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Patent 1089684 Summary

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(12) Patent: (11) CA 1089684
(21) Application Number: 260880
(54) English Title: PRIMING COMPOSITION AND TECHNIQUES
(54) French Title: COMPOSE ET TECHNIQUE D'AMORCAGE D'EXPLOSIFS
Status: Expired
Bibliographic Data
(52) Canadian Patent Classification (CPC):
  • 86/2
(51) International Patent Classification (IPC):
  • F42B 33/00 (2006.01)
  • C06B 21/00 (2006.01)
  • C06C 7/02 (2006.01)
(72) Inventors :
  • KNIGHTS, RICHARD N. (United Kingdom)
  • WHITTALL, PETER H. (United Kingdom)
  • SUTCLIFFE, GORDON R. (United Kingdom)
  • CARTER, GEORGE B. (United Kingdom)
  • HOBBS, JOHN F. (United Kingdom)
  • CROSS, ALAN (United Kingdom)
(73) Owners :
  • IMI KYNOCH LIMITED (Not Available)
(71) Applicants :
(74) Agent: SMART & BIGGAR
(74) Associate agent:
(45) Issued: 1980-11-18
(22) Filed Date: 1976-09-10
Availability of licence: N/A
(25) Language of filing: English

Patent Cooperation Treaty (PCT): No

(30) Application Priority Data:
Application No. Country/Territory Date
20065/76 United Kingdom 1976-05-14
11849/76 United Kingdom 1976-03-24
37386/75 United Kingdom 1975-09-11
37385/75 United Kingdom 1975-09-11

Abstracts

English Abstract






ABSTRACT OF THE DISCLOSURE
A method of producing explosive for priming manufactured explosive
devices wherein said explosive is produced in a succession of small quantities.


Claims

Note: Claims are shown in the official language in which they were submitted.



THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A method of priming a plurality of explosive devices
by incorporating a discrete body of priming explosive with an
element of each device wherein the priming explosive is produced
at a rate which substantially corresponds to the rate of incor-
poration thereof with the elements of the devices so that there
is substantially no off-line storage of priming explosive and
wherein production of the priming explosive involves a chemical
reaction forming a primary explosive.


2. A method as claimed in claim 1 wherein said explosive
is produced in a plurality of small quantities.


3. A method as claimed in claim 2 wherein each quantity
corresponds to the quantity required for each body of explosive.


4. A method as claimed in claim 2 wherein each quantity
is a batch sufficient for a plurality of such bodies of explosive.


5. A method as claimed in claim 3 wherein said explosive

is produced in situ.


6. A method as claimed in claim 1 wherein production of
the priming explosive comprises production of a styphnate primary
explosive.



7. A method as claimed in claim 6 wherein the styphnate
is produced by double decomposition.

36


8. A method as claimed in claim 6 wherein said styphnate
is produced by reaction between styphnic acid and a compound
including a heavy metal.


9. A method as claimed in any one of claims 1 to 3
wherein production of the priming explosive comprises production
of an azide primary explosive.


10. A method as claimed in claim 1 wherein production of
the priming explosive comprises production of a multiple salt.


11. A method as claimed in claim 10 wherein said multiple
salt is lead nitrato-hypophosphite.


12. A method as claimed in claim 1 wherein production of
the priming explosive comprises reacting components to produce a
primary explosive and a by-product which remains in the primary
explosive.


13. A method as claimed in claim 12 wherein said by-
product will function as an oxidiser.


14. A method as claimed in claim 12 or 13 wherein said
by-product is a nitrate.



15. A method as claimed in claim 12 or 13 wherein said
primary explosive is a heavy metal styphnate.


16. A method as claimed in claim 12 or 13 wherein said
by-product forms a substantially anhydrous crystal.

37


17. A method as claimed in claim 12 wherein said primary ex-
plosive is lead styphnate and said by-product is sodium nitrate.


18. A method as claimed in claim l wherein production of the
priming explosive is effected by taking a substantially dry pre-
mix comprising components that will react together in the
presence of a liquid medium to form a primary explosive compound
and combining said liquid medium therewith.


19. A method as claimed in claim 18 for forming said priming
explosive in situ wherein an appropriate amount of said premix
is dosed into an element of each device and the liquid medium is
combined, in the element, with said premix.


20. A method as claimed in claim 19 wherein said premix is
dosed into said element and the liquid medium is then added
thereto.


21. A method as claimed in any one of claims 18 to 20 wherein
the premix additionally comprises one or more ingredients of a
priming composition.


22. A modification of a method as claimed in any one of
claims 18 to 20 wherein at least one of said components and/or
ingredients is initially contained in the liquid medium.



23. A method of incorporating a body of priming explosive
with each of a plurality of containers therefor, each container
forming, or intended to form, part of a unit of ammunition, the

38


method comprising the steps of dosing an amount of a substan-
tially dry premix into each container, said premix comprising
components that will react together in the presence of a liquid
medium forming a primary explosive compound, and combining, in
each container, an amount of said liquid medium with the premix.


24. A method as claimed in claim 23 wherein said amount of
liquid medium is dosed into each container after the premix has
been dosed thereinto.


25. A method as claimed in claim 23 or 24 wherein said premix
additionally contains one or more ingredients of a priming
composition.


39

Description

Note: Descriptions are shown in the official language in which they were submitted.



The present invention relates to the priming of explosive
devices, that is to say the incorporation of a priming explosive
with elements of priming-explosive utilizing devices.
In current practice, primary explosive for use in priming
of explosive devices (e.g. ammunition cartridges and detonators)
is manufactured away from the priming zone in a large batch or at
the maximum possible continuous rate and is then storedO In the
case of ammunition, at the priming stage, primary explosive is
drawn from store and is mixed with one or more other ingredients
of the priming explosive in a substantial batch which is then dis-
tributed between elements of the devices ~e.gO cap shells, cart-
ridge cases or detonator cases). ~his sequence involves bulk
storage, transport to a mixing station, the mixing operation it-
self, transport of the mixture to the priming zone, and distrib-
ution between said elements. Since primary explosives are in-
herently dangerous to manufacture and handle, each stage of the
sequence is hazardous and needs special precautions, particularly
where explosive is present in bulk. However, in the case of det-
onators, certain primary explosives may be used alone as the prim-

ing explosive, in which case mixing of the primary explosive withone or more other ingredients is unnecessary. Nevertheless, the
bulk storage and distribution aspects alone are very hazardous.
According to the presen~ invention there is provided a
method of priming a plurality of explosive devices by incorporat-
ing a discrete body of priming explosive with an element of each
device wherein the priming explosive is produced as hereinafter
defined, at a rate that is, as hereinafter defined, continuous
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with incorporation thereof with the elements of said devices.
By the term "continuous", there is meant that the priming
explosive is produced at such a rate that there is substantially
no oEf-line storage of bulk priming explosive.
The priming explosive may be produced in a batch suf-
ficient for a plurality of individual utilisation demands, but
small relative to conventional batches. In order to satisfy total
output demand over a period, a series of such batches may be pro-
duced in the period and these batches can be separated by a dis-

