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EXPLOSIVES 383

CHIMIA 2004, 58, No. 6

Chimia 58 (2004) 383–389


© Schweizerische Chemische Gesellschaft
ISSN 0009–4293

Military High Explosives


Jörg Mathieu* and Hans Stucki

Abstract: Military high explosives are safe to handle, have a long shelf life, their energy density is high and the
propagation of the explosion (detonation reaction) is very fast. The energetic compounds are combined with
polymers and other substances to match the properties as required. To initiate a detonation, a shock wave is
needed. This is accomplished with a small quantity of a primary explosive. Modern, extremely insensitive formu-
lations have been developed in most countries to eliminate accidents with ammunition. Apart from insensitive
energetic compounds, new inert or energetic binder systems will be introduced to improve the vulnerability. The
search for new energetic materials with highest performance characteristics is a never-ending task.

Keywords: Energetic binder · Explosives chemistry · Performance · Safety · Vulnerability

1. Development of Military High 1.2. Traditional Military Explosives curity level is the state-of-the-art. The latest
Explosives The first high explosive to be put into developments try to increase the safety of
service was 2,4,6-trinitrophenol, called the explosive products while handling and
1.1. General Aspects ‘picric acid’. It was first demonstrated in in case of fire or other unwanted external in-
The properties of the first known explo- France in 1885 and it was widely used in the fluences like impact, falling and being fired
sives like black powder and dynamite could time of World War I. Unfavorable are the on.
not fulfill the requirements of use in muni- high melting point, making the process of
tions. Reliability in use and handling, un- filling shells difficult, its reaction with 2. Primary Explosives and
predictability and the risk of unwanted ex- heavy metals and formation of toxic com- Detonators
plosions as well as the low performance of pounds and its sensitivity.
the detonation was not sufficient. The first explosive to fulfill the expecta- 2.1. General Aspects
The ideal military explosive is power- tions of producers and users was 2,4,6-trini- The start of a detonation is normally
ful, safe and easy to handle, can be stock- trotoluene (TNT). This compound was first performed by a primary explosive which
piled for long periods of time in any climate synthesized in the 1860s, was produced in produces a detonation wave when decom-
and is hard to detonate except under pre- large quantities during World Wars I and II posed. These compounds have low activa-
cisely specified conditions. It also has to be and is still used today in explosive mixtures. tion energy. Impact, friction, electric sparks
loaded into shells, bombs and other objects It is cheap and relatively insensitive, can be or sudden heating can initiate the decompo-
without any difficulties. The energetic com- melted at low temperatures and poured in sition. The deflagration to detonation tran-
pound is normally mixed with binders and bombs and shells easily. sition occurs within a very short distance
additives, so that a suitable production For higher performance the nitramine and the detonation wave is sufficient to ini-
process can deliver the required explosive compounds hexahydro-1,3,5-trinitro-1,3,5- tiate a secondary explosive in the neighbor-
objects. Primary explosives are responsible triazine (RDX) and later octahydro-1,3,5,7- hood. Because of their sensitivity, primary
that the propagation of an explosion is ini- tetranitro-1,3,5,7-tetrocine (HMX) were in- explosives are manufactured under special
tiated. Primary explosives are also ex- troduced. In the pure state these compounds conditions to avoid any shock, mechanical
plained in this article. are too sensitive and can only be used with load or electric spark. In igniters and deto-
insensitive additives or in mixtures with nators only small quantities of primary ex-
TNT. In Switzerland, the nitrate ester 2,2- plosives in the range of 20–100 mg are
bis[(nitroxy)methyl]-1,3-propanediol, di- used.
nitrate (PETN) was often used for special
applications. 2.2. Primary Explosives and Their
Properties
1.3. Trends and New Products For many years mercury fulminate,
The search for new energetic com- Hg(ONC)2, was the compound mainly em-
pounds with increased performance is pro- ployed for initiation, either by itself or
gressing rather slowly. The design of new mixed with other substances such as potas-
*Correspondence: J. Mathieu
armasuisse
molecules with a high energy level is fasci- sium chlorate. It is easy to prepare by the re-
Science and Technology nating, but the demanded stability is hard to action of mercury with nitric acid and
Feuerwerkerstrasse 39 achieve. Manufacturing of blended and ethanol. Mercury fulminate is toxic, lacks
CH-3602 Thun polymer-bonded explosives meeting the de- stability when stored for a long time and re-
Tel.: +41 33 228 44 64
Fax: +41 33 228 46 01 sired demands such as easy processing and acts with metals in a moist atmosphere. Its
E-Mail: joerg.mathieu@armasuisse.ch handling together with keeping a high se- use has been abandoned in most countries.
EXPLOSIVES 384
CHIMIA 2004, 58, No. 6

