Patented Got.
1%, 1939
. entree STATES PATENT OFFICE
2,175,826
CHEMICAL COMPOUNDS
Willi Brun, Bridgeport, Com, assignor to Rem
ington Arms Company, Inc., a corporation of
Delaware
No Drawing. Application August 26, 1937,‘
, Serial No. 161,031
5 Claims.
This invention relates to certain new compo
sitions of matter of an explosive character and
the use'of such compositions in detonators and
ammunition priming compositions.
In. patent application Serial No. '122,240 ?led‘ the formation of a double salt of the metal pres- 5
April 25, 1934, now Patent No. 2,116,878, May 10,
1938, by Brun and Burns there is disclosed the’
use, as an ingredient of ammunition priming mix
tures, of a reaction product of lead nitrate vand
lead hypophosphite, this product probably being
‘ a double salt of lead nitrate and lead hypophos
phite in molecular proportions. It is identi?ed
in said patent as lead nitrato hypophosphite, and
is preferably prepared by ?rst mixing lead nitrate
15 and lead hypophosphite in a dry condition and
subsequently moistening the mixture. This
. compound contains in the same crystal both an
oxidizer and a fuel which tend to react with each
other under such a stimulus as a comparatively
20 light blow. The use of compounds of this char
acter in ammunition priming mixtures is very
advantageous since the usual intergranular space
separating fuel and oxidizer is wholly eliminated.
The present invention comprises the discovery
25 of certain other compositions which, like lead ni
trato hypophosphite, probably are or contain
complex compounds having within each crystal
both a fuel and an oxidizer. ‘They are likewise I
similar to lead nitrato hypophosphite in that
30 they are formed by the reaction of a nitrate and
a hypophosphite, and preferably in the presence
of a quantity of water inadequate to e?ect com
plete solution. ' _
The most desirable'nitrates are those of lead
35 and calcium. A nitrate of mercury may be used
with non-alkaline hypophosphites. Withcalcium
nitrate‘ or lead nitrate there may be combined
any solublehypophos‘phite, ‘such as a hypophos
phite of ammonia, potassium, sodium, calcium,
strontium, barium, manganese, or lead. Each of
the resulting compositions has certain character
istics which associate it with the nitrate from
which it is derived. The group of nitrato hypo
phosphites derived from lead nitrate all exhibit
45 certain properties which are characteristic of
lead nitrato-lead hypophosphite, while each of
those derived from calcium nitrate exhibit prop
erties which are characteristic of calcium nitrato
‘calcium hypophosphite. However, each individ
ual member of each group possesses properties
which quite de?nitely identify it as a composi
tion of matter distinct. from all other members of
either group. The reaction between the ingre
dients is probably incomplete especially under
the method of ?rst preparing a dry mixture of
55
2,175,826
(Cl- 52-4)
the reacting ingredients and subsequently mois
tening the dry mixture with a quantity of water
inadequate to bring about complete solution.
The. group characteristics are probably due to
ent in the nitrate; for grample, lead nitrato hy
pophosphite has been quite de?nitely identi?ed
in the reaction product of lead nitrate and cal
cium hypophosphite, and indthe reaction product
of lead nitrate and strontium hypophosphite. 10
This reaction product possesses properties of ex
plosiveness and stability quite similar to the prop
erties of lead nitrato hypophosphite itself. It is
non-hygroscopic, retaining its crystalline and.
explosive character after prolonged exposure to 15
conditions of high humidity and temperature.
This fact is surprising since theoretically a re
action resulting in the formation of lead nitrato
hypophosphite should leave a residue’ of hygro
scopic calcium nitrate. In ammunition priming 20
mixtures the product performs the same func
tion as lead nitrato hypophosphite produced in
the usual manner. The calcium is apparently
combined in some crystalline non-hygroscopic
salt, which may be calcium nitrato hypophos- 25
phite. The formation of this compound is theo
retically possible according to the equation:
30
X-ray diffraction pictures show lines which are
characteristic of lead nitrato hypophosphite.
‘
They do not show lines associated with calcium
nitrato hypophosphitebut this may be due to the
extreniely high absorption of X-rays by lead 35
compounds, and their comparatively slight ab
sorption by calcium compounds. » -
The reaction product of calcium nitrate and
lead hypophosphite possesses properties which
di?’er substantially from the properties of the re- 40
action product of lead nitrate and calcium hypo
phosphite; both being prepared by the technic of
moistening dry mixtures of the reacting mate
rials with a quantity of water insuf?cient to e?ect
complete solution. In the reaction product of 45
calcium nitrate and lead hypophosphite thus
treated, both lead nitrate and calcium nitrato
calcium hypophosphite have been identi?ed.
