Koch-2008-Propellants, Explosives, Pyrotechnics PDF
Koch-2008-Propellants, Explosives, Pyrotechnics PDF
Koch-2008-Propellants, Explosives, Pyrotechnics PDF
3 (2008) 165
Review
Received: April 03, 2007; revised July 17, 2007; accepted October 02, 2007
DOI: 10.1002/prep.200700212
This paper reviews the military applications of phosphorus in Obscurants fulfil a prominent role in today=s warfare in
obscurants, incendiaries, float and smoke signals, friction igniters that they serve for screening, blinding, deception and
and decoys. Whereas white phosphorus (WP) is still in use as both
incendiary and obscurant ammunition it has been mainly replaced training. An obscurant smoke is an aerosol cloud brought
today by red phosphorus (RP). For part VI see Ref. [1]. into the line of sight (LOS) between an observer and a target
(Figure 1).
Keywords: Incendiaries, Obscurants, Red Phosphorus, White To evaluate the performance of obscurant materials both
Phosphorus
yield factor Yf (–) and mass extinction coefficient al (m2
kg1) have to be considered as figures of merit.
1 Introduction and Scope of Work The yield factor Yf gives the ratio between the mass of the
aerosol ms and the mass of the pyrotechnic payload mp. It is
Phosphorus is one of the most versatile elements applied dependent on the chemistry of the combustion products and
in chemical warfare. Among the fuels applied in pyrotech- on potential secondary reactions of the aerosol in the
nics the exposed position of phosphorus is mainly related to atmosphere such as, for example, hydration reactions.
its low ignition temperature – and even pyrophoricity as in
the case of the white phosphorus (WP) – its high reactivity ms
Yf ¼ ð1Þ
towards oxygen making it thus virtually inextinguishable, its mp
high enthalpy of combustion and the impressive obscuring
power not reached by any other material. The mass extinction coefficient, al, is given by Lambert
Hence, the main military applications for phosphorus and Beer=s law, Eq. (2).
its compounds are igniters, incendiaries, screening smoke
ammunition, flame and smoke signals and decoys just to ln Tobsc
al ¼ ð2Þ
name the most important ones. The combustion chemistry cl
of red phosphorus (RP) and WP as well as hazardous
reactions and toxicity of both RP and WP have been where c is the concentration of obscurant aerosol in
discussed by the author recently [2]. From this it is obvious obscurant cloud (kg m3), l the optical pathlength within
that WP is inadmissible in today=s military applications. the obscurant cloud (m) and Tobsc is the dimensionless
Nevertheless very weak specifications for the quality of RP degree of transmission (–), that is
on the other hand still feed the ?phosphine (PH3)-problem-
atic= known since some 50 years now. Thus, it is highly It
Tobsc ¼ ð3Þ
desirable that military users and procurement agencies I0
together with the defence industry define new standards for
the quality of RP for further safety of ammunition [3]. in this context the absorbance A is defined as
In the following the application of phosphorus in a variety
of military applications will be discussed. I0
A ¼ ln ð4Þ
It
where I0 is the initial radiant intensity emanating from the humidity RH (%) in the air which itself is a function of the
target and It is the fraction of radiant intensity transmitted ambient temperature. Figure 2 gives the maximum water
after passing the aerosol cloud. content of the atmosphere as a function of the temperature.
Considering an obscurant aerosol one has to distinguish Table 1 displays al and Yf values for different obscurant
between hygroscopic and non-hygroscopic aerosols. In materials at different relative humidities at 25 8C taken from
contrast to non-hygroscopic smoke materials such as Ref. [4, 5].
carbonaceous soot and brass particles the performance of From Table 1 it becomes obvious that phosphorus pent-
hygroscopic aerosols like, for example, LiCl(s) [4], ZnCl2(s) oxide (P4O10) is superior to any other smoke material in
[5] or P4O10(s) [5] is always dependent on the relative terms of yield factor.
