Study of Heat Resistant Commercial Explosives

Kenji TANAKA, Shinya TANAKA, Tetsuya SAWADA,

Fumihiko SUMIYA, and Yukio KATO
NOF Corporation Taketoyo-Plant R&D Department
61-1 Kitakomatsudani Taketoyo-cho Chita-gun Aichi 470-2398 JAPAN

When explosives are heated under an acidic environment due to metal sulfide and sulfuric acidity, their
decomposition temperature falls remarkably and decomposition reaction occurs quickly, and then explosives have the
risk of the deflagration to the detonation transition. Heat resistant commercial explosives which can be used under
conditions of high temperature of 200ºC and an acidic environment were studied. We developed the explosive
composition consisted of ammonium perchlorate (AP) as oxidizer, saturated hydrocarbon oil as fuel and binder, and
calcium carbonate as decomposition inhibitor. The characteristics of this explosive composition show a heat resistance
over 24 hours at 200ºC, and a detonation velocity over 2,500 m s-1. This explosive composition has a cap-sensitivity at
temperature higher than 100ºC. Cost effective heat resistant commercial explosives were created by the optimization
of the grain size of AP as a main component, the addition of saturated hydrocarbon oil and calcium carbonate, and the
control of bulk density by the addition of micro-balloons.

1. Introduction
In some underground metal mines, the ground temperature rises remarkably as the depth increases, and the mining
operation is conducted under a temperature higher than 100ºC. It is not always sufficient to cool drift walls by means
of atomizing cold water or increasing the ventilation. In the mine containing metal sulfides such as pyrites in ore, the
explosives have the risk of sudden decomposition by the contact with pyrites under a high temperature environment. It
is considered that the decomposition of the oxidizer as the principal ingredient of explosive is promoted by contact
with pyrites.
The heat stability and reactivity of industrial explosives with pyrites were studied by some researchers 1)-4). They
showed that potassium oxalate, urea, zinc oxide, magnesium oxide, calcium carbonate, etc were found to be effective
to prevent the reaction between the explosives and the pyrites.
An emulsion explosive with heat resistance up to 160ºC had been already developed in our laboratory, and had been
used in some metal mines 5). Also, an explosive which can be used at a similar temperature is being supplied by
another company 6). Recently, ground temperatures of 200ºC have been confirmed by prospecting in a metal mine.
However, an explosive which can be used at such a high temperature has not been developed yet. In blasting operation,
the safety of the explosives is the highest priority. We started the study of heat resistant commercial explosives which
could be used under a high temperature condition of 200ºC and an acidic environment.
For heat resistant commercial explosives, it is necessary to have high stability at high temperature. A preliminary
examination was conducted into the stability of an emulsion explosive with heat resistance in which the addition rate
of the decomposition inhibitor was increased, and into the stability of explosive compounds such as RDX, HMX and
HNS whose decomposition temperature were 200ºC or higher. As a result, the emulsion explosive was decomposed
in a short time at 200ºC. This result did not satisfy the target heat-resistance that decomposition would not be
observed within 24 hours. Also, it was found that when these explosive compounds were heated under an acidic
environment due to metal sulfide and sulfuric acidity, their decomposition temperature fell remarkably and a
decomposition reaction occurred quickly, and explosive compounds had the risk of the deflagration to the detonation
transition. It was concluded that the emulsion explosive and explosive compounds such as RDX, HMX and HNS

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could not be used at a temperature higher than 200ºC. Thus the composition based on AP which has heat stability at
temperature higher than 200ºC was examined.

