295 309 (1982).