When it comes to the design of phosphorus-based
obscurants for the visual (Vis ¼ 0.36 – 0.76 mm) to near
infrared (NIR ¼ 0.76 – 1.3 mm) range the particle size of
the aerosol constituents is the major factor that affects the
mass extinction coefficient al. The extinction coefficient for
– virtually – non-absorbing spherical particles can be
calculated on the basis of Mie theory [6]. Figure 3 displays
a(l) function for different particle radii with an assumed
refractive index n(0 – 14 mm) ¼ 1.33.
It can be seen that for small wavelength that is the UV, Vis
and NIR the mass extinction coefficient is very large.
Recalling that typical natural clouds contain water droplets
having mean radii of 20 mm [7] this is consistent with our
natural perception that these clouds are opaque at least in
the Vis. Milham et al. have investigated the infrared optical
properties – mass extinction coefficient, real and imaginary
parts of complex refractive index (see Section 2.3) of RP-
based aerosol at various relative humidities. They found the
composition of the smoke droplets to be a function of the
Figure 2. Maximum water content of the atmosphere. relative humidity and hence time [8]. That is at high relative
Table 1. Yield factor and visual mass extinction coefficient for different obscurants at various relative humidities at STP according to
Ref. [4, 5].
Parameter Water Mist RP RP/NaNO3/Binder LiClO4/B C2Cl6 · ZnO/Al
H2O P4O10 P4O10 LiCl ZnCl2
Yf
20% RH – 3.73 2.99 n.a. 1.25
50% RH – 4.32 3.45 n.a. 1.58
80% RH – 5.77 4.61 n.a. 2.77
a0.4–0.7 mm (m2kg1)
20% RH n.a. 3.5 3.5 0.8 3.5
50% RH n.a. 4.2 4.2 1.2 3.9
80% RH n.a. 3.8 3.8 1.6 2.9
100% RH 1.33 n.a. n.a. 1.8 n.a.
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168 E.-C. Koch
* RP 75 wt.-%
* Copper(II) oxide 10 wt.-%
* Magnesium 11 wt.-%
Despite the actual chemical constitution of the aerosol
* Binder 4 wt.-%
very often H3PO4 is considered as a model substance. The
extinction coefficient al of H3PO4 is not steady from the
2.3 Third Generation Smoke Materials Based on Red visual to the infrared wavebands (0.38 – 14 mm). This stems
Phosphorus from the fact that the extinction coefficient al itself is the
sum of both contributions from scattering of radiation and
Although visual smoke performance with second gener- absorption of radiation (Eq. 5).
ation smoke materials is satisfactory, the increasing use of
electro-optical sensors operating in the mid and far infrared aðextÞl ¼ aðscatÞl þ aðabsÞl ð5Þ
has forced the development of obscurant munitions capable
of screening the infrared wave band. Hence, the above- Whereas the scattering coefficient a(scat)l is majorly
described systems no longer fulfilled the requirements. dependent on the size and morphology of the aerosol
When looking at RP-based smoke systems, the major constituents, the absorption coefficient a(abs)l is only
constituents of the aerosol in the case of RP/NaNO3 dependent on the chemical composition of the aerosol
compositions are either cyclotetrametaphosphates (P4O4 12 ) constituent. Both coefficients are a function of the complex
or dihydrogen diphosphates (H2P2O2 7 ). In the case of RP/ ~ ¼ n þ ik, where n(l) is the real part of
refractive index n
NaNO3/Mg compositions the major constituents are hydro- complex refractive index and k(l) is the imaginary part of
genphosphates (HPO2 4
4 ) and diphosphates (P2O7 ) [23]. complex refractive index.
The major vibrational transitions of P O H M compounds A detailed description of the complex refractive index can
are listed in Table 2. Also pure P4O10 displays useful be found in the chapter by Schmieder and Walker [27].
absorption bands at either 7.13, 9.89 or 13.10 mm [24]. On the basis of aforementioned explanation obscurant
Figure 4 displays the mass extinction coefficient of RP payloads for the infrared range, that is 3 – 14 mm, require
aerosol. The extinction coefficients of RP aerosols have either aerosol particles having large particle diameters
been determined in Ref. [25, 26] compared to wavelength of incident electromagnetic radi-
Table 2. Important vibrational modes of PHOM compounds present in obscurant phosphorus-based aerosols.