Lead azide, Pb(N3)2, was developed af- 2.3. Trends expected for safety in handling and storage
ter World War I and is now the most com- Unpredicted explosions, corrosion and of the products.
monly used material for detonators. It is erosion of gun barrels and materials, and
produced by the reaction of lead nitrate or toxic pollution are the reasons for new im- 3.1.2. Production and Chemical
acetate with sodium azide in a basic envi- provements in this field. Igniters containing Aspects
ronment, to avoid formation of hydrazoic mercury fulminate and chlorates had corro- Most of the substances used belong to
acid, which is instable. The addition of sive as well as toxic properties. The devel- the family of the aromatic nitro compounds,
thickeners like dextrin to the solution, leads opments in this field led to the primer com- the aliphatic nitramines and the nitrate es-
to aggregates with purities of only 92– position SINOXID containing lead styph- ters. They are produced by liquid-phase ni-
97 %, but with good stability and handling nate, tetrazene and inorganic nitrates. This tration with acid, a classical chemical pro-
safety. composition has conquered the whole cedure. For special compounds, used only
Lead trinitroresorcinate or lead styph- world, it guarantees almost no corrosion in small quantities, syntheses in several
nate (Fig. 1) is prepared by the reaction of and no erosion in the gun, it has excellent steps and nitration with nitrous oxides are
the magnesium salt of 2,4,6-trinitroresorci- stability and storability and ensures precise applied too. Byproducts, isomeric com-
nol with lead nitrate. The precipitated lead inflammation of the propellant [2]. pounds and acid residues have to be re-
styphnate is a primary explosive. This com- With modern target practice in indoor moved to obtain a pure, stable and constant
pound has good stability, is compatible with rifle ranges, the lead dust in the air reached product. One example is crude 2,4,6-trini-
most metals, is easy to initiate by impact or intolerably high levels. To eliminate lead trotoluene, which contains 2–5% of iso-
heat and is especially sensitive to sparks. It and other toxic metals, the SINTOX pri- meric trinitro and dinitro compounds,
is widely used in combination with lead mary composition without any toxic metals whereas the demanded TNT purities in mu-
azide in detonators, in electric igniters and was developed. The primary explosives are nitions production are in the range of
in primary compositions to ignite burning. 2-diazo-4,6-dinitrophenol and tetrazene 99–99.7%. The technical conditions for the
The main sensitivity and performance combined with the pyrosystem zinc perox- synthesis, cleaning, and refining proce-
properties of widely used primary explo- ide and titanium. dures of the classical compounds are wide-
sives are listed in Table 1. The correspon- There is also a trend to develop detona- ly published [1][3]. In Table 2 the chemical
ding test methods are described by Köhler tors without primary explosives. The ex- data and impact sensitivity of commonly
and Meyer [1]. The figures listed are pub- ploding bridge wire initiation delivers an al- used energetic compounds are shown and in
lished data [1] and experimentally deter- ternative possibility to start a detonation. A Fig. 2 the corresponding structures are pre-
mined in our laboratories. metal wire embedded in secondary high ex- sented.
Other compounds used as primary ex- plosive material is charged with a very high For special applications a lot of
plosives or as a component in primary mix- electrical current. The sudden evaporation other energetic compounds are used,
tures are silver azide, tetrazolyl-guanyl- of the wire and the resulting shock-wave is e.g. 1,3,5-trinitrobenzene (TNB), 3,3-
tetrazene-hydrate (tetrazene) and 2-diazo- sufficient to initiate the surrounding sec- bis(2,2’,4,4’,6,6’-hexanitrostilbene) (HNS),
4,6-dinitrophenol (DDNP). ondary explosive. 1,3,5-triamino-2,4,6-trinitrobenzene
An other new method is the direct initia- (TATB).
tion of secondary explosives by a laser beam.
3.1.3. Physical Properties
The knowledge of the energetic and
3. Secondary Explosives physical properties is important for the de-
velopment of explosive charges with a de-
3.1. Energetic Compounds fined performance. Table 3 shows the ener-
3.1.1. General Aspects getic data of commonly used energetic
Energetic compounds for use as high compounds. The optimization of the main
explosives have to be powerful because goals, high performance when detonating,
their energy is mainly responsible for the safety and low vulnerability are almost con-
performance of an explosive charge. Com- tradictory. The common practice of adding
patibility and misciability with other explo- waxes and polymers to increase the stabili-
sives, polymers, and additives must be pos- ty reduces the performance of the energetic
sible, also processes like pressing, melting, components.
cast cure, and extruding are required in the
manufacturing process. Compatibility with
Fig. 1. Lead styphnate other materials and long-term stability is 3.1.4. Trends and New Energetic
Compounds
Several known and many new energetic
Table 1. Properties of primary explosives. The lead block test measures the expansion of a defined
molecules were tested in regard of their po-
cavity, caused by detonation of a substance.
tential for the new generation of insensitive
Substance Friction Impact Electrostatic Performance Minimal high explosives (IHE). One of them is 3-ni-
sensitivity sensitivity sensitivity lead block test quantity to tro-1,2,4-triazol-5-one (NTO) (Fig. 3).
[N] [Nm] [mJ] [cm3/10 g] initiate PETN NTO is easy to prepare: In a first step
the condensation of semicarbazid hy-
drochloride with formic acid leads to tria-
Mercury fulminate 8 1–2 10 130 0.17 g
zole and the second step is a conventional
Lead azide 0.1–1 (pure) 2.5–4 0.4 110 0.02 g nitration. The resulting NTO is very insen-
Lead styphnate 8 2.5–5 1–10 130 0.55 g
sitive and hard to set on fire. After initiation
it has a high detonation velocity (8590 m/s).
Tetrazene 7 1 180 155 difficult Disadvantages are the high solubility in wa-
ter, the acid reaction by hydrolysis and the
EXPLOSIVES 385
CHIMIA 2004, 58, No. 6

