Full Paper

1 DOI: 10.1002/prep.201700282
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Study on a New Cleaner Emulsion Explosive Containing
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Common Clay
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Guoan Zhou,[a] Honghao Ma,*[a, b] Zhaowu Shen,[a] Peiyuan Chen,[c] and Yong Yu[d]
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11 Abstract: This paper introduces a novel emulsion explosive, the weaker are the detonation properties under the con-
12 which has three primary advantages, namely, the ability to dition of our experimental ratios (HGMs: from 5 wt.% to
13 easily adjust various detonation properties to desired val- 15 wt.%; common clay: from 0 wt.% to 20 wt.%). Fur-
14 ues, decrease the overall cost of civil explosive products, thermore, a comparison of four alternative emulsion ex-
15 and minimize environmental pollution during use. Immedi- plosive compositions reveals that the longest storage time
16 ate and time-related experiments are performed in order to in this study is 5 weeks with No. 3-3, which contains
17 identify changing detonation properties of these new for- 15 wt.% HGMs and 10 wt.% common clay. In addition, non-
18 mulas. Our results show that both common clay and hollow linear attenuation is observed and explained for that peri-
19 glass micro-spheres (HGMs) function as thermal diluents, od.
20 which indicates that for a larger quantity of these additives,
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Keywords: New emulsion explosive · Common clay · Content · Detonation properties
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25 1 Introduction have reported different interpretations of this non-ideal det-
26 onation process. Sil’vestrov posed an empirical model for
27 Owing to the growing demands of the mining, con- the detonation of explosives of the second group (including
28 struction, and extraction industries, the production of civil emulsion explosives) [12], which contains three parameters
29 explosives has increased globally [1, 2]. In 2012, 11 million that are dependent on the condition of the best-fit result of
30 tonnes of civil explosives were produced worldwide [3], and experimental data. Although physical and chemical reasons
31 that figure is expected to reach 16 million tonnes in 2018 for the increase in the reaction-zone width are not consid-
32 [4]. The main industries that utilize this product are: coal ered in this model, they proposed that the reaction-zone
33 mining (about 68 % of the total demand); non-metal mining width also increased with an increase of the high-explosive
34 and quarrying (16 %), and construction along with metal (HE) density, which eventually leads to a decline of the det-
35 mining (16 %). onation velocity.
36 For many years, studies on traditional civil explosives, On the other hand, the latest reports about the “hot
37 such as ammonium nitrate and fuel oil (ANFO), emulsion ex- pots” theory and non-ideal detonation developed by Med-
38 plosives and dynamite, have focused on risk assessments vedev et al. [9, 13] have shown the derivation of a functional
39 and environmental side effects. In particular, an increasing
40 number of rules and regulations have been established in [a] G. Zhou, H. Ma, Z. Shen
41 this area in the past few decades. CAS Key Laboratory of Mechanical Behavior and Design of Mate-
42 As an important part of civil explosives, typical emulsion rials (LMBD)
43 explosives containing emulsion matrixes and sensitizers Department of Modern Mechanics
44 have been used in various fields, such as the formation of University of Science and Technology of China
45 metal parts, explosives for the mining and welding in- Hefei 230027, Anhui, P. R. China
*e-mail: hhma@ustc.edu.cn
46 dustries [5–8]. Because the emulsion matrix involves mixing [b] H. Ma
47 an ammonium nitrate aqueous solution, mineral oil, and an State Key Laboratory of Fire Science
48 emulsifier [9], typical emulsion explosives always exhibit University of Science and Technology of China
49 good water-resistance performance. However, it is widely Hefei 230027, Anhui, P. R. China
50 known that the emulsion matrix cannot be detonated, and [c] P. Chen
51 a kind of sensitizer should be added to transform the matrix School of Civil Engineering and Architecture
52 to a detonable state. Hollow micro-balloons, which are also Anhui University of Science and Technology
Huainan 232001, Anhui, P. R. China
53 known as hollow glass micro-spheres (HGMs), are normally [d] Y. Yu
54 used as the sensitizers [5, 6, 10, 11]. Department of Civil Engineering
55 With respect to the detonation mesomechanism of tra- Anhui Jianzhu University
56 ditional emulsion explosive products, different researchers Hefei 230601, Anhui, P. R. China

Propellants Explos. Pyrotech. 2018, 43, 789–798 © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 789
 Full Paper G. Zhou, H. Ma, Z. Shen, P. Chen, Y. Yu

