CA1168052A - Poly-base propellant - Google Patents
Poly-base propellantInfo
- Publication number
- CA1168052A CA1168052A CA000342521A CA342521A CA1168052A CA 1168052 A CA1168052 A CA 1168052A CA 000342521 A CA000342521 A CA 000342521A CA 342521 A CA342521 A CA 342521A CA 1168052 A CA1168052 A CA 1168052A
- Authority
- CA
- Canada
- Prior art keywords
- propellant charge
- weight
- blasting
- nitrocellulose
- charge powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B25/00—Compositions containing a nitrated organic compound
- C06B25/18—Compositions containing a nitrated organic compound the compound being nitrocellulose present as 10% or more by weight of the total composition
- C06B25/24—Compositions containing a nitrated organic compound the compound being nitrocellulose present as 10% or more by weight of the total composition with nitroglycerine
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- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Medicinal Preparation (AREA)
- Fats And Perfumes (AREA)
- Electrostatic Spraying Apparatus (AREA)
- Powder Metallurgy (AREA)
- Developing Agents For Electrophotography (AREA)
- Cosmetics (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A multi-base propellant charge powder for tubular weapons and missiles is disclosed, which contains two or more blasting oils having different energy contents in addition to nitrocellulose and optionally at least one other nitro compound as energy carrier. It is possible to adjust any desired heat of explosion within a wide energy range without using energy-consuming materials, by suitable calculation of the proportions of the various blasting oils. In addition, the migration of the blasting oil into the combustible shell material of ammunition cartridges is clearly less than with propellant charge powders containing only one blasting oil.
A multi-base propellant charge powder for tubular weapons and missiles is disclosed, which contains two or more blasting oils having different energy contents in addition to nitrocellulose and optionally at least one other nitro compound as energy carrier. It is possible to adjust any desired heat of explosion within a wide energy range without using energy-consuming materials, by suitable calculation of the proportions of the various blasting oils. In addition, the migration of the blasting oil into the combustible shell material of ammunition cartridges is clearly less than with propellant charge powders containing only one blasting oil.
Description
3 1 ~052 BACKGROUND OF THE INVENTION
Field of the Invention This invention relàtes to a poly- or multi-base-propellant charge powder for tubular weapons and missiles with nitro-cellulose, blasting oils, and optionally other nitro compounds as energy carriers.
Desciption of the Prior Art_ The purpose of the blasting oil in multi-bas~
propellant charge powders of this type is to increase the energy content of the propellant charge powder, which is characterised by the heat of explosion, above a value which can be reached by using so-called mono base powders consisting substantially only of nitrocellulose. The value of the heat of explosion corresponds in practical terms to the energy content of the nitrocellulose itself (eg approx.
4000 j!g). In addition, the blasting oil is used as a gelatinator for nitrocellulose. Occasionally, oils which ) are used to cause the nitrocellulose to gelatinate, but which have an energy content of less or at best equal to that of the lowest nitrated nitrocellulose, which is still used for powders, are not called blasting oils because of the energy increase which is aimed for.
The following alcohol nitrates are technically important blasting oils in the above sense:
25 Nitroglycerine tH2 ~ ~ NO2 heat of explosion (= NGL) CH - ~ NO2 6322 J/g CH2 - - NO2 oxygen value + 3.5 .~, . . .
.~
~ ~ 6805~
.
Diethylene glycol CH2 - 0 - N02 heat of explosion dinitrate CH2 4~57 J/g (= ~iglycol dinitrate CH2 oxygen value - 40.8 5 = DEGN) CH2 ~ ~ NO2 ' ' ' 1,2,4-butane triol CH2 ~ ~ NO2 hea~ of explosion trinitrate CH2 5945 J/g CH2 - 0 - N02 oxygen value -16.6
Field of the Invention This invention relàtes to a poly- or multi-base-propellant charge powder for tubular weapons and missiles with nitro-cellulose, blasting oils, and optionally other nitro compounds as energy carriers.
Desciption of the Prior Art_ The purpose of the blasting oil in multi-bas~
propellant charge powders of this type is to increase the energy content of the propellant charge powder, which is characterised by the heat of explosion, above a value which can be reached by using so-called mono base powders consisting substantially only of nitrocellulose. The value of the heat of explosion corresponds in practical terms to the energy content of the nitrocellulose itself (eg approx.