tance and/or in a manner facilitating isolation of an explosionin any one batch. The batches can be produced in regular succes-
sion, for example at predetermined time intervals, thereby facil-
itating adequate spacing and subsequent handling.
The maximum permissible size of each batch will depend
upon the type of priming explosive and the conditions under which
it has to be produced. The sensitivity, explosive energy, re- ~-
quired production conditions and divisibility for use of the ex-
plosive will all affect the batch size. The total output demand
per unit time will also influence the batch size, as will the
precautions taken to isolate individual batches. Conventional
priming explosive for rimfire cartridges includes lead styphnate
as primary explosive: a batch of styphnate sufficient for, say,
20 priming charges for rimfire cartridges could be made and
divided between the rimfire cases in a continuous operation:
corresponding arrangements could be made for priming shotgun cap
shells and detonator cases. Larger batches will obviously in-
volve extra precautions~ but batches as large as several ounces
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could be produced at intervals of about one minute.
Batches may also be combined for an individual utilisation
demand. ~lowever, neither combination nor division of batches is
preferred, since both incur additional hazards. The preferred ar-
rangement is one in which a batch is matched to an individual
uti]isation demand, for example each batch in a series is just
sufficient for a priming charge for one rimfire cartridge, shot-
gun cap or detonator and in this arrangement the priming explos-
ive is preferably produced in situ, for example in an element of
a utilising device.
For the avoidance of doubt, the following explanation is
given for the terms "utilising device" and "production in situ":-
Utilising device - refers to a combination of at least two ele-
ments of an explosive device~ at least one of which element is a
discrete body of said priming explosive. The other element may
be a mere container or carrier for the explosive, such as a rim-
fire cartridge case, a detonator case or a cap shell. The util-
ising device may be a finished explosive device, but it is more
likely to be only partly finished; for example (a) further
elements may have to be added to it to make up the explosive de-
vice, such as propellant and a bullet for a rimfire cartridgeJ or
an electric match or a fuse for a detonator; (b) the elements
may have to be reshaped, or relocated relative to each other as
when priming explosive in a rimfire cartridge case is forced into
the rim of the case by a conventional spinning punch.
Production in situ - means that the priming explosive is produced
in relation to at least one other element so as to provide said
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combinationO Where the other element is a container, the priming
explosive will normally be produced within it. If the other ele-
ment were a carrier, the priming explosive could be produced as a
body around a portion of the carrier. As indicated above, pro-
ducing in situ does not necessarily imply that the combination is
immediately ready for final use.
The explosive may be produced in a stream and the stream
may be separated into successive "lengths" by explosion barriers.
The term "continuous" as defined above does not necessar-

ily imply immediate utilisation of the priming explosive in prim-
ing; in practice, there will inevitably be a degree of "live
storage" in cases where production is not effected in situ and
this live storage can be adjusted as required to fit production
circumstances. However, there will be a continuous flow path be-
tween the production and utilisation stages, so that off-line
storage of dangerous substances is substantially eliminated. To
this end, the production rate and the utilisation rate are matched
or substantially matched, at least on average over a period.
A production process in accordance with the invention is
preferably automated. The materials required for production of
the priming explosive may be automatically metered into a stream
or into batches under controlled thermal conditions, even where
small quantities are required. Preferably, too~ an automated
production process is integrated with an automated utilisation
stage producing at least a partially finished explosive device;
for example, in the case of rimfire cartridge priming, priming
explosive production can be continuous with an automatic line for




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receiving primed cases, loading propellant, and inserting the
bullet.
The priming explosive should be sensitive to each or any
of heat, friction, flame, electric spark, percussion or other
predetermined initiating event. The explosive may be designed
to produce heat or flash, rather than substantial quantities of
gas, or a detonating shock. Heat and flash producing explosives
may be required for initiation of propellants, while shock pro-
ducing explosives will generally be required for initiation of
secondary high explosives such as base charges of detonators.
The following explanation is given of terminology used
in this specification hereinafter;-
(a) the word "material" is used in a general sense,
~b) the word "ingredient" is used to indicate a part of
a composition in which the ingredient remains individually
identifiable,
~c) the word "component" is used to indicate a material
which reacts with another component or other components to pro-
duce a further material.
~0 The priming explosive may be in any required physical
form. It may consist of a primary explosive compound, for ex-
ample a salt, or of a priming composition containing a primary
explosive compound which may be produced in a mixture of some or
all of the other ingredients of the composition: for example,
an explosive compound may be produced in a mixture which comprises
a fuel and/or an oxidiser and/or a frictionator: such a compo-
sition is disclosed in United States Patent Specification No.
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2,239,547 to Brun.
In any process according to the invention, the materials
which are brought together to produce the priming explosive are
preferably comparatively insensitive, thereby mitigating storage,
mixing and charging problems. However, it may be necessary to
use some sensitive starting materials: for example, a priming
composition may comprise a plurality of sensitive ingredients, and
it may be difficult or impossible to produce all of the sensitive
ingredients simultaneously in the composition: for example it
would be difficult to produce lead styphnate and tetrazene simul-
taneously in a rimfire ammunition priming composition, although
both these ingredients may be required. Accordingly the inven- ;
tion includes within its scope the use of sensitive starting mat-
erials, but where these are used they preferably constitute a
minor proportion, preferably a small proportion, of the starting
materials.
It is within the broad scope of the invention to form a
sensitive explosive, say from relatively insensitive starting
materials, and then to combine it with additional ingredients of
a composition: this may be necessary if the additional ingredi-
ents would interfere with the formation of the sensitive explos-
ive. However, it is preferred to avoid such addition, where pos-
sibleJ as it clearly introduces additional hazards.
Production of the priming explosive may be effected in a
liquid medium, preferably water. The liquid medium may be driven
off or otherwise removed after formation of the explosive. The
liquid medium may perform either or both of the following .


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functions:-

1. it may act as a desensitiser for solid sensitive in-
gredients, which should be damp until the composition has formed;
2~ it may act as a reaction medium enabling components
to Eorm a new material.
A component which is soluble in a reaction medium may be
taken into solution by the medium and thereaf-~er brought together
with another component. Alternatively, the components and medium
may be independent of each other before being brought together.
Further, where components will not react dangerously in the ab-
sence of a medium, they may be brought together before being
brought together with the medium.
Production of priming explosive in accordance with the
method of the invention involves a chemical reaction forming a
primary explosive. The desirable characteristics of such a re-
action for the purposes of the present invention are set out
below:-

~ a) Simplicity: The reaction should preferably involveonly a single stage, without prolonged stirring (preferably re-

quiring none at all) and without requiring closely defined crit-
ical conditions such as temperature or pH.
~ b) Speed: The reaction should preferably be completed
in a short period. However, this will not be essential if an
incomplete reaction does not prevent further processing, for ex-
ample spinning, drying, addition of propellant and bullet in pro-
duction of ammunition, and provided the reaction has been com-
pleted by the time the product is required for final use.
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~ c) Compatibility with containers: The solutions or
other materials involved in the reaction should clearly be com-
patible with the material of the container in which the reaction
takes place. Some acids will be excluded from reactions which
occur in metal containers such as brass rimfire cartridge cases.
~ d) By-products: There should be no unduly deleterious
by-products. In some cases it may be possible to use by-products
of a reaction, for example as oxidisers in a priming composition.
Where this is not possible, the by-products may be inert, gaseous,
volatile or vapourisable, or at least not seriously deleterious.
(e) Starting materials: These should be easily and safe-
ly handlable in bulk form. Small proportions of sensitive mat-
erials, for example tetrazene, may be included in the starting
materials, preferably in a desensitized form.
A metathetic reaction will normally best satisfy require-
ments ~a) and ~b) above. The formation of covalent bonds is us-
ually a relatively slow process. Suitable metathetic reactions
will be double decomposition reactions and acid base reactions.
In addition to metathetic reactions, however, the formation of
mixed crystals has also been found to be a suitable reaction under
criteria ~a) and ~b) above. Priming explosives comprlsing mixed
crystals are already well known in the exploslves art~
The required characteristics of the priming explosive are
in particular, the following:-