1 dependence of the reaction time and non-ideal detonation field) as the inert additive is developed, rather than using
2 velocity on the volume fraction of micro-balloons (HE veloc- above-mentioned traditional defective additives.
3 ity), micro-balloon diameter, and charge diameter. All of the
4 previously made interpretations reported by researchers
5 have confirmed that detonation properties, such as the det- 2 Experimental Section
6 onation velocity, can be adjusted in one way or another by
7 varying the reaction-zone width. 2.1 Preparation of Experimental Samples
8 However, although these detonation properties have
9 been shown to be adjustable, traditional emulsion-ex- Materials which are used to prepare the new emulsion ex-
10 plosive products remain unsuitable for use in specific in- plosive are all commercially available or can be easily
11 dustries, such as the explosive welding sector, which re- sourced. The emulsion matrix, which has a density of about
12 quires a low detonation velocity of about 2000 ~ 1.45 g cm3, is obtained from the Shuntai Chemical Corpo-
13 3000 m s1[8, 14, 15]. This is because inert additives which ration of Huainan, and its chemical composition is listed in
14 weaken the performance of traditional emulsion-explosive Table 1 [22], where C14H44O6 is the emulsifier used in the
15 products, such as industrial table salts [16], sifted gravel [17] emulsion matrix. For the sensitizers, we used HGMs, which
16 or various wasted oils [18], are all observed drawbacks dur- are usually extracted from the waste products of cogenera-
17 ing their usage. For instance, although Shvedov et al. re- tion plants, as seen in Figure 1(a), using the tungsten fila-
18 ported that most industrial explosives for mining operations ment scanning electron microscope (machine model: EVO/
19 and mixtures for explosive welding were of this type, utiliz- MA15). Their average size, density, pH value and softening
20 ing industry salt as an additive, the long-term use of this temperature of are about 60 mm, 0.14 g cm3, 9.5 and
21 product can lead to irreversible land salinization, which has 600 8C, respectively. These HGMs were purchased from the
22 been a serious envirmental concern in recent years. Further, Minnesota Mining and Manufacturing Corporation of USA.
23 the usage of sifted gravels can increase the overall cost of With respect to the common clay, it was first collected
24 modified emulsion explosives, which would limit the popu- from a local nature environment at no cost, and then left
25 larization of this product. undisturbed in water for 2 days. Then, the clay was scooped
26 Therefore, to overcome those disadvantages of current from the bottom and dried in a drying oven (machine mod-
27 emulsion-explosive products, broaden their applications, el: GZX-9030 MBE) at 120 8C for 2 h. Finally, before being
28 i. e., using in the field of explosion spraying, which also re- added to HGM-sensitized emulsion matrix, the common
29 quires a low detonation velocity of less than 3500 m s1[19– clay was sifted using sifters in order to obtain an average
30 21], and minimize environmental pollution during usage, a size of about 100 mm, as seen in Figure 1(b), and the final
31 new and much cleaner emulsion explosive which adds com- density of them is about 1.07 g cm3. Using the X-ray spec-
32 mon clay (never been used before in the civil explosive tral fluorometer (machine model: XRF-1800), we reveal that
33 the main chemical composition of common clay is: Quartz
34 (66.3 wt.%) and Kaolinite 1 A (24.5 wt.%).
35 In the following experiments, samples are prepared ac-
36 Table 1. Chemical composition of emulsion matrix. cording to Table 2. With respect to the time-related issue,
37 four formulas (No. 1-1, No. 3-1, No. 3-3 and No. 3-5) are se-
Component NH4NO3 NaNO3 C18H38 C12H26 C14H44O6 H2O
38 lected as experimental subjects, and were fully tested (time-
39 Mass ratio 75 10 4 1 2 8 related detonation velocity, explosive brisance and under-
40 (wt.%) water detonation parameters) until No. 3-3 and No. 3-5 (for-
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56 Figure 1. Average sizes of additives in this study (a: the HGMs, b: common clay).