The product has something of the hygroscopic
nature which is characteristic of calcium nitrate 60
and appears to be somewhat less desirable as an
‘explosive than the reaction product of lead ni
trate and calcium hypophosphite. The same is
generally ‘true of the reaction products of the
nitrates oi lead and calcium respectively with the 55
 2,175,826
soluble hypophosphites heretofore mentioned.
The reaction product of each of the hypophos
phites with lead nitrate appears to contain lead
nitrate hypophosphite, each maybe exploded by
?ame or impact, and each is substantially non-é
hygroscopic. . The metal of .the hypophosphite
used, like the calcium in the reaction product
of lead nitrate and calcium hypophosphite, is
present in an unidenti?ed ‘but stable form.
The above-mentioned compositions of matter,
particularly the reaction product of lead nitrate
and calcium hypophosphite, have been found to
serve the same purposes as lead nitrato hypophos
phite in ammunition priming mixtures and deto~
15 nators, particularly detonators for such purposes
as seismographic work.
A composition in accordance with the present
‘invention may be prepared as follows: Dry cal
cium hypophosphite and dry lead nitrate of suit
able granulation are thoroughly mixed in the pro
' 20'
portions of 1.7 grams of calcium hypophosphite to
3.3 grams of lead nitrate. After thorough dry
- mixing, a quantity of water is added which is I uses for such compositions, the appended claims
su?‘icient to completely wet the mixture without
25 completely dissolving its components. The mois
tened mixture is then thoroughly kneaded. After
about two minutes of kneading the granular
'structure of the mixture begins to disappear.
There is a loss in volume and a cement-like paste
341) is formed. The kneading is continued during the
formation of this paste to prevent the setting
of the composition into a rock-like mass and until
the mixture is of uniform texture throughout.
‘The occurrence of a reaction and'the presence of
35 a reaction product are established by the change
in texture and the loss in volume as well as by the
behavior of the product when smeared ona plate.
The moisture of the smear quickly evaporates
leaving a ?nely crystalline residue.
40 After drying, the composition prepared in the
manner above described may be used in ammuni
tion priming mixtures and detonators in the same
manner as lead nitrato hypophosphite. Am
munition priming mixtures may also be prepared
45 according to the method described in the above
mentioned patent, that is, by preparing a dry pre
mix of lead nitrate and calcium hypophosphite
with the inert ingredients of a priming mixture,
adding to the dry pre-mix an explosive ingredient
to and the requisite amount of water and kneading
the mixture until the completion of the reaction
between the lead nitrate and the calcium'hypo
phosphite; for example, the pre-mix may com
prise 5 to 25 parts of calcium hypophosphite, 10 to
50 parts of lead nitrate, 6 to 12 parts of lead sulfo
cyanate, and 12 to 25 parts of glass. To this pre
mix is added 20 to 40 parts of such an explosive as
. ,
lead styphnate and the amount of water neces
sary to produce a mixture of the desired consist
ency. A speci?c example of such a mixture is as
' follows:
, _ Parts 5
Lead styphnate _________________________ _._ 33
Calcium hypophosphite __________________ __ 7
Lead nitrate _' __________________________ __-_ M
Lead sulfocyanata"; _________ __, ________ __ 10
Glass / 20 10
Barium nitrate 16
Mention has been made above of the double salt
of calcium nitrate and calcium hypophosphite
called, for convenience, “calcium nitrato hypo
phosphite.” This compound has been identi?ed 15
by its X-ray di?’raction picture in the reaction
product of calcium ‘nitrate and calcium hypophos
phite, mixed dry and moistened with a quantity of
water insuilicient to effect complete solution.
Applicant having disclosed compositions of mat 20
ter which are wholly new in themselves, as-well as
are to be broadly construed.
What is claimed is:
1. .An explosive composition of matter which is 25
the product of the reaction resulting from the
moistening without complete solution of a dry
mixture of a nitrate selected from the group con
sisting of the nitrates of lead and calcium, with a 30
hypophosphite selected from the group consisting
of the hypophosphites of potassium, sodium, cal
cium, strontium, ammonia, barium, and manga
nese. ' "
2. An ammunition priming mixture containing
an explosive composition of matter which is the
product of the reactionlresulting from the mois
tening without completesolution of a dry mixture ‘
of a nitrate selected from the group consisting of
the nitrates of lead and calcium, with a hypo 40
phosphite selected from the group consisting of
the hypophosphites of potassium, sodium, cal
cium, strontium, ammonia, barium, and manga
nese.
3. The explosive composition of matter calcium 45
nitrato calcium hypophosphite.
4. An explosive composition of matter which is
the product of the reaction resulting from the '
moistening with a quantity of water insu?icient
to effect complete solution of a dry mixture of
lead nitrate and calcium hypophosphite.
5. An ammunition priming mixture containing
an explosive composition of matter which is the
reaction product resulting from the moistening
with a; quantity of water insu?icient to e?ect'
complete solution of a dry mixture of lead nitrate
and calcium hypophosphite.
WILLI BRUN.