Fig. 3. Nitrotriazolone (NTO)

Fig. 4. Trinitroazetine (TNAZ)

large critical diameter needed for the con-


tinuation of the detonation.
Fig. 2. Structures of commonly used high explosives 1,3,3-trinitroazetine (TNAZ) (Fig. 4) is
another new energetic and insensitive mol-
ecule. TNAZ has potential properties as an
insensitive explosive. The low melting
Table 2. Chemical properties and impact sensitivity of high explosives
point allows its processing by melting. For
Name of explosive Melting point Deflagration point Impact Density
its preparation seven steps are necessary
[ºC] with 20 ºC/min [ºC] sensitivity [Nm] [g/cm3] and therefore production is very expensive.
Another compound with potential prop-
TNT: 2,4,6-trinitrotoluene 80.8 300 > 20 1.654 erties as an IHE is ammoniumdinitramide
PETN: pentaerythritol 141.3 202–205 2 1.770
NH4N(NO2)2 (ADN). This new substance
tetranitrate has a good oxygen balance and contains
much energy, but it is difficult to produce in
RDX, Hexogene: 204 decompos. 230 4 1.820 a pure quality.
Cyclotrimethylenetrinitramine
3.1.5. Hexanitrohexaazaisowurtzitane
HMX, Octogen: 282 decompos. 287 3 1.907
as a Newcomer
Cyclotetramethylenetetramine
The new molecule 2,4,6,8,10,12-(hexa-
Tetryl: 129.4 185–195 2 1.730 nitro-hexaaza)-tetracyclododecane (HNIW
N,2,4,6-tetranitroaniline or CL-20) is a nitramine compound, similar
to RDX and HMX. HNIW has a high den-
sity (2.04 g/cm3, ε-modification) and there-
fore a calculated [4] theoretical detonation
Table 3. Energetic data from the armasuisse explosives database. The lead block test measures the velocity of 9400 m/s which cannot be
expansion of a defined cavity, caused by detonation of a substance.
reached by any other organic explosive at
the present time. Scheme 1 shows the syn-
Name Heat of explosion Detonation velocity Max. detonation Lead block test
thesis of HNIW.
[kJ/kg] [m/s] pressure [GPa] [cm3/10 g]
CL-20 was invented and synthesized by
TNT 3.72 6900 22.3 300 A.T. Nielsen [5] in 1989 at the US Navy test
center China Lake, which is why the name
PETN 6.31 8400 33.5 523 ‘CL’ was selected. The synthesis needs
three steps, as described in the patent of
RDX 5.62 8750 34.1 480 Nielsen [6]. In the first step the cage struc-
ture is formed by condensation of benzyl-
HMX 5.60 9100 39.0 480 amine with glyoxal. Then a partial deben-
zylation and an acylation are followed by
Tetryl 4.25 7850 26.9 410
reductive acylation in acetic anhydride. In
the third step the debenzylation is complet-
EXPLOSIVES 386
CHIMIA 2004, 58, No. 6