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 Study on a New Cleaner Emulsion Explosive Containing Common Clay

1 Table 2. Different formulas of experimental samples.

2
Experimental Mass ratio (wt.%) Bulk density
3
numbers Emulsion HGMs Common (g cm3)
4 matrix clay
5
6 No. 1-1 Balanced 5 0 1.49
7 No. 1-2 Balanced 5 5 1.47
No. 1-3 Balanced 5 10 1.43
8
No. 1-4 Balanced 5 15 1.40
9 No. 1-5 Balanced 5 20 1.38
10 No. 2-1 Balanced 10 0 1.42
11 No. 2-2 Balanced 10 5 1.39
12 No. 2-3 Balanced 10 10 1.37
13 No. 2-4 Balanced 10 15 1.35
14 No. 2-5 Balanced 10 20 1.32
No. 3-1 Balanced 15 0 1.36
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No. 3-2 Balanced 15 5 1.34
16 No. 3-3 Balanced 15 10 1.30
17 No. 3-4 Balanced 15 15 1.28
18 No. 3-5 Balanced 15 20 1.25
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21 mulas of the new emulsion explosive products) cannot be Figure 2. Schematic of detonation velocity and explosive brisance
22 detonated again. testing system (a: detonation velocity, b: explosive brisance).
23
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25 2.2 Experimental Procedure a depth (H) of 5 m, as seen in Figure 3. A PCBW138A25
26 ICP-type pressure sensor, which corresponds with a PCB-
27 Tests on detonation velocity and explosive brisance are per- 482A22 signal conditioner bought from PCB Piezotronics,
28 formed in a steel vessel which is located on a soft base, and Inc. USA, was used to detect pressure signals caused by 30-
29 the vessel is about 2.5 m in diameter and 5 m long. Ex- g emulsion explosives initiated by a standard No. 8 deto-
30 perimental samples are all horizontally suspended in the nator on the top. Finally, the pressure-time data are re-
31 centre of the vessel and initiated by standard No. 8 deto- corded and stored by a Tektronix 7401 digital oscilloscope
32 nators on the left. A detailed diagram of the measurement bought from Tektronix, Inc. USA.
33 system for detonation velocities is shown in Figure 2(a). The To be specific, experimental parameters of this study
34 velocities are measured by short-circuit sensors, which are were set as follows: samples which are vertically hung in the
35 manufactured from two insulated copper wires, and one
36 end of these electric probes is connected to a high-reso-
37 lution electric timer (machine model: 2BS-110) to record the
38 time gap (Dt) between adjacent probes (DL), while the oth-
39 er end is inserted into samples. To be specific, the length
40 and diameter of explosive charge used to evaluate the det-
41 onation velocity is 300 mm and 32 mm, respectively. And in
42 order to obtain a stable detonation of the test section, dis-
43 tance between the detonator and the first ionization probe
44 is set to 150 mm, nearly five times the diameter of the
45 charge.
46 With respect to the explosive brisance experiment, a
47 standard lead cylinder, which is about 40 mm in diameter
48 and 60-mm long, is set under a matched steel plate, while
49 50 g emulsion explosives are placed above the plate, as
50 seen in Figure 2(b). All the above-mentioned items are con-
51 strained by weak restraints, such as stiff papers or plastics,
52 and after the experiment is complete, the compression of
53 the standard lead cylinder is measured to represent the ex-
54 plosive brisance. Figure 3. Arrangement of the underwater explosion-testing system
55 All the underwater explosion experiments are con- (1 – signal conditioner: PCB-482A22, 2 – digital oscilloscope: Tek-
56 ducted in a steel water tank with a diameter (D) of 5 m and tronix 7401).

Propellants Explos. Pyrotech. 2018, 43, 789–798 © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.pep.wiley-vch.de 791
 Full Paper G. Zhou, H. Ma, Z. Shen, P. Chen, Y. Yu