~ a) it must be effective for its required application -
for example ignition of propellant or initiation of a secondary

explosive,




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(b) it must satisfy special requirements dependent upon
its specific use, for example ballistics tests in production of
ammunition;
(c) it must provide the required sensitivity, which will
clearly have both upper and lower required values (in ammunition
production these are represented by "all fire" and "no fire"
heights for sensitivity drop tests of primed cases);
~ d) it must be compatible with its surroundings - the
container and any adjacent explosive such as propellant or second-

ary explosive; and
(e) it must be reasonably stable in storage in the ex-
pected conditions of use which may involve high or low tempera-
tures and/or humid conditions.
Where an explosive compound is produced in situ in a
method of the invention it is not necessary to produce a so called
"free flowing" crystal form. The provision of such a crystal
form is a long standing problem in the explosive art and can be
avoided by the in situ technique. Further, by using that tech-
nique, the nature and sensitivity of the priming explosive may be
chosen solely in dependence upon its final use rather than, as
hitherto, upon the technique used to load the explosive into de-
vices. In the past, many suitable initiating compounds had to be
rejected because they proved ~oo dangerously sensitive for use in
conventional priming techniques involving distribution of priming
explosive from a batch between explosive devices. Examples of ~ -
suitable materials are cited below.
According to the preferred method in accordance with the
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present invention, predominantly relatively insensitive materials
are brought together to produce a priming explosive in a quantity
suitable for priming an individual explosive device. Preferably
the quantity is one of a series of such quantities. Production
of the explosive is preferably effected wholly in situ in a de-
vice. Ilowever, it is within the broad scope of the invention to
complete production of the explosive away from the device, the
product thereafter being supplied to the device, or to bring the
materials together away from the device and to complete produc-

tion of the explosive in situ.
Apparatus for use in the method of the invention may com-
prise means for bringing together materials, which together will
form said explosive, at a low rate and/or in a succession of small
quantities preferably appropriate to individual utilisation de-
mands, and/or on a flow path continuous with means for supplying
partially or completely formed explosive to a succession of other
elements of utilising devices.
Where it is desired to produce explosive in a plurality
of small quantities, the apparatus may comprise a plurality of
~0 dispensing means, each adapted to dispense predetermined doses
of material to respective receivers therefor so that each receiver
will receive a dose from each dispensing means of said plurality.
The materials dispensed may comprise components of an ex-
plosive and a medium in which said components can interact.
Where production is not effected wholly in situ, starting
materials may be fed continuously to a mixing zone. The starting
materials may comprise some ingredients of an explosive compo-
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sition and components which will react forming an explosive com-
pound. In the mixing zone, they may be brought together in
small quantities or at a low rate. The mixture may leave




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the zone as a series of small discrete quantities, or as a stream of small
dimensions. Such a stream may be interrup-ted at intervals to reduce explo-
sion hazards; for example, there may be explosion barriers so that an explo-
sion a-t a particular location in the s-tream will be limited to the region be-
tween successive barriers.
The mix-ture may be transferred continuously from the mixing zone
to a utilisation zone. Where the mixture leaves the mixing zone as a series
of small quantities, each quantity may be of a size appropriate to an indi--
vidual utilisation demand, for example shotgun cap, rim-fire cartridge or det-

onator. The series of quantities may therefore be dispensed direc-tly into a -
corresponding series of containers for the explosive devices. It would be
possible to produce a series of small quantities each of which represents a
plurality of utilisation demands, with a subsequent division of each quantity
between those demands. However, this is not preferred as it involves an ex-
tra processing stage. Where the mixture leaves the zone as a stream of small
dimensions, those dimensions may be selected to facilitate division of the
stream into quantities appropriate -to individual utilisation demands. For
example, the cross-section of the stream might be appropriate to an individual
rimfire cartridge, cap shell or detonator.
Preferably the materials are mixed in substan-tially predetermined
proportions in said mixing zone.
The mixing zone may be such that it is freely accessible to flow
paths by which the materials are supplied to it. Alternatively, there may be
means for controlling access to the mixing zone from such flow paths. For ex-
ample, the materials may be circulated through closed flow paths normally sep-
arated from the mixing zone, there being tapping means to tap off quantities
of materials to the mixing zone.
Mixing in the zone may be effected by any convenient means for
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example by turbulence, by mechanical intervention, or by passing gas bubbles
through the mixing ~one.
The following are examples of explosives which can be made by methods
in accordance with the invention as applied to priming rimfire cartridge cases.
In these examples, which refer to production of rimfire ammunition,
reference is made to sensitivity tests. These involve dropping a 2 o~ ball
onto a bar striker which then indents the rim of a cartridge case. The re-
sults are quoted in terms of the "mean fire height" - that is, the release
height of a ball above the striker required to give a 50% chance of firing a
cartridge in a given sample, usually of 50 cartridges: this is obtained by a
statistical calculation, and the associated standard deviation is also quoted.
Occasionally the "all fire height" is quoted - this is the release height of
the ball at which all cartridges in the sample fired.
EXAMPLE l STYPHNATES

-
~a) by double decomposition:

The following materials were used in the indicated proportions by

weight:-


Sodium styphnate27 parts ;~

Lead hypophosphite 7 parts DRY

Grit 25 parts
,
. . ,
Lead nitrate 31 parts


Tetrazene 3 parts

Gum Arabic - WET

Lissapol

The first three materials are relatively insoluble in water when

compared with lead nitrate, and they were provided in powder form in a rimfire

- 12 _




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cartridge case, in a predetermined dose. The dose required depends upon the
quantity of initiating composition required to ensure ignition of the propel-
lant. In a cartridge designed to contain about 80 mg of nitrocellulose base
powder as propellant, the quantities of the reacting components were such as
to produce about 20 mg of initiating composition. This can be adjusted as re-
quired to give designed ballistic characteristics for the combination.
Lead nitrate is soluble in water, and was added in the form of a
solution thereof to the dry materials. The tetrazene was dispersed in the
lead nitrate solution, this being a dangerous material to handle dry. The gum
arabic and Lissapol were present in small proportions for reasons well known
in the art.
The reaction between the lead nitrate and the sodium styphnate then
occurred in the cartridge case, giving lead styphnate and sodium nitrate in
the resultant mixture. The product was dried out after the reaction, and then
approximately 10% by volume of water was added to the dried mixture to render
it mouldable. The rimfire case containing the mouldable composition was then
passed to a conventional spinning punch to force the composition into the rim
of the case in the conventional manner. The moulded composition was then
passed through a conventional drying arrangement and the primed case was sub-

sequently handled in the conventional fashion.
In order to prime cap shells, antimony sulphide, in dry powder formmay be substituted for the grit at least partially.
The double decomposition reaction described above was carried out at
room temperature. Increased temperature may lead to larger crystal sizes for
the lead styphnate and this may affect sensitivity of the composition. In-
crease of temperature runs the risk of decomposition of the tetrazene, this
being a particular problem above about 70C. However, the highest possible