2. Experimental
2.1 Sample explosives
The composition based on AP as an oxidizer was examined. However, it is known that the decomposition
temperature falls remarkably under contact with pyrites. Thus it is necessary to contain the decomposition inhibitor in
the explosive composition. It was reported that calcium carbonate and barium carbonate, etc. are effective as a
decomposition inhibitor for AP 7). Calcium carbonate was selected as a decomposition inhibitor because a heavy
metal salt such as barium carbonate is toxic. Also, a composition containing sodium nitrate whose decomposition
temperature was higher than AP was examined.
The sample explosives were prepared using AP and the content of each ingredient such as oil, decomposition
inhibitor, water absorption agent and density control agent was changed. The heat resistance and initiation sensitivity
of these samples were compared, and the influences of each ingredient on the performance were investigated. The
composition of sample explosives are shown in Table 1. The mixture ratio of AP and oil was adjusted to be 9:1
considering the dispersion condition of the oil and oxygen balance. Also the hydrogenation refinement oil used in
these compositions has high heat stability and the anti-oxidation property. Sample explosives were prepared for the
following comparisons:

Sample A; Relationship between grain size of AP and heat resistance.

Sample B; Relationship between addition rate of calcium carbonate and heat resistance.
Sample C; Relationship between grain size of AP and initiation sensitivity.
Sample D; Relationship between addition rate of calcium carbonate and initiation sensitivity.
Sample E; Relationship between adjustment of bulk density by glass micro-balloon (GMB) and explosion
performance.
Sample F; Relationship between addition rate of sodium nitrate and heat resistance.
Sample G; Relationship between addition rate of a water absorption agent and initiation sensitivity.
Sample H; Relationship between adjustment of bulk density by resin micro-balloon (RMB) and initiation sensitivity.

2.2 Thermal analysis

The thermal analysis was performed by means of DSC (differential scanning calorimeter) to study the influence of
grain size on heat stability of AP. The DSC apparatus used was Seiko Instruments Inc. DSC200. The measurements
were carried out for AP of 10, 35, and 200µm in diameter respectively. The measurements were performed using
sealed stainless cell and setting the gradient temperature of 10K min-1 .

2.3 Heating test

The heating test was carried out to evaluate the heat stability of the sample explosives. Mine water containing
pyrites generally shows strong acidity attributed to the dissolution of pyrites. The mine water is concentrated under the
high temperature, and a strong acidity is formed. Its pH value is in the range of 2 to 3. When the explosive is used
under such conditions, the explosive can contact pyrites and mine water. It is very important to evaluate the heat
stability of the explosive under such conditions, because pyrites and mine water do promote the decomposition of the
explosive. The explosive, pyrites and mine water were completely mixed to imitate the severest situation, and the
mixture was used as the sample for the heating test. Figure 1 shows the apparatus used for the heating test. The test
sample was prepared by complete mixing 30g of the sample explosive, 30g of crushed pyrites and 5g of mine water,
and that mixture was filled in a test tube made of glass (30mm inside diameter). This test tube was set in steel tube
(32mm inside diameter), and heated to 200ºC with a rubber heater that wrapped outside of steel tube. The temperature
of the test sample was measured with a thermocouple, and the start of the decomposition of the test sample was

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measured. The start of the decomposition was defined as decomposition delay time. The analysis of pyrites and mine
water used for the heating test are shown in Table 2.

2.4 Steam heating test

A container which has high heat stability is necessary for testing heat resistance commercial explosives used in a mine
with a high ground temperature. If only heat stability is considered, a metallic container such as aluminum is suitable.
However, a metallic container causes problem in the smelting process of ore. Then a silicon rubber tube with high heat
stability was selected. Another problem to be considered in a mine with high ground temperature is steam. In using a
resin container such as silicon rubber tube, it is necessary to minimize the influence of steam from the hot ground. To
evaluate the influence of the steam, a steam heating test was examined. The sample explosive charged in the silicon
rubber tube was set in the steel tube which imitated a bore hole, and steam was blown in this steel tube. This set-up
was heated to 100ºC. After the steam heating test, the sample explosive was set in the steel tube, and initiated by a
heat resistance electric detonator to investigate its detonability.

2.5 Initiation test

The initiation test was carried out to evaluate the cap sensitivity of the explosives under a high temperature
environment. The sample explosive was charged in a silicon rubber tube (32mm inside diameter), and the opening of
the tube was sealed with a silicon rubber plug. This set-up was heated to 150ºC in the thermostatic chamber. Five
hours later, it was set in a steel tube (42mm inside diameter), and the sample explosive was initiated by a heat
resistance electric detonator at 150ºC to investigate its detonability. Moreover, the detonation velocity of the sample
was measured by the ionized gap method.