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16 Figure 4. Variation of detonation properties with content of clay (a: the detonation velocity, b: the explosive brisance)
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19 centre of the tank as well as pressure sensors were both The negative relationship between detonation proper-
20 fixed at a depth of h = 2.0 m below the water surface, and ties (detonation velocity, explosive brisance) and the con-
21 the test distance (dt) from the sample centre to the pressure tent of common clay or HGMs indicates that under the con-
22 sensor is 1.0 m, as seen in Figure 3. dition of our experimental ratios (HGMs: from 5 wt.% to
23 15 wt.%; common clay: from 0 wt.% to 20 wt.%), these two
24 additives both function as thermal diluents and make no
25 3 Results and Discussion contribution to the detonation propagation. Furthermore,
26 as seen in Figure 4, these linear plots of different formulas
27 3.1 Immediate Measurements of Detonation Parameters are nearly parallel to each other, which suggests that the
28 influence of common clay on the new emulsion explosive is
29 Generally, the detonation parameters, explosion energy, and independent of the content of HGMs, and vice versa.
30 energy structure of a civil explosive are normally specified Results presented above show that the decreasing ten-
31 in order to characterize its performance. Because the deto- dencies of detonation velocity and explosive brisance real-
32 nation velocity and explosive brisance are widely acknowl- ized by increasing the amount of common clay or HGMs
33 edged in the commercial explosive field [23–26], these pa- make this kind of new emulsion explosive more suitable
34 rameters are first measured under the rule of testing as when used in some specific industries, requiring rather poor
35 soon as experimental samples are prepared. detonation properties, such as explosive spraying or the for-
36 Each formula was tested three times under the same mation of metal parts [19–21].
37 condition, and the average experimental results of deto- With respect to underwater explosion tests, the pres-
38 nation velocity and explosive brisance are obtained and sure-time history curves detected by the PCB-W138A25 ICP-
39 plotted in Figure 4(a) and Figure 4(b), respectively. type pressure sensor, which contain the peak over-pressure,
40 The R-Squares of these linear plots in Figure 4(a) and the impulse, the specific shock energy, the specific bubble
41 Figure 4(b) are 0.9865, 0.9899, 0.9775, 0.9592, 0.9338 and energy and the specific total energy, are all recorded more
42 0.9269, respectively, using the software: Origin 2017. It can completely and precisely than in air thanks to the in-
43 be clearly found that both detonation velocity and ex- compressibility of water. Four representative formulas (typi-
44 plosive brisance of these emulsion explosive products all cal traditional emulsion explosives: No. 1-1 and No. 3-1, and
45 decrease with the increase of the content of common clay the new emulsion explosive products: No. 3-3 and No. 3-5)
46 or HGMs. According to the hot-spot model [9], the pre- were selected for this kind of test, following the same rule
47 diction of the chemical energy released from the deto- of testing as soon as these formulas are developed.
48 nation reaction can be given as Eq. (1): With the exception of the peak over-pressure (MPa),
49 pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi which characterizes the strength of a shock wave and can
50 D0 ¼ Fin 2ðn2  1ÞQ ð1Þ be read directly from the pressure-time history curves (as
51 seen in Figure 5), other underwater explosion parameters
52 where D0 is the detonation velocity (m s1), Fin is an inert need to be calculated as follows: the impulse (I/Pa s) repre-
53 component, n is the heat capacity ratio of gas products and sents the momentum upon impact into water by the deto-
54 Q is the chemical energy released during detonation nation shock wave, and can be formulated as Eq. (2) [27]:
55 (kJ kg1).
56

792 www.pep.wiley-vch.de © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Propellants Explos. Pyrotech. 2018, 43, 789–798
 Study on a New Cleaner Emulsion Explosive Containing Common Clay