temperature, subject to other restraints,
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is advantageous in facilitating crystallisation of the lead styphnate from
the gel which forms in the early stages of the double decomposi-tion reaction.
No steps were taken to control the pH of the mixture in the car-
tridge case. This would be slightly acid because of the presence of the lead
nitra-te solution, and slight acidity is necessary for crys-tallisation of the
lead styphna-te. A pX in the range 3 to 6 is suitable.
The quan-ti-ty of water used was ~ust sufficient to take the lead
nitrate into solution. This gives a paste consistency to the mixture af-ter
addition of the solution. It is desirable to minimise the quantity of water
used since it has to be driven off after -the lead styphnate has formed.
The bulk of the star-ting materials referred to above are insensi
tive when compared with the lead styphnate. However, tetrazene is a primary
explosive and dry sodium styphnate can be caused to explode if ignited by a
black powder fuse.
It may therefore be necessary to keep these materials wet in store ;
and in feeding them to the cartridge case. It will be noted however that the
proportion of preformed primary explosive in the starting materials is very
small - well under 10% even if the indicated propor-tion is increased slightly.
Further, only small quantities of materials are involved in each individual
reaction, so that it is possible to use a starting material having quite sub-
stantial sensitivi-ty, although preferably less than the eventual primary ex-
plosive. For example~ in United States Patent Specifica-tion No. 2,239,547 to
Brun, there is described a method of making normal lead styphnate by admix-
ture of reacting quantities of basic lead styphante, styphnic acid and other
priming composition ingredients, the normal lead styphnate being formed in
the mixture. The process described in that specification therefore involves
the conversion of one explosive, basic lead styphnate, into a more sensitive
explosive, normal lead styphna-te, in a mixture of o-ther ingredients. Such a
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process could be adapted to the presen-t invention.
Where the heavy metal is lead, the process conditions are prefer-
ably controlled so as to result in forma-tion of normal lead styphnate, but a
proportion of basic lead styphnate may be found acceptable depending upon the
required circumstances of use. The yield of lead styphnate can be improved
by thorough mixing of the components, so as to minimise the proportion of tm-
reacted feedstock remaining in the composition. Where the process is carried
out on a small scale, as in the example cited above of priming of rimfire
cases by reacting components in situ, mixing can be effected by vibration of
the reacting components. The yield of normal lead styphnate can be improved
by control of the pH, and it may be necessary to add free acid to ensure the
required acidity in -the reacting mixture.
The first stage of the double decomposition reaction is the forma-
tion of a gel from which the heavy metal styphnate crystallises. The time
required for crystallisation ~rom the gel stage depends upon the temperature
and the concentration of the mixture, the time being longer for lower -temper-
a-tures and higher concentrations. Where the composition is being produced
in situ, maximum concentration is desirable to avoid having to drive off the
solvent, usually water. Thus maximum permissible temperature is also desir-

able, but this will be limited by the tendency towards thermal decompositionof reacting components and resulting products, and possibly also by the ef~
fects of increasing temperature upon crystal size of the styphna-te.
b) by reaction with styphnic acid:
A mixture was produced of the following materials in the s-tated
proportions by weight:-




:: . - , . , . . :............................ . : : :. ~ , , :


, " ' ' '~,' -., ,' ." ;, , '~ . , ' ' : ' , :: ,

8~~

a) styphnic acid 100 parts
b) white lead 100 parts
c) ground glass 50 parts
d) barium nitrate 50 parts
All of the ma-terials were in dry powder form, and all powder par-
ticles passed through a 100 mesh sieve. When distributed between rimfire
cartridge cases, the mixture was moistened with water and permitted to react
in situ in the cases. It was found that the resulting primed case could be
made to explode satisfactorily with a substantial flame. The quantity of
0 priming composition in each case was of the order of 14 to 15 mg.
The styphnic acid was of a type obtainable from the Royal Ordnance
Factory at Bridgwater. White lead is basic lead carbonate of a type commonly
used in paint pigmeNts and of the chemical formula 2 PbC03.Pb(OH)2.
The styphnate route is not limited to the production of lead com-
pounds. Other heavy metal styphnates might be produced in a similar manner,
and have previously been suggested for use in initiating compositions. Fur-
ther, the acid reaction is not limited to the use of white lead (lead car-
bonate) or lead oxide (PbO). An alternative possibility is lead hydroxide.
The use of lead oxide is particularly desirable, however, in tha-t there are
no resulting by-products, the lead oxide and styphnic acid combining exactly
to produce lead styphnate. The use of lead hydroxide is also acceptable on
this ground, however, since bheonly resulting by-product is water, which is
in any event present as an ionising medium. A further possibility would be
a reaction between lead acetate and styphnic acid. In this case, the ex-
pected by-product would be acetic acid, which would be volatile and could be
driven off during the reaction. The by-product of white lead is C02 which is
driven off. Further information on production of styphnates is contained in
United States Patent 2,295,104 and German Patent Specification 2,531,997.

- 16 -




.. ., '.: .' . : ''" :' .: ' ' ' ' ', ' . . :

~L~8~ 4

EXAMPLE 2 MULTIPLE SALTS ESPEC_ALLY NITRATO-HYPOPHOSPHITES
The double salt lead nitrato-hypophosphite is described in German
Patent Specification Mo. 289,016, and the use of it in a priming composition
is discussed in United States Patent Specifications Nos. 2,160,469 and
2,116,878.
In one test, the following materials were used in the indicated
percentages by weight:-
Lead nitrate 40%)
Gum Arabic - ) WET
Lissapol - )

. . _ . . _. . _
Lead hypophosphite 40%) DRY
Grit 20%)

The last two materials are relatively insoluble in water, and are
proviaed in the rimfire case in the form of mixed powder. A concentrated
aqueous solution of lead nitrate, incorporating small proportions of gum and
Lissapol is then added to the powder in a predetermined dosage. The double
salt lead nitra-to-hypophosphite will separate from the solution at ambient
temperature. The product can then be dried until it is in a mouldable form,
whereupon the case can be passed -to a conventional spinning punch -to compact
the composition into the rim. The Lissapol functions as a surfactant in this
example, but may be found unnecessary.
Drying may be effected at tempera-tures up to a-t least 100C., to
produce a product containing approximately 10 to 12% water, which will
be suitable for compaction. The produc-t may then be dried completely.
If preferred, the initial product can be dried completely, and a




- 17 -




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,, . , :, .... ~ , .. .,: ,
, . , , ~ :
,:.- ', ' : ' ' '.:

8~
predetermined dosage of water added to produce the mouldable composition.
A further drying step is needed after compaction as in the alternative
process.
In an alternative method of forming a priming cornposition, the lead
ni-trate, lead hypophosphite and grit are mixed as dry powder, and a pre-
determined quan-tity of dry powder is inserted in -the rimfire case. About
10 to 12% by weight of water, -together with the Gum Arabic and Lissapol,
is then added to the mixed powders, and the mixture forms the double salt
generally as described above. Since the mixture now includes the required
percentage of water to render it mouldable, there is no need for a drying
operation before the case is passed to the spinning punch, or other device,
for compacting the mixture into the rim of the case. In this method, the
powders may be pre-mixed before they are inserted into the case, or they
may be inserted independently and the case may then be vibrated to mix the
powders therein. The mixing step has been omitted from some tests and a
satisfactory product was nevertheless obtained.
It will be noted that ina method as described above, whether or not
powders are premixed or the slurry is agi-tated during reaction, the double
salt is permitted to crystallise substantially freely, that is without
precautions to control crystal size as described in United S-tates Specifica-
tion 2,160,~69. The formation of "extended crystals" referred to in that
patent can be permitted in situ in an explosive device.
It is most convenient to form the composition at ambient temper-
ature, and this has been found satisfactory~ Xowever, the method is not to
be limited to such temperatures; it may be desired to control the temperature
at which the product forms, and possibly to supply heat to raise the tem-
perature above ambient. Temperatures up to ~5 C. have already proved
satisfactory; higher temperatures may be used~ sub~ect to decomposition
- 18 -




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.
:
. .,. : ~:, . . ~ , ; :

9~

of the compounds.
It has also been found possible to form the double salt with a pHvalue in the region 1-3, although -this is believed more acid than is nec-
essary. Undue acidity is undesirable because of the possibility of an attack
upon the material of the case by the solutions therein. On the o-ther hand,
undue alkalinity of the solutions may cause stress corrosion of the case. A
pH of 3 to 5 is believed suitable. The pH will usually be determined by the
pH of the lead nitrate component.
The molecular weights of lead nitrate and lead hypophosphite are
approximately the same; the powders are therefore preferably used in approx-
ima-tely equal weight proportions. However, a slight excess of either powder
may be found desirable in practice depending upon the circumstances. The in-
vention is not to be limited to substantially equal weight proportions, how-
ever, since an excess of up to 100% of either component has been found to
produce a product having satisfactory sensitivity and initiating powder. As
the excess of either product increases, however, adequate mixing of the com-
ponents may become a problem, and "patches" of ~mreacted component may be
found in the case rim.
Where a solution of lead nitrate is to be added to lead hypophos-

phite powder, it is desirable to make the solution as concentrated as pos-
sible, to minimise the amount of water to be driven off before compaction.
A series of rimfire cartridges primed with lead nitrato-hypophos-
phite produced by the first method outlined above has been subjected to a
series of tests, the results of which are summarised in the following para-
graphs:
Sensitivity
Mean fire height - ~.71 - 1.18 inches
All fire height - 9 inches
- 19 - ,`




- . :,:

~:: - ' ' ' , ' , " ,' ,, ' ' . ' ' '':
,' : ., ' , ' . . ~: ~:
' ' ' ' ~: ' ' ' ' ~ :
,,

This indicates a sensitivity greater than that of conventional
priming compositions comprising lead styphnate and tetrazene.
The sensitivi-ty was found to depend on the proportion of the fric-
tionator, i.e. grit in the example quoted above. If the frictionator was
no-t provided, it was found -that the product would not fire even in a gun
breech. Alternative frictionators comprise powdered glass and carbon par-
ticles (coke). The sensitivity was also found to be dependent to a certain
extent upon the proportions of the lead nitrate and lead hypophosphite,
slightly lower sensitivity being found with an excess of hypophosphite.
Barrel time
This is the time between the fall of the striker of the gun and the
emergence of the bullet from the barrel. The time was measured at 2.59 -
0.13 milliseconds. The rangeOf measurements was 0.58 millisecond. This is
satisfactory in comparison with the conventional priming composi-tions men-
tioned above.
The barr 1 time will be dependent -to some extent upon the relative
proportions of the priming composition and the propellant. In the -tests
mentioned above, the propellant was the disc-type single base propellant
sold by ICI Limited under the name "Acurex". In the tests the cartridges
contained about 80 mg of propellant, and the quantity of priming composi-tion
was about 20 mg in each case. This is within the range of quantities of
conventional priming composition.
Pressure and Velocity
The driving pressureProduced by the tested cartridges averaged 5.78
tons/sq. in., giving a velocity of approximately 1,056 feet/second. This is
slightly lower than the pressure and velocity found with conventional prim-
ing compositions, but is satisfactory. After storage in humid conditions,
the cartridges were found to give a pressure of about 5.68 tons/sq. in. and
- 20 -




,,


: '~ '''

,, . , : : , :

a velocity of 1,038 feet/second.
Mass explosibility
This is the percentage of cases ini-tiated by an explosion of one
case in a group. I-t was found that 90+% of the group could be initiated in
this manner, possibly because of the very high sensitivity of the priming
composition. Thismay be dealt with to some extent by using additives, such
as glass "flour" and other inert subs-tances (see United States Patent Spec-
ification 2,356,210) or polyvinyl alcohol (see United States Patent Specif-
ication 2,341,262), or by adding a layer of varnish over -the priming composi-

tion in the primed cases. An alternative method of dealing with the problemwould be to produce cartridges in a continuous line, avoiding groups of
primed cases at any point along the line.
The priming composition may include further additives to give ad-
ditional properties or modify the properties of the composition. For ex-
ample, additives may be included to reduce mass explosibility as referred to
above, or to improve workability as described in United States Patent Spec-


ifications 2,327,867, 2,377,670 and 2,662,818. Other additives may providefuel: for example, antimony sulphide may be included for this purpose and
results in a bigger n ame. Silicon and calcium silicide bo-th give sparks.
20 Fuels may be particularly important in priming of caps. The double sal-t
lead nitrato hypophosphite can be formed in the presence of each of the fuels
referred to, and it has been found that each of these fuels tends to increase
sensitivity of the composition, reducing the proportion of frictionator re-
quired. The composition may also include small proportions of other primary
explosives, if required.
In themethod of producing the multiple salt, it is not necessary to
perform the operation wholly within the container of the device, that is the
rimfire case, cap or the detonator case. The components may be brought to-


- 21 -



. ~
. ~ . . .. : ,


. , . . -


. :, : , : . : . . :: : :
.. . : :. : . ~ . : .


gether outside the device, formation being completed in situ. Alternatively,
the formation may also be completed ou-tside thedevice, and the formed product
may be charged into the device. It is preferred to produce the multiple salt
in small quantities, preferably appropriate -to individual explosive devices,
because of its high sensitivity and the explosion risk associated with a
large batch.
The use of multiple salts in a method according -to the invention
is no-t limi-ted to the double salt lead nitrato hypophosphite. Similar mul-
tiple salts are referred to in Uni-ted States Patent Specifications 2,175,826,

2,292,956 and 2,352~,96L~ and others may also prove suitable.
EXAMPLE 3 AZIDES
All solutions referred to in this example are in water. Unless
otherwise indicated, all tests involved formation of composition in a car-
tridge case, complete drying of the composition, re-wetting to mouldability,
compaction into the case rim and re-drying. Unless otherwise indicated, re-
acting components react in stoichiometric proportions and mixing of materials
was effected in the case, usually by vibration thereof.
Test 1: 5.4 mg of sodium azide, of particle size lower than 100 mesh, weEe
mixed in powder form wi-th 5.LI mg of powdered glass, and this dose was in-

serted into a .22 rimfire cartridge case. 10.8 ~1. of lead nitrate were added
to the case in a 50% solution. The sodium azide and lead nitrate reacted in
the case to produce lead azide and sodium nitrate. The resulting composition
was dried but was not spun into the rim of the case. ~`
This mixture involved a subs-tantial excess of sodium azide over
lead nitrate relative to stoichiometric proportions. Nevertheless, in sen-
sitivity tests~ the mean fire height for primed cases was 6.2" 0.7".
Test 2: 3.5 mg of sodium azide mixed with 3.5 mg of powdered glass were
provided in a rimfire cartridge case and dosed with 17.8 ~1. of a 50% solu-
- 22 -

