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CHAPTER 7

SUMMARY AND MAJOR FINDINGS OF THE THESIS

7.1 ANALYSIS OF ACCIDENT DATA OF FIREWORKS

INDUSTRY

Most of the fatal accidents in fireworks industry occurred in

filling and mixing sections.

Mechanical sensitivity effects and chemical reactivity were

found to be major contributors to accidents.

As per analysis, the processing of crackers and tip compositions

were more hazardous than that of other fireworks mixtures

The extensive review revealed that detailed studies were not

available for ternary fireworks mixtures, currently employed in
the fireworks industry.

The only ternary mixture studied in detail was the flash

mixtures containing potassium nitrate, sulphur and aluminium

Literature studies on thermal analysis of fireworks chemicals

revealed there was a need to initiate a comprehensive study on
thermal analysis of fireworks mixtures to address the causes of
frequent blast accidents.
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There was a need for a comprehensive study on thermal and

mechanical sensitivity of ternary firework mixtures currently
employed in fireworks industry

The consequences of fireworks accident are devastating, it is

important to know the TNT equivalence of fireworks mixtures
in order to determine the blast effects or scaled distance

7.2 THERMOKINETICS OF FIREWORKS MIXTURE USING

DIFFERENTIAL SCANNING CALORIMETER (DSC)

The DSC heat flow responses for atom bomb cracker, Chinese
cracker and palm leaf cracker mixtures show a sharp single
exothermic transition in the temperature range 320-355°C

Of the three cracker compositions, atom bomb cracker has the

earliest exothermic peak temperature. The behavior of this
mixture can be attributed to the high concentration of potassium
nitrate (oxidiser) in its composition

DSC plots with varying water content for ground spinner tip
mixtures revealed that with increase in water content, heat
release pattern also increased in the temperature range of 300-
340°C.

The exothermic activity was much higher than for ground

spinner tip mixture. Further a secondary exotherm was observed
at temperature beyond 390°C. The occurrence of secondary
exotherm could be due to incomplete oxidation of the event or
the product of the primary event could undergo further
exothermic action.
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Kinetics treatment by Ozawa and Kissinger’s method revealed a

fair agreement of activation energy of 179.38 and 178.9 kJ mol -1
respectively. Ozawa and Kissinger’s methods confirm that they
can be satisfactorily employed to determine the kinetics of atom
bomb cracker mixture. Chinese cracker, palm leaf cracker,
flower pot tip and ground spinner tip follow Ozawa and
Kissinger’s kinetic procedure.

7.3 THERMAL HAZARD ASSESSMENT OF FIREWORKS

MIXTURE USING ACCELERATING RATE
CALORIMETER (ARC)

The sharp and sudden rise in temperature shows the

vulnerability of this mixture to undergo violent decomposition.
The discontinuity in both the self heat rate plot and time versus
temperature plot is an indication of multiple exothermic
activities.

The self heat rate plot shows a maximum heat release rate of
1088.1°C min-1 at 320°C. The observed large heat release rate
confirms the vigor of exothermic explosive process of atom
bomb cracker mixture.

One gram of atom bomb cracker mixture can contribute to a

peak pressure rise of 25.9 bar at 342.3°C.

The ARC data showed that the fireworks mixture

decomposition process under adiabatic condition was vigorous
and therefore dangerous. Although explosive potential is
required for it to be a cracker, the same property could be
dangerous if the event occurs during handling, manufacturing,
storage or transport.
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While the percentage of KNO 3 in palm-leaf is less than that of

Chinese cracker, early onset is perhaps due to the presence of
another oxidiser Ba(NO 3)2 and a large quantity of different
grades of aluminium

Both Chinese and palm-leaf crackers show delayed onset

temperatures of 295°C and 290°C respectively unlike that of the
atom bomb cracker mixture. The delay in initiation of the
exothermic activity can be related to their mixture composition,
especially the quantity of the oxidiser KNO3.

The time versus temperature plot shows that the exothermic

activity is sudden and sharp as observed with atom bomb
cracker mixture.

A second self heating process for the ground spinner tip mixture
started at 220°C and peaked at 320°C with a heating rate of
100°C min-1; the self heating process ended at this point perhaps
due to complete depletion of the samples. The sudden jump in
self heat rate from 10 to 50 °C min -1 and finally to 100°C min -1
(in a discontinuous manner) indicated the explosive nature of
the process.