1 where a and b are both constants obtained from Eq. (7) us-
2 ing the least-square method, and Ph is the total hydro-static
3 pressure of the experimental samples (Pa).
4
5 tb ¼ aW 1=3 þ bW 2=3 ð7Þ
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7 According to Lin, et al., constants a and b have been de-
8 termined in the previous research, where a = 0.2849 and
9 b =-0.07463, using the same underwater testing system
10 [29].
11 With respect to the specific total energy, which contains
12 the specific shock energy and the above-mentioned specific
13 bubble energy, it can be formulated as Eq. (8) [27]:
14
15 E ¼ Ks ðmEs þ Eb Þ ð8Þ
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17 Figure 5. Peak overpressure curves of underwater explosion tests. where Ks is the nonspherical correction factor of ex-
18 perimental samples, whose value is set to 1.05 in this study.
19 According to Bjarnholt, m is the loss factor of the shock
Z
20 6:7q wave during its propagation [27], which can be calculated
I¼ pðtÞdt ð2Þ from Eq. (9) [30]:
21 0
22
23 where p(t) is the pressure-time history curve (Pa), q is the m ¼ 1 þ 1:3328  101 pCJ  6:5775  103 p2CJ
ð9Þ
24 time constant (s), which equals the duration from Pm to Pm/e þ1:2594  104 p3CJ
25 on the pressure-time history curve, and e is the mathemat-
26 ical constant, which is around 2.71828. where PC-J is the the value of the detonation pressure (GPa),
27 With respect to the specific shock energy (ES/MJ kg1), which can be formulated as Eq. (10):
28 one part of the total energy released by the detonation, can
29 be calculated as Eq. (3) [27]: 1
pCJ ¼ 1D2 ð10Þ
30 ð1 þ gÞ
2 Z 6:7q
31 4pd
Es ¼ t
p2 ðtÞdt ð3Þ
32 W1W CW 0 where g is the heat capacity ratio of emulsion explosive
33 products, which approximately equals to 3, 1 is the density
34 where dt is the distance from the experimental sample’s of experimental samples (kg m3) and D is the detonation
35 centre to the pressure sensor (m), W is the mass of the ex- velocity of these testing formulas (m s1).
36 perimental samples (kg), 1w is the density of water (kg m3) To date, all the calculation methods of underwater pa-
37 and Cw is the sound of speed in water (m s1). rameters are presented above. The experimental values of
38 As another part of the total energy released by the det- selected four formulas are calculated and given in Table 3.
39 onation, the specific bubble energy (Eb/MJ kg1) represents It can be clearly found that underwater detonation pa-
40 the pulsation characteristics of explosive gas products, and rameters and energy structures have been significantly ad-
41 plays an important role in evaluating a new civil explosive justed by adding common clay or HGMs. For instance, the
42 product owing to the accessibility of reflecting influences of specific total energy decreased dramatically by about
43 these additives [28]. According to Bjarnholt, modified 73.24 %, 3.3568 MJ kg1 with No. 1-1 and 0.8984 MJ kg1
44 Eq. (4), which considers the surface and bottom effects, is with No. 3-5, while the impulse decreased only by about
45 performed to calculate the specific bubble energy [27]: 5.62 %, 609.45 Pa s with No. 1-1 and 575.17 Pa s with No. 3-5.
46 Once again, the property which allows for the easy ad-
47 1 pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi justment of various detonation properties to the desired
Eb ¼ 3 3 ð 1 þ 4Ctb  1Þ3 ð4Þ
48 8WC K1 values makes this new emulsion explosive product much
49 more competitive in the civil explosive sector. In Section 3.2,
50 where tb is the first bubble period (s), C and K1 are both con- another way of changing detonation properties through
51 stants which depend on experimental conditions, and can storage is presented.
52 be formulated as Eqs. (5) and (6), respectively.
53
54 C ¼ b=a2 ð5Þ
55
56 K1 ¼ 1:13511=2 5=6
W =Ph
ð6Þ

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 Full Paper G. Zhou, H. Ma, Z. Shen, P. Chen, Y. Yu