~`v~


tion of lead nitrate. The mean fire height was 4.63" - 0.7".
Test 3: 7.7 mg of a powder having the following proportions by weight were
located in a rimfire cartridge case:-
sodium azide 50%
powdered glass 25%
antimony sulphide 25%
20 ~1 of 50% lcad nitrate solution were dosed into the case. The resulting
mean fire height was 6.4" - 1.78", and it was noted -that the composition pro-
duced more flame than that given in Tes-t 2. This latter result is to be ex-
pected because of the addition of the antimony sulphide. This type of com-
position would be suitable for use in a shotgun cap shell.
Test 4 4 . 5 mg of powdered glass were fed into a rimfire cartridge case.
12. 5 ~1 of a 28% solution of sodium azide were then dosed into the case, and
were followed by 18 ~1 of a 50% solution of lead nitrate. The case was vi-
brated during addition of the solutions, but the resulting composition was
not spun into the rim. The composition was -thoroughly dried.
The resulting mean fire height was 7.1" - 2.3". However, after
addition of 4 ~1 of water, the resulting mouldable composition was spun into
the rim of the case head, and the mean fire height, after drying, was mea-
sured at 5.1" - 0.89". Cases treated in this way gave an "all fire" height
of 9" for a batch of 50 cases.
Test 5: 16 mg of a dry powder of the following weight proportions were in-
serted into a rimfire cartridge case after thorough mixing:-
lead nitrate 53%
sodium azide 20%
powdered glass 27%
This powder was wetted with 2.4 mg (15 weight %), of water and the resul-ting
composition was spun into the rim of the head, and then dried. The composi-
-- 23 --


. .
.. . . . - . .


: ' .: ~ ' . , ~ . , . . ' , . '. ,, -: . ~ ` ,. : ~ ,~ ,
.: .. . . : ,
... . .
:, . .: ,, . , : :.

tion was observed to be somewhat powdery, and it is believed that insuffi-
cient water had been added to ensure complete reaction. Nevertheless, cases
primed by this method could be fired and the mean fire height was measured

at 10. 2" - 1.28" .
Test 6: 4 mg of powdered glass were metered into a rimfire cartridge case,
and the~ollowing solutions were added in the order indicated:-
a) 12 ~l lead nitrate solu-tion containing 6 mg of solid, and
b) 24 ~1 barium azide solution containing 4 mg of solid.
The mean fire height was calculated at 6.45" - 1.08".
Test 7: 9.3 mg of powder, comprising 6.7 mg of lead hypophosphite and the
remainder powdered glass, were metered into a rimfire case. 9. 5 ~1 of a 28
solution of sodium azide were added to the powder, giving a total priming
weight of 12 mg.
The mean fire height was calculated as 9.35" - 3.34". It was ob-
served -that -this composition gave a large flame, indicating that it may be
suitable for use in priming of cap shells for shotgun cartridges.
Test 8: As Test 7, but with 26.5 ~1 of barium azide solution (concentra-tion
166 grammes per litre) substituted for the sodium azide, giving a total prim-
ing weight of 14 mg.
The mean fire height was calculated at 6.95" - 1.26". Again, a
large flame was observed on ini-tiation of this composition.
Test 9: 13 mg of a powder, comprising a 50:50 mixture of lead nitrate and
powdered glass, were dosed into a rimfire case, and 9 ~1 of a 28~ solution
of sodium azide were added. The total priming weight was 15 1/2 mg.
The mean fire height was calculated at 5.2" - 0.99".
Teæt 10: As Test 9, but with 4.4 mg of barium azide, in the lowest quantity
of water capable of taking the azide into solution, substituted for the so-
dium azide.
- 24 -


.. . . ..
. . .: . ~ .: . ,

,,
,.
::

' ' ; ~ ~ ' '' ' '' ~.


The mean ~lre height was calcula-ted at 4.5" - 1.59".
In Test 6 above, barium azide and lead nitrate will react to pro-
duce lead azide and barium nitrate. The latter is the oxidiser used in con-
ventional priming compositions, but lead azide does not require an oxidiser.
A diluent may be required to reduce the explosive violence o~ the azide, and
barium nitra-te can function in -this fashion. Sodium nitrate produced in the
reaction o~ lead nitrate with sodium azide can ~unction similarly to barium
nitrate. The oxidiser can also supply oxygen to subsidiary fuels such as
antimony sulphide.
Use~ul azides are not limited to these cited above. Theoretically,
alternative heavy metals may be used, although lead is virtually universal
in practice. Alternative lead salts may be used as a reaction componen-t, and
soluble lead salts are pre~erred. In particular, lead acetate is a possible
alternative to lead nitrate, since it is conventionally used in production o~
lead azide. The resulting sodium acetate would not function as an oxidiser,
but it would ~unction as a moderator in the manner discussed above. Other
soluble lead sal-ts are:- chlorates, citrates, isobutyra-tes, lactates, ni-t-
rites, peroxydisulphates and dithionates. However, lead chlora-te should not
be used in production of priming composition ~or ammunition, since combus-tion
o~ a chlorate would produce chloride ions which would cause rusting o~ a gun
barrel.
It is most convenient to form the priming explosive in an aqueous
medium, but-this is not essential. In the Tests given above, the reac-tions
occurred at room temperature, but this is also not essential. However, it
is pre~erred no-t to reduce reaction tempera-tures since this lowers solubility
o~ the components in water and necessitates extra water in the case. In the
above Tests, no particular steps were taken to control -the pH o~ the reacting
mixture and a suitable pH value can be established empirically~
- 25 -




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.' : ' :' , . . : .. ' . '''' :, ' : .

'~13E~6~

In Tests 7 and 8, it is believed that the sodium and barium azidesundergo double decomposition with the lead hypophosphi-te -to produce lead




_ 25a -




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..
" , " ~ "' " ', " ' ' . , ' ' .:
.
- ' ' ~ ' . . ': ': ' :~,


azide and sodium or barium hypophosphite. However, it is possible
that a sodium or barium a~ide: lead hypophosphite double salt is
formed and provides the or an explosive ingredient in the compo-
sition. The Eormation of such a double salt alls within the
scope of the present invention as exemplified by Example 2 above.
By way of example, embodiments of apparatus in accordance
with the invention will now be described with reference to the
accompanying diagrammatic drawings in which:
Figure 1 is a plan view of an ammunition priming apparatus
in accordance with the invention; and
Figures 2 to 4 are diagrams of different feed systems for
use in continuous production techniques according to the invention
Figure 1 illustrates a series of rotatableJ pocketed
modules, three of which are shown at 10, 12 and 14 respectively.
The use of such modules enables different process times to be
accommodated on different modules while permitting uniform motion
of transported articles through the transport system as a whole,
i.e. without acceleration and deceleration.
Module 10 accepts rimfire cartridge cases from a suitable
feed indicated by arrow 16 and passes them at a predetermined
rate to module 12. Here, each case receives a predetermined dose
of a first component required for a chemical reaction to produce
a primary explosive, as indicated by arrow 18. The cases are then
passed in succession to module 14, where they receive a predeter-
mined dose of a second component required to produce the explos-
ive, as indicated by arrow 20. At least one of these modules
will dispense a liquid, preferably comprising water. One or both
_ 26 -




::: . .
.~ . . . . .. :
. .