Parameter H3PO4 Assignmnt. H2P2O72 Assignmnt. P4O124 Assignmnt. P2O74 Assignmnt.
mm mm mm
3.8 PH 8.1 POH 8.5 – 8.9 PO2 8.7 – 9.5 PO3
7.1 PO2 8.7 PO2 13.2 – 13.9 POP 13.3 POP
9.2 PO2 9.3 PO2
9.9 PO2 10.9 – 11.5 POP/POH
13.1 POP 14.1 POP
17.4 POP
References [88] [28] [29] [30]
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Special Materials in Pyrotechnics V 169
ation and/or aerosol particles having distinct vibrational [34]. As expected from the low thermal conductivity of RP
transitions in the same range. the burn rate decreases linearly within the range of 30 –
Since there is no superior obscurant agent available 60 wt.-% RP with increase in RP content. However, the
compared to RP the only way to increase the extinction in performance – that is attenuation of radiation – increases in
the infrared is to alter the concentration of the aerosol the same direction. The same author has disclosed mass
requiring thus that the mass consumption rate, m _ (g s1 extinction coefficients of said RP-based obscurant compo-
2
cm ) of mentioned payloads has to be increased. Thus, sitions in a patent [35].
smoke ammunition for the infrared requires greater Another possibility of increasing the aerosol concentra-
amounts of RP combustion products to be released in a tion is by increasing the number of condensation nuclei in
shorter time scale in order to provide higher aerosol the air. This can be achieved by generating ions upon
concentration c (g m3) as the only factor as to increase the combustion of the smoke material. Such a smoke material is
extinction of radiation. that developed by Weber in 1983 comprising either caesium
Higher mass consumption rates of RP-based systems or rubidium salts as modifiers to conventional obscurant
require the following steps to be taken: mixtures [36].
A castable RP-based smoke mixture based on Mg/MNO3
* Increase the density of composition at atmospheric
(with M ¼ Na, K) and polyester binder has been disclosed in
pressure to allow for better thermal conductivity.
Ref. [37].
* Increase combustion pressure at low composite densities
Steinicke et al. have proposed to use potassium peroxo-
in order to increase mass consumption rate due to
disulphate (K2S2O8) as a more fierce oxidiser compared to
filtration of gaseous combustion products into composite
nitrates in RP-based composites [38]. The use of a sulphur-based
and thus enhancement of rate of reaction. For complete
oxidiser also gives rise to the release of SO2, which is known to
confinement Section 10.
have strong vibrational transitions at l ¼4.0, 7.4 and 8.7 mm. On
* Increase the thermal conductivity of composite to
the other hand sulphur compounds are not environmentally
provide faster rate of reaction.
acceptable and may also pose harm to humans.
* Increase the exothermicity of the combustion process.
Composition 4 for ?Heavy duty smoke payloads=
* Increase the surface area of the composition by using
either sheets or fine granules of composition. * Magnesium 5 wt.-%
* Improve ignition process – vide ?detonative ignition= * RP 65 wt.-%
discussed in Section 2.1. * Potassium peroxodisulphate 18 wt.-%
* Polychloroprene binder 12 wt.-%
Whereas increasing the density can be done by increasing
the pressure upon pressing pellets, the increase in combus- Two operational Mg-based smoke compositions are given
tion pressure requires a design which allows for the built-up below
of pressure inside a combustion chamber with a vent hole Composition 5 designated Z 97 [39]
area designed as to match with the temporal internal grain * Magnesium 7 – 12 wt.-%
surface area. * RP 65 – 70 wt.-%
Increasing the thermal conductivity requires an appro- * Polytetrafluoroethylene 17 wt.-%
priate percentage of metallic fuels or carbon fibrils to be * Polychloroprene binder 6 wt.-%
incorporated in the composite. Nielson and Lester have
proposed to increase the burn rate of pyrotechnic compo- Composition 6 [87]
sitions by imparting carbon fibres having l/d ratio of > 5 with * RP 66 wt.-%
length ranging from 1 to 10 mm [31]. * Potassium nitrate 16 wt.-%
Increasing the exothermicity of the combustion process * Magnesium 12 wt.-%
requires an energetic filler to be added to the RP payload. * Polyvinylacohol 6 wt.-%
These can be high energetic composite materials such as
* metal/nitrate
* metal/fluorocarbon
2.3.1 Problems Associated with the Use of Magnesium in
* metal/oxide
RP-based Obscurant Compositions
* and virtually any homogeneous energetic material.