4000 j!g). In addition, the blasting oil is used as a gelatinator for nitrocellulose. Occasionally, oils which ) are used to cause the nitrocellulose to gelatinate, but which have an energy content of less or at best equal to that of the lowest nitrated nitrocellulose, which is still used for powders, are not called blasting oils because of the energy increase which is aimed for.
The following alcohol nitrates are technically important blasting oils in the above sense:
25 Nitroglycerine tH2 ~ ~ NO2 heat of explosion (= NGL) CH - ~ NO2 6322 J/g CH2 - - NO2 oxygen value + 3.5 .~, . . .
.~
~ ~ 6805~
.
Diethylene glycol CH2 - 0 - N02 heat of explosion dinitrate CH2 4~57 J/g (= ~iglycol dinitrate CH2 oxygen value - 40.8 5 = DEGN) CH2 ~ ~ NO2 ' ' ' 1,2,4-butane triol CH2 ~ ~ NO2 hea~ of explosion trinitrate CH2 5945 J/g CH2 - 0 - N02 oxygen value -16.6
2 N 2 .
10 Methriol trinitrate CH2 - 0 - N02 heat of explosion
10 Methriol trinitrate CH2 - 0 - N02 heat of explosion
3 I CH2 0 - N02 5175 J/g CH2 ~ 0 - N02 oxygen value -34.5 %
Conventlonal propellant charge powders contain a single blasting oil. The blasting oil ~sed in any particular formulation, its content, the nitro-cellulose content and its degree of nitration determine the properties of the propellant charge powder and its behaviour during production. The typical degree of nitration lying between 11.8 and 1~.4 ~ N2 therefore influences the production process and the energy content of the propellant charge powder. l~his applies to a greater extent for the blasting oil which is used in any particular case.
Since the blasting oils differ, for example, in .
. . . . .
~ 3 ~052 the gelling behaviour relative to the nitrocellulose, the heat of explosion and the oxygen value, propellant charge powders having different properties can therefore be produced from them.
The propellant charge powders which are richest in energy are obtained by using nitroglycerine. Thus,.
for example, a double-base propellant cha~ge powder produced with solvent with about 40 ~ of nitroglycerine can be - ~ adjusted to a heat of expiosion of 5,000 j/g. On the other hand, a comparable propellant;charge powder with diglycol dinitrate produces a heat of explosion of .
42~0 J/g~
Taking into consideration the production process ~or a propellant charge powder, the heat of explosion thereof is virtually unable to rise beyond a specific value which is dependent on the blasting oil used at any time. Thus, for example, it ls impossible, wlthout the .. use of solvents, to produce a propellant charge powder containing diglycol dinitrate as blasting oil and having 20 a heat of explosion of 4750 J~y. In the past, it was normalin such cases to adjust the.heat of explosion reguired by using a higher calorific oil, i.e. nitro-glycerine in the example above, and by simultaneously incorporating energy consuming matexials such as, for example, centralite or phthalates. It is necessary to use energy-consuming materials because propellant
Conventlonal propellant charge powders contain a single blasting oil. The blasting oil ~sed in any particular formulation, its content, the nitro-cellulose content and its degree of nitration determine the properties of the propellant charge powder and its behaviour during production. The typical degree of nitration lying between 11.8 and 1~.4 ~ N2 therefore influences the production process and the energy content of the propellant charge powder. l~his applies to a greater extent for the blasting oil which is used in any particular case.
Since the blasting oils differ, for example, in .
. . . . .
~ 3 ~052 the gelling behaviour relative to the nitrocellulose, the heat of explosion and the oxygen value, propellant charge powders having different properties can therefore be produced from them.
The propellant charge powders which are richest in energy are obtained by using nitroglycerine. Thus,.
for example, a double-base propellant cha~ge powder produced with solvent with about 40 ~ of nitroglycerine can be - ~ adjusted to a heat of expiosion of 5,000 j/g. On the other hand, a comparable propellant;charge powder with diglycol dinitrate produces a heat of explosion of .