new series of explosives by the US Army is


worth watching closely. It is based on the
binder 2,4 dinitroanisol (DNAN) [9] which
is a yellow crystalline substance at room
temperature and has a melting point of 94.5
°C.

3.2.2. Plastics
Until the 1960s mainly waxes and
paraffins were used as classic binder sys-
tems for pressed explosive formulations. In
modern pressed and diecast formulations,
particularly in the field of insensitive high
explosives (IHE), mainly polymers are used
due to their wide range of properties. The
development goes back to the 1950s, when
in the formulation of pressed explosives
mainly thermoplastics were used, which
were known from civilian applications (e.g.
Scheme 1. The synthesis of HNIW/CL-20 in three steps nylon, Teflon, polyisobutylene). However,
the mechanical properties of most of the re-
spective formulations showed undesirable
hardness, which has a negative effect on the
ed and a mild nitration by nitrosonium and the crystalline energetic compound with a sensitivity. Therefore elastomers (rubber),
nitronium tetrafluoroborate forms the binder system, the formulation is desensi- with hardness from soft to stiff and elonga-
nitramine groups. tized. During processing, in the curing tion of up to 400%, are being increasingly
In the industrial synthesis slightly mod- stage, the formation of a solid binder matrix used in modern formulations. From the
ified processes have been established, in is achieved. The type of binder significant- 1960s onwards, the development and avail-
particular for the hydrogenolysis, described ly influences the mechanical properties and ability of tailored resin/hardener systems
in the patent of R.B. Wardle [7]. A uncom- consequently the vulnerability of the explo- led to the introduction of the ‘cast-cure’
plicated synthesis procedure, to produce sive charges. A possible further addition of technology. Today the used polymers are
large quantities of CL-20 at an acceptable bonding agents and plasticizers allows a often matched to their specific application
price, is not available today. systematic modification of the characteris- in the formulation of explosives. A novel
Pure CL-20 is too sensitive for safe pro- tics of the binder. The development of new, energetic binder system containing nitro or
cessing, handling, and storage. Mixtures less sensitive explosive formulations is acido groups is now available. The me-
with insensitive materials only or a surface mainly achieved by technical innovations in chanical properties of this binder system
coating of the CL-20 particles results in ac- polymeric binder systems. Below an can be controlled by means of the selective
ceptable safety data. But the addition of in- overview of the different binder types and arrangement of hard and soft block seg-
sensitive substances reduces the perform- of current trends in this area is given. ments.
ance of this material.
Another problem in using CL-20 is the 3.2.1. Energetic Compounds with a 3.2.2.1. Plastic Binders for Pressed
polymorphism: the crystalline CL-20 can Low Melting-point Formulations
form six different modifications. Normally For castable explosives energetic com- Mainly thermoplastics and elastomers
CL-20 exists in the ε-modification, which is pounds with low melting points (70 to 110 are used as binders for pressed formula-
thermodynamically stable at room temper- °C) are used directly as binders. The condi- tions. The granulates used to manufacture
ature. Processing this material at elevated tion for the use of an energetic compound the pressed charges consist of surface-coat-
temperatures and high pressures facilitates for this purpose is a sufficient separation ed (each crystal is individually coated with
a transformation to the less stable γ- or oth- between melting point and start of the a thin polymer film) crystalline energetic
er modifications. The polymer binder used, chemical decomposition reaction. Pure compounds.
which is in contact with the surface of the TNT melts at 80.8 °C; however the thermal The distinction between thermoplastics
CL-20 crystals, influences these transfor- decomposition does not start before 290 °C. and elastomers is not totally clear in every
mations. A process control is necessary to In charges consisting of homogeneous TNT case. In the field of pressed explosives al-
be certain that no unstable modifications only, TNT acts as an energetic compound most exclusively non-branched polymers
are formed. Using IR spectroscopy, the dif- and as a binder. In addition, e.g. in mixtures are used, which are defined as thermoplas-
ferent modifications can be distinguished with up to 80% insoluble energetic com- tics. However, there are a number of poly-
by the control of the peaks in the finger pounds of high performance like hexogen mers which are partly hardened or originate
print region in the spectra [8]. (hextro formulations) and octogen (octol from the family of block-co-polymers and
CL-20 has the potential to be used in the formulations), TNT has the function of a therefore show very high molecular
future for explosive charges for highest per- binder. weights or very long chains. In this case the
formance and as an energetic additive in Cast charges based on TNT as binder do mobility of the chains is limited and the be-
rocket propellants, but the material is still not meet today’s criteria for insensitive am- havior corresponds more to that of an elas-
too expensive for common use. munition. Alternatives for TNT were tomer. We will subsequently define the type
sought. These alternative substances must of binder polymer based on the behavior
3.2. Binder Systems allow the production of charges with con- and not on the degree of cross linking.
Basically, the selection of the binder ventional casting facilities and also meet As the following examples will show,
system determines the processing technolo- the criteria for active components in insen- polymers with very different chemical ori-
gy of an explosive. By coating or mixing sitive ammunition. The development of a gins are used in explosive formulations.
EXPLOSIVES 387
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‘cast-cure’ binders includes cureable