3. Result and discussion

3.1 Thermal analysis
The chart of DSC of AP in each grain size is shown in Figure 2. After the phase transition from diagonal to cubic at
about 240ºC, pyrolysis of AP appears separately on two stages. One is the low temperature decomposition area at
about 250ºC, and the other is the high temperature decomposition area at about 350ºC. Regarding the pyrolysis of AP,
it is shown that the decomposition temperature at the high temperature area shifts to the lower temperature side as the
grain size becomes smaller, while the grain size does not influence the decomposition temperature at the low
temperature area 8). It was confirmed in our analysis that the low temperature decomposition in each grain size was
observed at about 250ºC, and the high temperature decomposition shifted to the lower temperature side as the grain
size became smaller.

3.2 Heating test

The results of the heating test for sample explosive A is shown in Table 3. As shown in Table 3, the sample
explosive prepared using AP with small grain size showed a lower heat stability. It is thought that the decomposition
reaction is promoted because AP contacts with pyrites on a large area. The relation between the content of calcium
carbonate and the decomposition delay time at 200ºC is described in Figure 3. This investigation was carried out using
the sample explosive B in which the content of calcium carbonate was varied. It becomes clear that the addition of
28% or more of calcium carbonate is necessary to obtain heat stability for over 24 hours at 200ºC as shown in Figure 3.
The decomposition inhibitory mechanism of AP by the calcium carbonate was studied 9). The species of ClO4- and
ClO2- generate in the early period of the decomposition reaction of AP, and promote its reaction as the active species.
Calcium carbonate decreases the active species and inhibits the decomposition reaction by bonding with these active
species. Furthermore, Ca(ClO4)2/CaCl2 that has a higher heat stability than AP is formed by bonding with calcium
carbonate and the active species, and the decomposition rate is decelerated. It is assumed that the difference on
decomposition reaction in Table 3 due to the size of the grain size of AP used in sample Ais attributed to the progress
of the self catalytic reaction. In other words, small grain size of AP can generates large amount of active species in the

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early period of the decomposition reaction, and the self catalytic reaction which accelerates the decomposition
reaction is promoted by reaction heat.
The results of the heating test for sample explosive F is shown in Table 4. It was shown that sample explosive F to
maintains heat stability for over 24 hours at 200ºC even if the addition rate of calcium carbonate is decreased to 25%
by adding 10% sodium nitrate. This is due to the high decomposition temperature of sodium nitrate which is higher
than 340ºC.

3.3 Steam heating test

The results of the initiation test after steam heating test for sample explosive G is shown in Table 5. The initiation
sensitivity of the sample explosive which had not added the water absorption agent (Molecular sieves) was decreased.
The electron microscopic photograph of sample explosive G before and after steam heating test are shown in Figure 4.
It is shown that the grain size of the sample explosive G after steam heating test is larger than that before the steam
heating test.
The silicon rubber tube used as an explosive container could resist high temperature, but it could not prevent the
penetration of high temperature steam. Consequently, the sample was coagulated, and its initiation sensitivity was
decreased. The sample explosives containing molecular sieves which have good water absorptivity and water
retentivity at high temperature maintain the initiation sensitivity. The optimal content of molecular sieves was found to
be 6%.