42~0 J/g~
Taking into consideration the production process ~or a propellant charge powder, the heat of explosion thereof is virtually unable to rise beyond a specific value which is dependent on the blasting oil used at any time. Thus, for example, it ls impossible, wlthout the .. use of solvents, to produce a propellant charge powder containing diglycol dinitrate as blasting oil and having 20 a heat of explosion of 4750 J~y. In the past, it was normalin such cases to adjust the.heat of explosion reguired by using a higher calorific oil, i.e. nitro-glycerine in the example above, and by simultaneously incorporating energy consuming matexials such as, for example, centralite or phthalates. It is necessary to use energy-consuming materials because propellant
- 4 - .
. . .
I ~1 6~52 charge powder demands a specific minimum quantity of blasting oil, i.e. nitroglycerine in the example, for reasons of production, for example its homogenisation and gelatination on hot rolling mills. However, this minimum.
quantity of blasting oil would result in exceeding the required heat of e~plosion if energy-consuming materials were not used. On the other hand, the energy-consuming .. ~ material in the propellant.charge powder can be ballast . for the actual operation thereof, which can adversely affect desired properties of the propellant charge powder under certain circumstances.
The known tri-base propelLant charge powders, for example.nitroguanidinè~containing nitroglycerine powder or nitroguanidine-containing diglycol dinitrate powder, known as gudol powder, also contain only one blasting oil each. When using these tri-base propellant charge powders, it is not therefore possible to adjust a heat of explosion .~ which is predetermined as desired within a considerable range ~ithout energy-consuming materials. The other energy carrier contained in tri-base propellant charge powders, for example nitroguanidine, cannot be used for such adjustment because it does not induce gelatination but instead is a filler which can be incorporated lnto the nLtrocellulose blastlng oil gel only to a limited extent.
. SUMMARY OF THE INVENTION
An object of the invention is to provide a new . O
I ~ 6~52 multi-base propellant charge powder. This powder should, in particular, be adjustable within a wide energy range to a desired hea-t of explosion, be easy to produce and, in addition, also be further improved in its other properties, in particular in its blasting behaviour and its storage ability compared to conventional propellant charge powders.
I'he invention thus provides a multi-base propellant charge powder which contains two or more different blasting oils instead of the conventionally used sinyle, chemically uniform blasting oil.
In accordance with the present invention there is provided a multi-base propellant charge powder for tubular weapons and missiles having a specific, predetermined heat of explosion, comprising nitrocellulose and at least two different blasting oils selected from the group consisting of nitroglycerine, diglycol dinitrate, methriol trinitrate and 1,2,~-butane-triol trinitrate, wherein:
(a) the propellant charge powder is made in a production process without the use of solvents and the total blasting oil content is determined with regard to optimum homogenization and gelatination in the production process, the total blasting oil content amounting at most to 100% by weight, based on the content of nitrocellulose;
and wherein (b) the proportion of higher calorific blasting oils in the total blasting oil content is chosen to produce the specific, predetermined heat of explosion.
In accordance with the present invention there is ~, - -6-~ 3 681)5Z
further provlded a method of producing a multi-base propellant charge powder for tubular weapons and missiles having a specific, predetermined heat of explosion, com-prising the steps of:
(a ? mixing together the components of a raw mixture comprising nitrocellulose and at least two different blasting oils selected from the group consisting of nitro-glycerine, diglycol dinitrate, methriol trinitrate and 1,2,4-butane-triol trinitrate. The total blasting oil con-tent being determined with regard to optimum homogenization and gelatination of the mixture and amounting at most to 100% by weight based on the nitrocellulose content. The higher calorific blasting oils in the total blasting oil content being chosen to produce the specific heat of ex-plosion;
(b) pressing the gelatinized mixture through a die into strands of the desired diameter for use as a propellant charge in ammunition.
DETAILED DESCRIPTION OF THE INVENTION
With the propellant charge powder according to the invention, it is possible in a surprisingly simple way to adjust precisely a specific, predetermined heat of explosion without using energy-consuming materials merely by suitable variation of the proportions of the at least two different blasting oils, which also differ in their energy content. The adaptability resulting from the incorporation of two or more blasting oils allows the precise adjustment of a required heat of explosion, even taking into -6a-.
' I ~ 68052 consideration limits for the composition which are brought about by the production procedure, and taking into consideration other properties which are to be demanded of a propellant charge powder.