polyurethanes. The basis for the crosslink-
age reaction are hydroxyl terminated poly-
mers, which can be cross linked with iso-
cyanates. Scheme 2 shows the schematic
description of the crosslinkage process.
Depending on the functionality of the
alcohol and isocyanate used (di-, tri-, tetra-
functional) the degree of crosslinking and
hence the mechanical properties can be
Fig. 5. Structure of ESTANE [10]
controlled. This fact, together with the mul-
titude of basic substances (polyols), makes
it possible to create ‘made-to-measure
binder systems’.
Among the so-called crosslinkable
polyether prepolymers there are both inert
and energetic representatives. While in to-
day’s classical formulations mainly poly-
ethylene glycol or polypropylene glycol is
used, polymers used in the future will be
modified with energetic groups in the mol-
ecule. The filling capacity of diecast explo-
sives is limited by the viscosity of the ex-
plosive mass to be processed. The relative-
Fig. 6. Structure of HYTEMP
ly high percentage of binder material
(>10%) leads to a reduced performance. In
order to partially compensate for this, ener-
getic prepolymers were developed. Due to
their OH groups on the end of the chain,
dialcohol they can be crosslinked to polyurethans by
means of isocyanates too. Moreover, there
is the possibility of producing energetic
block-co-polymers from such prepolymers,
consisting of hard and soft segments, reach-
ing comparable mechanical properties to
the thermoplastic elastomers (TPE).
The type of the soft segment influences
the glass transition temperature of the poly-
mer, the hard segment influences the melt-
Scheme 2. Crosslinking of polyurethanes ing temperature. By combining hard and
soft segments (type, distribution of molec-
ular weight, arrangement of segments) the
properties of these binder systems can be
ESTANE (Fig. 5), for example, is a acrylic elastomer is resistant to ageing, heat controlled and adjusted to the specific
polyester with an OH group on the end of and fatigue. Moreover HYTEMP is resist- needs [11].
the chain, whose free alcohol functionality ant to oxygen, ozone, oil and UV light; its Thermoplastic elastomers are processed
is cross-linked to a polyurethane with an stability in hot water and water vapor is un- at higher temperature than crosslinked
isocyanate (4,4’-diisocyanatdiphenyl- der certain conditions only just sufficient. polymers (pressed, extruded etc.). During
methan). ESTANE is a classical binder Most formulations based on HYTEMP processing at higher temperatures the ther-
which is commercially used in the formula- contain the softening agent dioctyladipat moplastic elastomer forms a liquid film
tion LX-14. Based on the distinct thermo- (DOA), which is added in a ratio of 1:3 which embeds the energetic compounds.
plastic behavior of ESTANE (softening (w/w). Particularly if the percentage of After cooling down, a solid energetic
starts at 50 °C) the respective formulations binder is high, the explosive has a soft and charge is obtained. The mechanical proper-
are processed under elevated temperature crumbling consistency. This makes the me- ties are comparable to a product manufac-
conditions (90–110°C). Depending on the chanical processing of the respective tured with a crosslinked polymer. The best
chain structure, such polyurethanes show charges very difficult. known energetic thermoplastic elastomers
very different mechanical properties. The In addition fluorinated co-polymers and used today are based on a block-co-
esterification with tri- and tetra-alcohols silicone rubbers are also used as binders. polymer consisting of 3-azidomethyl-3-
can be used to achieve additional cross link- methyloxetan (AMMO) and poly[3,3-
ing. In hot water or water vapor atmos- 3.2.2.2. Plastic Binders for ‘Cast-cure’ bis(azidomethyl)oxetan) (BAMO) seg-
phere, the polymer decomposes through Formulations ments (Fig. 7) [12].
hydrolysis. Plastics which are used as binders for In the field of crosslinked polymers
HYTEMP (Fig. 6) is another binder the cast-cure technology of explosives are GAP (glicidyl-acid polymer) (Fig. 8) is be-
based on an ethyl-/butylacryl-co-polymer. based on resin/hardener systems. The for- coming increasingly important for many
It contains a small percentage of chloric mulation is homogenized in a mixer, filled applications.
monomers, mostly 2-chlor-ethylvinylether, into a mould or case and then cured at ele- Hydroxyl terminated polybutadienes
which are used for cross linking. The vated temperature. The main group of (HTPB) (Fig. 9) cannot be fitted into the
EXPLOSIVES 388
CHIMIA 2004, 58, No. 6