As mentioned above suitable energetic fillers may also be (a) Although high in caloric energy magnesium generally
metal fluorocarbon pyrolants. In these systems Mg/PTFE imparts a series of problems into pyrotechnic payloads. This
are applied in stoichiometric proportions to provide max- is even more pronounced with RP-based Mg-containing
imum heat output. Cudziło has investigated obscurants payloads. Since modern RP-based payloads have sub-
based on RP/Mg/KNO3, and compared them with RP/Mg/ stoichiometric oxidiser content, reactions between the
PTFE [32, 33]. He obtained qualitatively higher aerosol phosphorus and the metal fuel are likely. In the case of Mg
temperatures with the latter system. Cudziło also deter- as fuel this leads to Mg3P2 formation.
mined combustion characteristics and obscuration perfor-
mance of compositions based on Mg-Al alloy/PTFE and RP 2 PðredÞ þ3 MgðsÞ ! Mg3 P2ðsÞ þ465 kJ mol1 ð6Þ
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170 E.-C. Koch
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Special Materials in Pyrotechnics V 171
From BIOS reports it is evident that [51] a German Composition 9 designated B 300
105 mm mortar incendiary grenade for use with the 10 cm * Magnesium 13.5 wt.-%
Nebelwerfer 35 contained: * RP 42.5 wt.-%
* Cotton Wool 40 g * Potassium nitrate 11.0 wt.-%
* Naphthalene 300 g * Gasoline/benzene(50 : 50) 31.0 wt.-%
* Phosphorus, white 750 g * Polystyrene 2.0 wt.-%.
A similar looking American disclosure teaches the Krien has investigated thermochemistry of B 299 and
application of mixtures constituted from naphtha, kerosene, solvent-free B 300 [22].
wax and WP as filler for infantry ammunition [52]. A major drawback of the composition B 299 is the
intermittent combustion caused by slug formation. In
addition the incendiary composition is a powder and thus
3.2 Red Phosphorus will not adhere to walls and inclined planes. Thus, Assmann
has developed a composition comprising an additional
Although RP is safer to handle than WP, incendiaries amount of aluminium granules coated with aluminium
based on it were not developed until some 30 years ago. stearate [55]. Upon combustion the aluminium stearate
Even after World War II RP was still regarded not suitable eventually vaporises and bursts the slag and thus impedes
for incendiary purposes since it does not ignite spontane- occlusion of unburnt phosphorus.
ously and is not soluble in common solvents [53]. Never- A similar composition has been used in the formerly used
theless, the high heat of combustion of RP as well as the fact Blend-Brandhandgranate (Combined ?Stun-Incendiary
that RP upon combustion yields liquified yellow phosphorus grenade=). This device consists of a frangible plastic shell
that may adhere to different substrates suits it to be applied of unplasticised polystyrene and a loose granulated payload
as incendiary material. In addition RP-based pyrotechnic from RP/Mg/polychloroprene which was ignited indirectly
compositions will once ignited not extinguish, even if by means of a heating charge pressed in a sealed brass
submersed in water due to inherent formation of yellow cylinder. The powder charge adjacent to the heating
phosphorus – from quenching of primary combustion cylinder will be heated up to ignition point and catch fire.
products with water – which is spontaneously combustible A single shot flamethrower formerly used with the
in air. Thus, RP is a safer candidate for incendiary German Army was the Handflammpatrone DM 24A1B1
applications. later succeeded by DM 34. This device consisted of a plastic
Incendiary payloads based on RP may be structured into barrel filled with an RP-based payload which is fired up to
two classes. The first comprising distances of 90 m. Upon impact or after a certain delay the
payload was ignited and disseminated with a bursting charge
* only RP and optional binder,
[56]. The composition of the payload according to Ref. [56] is
* the second class comprising RP and a reactive partner,
given in the following:
that may be either
Composition 10 for ?Handflammpatrone= DM 34
– coruscative in nature as, for example, sulphur or
magnesium or * Magnesium 17.85 wt.-%
– oxidative in nature such as nitrates and perchlorates * RP 62.50 wt.-%
(vide infra). * Iron oxide 10.72 wt.-%
* Chloroparaffine, liquid 5.36 wt.-%
It is obvious that coruscative systems are more potent * Chloroparaffine, solid 3.57 wt.-%.