- ,. : ' . :

of the modules may dispense ingredients of a priming composition
in addition to components which are to react in the case to form
a primary explosive.
Further processing depends on the chemistry of the re-
action involved. If required, mixing means may be used to mix
the materials in the case. There may be means for removing ex-
cess liquid in the case when it is no longer required for the re-
action. In any even~, the cases are finally passed to an oven9
diagrammatically indicated at 22, where the composition in the
cases is dried out. The dried primed cases may then be passed to
a line, preferably automated, for propellant charging and inser-
tion of the bullet, if the cartridge is not a blank.
Figures 2 to 4 show diagrammatically possible general ~ -
layouts of feed systems for use in continuous production tech-
niques according to the invention.
In the first embodiment shown in Figure 2 ingredients
that are to form part of a priming composition are fed along
paths 110 and 112 to a mixing ~one 114. Each ingredient is rel-
atively insensitive. Relatively insensitive components that will
react to produce a primary explosive are included respectively
in path 110 and path 112. It will be understood that two paths
are shown only as an example: there may be any number of incom-
ing flow paths, for example, one for each ingredient of the mix-
ture other than the sensitive explosive3 and one each for the
components required to produce the explosive. Preferably, how-
ever, the ingredients and components on the flow paths have been
premixed where that is possible. The ingredients and components
~ 27 -




.~ ,,


.. :
: ., . . : - ~ .

... . . i,. ~. . . .

, `' :: '; ~ ~ '

9~

are mixed in small quantities in the zone 114, and in the illus-
trated example they are immediately dispensed from that zone in
predetermined small quantities into a series of containers such
as the rimfire cartridge case indicated at 116.
There may be a suitable dispenser diagrammatically indi-
cated at 118 for controlling the quantity of mixture passed from
the zone 11~ to each case 116. Alternatively or in addition
there may be control gates 120, 122 in the flow lines 110, 112
for controlling feed of materials to the mixing zone.




- 27a -



~:c



: ... .. .
- . - - . .

': : . : ' . :'

In an alternative arrangement shown in Figure 3, the materials are
circulated continuously on closed flow paths 124, 126. The mixing zone is
indicated at 128 and there are controllable tapping devices 130, 132 for tap-
ping controlled quan-tities of ingredien-ts from the closed paths 124, 126
into the zone 128. Zone 128 has a dispensing outlet 13ll for supplying mix-
utre to a cartridge case, cap shell or detonator case. There must be suit-
able means for feeding material into each closed path to make up that tapped
off.
This aspect of the invention is not limited to immedia-te dispens-

ing of the formed mixture, nor to a "localised" mixing zone such as thatshown in Figures 2 and 3. Instead, ingredients may be fed on flow paths 136,
138 shown in Figure 4, to one end of a tubular mixing zone 140. Tube 140 may
be formed as a "Static Mixer" as supplied by Kenics Corporation of Danvers,
Massachusetts, United States of America. Such a mixer is described in the
June 1970 issue of Chemical and Process Engineering in an article entitled
"Static Mixer".
In any process in which the mixture is not to be supplied immediate-
ly to containers such as cases or cap shells, it may be pumped along a duct-
ing system. Such a system may have barriers at intervals along its length
dividing it into predetermined regions so that an explosion in the sys-tem
will be localised between explosion barriers. The cross-section of -the
stream may be such that it can be divided transversely for dispensing into
containers. However, division of the stream into predetermined quantities
may be effected by any suitable dispensing device a-t the output end.
In Figure 2, relatively insensitive materials may be gated into
the mixing zone in predetermined porportions appropriate to an individual
utilisation demand. The mixture may be immediately dispensed


- - 28 -


: : :

. .


. ~ ,'. , .


and further similar quantities gated into the mixing ~one. The
embodiment of Figure 3 may be operated in a similar mannerO Al-
ternatively, the dispenser at the outlet from the mixing zone in
either embodiment may be arranged to divide the mixture between a
series of devices. In any of the embodiments illustrated in
Figures 2 to 4, the output rate is substantially matched to the
demand rate on a production line for explosive devices continu-
ous with the illustrated apparatus.
The invention is not limited to details of the illustrated
methods and the explosiv0s referred to in the EXAMPLES.
In some instances, it may be found that deliberate mixing
of materials is unnecessary. For example, if at least one mat-
erial goes into solution which will penetrate a body of another
material without mixing, then a deliberate mixing step can be
omitted. In general, however, it will be preferable to include
deliberate mixing to ensure complete reaction.
Regarding the selection of a primary explosive, this must
depend upon the required conditions of production and use, bear-
ing in mind the criteria already set out above. The double salt
lead nitrate hypophosphite is a particularly desirable ammunition
priming explosive from the point of view of most of the criteria
for both reaction and productO It can be produced by a simple,
speedy reaction between lead nitrate and lead hypophosphite, both
of which are compatible with a brass rimfire cartridge case.
There are no by-products, and the starting materials are both non-
explosive. The product is sensitive, and compatible with the
container and propellant. It is capable of initiating propellant
- 29 -


. . :


- . . . . - . - . - : . . . - . : . : ,


', , . . . ~ ;. . . . . :: . ' ~ , :
.. . . .. .. ::. . , :.

powders. It has been found ~o give some difficulties in connec-
tion with humid storage conditions. However, these can be dealt
with by application of a sealing material, e.g. a bituminous
material, to the join between the bullet and a cartridge case.
A suitable material has been found to be "Ritolastic" produced
by Lancashire Tar Distillers Building Products of Church Road,
Litherland, Liverpool.
The acid-base reaction for production of lead styphnate
also satisfied the above requirements, and has the advantage that
it produces a product in close accordance with conventional prim-
ing compositions and which is known to be relatively insensitive
to humid s~orage conditions. This route is therefore preferable
to the lead nitrate/sodium styphnate route since the sodium nit-
rate produced by the latter route is hygroscopic. There is one
difficulty in the production of styphnates by either of the chem-
ical routes referred to, namely the necessity to incorporate
tetrazene to obtain required sensitivity in the product. Tetra-
zene is itself a sensitive primary explosive, and must therefore
be used in very low quantities in the feed stocks. Where one of
these feed stocks is in the form of a liquid, the tetrazene may
be included in that liquid as a dispersion and suitable dispersing
agents may be included in the solution to aid this. It would
however be desirable to substitute an alternative sensitiser for
the tetrazene if possible. Lead nitrate hypophosphite could be
produced simultaneously with lead styphnate, particularly where
a double decomposition reaction involving lead nitrate is used.
Lead azide satisfies most requirements, but is known to
30 -




~, ~



,
., . , ~ .. .
.
.: . , :
, , ' :
:. . : - ..


give corrosion difficulties when used in copper alloy containers
such as brass cartridge cases. It then produces a copper azide
through reaction with the copper in the alloy case, and this is
itself a sensitive initiating material.
It should be mentioned however that a reaction in accord-
ance with this invention does not have to take place in the final
container. It could occur in another type of receiver which may
be designed to apply




_ 30a -

~-................................................................... ' ' .