Fig. 7. Example of typical prepolymers which are used as hard and soft seg- Fig. 9. Hydroxyl-terminated poly-butadien (HTPB) type R45M [13]
ments

Isophorondiisocyanate 4,4’-Diisocynatdiphenylmethane

Fig. 8. Glicidyl-acid-polymer Fig. 10. Typical diisocyanate curing agents for the ‘cast-cure’ process of hydroxyl terminated pre-
polymers

system of cross-linkable polyesters and ed within a wide range. Plasticizers reduce 3.4. Performance
polyethers. Due to the outstanding mechan- the auxiliary valency forces between the The performance of an explosive formu-
ical properties of HTPBs, they have been polymer chains of a rigid crystallite struc- lation largely depends on the type and filling
used in the field of explosives since 1989 as ture and thereby soften it. The miscibility, capacity of the energetic compound and, if
crosslinkable prepolymers. Several com- compatibility, and migration stability of a energetic binders are used, on the energy they
mercial available explosives are qualified plasticizer within a polymer matrix is an ab- contribute to the conversion reaction. Since
with HTPB in the formulation. solute prerequisite for its applicability. the performance depends directly on the en-
The very high elasticity has a shock-ab- Typical representatives of low viscosity ergy density, there is a linear increase of det-
sorbing effect which drastically reduces the monomer plasticizers are dioctyl adipate in onation velocity and detonation pressure as
sensitivity of the respective explosive. A high HYTEMP and isodecyl pelargonat in the density of the formulation increases.
percentage of 1,4-crosslinkages with cis-dou- HTPB-polyurethane. But there are also en- The main parameters used to determine
ble bonds has a positive effect on elasticity ergetic plasticizers such as bis(2-fluor-2,2- the performance of military explosives are:
and lowers the glass transition temperature. dinitroethyl)formal (FEFO) or bis(2,2-dini- detonation velocity, detonation pressure and
1,2-crosslinkages have the opposite effect. tropropyl)acetal/formal (BDNPA/F) (Fig. the resulting capability to accelerate metals.
The use of a HTPB is also foreseen for mod- 11). These parameters can be determined experi-
ern diecast explosives on the basis of CL-20. mentally or calculated by means of suitable
The curing agents used for crosslinking 3.3.2. Other Additives computer codes. In Table 4 the performance
hydroxyl terminated polymers are di- or tri- To meet requirements, the properties of data of some common military explosive for-
isocyanates. The degree of crosslinkage can an explosive formulation can be modified mulations are listed.
be controlled by means of the functionality. by adding different additives. At the moment formulations based on oc-