1 Table 3. Experimental values of underwater explosion parameters.

2
Numbers of different formulas Peak over-pressure Impulse Specific shock energy Specific bubble energy Specific total energy
3
(Pm/MPa) (I/Pa s) (ES/MJ kg1) (Eb/MJ kg1) (E/MJ kg1)
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5 No. 1-1 9.794 609.45 0.7867 2.5238 3.3568
6 No. 3-1 8.059 662.53 0.6681 2.4047 3.0932
7 No. 3-3 7.808 614.27 0.6108 1.9236 2.5510
No. 3-5 5.372 575.17 0.2136 0.67981 0.8984
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Table 4. Detailed test results during storage.
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12 Test results Immediately One week later Two weeks later Three weeks later Four weeks later Five weeks later
13
Detonation velocity No. 1-1 4420 4485 4390 4347 4412 4407
14 (m/s) No. 3-1 3425 3360 3252 3200 3220 3226
15 No. 3-3 3150 3090 2927 2792 2665 2559
16 No. 3-5 2815 – – – – –
17 Explosive brisance No. 1-1 18.9 19.5 19.3 19.1 18.5 18.8
18 (mm) No. 3-1 11.9 11.7 11 10.9 10.8 10.7
No. 3-3 10.1 9.8 8.7 7.3 6.5 5.9
19
No. 3-5 7.9 – – – – –
20
Underwater Peak No. 1-1 9.794 10.046 9.513 9.756 9.833 9.732
21 explosion over-pressure No. 3-1 8.059 7.932 7.911 8.001 7.877 8.923
22 parameters (Pm/MPa) No. 3-3 7.808 7.791 5.449 5.811 5.768 5.883
23 No. 3-5 5.372 – – – – –
24 Impulse No. 1-1 609.45 505.24 580.69 519.32 549.36 513.45
25 (I/Pa s) No. 3-1 662.53 589.2 586.87 583.83 581.28 565.45
No. 3-3 614.27 538.01 410.26 283.21 234.82 193.68
26
No. 3-5 575.17 – – – – –
27 Specific shock No. 1-1 0.7867 0.6618 0.7291 0.6678 0.6647 0.6571
28 energy No. 3-1 0.6681 0.5732 0.5695 0.5647 0.5561 0.5663
29 (ES/MJ kg1) No. 3-3 0.6108 0.4956 0.2805 0.1852 0.1408 0.1398
30 No. 3-5 0.2136 – – – – –
31 Specific bubble No. 1-1 2.3238 2.419 2.2961 2.3511 2.3395 2.332
32 energy No. 3-1 2.4047 2.4954 2.4562 2.357 2.3192 2.298
(Eb/MJ kg1) No. 3-3 1.9236 1.7447 1.235 0.8408 0.6413 0.58
33
No. 3-5 0.67981 – – – – –
34 Specific total No. 1-1 3.1568 3.1125 3.0651 3.0505 3.0356 3.0202
35 energy No. 3-1 3.0932 3.0846 3.0397 2.9351 2.888 2.878
36 (E/MJ kg1) No. 3-3 2.551 2.252 1.521 1.0295 0.7843 0.7218
37 No. 3-5 0.8984 – – – – –
38 a) “–” means formulas cannot be detonated, no data.
39
40
41 3.2 Time-related Tests and Theoretical Explanation weeks, only formulas without common clay (traditional
42 products) were detonated successfully. Detailed results of
43 With respect to the storage and time-related experiments, formulas during that period are listed together in Table 4.
44 the same four representative formulas (No. 1-1, No. 3-1, Generally, the decrease in various detonation parame-
45 No. 3-3 and No. 3-5) are prepared sufficiently at the begin- ters of No. 1-1 containing only 5 wt.% HGMs and no com-
46 ning, about 2.0 kg each, and they are stored in sealed plas- mon clay, which belongs to traditional products, is almost
47 tic bags at room temperature. Once experimental samples negligible during the 5-week window (as seen in Figure 6).
48 are taken, these stored formulas are immediately sealed For example, as a representative parameter of the whole
49 again. Experiments are performed once a week, which im- energy of an emulsion explosive, the specific total energy
50 plies that the changing tendencies of various detonation just decreased by about 4.33 % (began with 3.1568 MJ kg1
51 parameters are all performed within a one-week interval, and ended with 3.0202 MJ kg1), and the detonation veloc-
52 until none of new emulsion explosive products (No. 3-3 and ity also decreased only by about 0.29 % (began with
53 No. 3-5) can be detonated again. 4420 m s1 and ended with 4407 m s1). This kind of almost
54 From all the experimental results, the longest storage fixed performance shown above makes traditional civil ex-
55 time of formulas containing common clay is about 5 weeks, plosive products unsuitable from time to time during us-
56 belonging to No. 3-3. With respect to experiments after 6 age.

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 Study on a New Cleaner Emulsion Explosive Containing Common Clay

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37 Figure 6. Variations for detonation parameters of different formulas (time-related). (a: the detonation velocity, b: the explosive brisance, c:
38 the total energy, d: the peak over-pressure, e: the impulse, f: the specific shock energy; g: the specific bubble energy)
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41 Similar tendencies were observed in No. 3-1, the com- ended with 2559 m s1). This verifies that there is another
42 promise option containing 15 wt.% HGMs but no common way of adjusting detonation properties of the new eco-
43 clay, as seen in Figure 6. The specific total energy decreased friendly products, and this makes them more flexible during
44 by about 6.96 % (began with 3.0932 MJ kg1 and ended usage.
45 with 2.8780 MJ kg1), and the detonation velocity decreased Finally, with respect to No. 3–5 (another formula of the
46 by about 5.81 % (began with 3425 m s1 and ended with new emulsion explosive products), which contains 15 wt.%
47 3226 m s1). HGMs and 20 wt.% common clay, there were significant de-
48 However, with respect to No. 3–3 (one kind of the new creases in various detonation parameters after the formula
49 emulsion explosive products), which contains 15 wt.% was developed, as seen in Figure 6. Even after one week,
50 HGMs and 10 wt.% common clay, the decrease in several of explosive samples of this kind cannot be detonated again,
51 its detonation parameters is significant over the five-week compared with the pressure-time history curve of a single
52 window, as seen in Figure 6, compared with the plots for detonator. This phenomenon reveals that this kind of new
53 No. 1-1 and No. 3-1. The specific total energy decreased dra- formula is not suitable for storage, and it is proposed that it
54 matically by about 71.71 % (began with 2.551 MJ kg1 and should be used soon after manufacture when applied in the
55 ended with 0.7218 MJ kg1), and the detonation velocity de- civil explosive field.
56 creased by about 18.76 % (began with 3150 m s1 and