. . " - . .. . ...


less stringent requirements on the reaction conditions. ~he formation of
explosive could even be completed in such a receiver and -the resultant "pel-
let" passed on for charging to the final container. Where explosive is pro
duced Oll or around a carrier, for example the bridgewire of a detonator
matchhead, the carrier could project into a receiver of this type. In some
instances, i-t may be possible to remove by-products which would o-therwise be
deleterious, for example if they were soluble in the reaction liquid which
could be decanted, drained away or sucked out of the receiver.
~here are further aspects of certain embodiments described above
which distinguish -them from the prior art referred to throughout the spec-
ifica-tion.
In a first aspect, an explosive is permitted to form freely, par-
ticularly, but not essentially, without interference with its crystal form.
We have already referred above to the free formation of lead nitrate hypo-
phosphite crystals, and compared this with the stirring suggested in United
States Specifica-tion 2,160,469. We have also referred to the avoidance of
the necessity to form "free flowing" and "reduced sensitivity" crystal forms
of azides and styphnates - for example as described in ~ritish Patent Spec-
ifications 1,336,561 and 519,340. Such crystal modification techniques are
not excluded from the present invention, but they may prove unnecessary if
the present proposals are adopted.




~ 31 _



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The priming of explosive devices according to the method
of the invention may, therefore) involve producing a priming ex-
plosive comprising a "multiple" salt of a hypophosphite, partic-
ularly where the multiple salt has been permitted to crystallise
freely during its formation. In the present specification the
term "multiple" salt is used to indicate a salt produced by co-
crystallisation of two or more component salts. Such a multiple
salt may be used with another explosive, for example a styphnate
which may be formed simultaneously, for example in situ~ with the
multiple salt.
We have established that it is not essential to mix the
components of lead nitrate-hypophosphite to obtain a satisfactory
product, although mixing will give added assurance of a uniform
product in large scale production of explosive devices. It ap-
pears that a solution containing at least one component can dif-
fuse through a body of undissolved material to produce the double
salt. Since only small quantities of material are involved in
the preferred embodiment the degree of diffusion is usually suf-
ficient to give the required resultO
The priming explosive may be a composition including
other, preferably non-explosive, materials, for example a fric--
tionator and/or a fuel. The multiple salt preferably comprises a
nitrate component and a hypophosphite component. Preferably both
components are lead salts~
Such a priming explosive may advantageously be used with
a nitrocellulose-based propellant. The propellant may be in the
form of discs, for example as supplied by Imperial Chemical
- 32 -
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Industries Limited under the name "Acurex". The propellant may,
however, alternatively be in the form of ball, flake or military
powders. Alternatively, such a priming explosive may be used in
priming detonators and may then be used with a secondary charge
of a detonator. This may be a base charge, for example tetryl or
PLTN.
In a second aspect, at least some by-products of an inter-
action which produces an explosive are retained in an explosive
composition. We have referred above to the ability to retain by-

products in some circumstances, particularly where they can actas an oxidiser or at least as a desired diluent.
The by-product preferably forms a substantially anhydrous
crystal, and preferably has a low degree of hygroscopicity. It
is preferably a nitrate where it is required to act as an oxidis-
er. However, there are other requirements which may have to be
met. For example, in the double decomposition reaction for pro-
duction of styphnates the styphnate feedstock should be as sol-
uble as possible. Sodium styphnate has an acceptable solubility,
and sodium nitrate performs satisfactorily as an oxidiser in a
mixture containing lead sytphnate, replacing the conventioanl
barium nitrate, Potassium and ammonium styphnate are also satis-
factory on the basis of solubility, but potassium and ammonium
nitrate have not performed satisfactorily as oxidisers. Magnes-
ium styphnate is the most soluble, but magnesium nitra~e includes
a substantial quantity of water of crystallisation, which is dif-
ficu]t to remove.
It is not necessary for the double decomposition reaction
- 33 -




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to provide all of the oxidiser required in a composition. For
example, a conventional oxidiser such as barium nitrate could be
added to a composition after formation of a heavy metal styphnate
therein. Addition of barium nitrate at an early stage in such a
reaction may result in the formation of barium styphnate which is
an insensitive explosive relative to lead styphnate.
An explosive and by-product may be produced in a mixture
of other ingredients, which may include each or either of a fric-
tionator and a fuel. Alternatively, other ingredients may be
added to the composition after the explosive and by-product have
been produced.
The nature of the explosive will depend to some extent
upon the intended use. For example, where it is required to
initiate a low explosive, including propellants such as ball,
flake, disc and military powders which usually include nitro-
cellulose and may be of single, double or triple base type, the
priming explosive is required to ignite the low explosive and
not to cause it to detonate. The priming explosive is therefore
required to produce flame, and/or heat and/or sparks, and may not
be itself a detonating explosive. Where the priming explosive
is intended to initiate a high explosive, for example the base
charge of a detonator, it will usually be required to produce a
shock, and a detonating initiator will then be required. An
actual detonator may have two or more primary charges, for ex-
ample a matchhead sensitive to heat produced by electric currents
and a priming charge sensitive to a spit from the match head.
Both of these primary charges may be produced by techniques in
- 3~ -




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accordance with the invention.
In any event~ priming explosive produced in a method of
the inventioll should be capable of initiating finished explosive
devices. Such devices will usually be arranged to produce sub-
stantial quantities of energy, for example in the form of heat
and/or gas and/or shock. All reasonable precautions must be
taken to ensure that such devices are not initiated except in
response to a predetermined event or events, and this can be done
by suitable choice of priming explosive and/or suitable choice
of container therefor.
The invention is intended for use in manufacture of
finished explosive devices and partly finished devices, for
example initiating devices such as caps. Manufacturing processes
will usually involve continuous or semi-continuous repetitive
operation over a substantial period, with a substantial total
output demand over that period. The invention enables production
of priming explosive to be spread over the relevant period in-
stead of concentrating it, thus avoiding production and storage
hazards. Thus, the rate of production of priming explosive in
a method in accordance with the invention is substantially
matched with the demand, although it may be acceptable if there
is a small deficit or a small surplus which could be handled by
a relatively simple explosive magazine. For manufacturing pur-
poses, it is desirable that chemical reactions involved should
be easily reproduceable with consistently reliable results.




- - 35 -

Representative Drawing

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Administrative Status

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Administrative Status

Title Date
Forecasted Issue Date 1980-11-18
(22) Filed 1976-09-10
(45) Issued 1980-11-18
Expired 1997-11-18

Abandonment History

There is no abandonment history.

Payment History

Fee Type Anniversary Year Due Date Amount Paid Paid Date
Application Fee $0.00 1976-09-10
Owners on Record

Note: Records showing the ownership history in alphabetical order.

Current Owners on Record
IMI KYNOCH LIMITED
Past Owners on Record
None
Past Owners that do not appear in the "Owners on Record" listing will appear in other documentation within the application.
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Document
Description 
Date
(yyyy-mm-dd) 
Number of pages   Size of Image (KB) 
Drawings 1994-04-13 1 26
Claims 1994-04-13 4 128
Abstract 1994-04-13 1 11
Cover Page 1994-04-13 1 27
Description 1994-04-13 39 1,582