incendiaries in that the metallic component provides much
higher combustion temperature as with RP alone and Incendiary compositions based on RP causing simulta-
provides more hot melt liquid slag that can adhere to a neous corrosive effect to optic materials have been inves-
target. Hence, modern incendiaries from the 1960s to 1980s tigated and developed by Keller and Schneider [57, 58].
– although now often banned in several armed forces – Composition 11 for corrosive incendiary payloads
typically comprise magnesium as reductive partner and * Antimony(III) fluoride 50 wt.-%
often sulphur as a complementary fuel [54]. * Collodium 25 wt.-%
* Phosphorus, red 25 wt.-%
3.2.1 Compositions for Bulk Use Nourdin [59] has come up with a series of complex
incendiaries comprising hydrocarbons, metals, oxidisers and
Koch and Licht give RP-based incendiary compositions RP for use in larger projectiles like, for example, mortar
[54]. shells. Sample compositions are given below. It is interesting
Composition 8 designated B 299 to note that Nourdin proposes RP/perchlorate and even
chlorate mixtures. Combinations that otherwise would not
* Magnesium 25 wt.-%
be considered safe to handle.
* RP 75 wt.-%.
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172 E.-C. Koch
Bullets may contain fluorinated polymers Likewise as with aerial infrared decoy flares, RP-based
Composition 13 designated BS 4 sheet-type flares are in use as infrared countermeasure
against heat IR guided anti-ship-missiles. Although effec-
* Zirconium 40 wt.-%
tive against older generation seekers, unrealistic high
* RP 50 wt.-%
radiation contributions in the 1.8 – 2.5 mm range, that is the
* Polytetrafluoroethylene 10 wt.-%
a-band, lead to discrimination of these flares. In addition it
Several American incendiary mixtures for use in bullets has been reported that these flares when drifting back to the
have been reported [60]. ship may cause fire on board.
Composition 14 designated IM 139 In view of the operational shortcomings with above-
mentioned ammunition the author has developed a dark
* Magnesium/aluminium alloy (50 : 50) 10 wt.-%
and comparatively cool IR countermeasure based on the on-
* RP 40 wt.-%
site neutralisation of phosphoric acid with alkaline solutions
* Barium nitrate 47 wt.-%
[65] see Eq. 9. In contrast to burning RP no emission in the
* Aluminium stearate 35 wt.-%
visible or near infrared takes place; thus discrimination by
Composition 15 designated IM 144 two colour seekers is avoided. Naturally this type of
countermeasure poses no danger of fire.
* RP 50 wt.-%
* Barium nitrate 50 wt.-%
3 LiOH þ H3 PD4 ! Li3 PO4 þ 3 H2 O þ 219 kJ mol1 ð9Þ
The Russian AK 47 incendiary ammunition has been
reported to be filled with aluminium/RP compositions.
A German patent teaches the use of apatite (Ca5(PO4)3 5 Primers and Igniters
(OH, F, Cl) as an oxidiser in aluminium-based incendiary
ammunition to suppress firefighting operations since Ca3P2- As has been discussed above, RP is very sensitive towards
based slug will evolve spontaneous highly toxic and self- friction and impact (vide infra). This property has been used
inflammable phosphanes [61]. in both friction igniter (vide or safety matches) and stab
primer applications.
