New method of calorimetric value determination for explosive

compositions using Parr oxygen bomb calorimeter

S.S. Mhase, S.K.Chaugule , Mrs. U.T.Meshram, Dr(Mrs) N.Sikder

High Energy Materials Research Laboratory , Sutarwadi, Pune-411021
ssmhemrl@rediffmail.com

Abstract
Calorimetric value (Cal.Val) of explosive compositions for quality control purpose, is
determined under vacuum (5 mm of Hg pressure) or inert atmosphere. However, this
method has the following disadvantages. First, an instrumentation needs additional facility
for creation of vacuum, which leads to increase in cost. Secondly, pressurization or
creation of vacuum leads to inconsistent results , particularly in case of powdery samples,
as latter fall from sample cup in to the bomb. Third and most serious drawback is that ,
some of the explosive compositions are not ignited at all under vacuum. In such case
spike, (combustible substance of known calorimetric value) is added to facilitate the
ignition. However, the cal.val with spike does not represent true value. This paper deals
with new method of calorimetric value ( cal.val ) determination of explosive
compositions. The cal.val in vacuum is calculated by applying air correction . In turn, the
air correction is calculated by subtracting the cal.val obtained by extrapolation of the
graph of cal.val Vs. pressure to zero pressure , from the cal. val in air at atmospheric
pressure. First of all, combustion vessel, called bomb of the Parr Bomb calorimeter
model No.6200, has been modified for holding the reduce pressure. The cal.val of
standard double based propellant , Polyvinyl acetate (PVAc) based fuel rich composition
and Picrite based fuel rich composition were determined in air at atmospheric pressure
followed by at various reduce pressure. New method of cal.val determination is accurate
, time saving , precise , cost effective and can be applied to all types of explosive
compositions , which are other wise not ignited in vacuum.
Keyword : Calorific value, Calorimetric value, Explosives ,Parr bomb calorimeter.

1.Introduction

One of figures of merit for energy evaluation of energetic materials is calorimetric

value ( cal.val) . In case of propellant it indicates the amount of heat which is actually
available for propellant to propel shell upto the bore. It is essentially the quantity of the
heat which is obtained by burning 1 g of propellant in absence of air or oxygen1. When 1g
of a combustible substance is burned in excess of air or oxygen at atmospheric pressure,
total amount of heat generated due to conversion of carbon to carbon dioxide and
hydrogen to water is more commonly known as “ CALORIFIC VALUE” (same as in fuel)
These two terms are some times confused by uninitiated. For quality control purpose
cal.val of propellant is determined in vacuum2 (5 mm pressure) or under inert atmosphere
such as nitrogen or Helium3.These methods have the following disadvantages. First,
instrumentation needs additional facility for creation of vacuum, which leads to increase
in cost. Secondly, pressurization or creation of vacuum leads to inconsistent results ,
particularly in case of powdery samples as latter falls from sample cup in to the bomb.
Third and most serious drawback is that , some of the explosives compositions are not
ignited al all under vacuum. In such case spike ,( combustible substance of known
calorific value) is added to facilitate the ignition. The cal.val with spike does not represent
true value. This paper deals with new method for cal.val determination of explosive
compositions. The cal.val of the explosive compositions is determined in air atmosphere
followed by calculation of cal.val in vacuum by applying air correction. The air correction
is calculated by estimation of cal.val of the explosives at different reduced pressures and
cal.val at vacuum is calculated by extrapolating the results to zero pressure. The
difference between cal.val under atmospheric pressure and under vacuum is air
correction. The method is validated with standard double based propellant.