Blasting oils which are preferably used for the propellant charge powder according to the invention are ... ~ . 7 .
-6b-~ ` I 16~05Z
nitroglycerine, diglycol dinitrate, methriol trinitrate and 1,2,4-butanetriol trinitrate. With the propellant charge powder according to the invention, it is preferred that the proportion of higher calorific blasting oils in the total blasting oil content is calculated in such a way that a specific, predetermined explosion heat is obtained without energy-consuming ballast materials such as phthalates - or centralites. It is thus advantageous to make the content of lower calorific blasting oils as large as possible and to incorporate higher caloriflc blasting oils into the propellant charge powder only in the quantity needed for obtaining the required heat of explosion, within the limits for the total blasting oil content. The lower limit is generally based on the production process and the upper limit on the properties of the powder. The bonding behaviour, for example, of the blasting oils is also considered with respect to the risk of exudation.
-~ The propellant charge powder according to the invention may be produced solvent-free (solventless ~ procedure~, for example on rolling mills and/or extruders.
The total blasting oil content is preferably determined with règard to optimum homogenization and qelatination in the production process. The total blasting oil-content in this embodiment generally amounts to at most 100 ~ by weight, preferably between 54 % by weight and 82 ~ by weight! based on ~he content of nitrocellulose. The powder ... ...... .... .
_ _ .. . . .. . .. ...
- I 1 68~52 generally contains approximately 33-52 ~ by weight diglycol dinitrate, preferably 41-43 ~ by weight diglycol dinitrate, and approximately 21-30 ~ by weight nitro-glycerine, preferably 24-26 ~ by weight nitroglycerine.
The propellant charge powder may be produced as a double-base or triple-base powder with a limited addition of solvent as gelatination agent (semi-solvent procedure) J
and the total blasting oil content in this case preferably amounts to up to 30 ~ by weight.
The propellant charge powder may also be produced by a conventional solvent process (solvent procedure), in which the total blasting oil content is determined in each case with regard to the heat of explosion to be adjusted and/or the proportion of nitroguanidine or nitramine to be incorporated. In this case the total blasting oil content is preferably`determined in such a way that up to 55 ~ by weight of nitroguanidine or nitra-mines such as hexogen or octogen can ~e incorporated into the nitrocellulose blasting oil gel. The total blasting oil content preferably amounts to up ~o 150 ~ by weight, based on the nitrocellulose content.
The advantageous adjustability of the heat of .
explosion in a propellant charge powder according to the invention is demonstrated by the ~ollowing comparison:
A conventional propellant charge powder A has the .
following composition:
~ .' ' ' .
.
Nitrocellulose with 13.1 ~ N252.00 ~ by weight Nitroglycerine 40.00 ~ by weight Plasticisers
. . .
I ~1 6~52 charge powder demands a specific minimum quantity of blasting oil, i.e. nitroglycerine in the example, for reasons of production, for example its homogenisation and gelatination on hot rolling mills. However, this minimum.
quantity of blasting oil would result in exceeding the required heat of e~plosion if energy-consuming materials were not used. On the other hand, the energy-consuming .. ~ material in the propellant.charge powder can be ballast . for the actual operation thereof, which can adversely affect desired properties of the propellant charge powder under certain circumstances.
The known tri-base propelLant charge powders, for example.nitroguanidinè~containing nitroglycerine powder or nitroguanidine-containing diglycol dinitrate powder, known as gudol powder, also contain only one blasting oil each. When using these tri-base propellant charge powders, it is not therefore possible to adjust a heat of explosion .~ which is predetermined as desired within a considerable range ~ithout energy-consuming materials. The other energy carrier contained in tri-base propellant charge powders, for example nitroguanidine, cannot be used for such adjustment because it does not induce gelatination but instead is a filler which can be incorporated lnto the nLtrocellulose blastlng oil gel only to a limited extent.
. SUMMARY OF THE INVENTION
An object of the invention is to provide a new . O
I ~ 6~52 multi-base propellant charge powder. This powder should, in particular, be adjustable within a wide energy range to a desired hea-t of explosion, be easy to produce and, in addition, also be further improved in its other properties, in particular in its blasting behaviour and its storage ability compared to conventional propellant charge powders.