The time vs. temperature plot of ground spinner tip shows two
discontinuous exothermic activities at 160-190 °C and 220-
320°C. The first self heating rate process proceeds slowly
compared to the second event.

Thus the self heating nature of the ground spinner tip mixture
and its reactive thermal hazards with water necessitated study of
the behaviour of these samples under iso-aging conditions.
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The neat mixture showed a maximum self heat rate of 143.48

°C min-1 at 339°C. The sample with 40% water (w/w) content
released a maximum heat of 4.19 °C min-1 at 147.65 °C.

The self heating nature of the ground spinner tip mixture and its
reactive thermal hazards with water under iso-ageing conditions
were at the lowest onset temperature of 40°C.

The self heating exothermic process for neat sample and a

sample with 40% water (w/w) were accompanied with the
maximum pressure release of 32, and 20 bar respectively.

This study (perhaps for the first time) could successfully

correlate the accident occurring conditions. The exothermic
onset of these samples at ambient conditions appeared to be
responsible for triggering blast accidents.

In fireworks industry, the unused water mixed ground spinner

tip mixture at the end of the day was left overnight for next day
use. Explosive accidents were reported after shutting down the
factory. The iso-ageing studies could be correlated to blast
accidents in fireworks industry involving ground spinner tip
mixture.

ARC studies of the fireworks tip mixture revealed that the

above mixture was susceptible to thermal decomposition in
ambient conditions.

The thermal decomposition contributes to substantial rise in

system pressure. The onset temperature for explosive
decomposition observed in accelerating rate calorimeter is
however the minimum temperature for triggering an accident.
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In practice this temperature can be attained by thermal and

mechanical stimulus. Therefore, this mixture is to be handled
carefully.

7.4 TNT EQUIVALENCE OF FIREWORKS

It can be observed that for the crackers and tip mixtures the
overpressure increases as the TNT equivalence increases. This
is because of the relationship between weight and TNT
equivalence. As the weight increases, TNT equivalence
increases since overpressure and TNT equivalence have a direct
correlation,

For crackers and tip mixture the scaled range increases as the
distance increases. This is because the weight of the sample is
kept constant and thus the TNT equivalence remains the same.

It can be observed that the overpressure decreases as the

distance increases for cracker samples and tip compositions.
This is because of the inverse relation between the distance and
the overpressure

The value of impulse largely depends on the positive

overpressure and the positive duration time. Larger the value of
these parameters, higher is the impulse which is nothing but the
maximum peak overpressure. The value of impulse also varies
for different firework mixtures.

The firework mixture, under certain conditions can be

equivalent to an explosive and hence has to be handled
carefully.
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7.5 MECHANICAL SENSITIVITY OF FIREWORKS

MIXTURES

Impact sensitivity measurements for different firecrackers

mixtures indicated that the impact energy varied when
concentration of the component of the mixture was changed.
This behavior showed that the impact sensitivity was directly
related to the reactivity of each component

Varying the quantity of KNO 3 and Al does not seem to have an

impact in increasing the sensitivity of the cracker mixture, while
higher concentration of sulphur is critical for increased impact
sensitivity.

All the cracker mixtures studied could be categorized as Class

III explosives of the Andrejev and Beljajev classification.

The tip mixtures did not show positive response for impact
sensitivity under the experimental conditions employed in the
study.

Frictional sensitivity of atom bomb cracker mixture shows that

increase in sulphur concentration from 13-34% increased the
friction sensitivity. Increase in potassium nitrate and aluminum
concentration in the mixture showed a significant increase in
friction sensitivity. A similar increase was noticed with Chinese
cracker mixture.

Friction sensitivity measurement of tip mixtures indicated that

in presence of dextrine the friction sensitivity showed increasing
trend.
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7.6 SUGGESTIONS FOR FUTURE WORK

Thermal and mechanical hazard assessment of modern fancy

aerial fireworks.

Mechanisation of hazardous unit operations such as mixing,

filling and fuse cutting.

Modernisation of manufacturing facilities of fireworks.

Thermo kinetic modeling for appropriate prediction of thermal

runaway decompositions of firework mixtures.