4 Decoys
5.1 Friction Igniters
Decoys are countermeasures that serve the imitation of
the electromagnetic signature of a target in a certain In general these devices apply the same stimulus as is done
electromagnetic band of interest. in every day product safety match. Baker et al. have invented
a high altitude friction igniter based on RP [66]. This igniter is
still applied in pyrotechnic infrared decoy flares of 36 mm
4.1 Aerial Infrared Decoys type such as MJU 8A/B. Figure 5 displays a drawing of that
igniter taken from the above disclosure. Item 1 designates the
Pyrotechnic aerial infrared decoy flares have been scratch wire coated with a mixture of RP and varnish (resin).
reviewed by the author recently [62, 63]. It has been Upon ejection of the flare pellet from its housing the pusher
reported that pure RP yields relatively cool flames of T < plate eventually stops at the end of the cartridge due to
1000 8C. Thus, burning RP has already appropriate temper- reduction in calibre. Thus, the flare pellet together with the
ature for spectral applications. Thus, further addition of igniter move through the scratch-wire, causing ignition of the
endergonic additives to RP-like silica, SiO2 or alkali halides ignition charge 2 consisting of potassium chlorate and varnish
further reduces combustion temperature and thus helps to and subsequent ignition of the igniter composition, 3, based
achieve the appropriate a/b ratio. For this purpose the wet on boron and lead dioxide. Due to accidents with this type of
RP is mixed with mentioned additives and water-soluble friction igniter and successive fires and explosions of flare
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Special Materials in Pyrotechnics V 173
Figure 5. Pull wire igniter, picture in accordance to Ref. [61]. RP not only yields a thick smoke upon combustion in the
open, but also yields an intense yellow – orange flame, which
is principally the result of continuum emission [73]. This
ammunition this type of igniter is now obsolete and has effect has been exploited in combined float and smoke
become substituted by bore-rider safety mechanism such as signals for applications such as marine location markers.
described in Ref. [67]. In addition to aerial infrared decoy Ellern [74] and Gilliam and Johnson [75] give composition
flares friction igniters find application in numerous signalling for such a signal-based magnesium, manganese dioxide,
pyrotechnics such as signal smoke and illuminating devices phosphorus, linseed oil and zinc oxide.
and also as simple scratch igniter in flash bang report devices Composition 20
for simulation purposes. * RP 51 wt.-%
* Magnesium 8 wt.-%
* Manganese dioxide 35 wt.-%
5.2 Stab Primers * Zinc oxide 3 wt.-%
* Linseed oil 3 wt.-%.
In the 1940s, the use of RP as a fuel in stab priming
compositions has been proposed by Pritham et al. [68]. A Operational compositions for combined float and smoke
typical composition 16 that may also include a small amount signals have been given by Liberman [76]
of glue or binder is given in Table 3. Composition 21
As the RP oxidised under the catalytic influence of typical * Magnesium 7.2 wt.-%
cup primer materials such as brass and copper it was * RP 51.5 wt.-%
proposed by Silverstein to cover these items with small * Manganese dioxide 35.1 wt.-%
layers of aluminium, zinc or tin, in order to prevent any * Zinc oxide 3.1 wt.-%
further oxidation [69]. * Linseed oil 3.1 wt.-%
To overcome the above-mentioned patents and to further
the performance of priming compositions, Woodring and Composition 22
McAdams [70] proposed to apply composition similar to * Magnesium 5 wt.-%
those mentioned above but that would comprise additional * RP 68 wt.-%
amounts of both primary explosives such as lead styphnate * Ammonium nitrate 20 wt.-%
and a highly sensitive secondary explosive such as PETN. * Calcium carbonate 3 wt.-%
Typical example compositions with (17) or without primary * Chloroprene 4 wt.-%
explosives (18) are given in Table 3.
Nevertheless it was found that the RP available that time Composition 23
based on ?archaic= MIL-P-211 was too impure and thus * Aluminium flakes 8 wt.-%
unstable to be applied in any long-term stable ammunition – * RP 71 wt.-%
a fact that caused perpetual worries with any RP-based * Sodium nitrate 15 wt.-%
ammunition introduced in the USA before the adopted use * Calcium carbonate 1 wt.-%
of stabilised RP most recently. In view of the improved * Titanium isopropoxide 1 wt.-%
stability of RP available today Busky et al. proposed to use * Cured HTPB 4 wt.-%
stab priming compositions based on RP similar to those
Vine and Fletcher have given composition and inves-
tigated failure causes of float and smoke signals [77].