1.1.High Energy Materials

The following high energy material compositions developed at HEMRL were used for
cal.val determination.
i) Standard Double based propellant
Nitrocellulose (59.9 % ); Nitroglycerine (38% ) Carbamite (0.6%), KNO3(1.50
%), Chalk (0.15 Pt) and Graphite (0.6Pt )
ii) Polyvinylacetate (PVAc) based fuel rich composition
Nitrocellulose (71%) , Cellulose(12 %),PVAc(16%) and Diphenylamine(1%)
iii) Picrite based fuel rich composition
Nitrocellulose (62 %), Cellulose (12%),Picrite (19%), Dibutylphthalate(6%) and
Diphenylamine (1%)
iv) Double base propellant
 Nitrocellulose (56.25 %), Nitroglycerine (37.98%), Carbamite(1.92%) and Additives
( 3.85%)
2.Experimentation
The cal.val of standard double based propellant , PVAc based fuel rich composition
and picrite based fuel rich composition were determined at different reduced
pressures using Parr bomb calorimeter model No.6200. Default design of the bomb is for
holding higher pressures, hence it was modified to hold reduced pressure.
2.1.Modification of Parr Oxygen Bomb
Bomb head assembly of the Parr oxygen bomb has two valves 4,5. One is needle valve
which is used to release the gases formed during combustion inside the bomb while
second is inlet valve( check valve) which is used to pressurize the bomb with oxygen or
inert gas. Once the bomb is pressurized, inlet valve ( check valve) is closed due to pressure
inside the bomb. If pressure inside the bomb is atmospheric or less than critical pressure
required to keep this valve close, gases formed during combustion of sample will leak out,
leading to erratic results. Secondly, this valve will not allow to create reduced pressure
inside the bomb. In order to overcome these problems, the inlet valve( check valve) was
replaced with another needle valve. Any one of the two needle valves was attached to
vacuum pump to create reduced pressure in the bomb. Pressure inside the bomb was
measured by single limb mercury manometer.
2.2.Determination of Cal.val
First of all cal.vals of standard double based propellant, PVAc based fuel rich
composition and Picrite based fuel rich composition were determined in air at
atmospheric pressure followed by at various reduce pressure using procedure given in
operating manual of Parr Bomb calorimeter model No.6200 6 . The cal. vals were plotted
against pressure ( Figure 1). The sample of standard double based propellant was in the
form of cut granules hence, no sample preparation was needed. However, cal.val of the
picrite based fuel rich composition was determined using samples in cut pieces as well as
powder form. The sample of PVAc based fuel rich composition in pieces form was
difficult to ignite hence , the sample in powder form was used for cal.val determination.
The composition being fuel rich, measurable quantity of residue remained due to
incomplete combustion. To study the cal.val of completely burn fuel rich composition,
cal.val of PVAc based fuel rich composition with spike was also determined ( Figure 2).

Figure 1 Graphs of Cal.Val Vs. pressure for high energy materials

Figure 2 Graph of Cal.Val Vs. spike % for PVAc based fuel rich compositions

In addition, cal.val of double base propellants and PVAc based fuel rich
composition (powder) were also determined under nitrogen and oxygen atmosphere at
different pressures to validate the results (Table 1).
Table1 Cal.val of high energy compositions under different conditions

S.N High energy compositions cal.val Condition in side the

(cal/g) bomb
1 Standard double based propellant 2125 O2 at 5 bar

2 Standard double based propellant 1214 N2 at 3 bar

3 Standard double based propellant 1188 Under Vacuum
4 PVAc based fuel rich composition 471 N2 at 3 bar

5 PVAc based fuel rich composition 3102 O2 at 5 bar

6 PVAc based fuel rich composition 3007 O2 at 3.5 bar
7 Double base propellant 1024 N2 at 3 bar
8 Double base propellant 1387 Air under atm. pressure