3.4 Initiation test

The results of the initiation test for sample explosive C is shown in Table 6. In the sample explosives using AP of a
single grain size, the sample explosive with smaller grain size demonstrated higher initiation sensitivity. Also, in the
sample explosives including AP of two grain sizes, the sample explosive with a high ratio of small grain sizes
demonstrated higher initiation sensitivity. Accordingly, it is clear that the initiation sensitivity depends on the grain size
of AP.
The results of the initiation test for sample explosive D are shown in Table 7. Calcium carbonate is expected to
decrease the initiation sensitivity of the explosives with an increase of the addition rate, because it is an inert substance
which does not contribute to the detonation reaction, although it is effective as a decomposition inhibitor of AP. As for
the addition rate of calcium carbonate, it is concluded that the addition rate of 28-30% is suitable from the results
shown in Figure 3(sample explosive B) and Table 7. In the case of sample explosive F containing sodium nitrate, the
initiation sensitivity was maintained because the addition rate of calcium carbonate is decreased to 25%.
The results of the initiation test and measurements of detonation velocity of sample explosive E are shown in Figure 5.
And the results of the initiation test of sample explosive H are shown in Table 8. To increase the initiation sensitivity,
the addition of a density control agent is necessary, because AP has lower reactivity than explosive compounds such as
RDX, and the sample explosive E without density control agent can not be initiated as shown in Figure 5 and Table 8.
The detonation velocity of 3000 m s-1 was observed with the sample explosive E containing 3% GMB. Moreover, the
result of Table 8 was similar, and the detonation velocity of 3300 m s-1 was observed with the sample explosive H
containing 1% RMB.
The relation between the temperature and the initiation sensitivity for sample explosive H is shown in Table 9. The
temperature sensitivity is very low so that the sample explosive can not detonate at less than 100ºC. However, this is
not a problem taking into account the actual environment in which this explosive is used. To the contrary, this fact
shows rather high safety in the handling of AP based explosive composition.

4. Conclusions
As a result of the investigation of the heat resistant commercial explosives which could be used at high temperature
of 200ºC even in acidic environment, a heat resistance over 24 hours at 200ºC was obtained by adding calcium

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carbonate to the explosive using AP as an oxidizer under coexistence with the a decomposition promoter such as
pyrites.

References
1) Miron Y., Ruhe T. C., Watson R. W., “Reactivity of AN-FO With Pyrite Containing Weathering Products”,
Bureau of Mines Report of Investigations, 8373, 1979.
2) Ikeda Y., Tanabe Y., Inoue A., and Yamamoto K., “Heat –resistant Properties of Emulsion Explosives”,
Journal of the Industrial Explosives Society, Japan, vol.45, pp.234-239, 1984.
3) Sato S., Tsubaki I., and Suenaga T., “Heat-resistant water gel explosives”, Journal of the Industrial
Explosives Society, Japan, vol.38, pp. 286-288, 1977.
4) Shimomura Y., and Sakai H., “The Blasting Method at the High Temperature Face where the Temperature is
to 160ºC Degree in the Bore Hole”, Journal of the Industrial Explosives Society, Japan, vol.23, pp.111-119,
1962.
5) Sawada T., Kurokawa K., Sumiya F., and Kato Y., “Heat resistant properties of industrial explosives”,
Journal of the Industrial Explosives Society, Japan, vol.53, pp. 212-218, 1992.
6) Galvin T., Ross T., and Cameron S., “When Not Only the Ground is Hot”, Proceedings of the Explo 2001:
Blasting Techniques & Technology-Today & Tomorrow’s, Hunter Valley, NSW, Australia, October 28-31,
2001, pp.115-120.
7) Simchen A. E., Inbar-Rozem L., “Thermal Analysis of Ammonium Perchlorate and of its Mixtures with
Inorganic Substances”, Israel Journal of Chemistry, vol.6, pp. 937-948, 1968.
8) Osada H., Sakamoto E., “Thermal Decomposition of Ammonium Perchlorate”, Journal of the Industrial
Explosives Society, Japan, vol.24, pp. 236-244, 1963.
9) Rastogi R. P., Singh G., and Singh R. R., “Effect of CaCO3 and CaO on the Thermal Decomposition of
Ammonium Perchlorate”, Journal of Applied Chemistry and Biotechnol, vol.28, pp. 889-894, 1978.

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Table 1 Composition of sample explosives.
Sample Ingredients
explosives AP OIL CaCO3 GMB SN MS RMB
A 90 10 8 - - - -
B 90 10 8-30 - - - -
C 90 10 8 3 - - -
D 90 10 8-40 3 - - -
E 90 10 30 0-7 - - -
F 90 10 25-30 3 0-10 - -
G 90 10 25 3 10 0-9 -
H 90 10 25 - 10 6 0-3.0
AP : Ammonium perchlorate, OIL : Saturated hydrocarbon oil, CaCO3 : Calcium carbonate
GMB : Glass micro-balloon, SN : Sodium nitrate, MS : Molecular sieves,
RMB : Resin micro-balloon

Table 2(a) Ingredients of pyrites tested.