Table 3. RP-based stab priming compositions. Composition 24 designated SR414
Composition wt.-% 16 17 18 19 * Calcium silicide 6 wt.-%
RP 25 17 25 25 * RP 60 wt.-%
Metal nitrate 58a) 53a) 70a) 65b) * Manganese dioxide 28 wt.-%
Metallic fuel 17c) – – 5d) * Magnesium 6 wt.-%
Secondary explosive – 5e) 5e) 5e)
Primary explosive – 25f) – – Glyde et al. investigated composition for float – smoke
a) Barium nitrate; b) Potassium nitrate;c) Antimony sulphide; d) signals based on RP and sulphates as oxdisers or on RP and
Aluminium; e) Pentaerythrite tetranitrate; f) Lead styphnate. heating compositions (based on magnesium or calcium
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174 E.-C. Koch
silicide and manganese dioxide) that allow for sublimation Nevertheless combustion in confined space that is dV ¼ 0
of RP [21]. They found that anhydrous calcium sulphate or under sufficient internal tampering of the loose compo-
provides the best performance when compared with potas- sition itself will dramatically accelerate and may eventually
sium barium and strontium sulphate. shock-up to slow order detonation as has been experienced
by the author in the course of different experiments. Thus,
utmost care has to be taken when designing RP-based
7 Red Phosphorus-Based Explosives ammunition and conducting experiments with RP-based
ammunition.
Hahma et al. have investigated the effect of RP as an In contrast to WP, which can be melt-cast under water, RP
additive to isopropyl nitrate in classical binary thermobaric is a powdery substance that has to be mixed with aqueous or
charges [78]. The results he obtained with these mixtures organic binders to give mostly pressable and seldomly
were not very promising. In contrast compositions made castable compositions. The inadvertent ignition of RP-
from nitramines and RP display an increase in blast pressure based payloads by set-back forces upon firing from mortars
by more than 35% compared to aluminised composition A3 and howitzers is most often due to inappropriate structural
(Hexal) in confined spaces as has been found by the author integrity of the RP grain having cracks and dislocations. In
[79, 80]. case of complete confinement of the combustion zone
(dV ¼ 0) this can lead to explosion and DDT.
8 Phosphorus Compounds
11 Conclusion
Golding and coworkers have reported about the inves-
tigation of polyphosphazenes substituted with nitrate ester Phosphorus is an indispensable fuel for military pyro-
groups and/or azidoalkyl groups and/or perfluoroalkyl technics. Within the last few decades the focus has changed
groups as binders in pyrotechnic flare and smoke compo- from WP to RP. With the advent of high energy materials-
sitions based on RP [81 – 84]. The polyphosphazenes have like P3N21 and polymer phosphazenes having azide and
the general make up (P¼N)(O-alkylidene nitrate ester/ nitrato-substituents molecular explosive applications of
azide)(O-perfluoroalkyl). The materials generally have phosphorus come closer.
interesting densities ranging from 1.5 to 1.6 g cm3.
Klapçtke et al. have reported about the successful
structural characterisation of an azide substituted
cyclo-phosphazene, P3N21 [85] known since some decades 12 References
[86].
[1] E.-C. Koch, D. Clement, Special Materials in Pyrotechnics: VI.
Silicon – An Old Fuel with New Perspectives, Propellants,
Explos. Pyrotech. 2007, 32, 205.
9 Operational Red phosphorus-based Ammunition [2] E.-C. Koch, Special Materials in Pyrotechnics: IV. The
Chemistry of Phosphorus and its Compounds, J. Pyrotech.
2005, 21, 39.
Table 4 gives information on RP-based ammunition [3] At the time of proof reading a draft specification for Red
introduced with either German, British or US forces. Phosphorus titled STANAG 4679 is in discussion with SG-1 of
NATO AC 326, May 2008.
[4] G. A. Lane, W. A. Smith, E. M. Jankowiak, Novel Pyrotechnic
10 A Word on Safety: Unexpected Explosion of Red Compositions for Screening Smokes, 1st International Pyro-
technics Seminar, Estes Park, Colorado, USA, August 12 – 17,
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