I'he invention thus provides a multi-base propellant charge powder which contains two or more different blasting oils instead of the conventionally used sinyle, chemically uniform blasting oil.
In accordance with the present invention there is provided a multi-base propellant charge powder for tubular weapons and missiles having a specific, predetermined heat of explosion, comprising nitrocellulose and at least two different blasting oils selected from the group consisting of nitroglycerine, diglycol dinitrate, methriol trinitrate and 1,2,~-butane-triol trinitrate, wherein:
(a) the propellant charge powder is made in a production process without the use of solvents and the total blasting oil content is determined with regard to optimum homogenization and gelatination in the production process, the total blasting oil content amounting at most to 100% by weight, based on the content of nitrocellulose;
and wherein (b) the proportion of higher calorific blasting oils in the total blasting oil content is chosen to produce the specific, predetermined heat of explosion.
In accordance with the present invention there is ~, - -6-~ 3 681)5Z
further provlded a method of producing a multi-base propellant charge powder for tubular weapons and missiles having a specific, predetermined heat of explosion, com-prising the steps of:
(a ? mixing together the components of a raw mixture comprising nitrocellulose and at least two different blasting oils selected from the group consisting of nitro-glycerine, diglycol dinitrate, methriol trinitrate and 1,2,4-butane-triol trinitrate. The total blasting oil con-tent being determined with regard to optimum homogenization and gelatination of the mixture and amounting at most to 100% by weight based on the nitrocellulose content. The higher calorific blasting oils in the total blasting oil content being chosen to produce the specific heat of ex-plosion;
(b) pressing the gelatinized mixture through a die into strands of the desired diameter for use as a propellant charge in ammunition.
DETAILED DESCRIPTION OF THE INVENTION
With the propellant charge powder according to the invention, it is possible in a surprisingly simple way to adjust precisely a specific, predetermined heat of explosion without using energy-consuming materials merely by suitable variation of the proportions of the at least two different blasting oils, which also differ in their energy content. The adaptability resulting from the incorporation of two or more blasting oils allows the precise adjustment of a required heat of explosion, even taking into -6a-.
' I ~ 68052 consideration limits for the composition which are brought about by the production procedure, and taking into consideration other properties which are to be demanded of a propellant charge powder.
Blasting oils which are preferably used for the propellant charge powder according to the invention are ... ~ . 7 .
-6b-~ ` I 16~05Z
nitroglycerine, diglycol dinitrate, methriol trinitrate and 1,2,4-butanetriol trinitrate. With the propellant charge powder according to the invention, it is preferred that the proportion of higher calorific blasting oils in the total blasting oil content is calculated in such a way that a specific, predetermined explosion heat is obtained without energy-consuming ballast materials such as phthalates - or centralites. It is thus advantageous to make the content of lower calorific blasting oils as large as possible and to incorporate higher caloriflc blasting oils into the propellant charge powder only in the quantity needed for obtaining the required heat of explosion, within the limits for the total blasting oil content. The lower limit is generally based on the production process and the upper limit on the properties of the powder. The bonding behaviour, for example, of the blasting oils is also considered with respect to the risk of exudation.
-~ The propellant charge powder according to the invention may be produced solvent-free (solventless ~ procedure~, for example on rolling mills and/or extruders.
The total blasting oil content is preferably determined with règard to optimum homogenization and qelatination in the production process. The total blasting oil-content in this embodiment generally amounts to at most 100 ~ by weight, preferably between 54 % by weight and 82 ~ by weight! based on ~he content of nitrocellulose. The powder ... ...... .... .
_ _ .. . . .. . .. ...
- I 1 68~52 generally contains approximately 33-52 ~ by weight diglycol dinitrate, preferably 41-43 ~ by weight diglycol dinitrate, and approximately 21-30 ~ by weight nitro-glycerine, preferably 24-26 ~ by weight nitroglycerine.
The propellant charge powder may be produced as a double-base or triple-base powder with a limited addition of solvent as gelatination agent (semi-solvent procedure) J
and the total blasting oil content in this case preferably amounts to up to 30 ~ by weight.