Elements (wt%)
Fe S Cu Pb Zn Mn SiO2 Al2O3
43.85 48.86 0.10 0.27 0.68 0.10 2.95 0.30
Table 2(b) Ingredients of mine water tested.
Elements (mg l-1)
Fe Fe2+ Zn Mn CaO Al2O3 MgO SO 3
1216 565 1298 641 305 604 340 8860

Table 3 Results of heating test for sample explosive A.

Average diameter of AP 35 -m 400 -m
Decomposition delay time 2.3 hour 5 hour
State of decomposition DDT Decomposition

Table 4 Results of heating test and initiation test for sample explosive F.
Content of Content of Results
sodium nitrate calcium Decomposition Initiation
(wt%) carbonate (wt%) delay time (hour) sensitivity
25 4 Detonation
0
30 over 24 Detonation
5 25 14 Detonation
10 25 over 24 Detonation

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 Table 5 Result of steam heating test for sample explosive G.
Content of molecular Heating time of
Results
sieves (wt%) steam (hour)
0 Detonation
0
2 Non-detonation
3 2 Detonation
2 Detonation
6 4 Detonation
5 Non-detonation
9 3 Non-detonation

Table 6 Result of initiation test for Table 7 Result of initiation test for sample
sample explosive C. explosive D.
Density Content of calcium Density
Ratio of mix Results Results
(g cm-3) carbonate (wt%) (g cm-3)
35 - -100%
m 0.85 Detonation 8 0.85 Detonation
200 -m-100% 1.09 Non-detonation 13 0.90 Detonation
400 -m-100% 1.03 Non-detonation 20 0.87 Detonation
35 -m:200 -m = 50%:50% 1.00 Detonation 30 0.95 Detonation
35 -m:200 -m = 20%:80% 1.05 Non-detonation 40 1.00 Non-detonation
35 -m:400 -m = 50%:50% 1.03 Detonation
35 -m:400 -m = 20%:80% 1.07 Non-detonation

Table 8 Result of initiation test for sample explosive H.

Content of Results
Density
RMB Initiation Detonation
(g cm-3)
(wt%) sensitivity Velocity (m/sec)
0 1.20 Non-detonation -
0.3 1.16 Non-detonation -
0.5 1.12 Detonation -
1.0 1.05 Detonation 3300
3.0 0.85 Detonation -

Table 9 Relation between temperature and

initiation sensitivity for sample explosive H.
Explosive temperature
50ºC 80ºC 100ºC
Sample H Non- Non-
Detonation
(RMB 1%) detonation detonation

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2003G Volume 1 - Study of Heat Resistant Commercial Explosives 7 of 9
 Th e r m o couple Recorder
Steel tube
Glass test tube Rubber heater
Thermostatic
Test sample controller

Fig.1 Apparatus for heating test.

92
84
75
67
)
59 10ƒÊm 35ƒÊm 200ƒÊm
mW
50
Hea t f low

42
34
Heat
25 flow (
17
8
0

50 100 150 200 250 300 350 400 450 500

Tempe ra tu re Ž
( •)

Fig.2 Chart of DSC of ammonium perchlorate.

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 50

Decomposition delay time (hour)

40

30 24hours

20

10

0
0 10 20 30
Content of calcium carbonate (wt.%)
Fig.3 Relation between content of calcium carbonate
and decomposition delay time at 200ºC.

Before After
Fig.4 Electron microscopic photograph of sample explosive G
before and after steam heating test.
Detonation velociy (m sec )

3500
-1

GMB5%
3000
GMB3%
2500
GMB7%
2000
1500
1000
500 GMB0%
0
0.85 0.95 1.05 1.15 1.25
Density of sample (g cm-3)
Fig.5 Relation between density of sample
explosive E and detonation velocity.

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