The isocyanates used most frequently in To improve the adhesion between the togen offer the highest performance potential
explosives are isophorondiisocyanate crystals of the energetic compound and the (see Table 4). By developing formulations
(IPDI) and 4,4’-diisocyanatdiphenyl- surrounding binder, metal-organic com- containing the new energetic compound CL-
methane (MDI) (Fig. 10). pounds based on titanium are used as 20, the performance of future explosive
In order to accelerate the crosslinking of ‘bonding agent’ in several explosives. N,N charges can be increased by 10–15%. For the
resin and curing agent systems, cure cata- 2-Hydroxyethyl-dimethyl-hydantion (Dan- first time the extraordinarily high detonation
lysts are used. For polyurethanes primarily tocol) is also widely used as a bonding velocity of 9280 m/s was measured in a for-
metallo-organic tin compounds are used for agent. mulation consisting of 98% CL-20 and 2% of
this purpose. Polymers, elastomers, thermoplastic the energetic polymer GAP [14]. Fig. 12
elastomers and in particular energetic poly- shows the detonation velocity versus density
3.3. Additives mers and plasticizers have to be protected curve of new high explosive formulations
3.3.1. Addition of Plasticizers from ageing and degradation with adequate containing the energetic polymer GAP.
By adding plasticizers, the mechanical stabilizers as e.g. strongly sterically hin-
Received: March 30, 2004
properties of binder systems can be adjust- dered bisphenyl.
EXPLOSIVES 389
CHIMIA 2004, 58, No. 6

Table 4. Performance data of military explosive formulations [1] J. Köhler, R. Meyer, ‘Explosivstoffe’, Wi-
ley-VCH, D-Weinheim, D, 9. Auflage,
Name Composition Density Detonation Pressure Processing
1998.
[% by weight] [g/ccm] [m/s] [GPa]
[2] U. Brede, R. Hagel, K.H. Redecker, W.
Comp A3 Hexogen/Wax 8520 26.0
Weuter, ‘Primer Compositions in the
1.67
91/9
Course of Time: From Black Powder and
SINOXID to SINTOX Compositions and

Pressed
LX-14 Octogen/Estane 1.81 8830 37.0 SINCO Booster’, Propellants, Explosives,
95.5/4.5 Pyrotechnics, 1996, 21, 113–117.
[3] Ullmann’s Encyclopedia of Industrial
PBXW-11 Octogen/Hytemp/DOA 1.79 8690 29.1 Chemistry, Vol. A10, 1987.
96/1/3 [4] H. Schubert, ‘Explosivstoffe für mili-
tärische Anwendungen’, Spektrum der
PAX 21 DNAN/Ammonium 1.73 8120 29.1 Wissenschaft, August 1996, pp. 97–101.
perchlorate/Hexogen [5] A.T. Nielsen, ‘Polycyclic Amine Chem-
34/30/36 istry’, in ‘Chemistry of Energetic Materi-
als’, Eds. G.A. Olah, R.D. Squire, Acade-

Cast
original blend TNT/ 1.72 7920 29.2 mic Press, San Diego, 1991, pp. 95–124.
Composition B Hexogen/Wax [6] A.T. Nielsen, US-Patent Nr. 5,693,794,
39.5/59.5/1 1997.
[7] R.B. Wardle, International Application
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Fig. 12. Calculated and measured detonation velocity of CL-20/GAP 98/2 compared to HMX/GAP
98/2