3.Results and Discussions

During cal.val determination of standard double based propellant , it is observed that
the samples are misfired ( not ignited) below 30 mm pressure . This is attributed to lack
of sufficient oxygen which is required for combustion of fuse wire. This problem is
overcome by applying few milligram of ammunition protective coating varnish on the
fuse wire in the form of thin layer which catches fire first and then transfers heat to the
sample leading to smooth ignition. However, in case of cal. val. determination of picrite
based fuel rich composition (pieces and powder), no difficulties are observed for ignition
of sample even under minimum pressure.
In case of standard double based propellant, no residue is left even at minimum
pressure and gaseous products are colorless , indicating complete combustion of the
sample. However, in case of fuel rich compositions black colored residue and brown
fumes are observed. The residue varies from 5% at atmospheric pressure to 10 % at
minimum pressure . The quantity of brown fumes increases with decrease in pressure.
Presence of black colour residue and brown fumes indicate incomplete combustion of the
sample. The graphs of cal.val against pressure (Figure 1) show continuous decrease in
cal.val with decrease in the pressure inside the bomb, which is attributed to decrease in
the quantity of oxygen available in the bomb. The best fit of the graph has regression
coefficient 0.988, 0.969,0.889 and 0.968 for standard double based propellant , picrite
based fuel rich composition ( pieces), picrite based fuel rich composition (powder) and
PVAc based fuel rich composition respectively. Lower regression coefficient of the
graph for picrite based fuel rich composition (powder) compared to picrite based fuel rich
composition( pieces) is due to loose powdery nature of the sample which permits unburned
particles to be ejected during violent burning as well as inhomogeneous nature of the
sample.
3.1 Validation of the method
The new method has been validated by calculating the cal.val of the standard double
base propellant in vacuum by extrapolating the graphs to zero pressure that is solving
the equation of the best fit line for zero pressure . The cal. val calculated by new method is
found to be 1193 cal/g( Table 1) against the standard value 1200 cal/g ( at 5 mm pressure)
proving the validity of the method. It is further supported by nearly identical cal.val of
the double based propellants in vacuum and inert (Nitrogen) atmosphere(Table 2).
The cal.val of standard double based propellant and PVAc based fuel rich
composition under 5 atm. oxygen pressure are 2125 cal/g and 3102 cal/g respectively
(Table 1) , which are higher by 34 and 240 % with respect to their cal.val in air. Increased
in cal.val. indicates that type of reactions taking place inside the bomb depend on the
composition of the sample as well as prevailing atmosphere. Higher value for PVAc
based fuel rich composition compared to standard double based propellant indicates its
fuel richness.
Table 2 Air correction for Cal.Val of high energy compositions
S.N High energy compositions cal.val cal.val under Air
in air vacuum ( cal/g) correction
( cal/g) ( cal/g)
1 Standard double based propellant 1588 1193 395
2 Picrite based fuel rich composition 963 502 461
(powder)
3 Picrite based fuel rich composition 1019 489 530
(pieces )
4 PVAc based fuel rich composition 885 364 521
3.2 Calculation of air correction
Air correction is calculated by subtracting cal.val under vacuum from cal.val in air at
atmospheric pressure. In turn, cal.val in vacuum is calculated by extrapolating the graph to
zero pressure that is solving the equation of the best fit line for zero pressure. The air
corrections are found to be 395, 461, 530 and 521 cal/g for standard double base
propellant , picrite based fuel rich composition( powder), picrite based fuel rich
composition ( pieces) and PVAc based fuel rich composition respectively( Table 2). Air
correction for fuel rich composition is too high as compared to double base propellant
supporting the validity of the method.
3.3 Cal.val with spike
As combustion of the PVAc based fuel rich composition samples, under prevailing
conditions is incomplete, cal.val was determined with addition of spike of standard
double based propellant , in different proportions at atmospheric pressure . The cal.val is
plotted against spike percentage ( Figure 2). It is observed that even with 95% of spike,
combustion is incomplete and the cal.val decreases with increase in spike %. Regression
coefficient of the graph is 0.7913 which indicates that the results are not linear . Decrease
of cal.val with increase of spike % and non linearity of results indicate that course of
combustion reaction, in turn heat of reaction varies with composition.
4.Conclusion
Detailed analysis of cal.val results for propellant (standard double based ) , resin
based and picrite based fuel rich composition reveals that:
The new method for Cal.Val determination is accurate, time saving , cost effective and
can be used for all types of explosive compositions which are other wise not ignited in
vacuum.

References

1) Surjit Singh. Hand book on solid propellant . CI(ME) Report No. 1/76 Volume-III,
page 209-221
2) Directorate General of quality Assurance New Delhi -11 00 11. DGQA guide on
propellants ( Analytical test method). 006 : 1995, page 61 – 63.
3) K.Kishor,S.Sankaralingam & A. Sameenabegum . Changes in the Calorimetric Value
and Ignition Temperature of Composite Solid Propellants During Ageing-A Note. Def
Sci J, Vol 36, No.4, October 1986,pp 525-428.
4) Web site -http://www.donserv.pl/images/img/wtlenie.pdf . Vertical section of Parr
oxygen bomb with head assembly.
5) Web site-http://www.parrinst.com/doc_library/G6p010B3.jpg. Photo of the Parr
oxygen bomb .
6) Web site - http://www.parrinst.com/default.cfm?page_id=275. Operating manual of
Parr Bomb calorimeter model No.6200.