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Figure 7. Micro-surface structures of a: common clay and b: HGMs.
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27
28
29
30
31 Figure 8. Vapor absorption experiments of common clay and HGMs. (a: with water steam, b: with C18H38 steam)
32
33
34 With respect to the theoretical explanation, the compar- However, with respect to the HGMs (specific surface
35 ison of No. 3-1 and No. 3-3 reveals that the presence of area: 2.120 m2 g1), as seen in Figure 7(b), the smooth un-
36 common clay significantly affects various detonation prop- broken micro-surface structure makes it quite hard to ab-
37 erties of the new emulsion explosive products during stor- sorb detonable components of the emulsion matrix (as
38 age, while HGMs fail to do so. It can be explained by the shown in Figure 8, respectively absorbed only 16.4 mg g1
39 difference in micro-surface structures between these two water steam after 16 h and 1.28 mg g1 C18H38 steam after
40 additives. As seen in Figure 7(a), the unconsolidated multi- 10 h, when the final ratio of test pressure (P) to saturated
41 cavity surfaces of common clay (specific surface area: vapor pressure (P0) is also about 0.9). This may explain why
42 20.05 m2 g1) makes it easy to absorb and fix detonable detonation properties of No. 1–1 and No. 3-1 are almost
43 components of the emulsion matrix: the ammonium nitrate constant during that period despite some slight decrease.
44 aqueous solution and mineral oil added to attain the stoi- This nearly stubborn explosive performance is responsible
45 chiometric ratio [9]. As shown in Figure 8, the common clay for the embarrassing situation of traditional emulsion ex-
46 absorbed about 70.8 mg g1 water steam after 16 h and plosive products in the civil explosive field.
47 22.0 mg g1 C18H38 (one of mineral oils used in the emulsion Furthermore, with respect to the attenuation tendencies
48 matrix, as shown in Table 1) steam after 10 h, respectively, of detonation parameters (as seen in Figure 6), such as the
49 when the final ratio of test pressure (P) to saturated vapor specific total energy of formula No. 3-3, the decline rate ac-
50 pressure (P0) is about 0.9. celerates to a peak after two weeks (tends to decrease by
51 During the absorbing process, the balance of the stoi- 0.75 MJ kg1 per week), before showing an increasingly
52 chiometric ratio was broken, as well as a decrease of the to- slower decay rate until the misfire after six weeks. This non-
53 tal number of detonable components. These two factors linear change can be explained by Darcy’s law and the es-
54 both contribute to the changing of various detonation tablished seepage flow model [31] which can be formulated
55 properties of the new emulsion explosive during storage. as Eq. (11):
56

796 www.pep.wiley-vch.de © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Propellants Explos. Pyrotech. 2018, 43, 789–798
 Study on a New Cleaner Emulsion Explosive Containing Common Clay

1 dH reduced overall cost of new emulsion explosive prod-

v ¼ K  ð11Þ
2 dS ucts.
3
4 where v is the seepage velocity, K is the osmotic coefficient
dH
5 and dS is the concentration gradient. Acknowledgments
6 Owing to the incompatibility of boundaries between
7 common clay and the emulsion matrix, which implies that We would like to acknowledge the financial support received from
8 there is a small osmotic coefficient K, the seepage velocity v the National Natural Science Foundation of China (Contract Grant
number: 51674229 and 51374189) and the Fundamental Research
9 is observed to be small during the first week. After that, Funds for Central Universities (Project Account: WK2480000002).
10 with the preparation of the first week and the significant
11 difference in the concentration of detonable components
12 between two sides of the boundary, the seepage velocity v References
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798 www.pep.wiley-vch.de © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Propellants Explos. Pyrotech. 2018, 43, 789–798