The propellant charge powder may also be produced by a conventional solvent process (solvent procedure), in which the total blasting oil content is determined in each case with regard to the heat of explosion to be adjusted and/or the proportion of nitroguanidine or nitramine to be incorporated. In this case the total blasting oil content is preferably`determined in such a way that up to 55 ~ by weight of nitroguanidine or nitra-mines such as hexogen or octogen can ~e incorporated into the nitrocellulose blasting oil gel. The total blasting oil content preferably amounts to up ~o 150 ~ by weight, based on the nitrocellulose content.
The advantageous adjustability of the heat of .
explosion in a propellant charge powder according to the invention is demonstrated by the ~ollowing comparison:
A conventional propellant charge powder A has the .
following composition:
~ .' ' ' .
.
Nitrocellulose with 13.1 ~ N252.00 ~ by weight Nitroglycerine 40.00 ~ by weight Plasticisers
5.50 ~ by welght Stabilisers . . 2.50_% by weiqht ~00.00 ~ by weight The heat of explosion amounts to about 4600 J/g.
A different conventional propellant charge powder B has the following composition:.
: Nitrocellulose with 12.6 ~ N256.00 ~ by weight 10 Nitroglycerine .38.80 % by weight.
- Stabilisers 5.10 ~ by weight Magnesium oxide + Graphite0.10 ~_~y weiqht 100.00 % by weight The heat of explosion amounts to about 4,600 J~g.
A propellant charge powder C according to the invention has the following composition Nitrocellulose with 13.0 ~ N259.50 % by weight Diglycol dinitrate24.80 ~ by weight Nitroglycerine 14.90 ~ by weight 20 Stabilisers 0.70 ~ by weight Magnesium oxide + Graphite0.10 ~ by weight . 100.00 % by weight The heat of explosion again amounts to about 4l600 Joule~g.
The propellant charge powders A and B contain _ g _ l l 6gos2 a much higher proportion of stabilisers and plasticisers and of stabilisers, respectively, than necessary. The excess proportion serves only to consume the energy, ~y means of which the heat of explosion is adjusted to the value indicated. With the propellant charge powder C
according to the invention, however, the same explosion heat is obtained without special energy consumption by the incorporation of two blastlng oils in suitable proportions.
In order to compare the properties of the powders, o ~ the propellant charge powders B and C were inserted in a -105 mm calibre weapon~ In this process, it was found that the propellant charge powder C according to the invention has a much more ~avourable external temperature-pressure behaviour than the propellant charge powder B.
The propellant charge powder B demonstrated a rise in pressure which should be judged as critical at only -40C, but this did not occur under otherwise identical conditions with the propellant charge powder C.
The blasting properties of the propellant charge powders A and C were compared with a 120 mm calibre weapon. It was found that the propellar.t charge powder C according to the invention prod~ced blasting rates which were only achieved by the propellant charge powder A at pressures which were 100 to 200 bar higher.
The propellant charge powder according to the invention with several blasting oils is therefore of .....
_ _ .. .. .... .. . ..
1 1 ~gO52 clear ballistic superiority relative to conventional propellant charge powders.
The propellant charge powder according to the invention exhibits another advantageous property:
Combustible cartridge shells are being used more and more in modern weapon systems instead of the conventional metal cartridges. They consist, for example, ~` of a high proportion of nitrocelluloses and additional neutral fibres, a resin binder and a chemical stabiliser for the nitrocellulose. Owing to their material compositionr they can absorb softeners and blasting oils in contact with propellant charge powders. However, in - order to guarantee that ammunition with combustible casings can be stored for a long time, it is important that the propellant charge powder releases a minimum amount of blasting oil into the casing material.
Examination of the propellant charge powder according to the invention in this respect surprisingly revealed that it releases considerably less polyalcohol nitrate into combustible casing material than conventional propellant charge powders.
In particular, an investigation was carried out with the above-mentioned propellan~ charge powders A and C by pressing propellant charge powder between two pieces ~ combustible casing material and storing it in well sealed bottles at 65C and 80C. 'l'he increase in the .
- -- 11 -- .
.. . . . . .....
1 1 6~3052 weight of the combustible casing material was followed over a period of time.
At 80C storage temperature, the following increases in weight were determined.
Powder A Powder C Difference After one week 9.0 ~ 7.3 ~ 1.7 %
After three weeks 16.7 ~ 12.0 ~ 4.7 ~
~j After six weeks 21.4 % 14.5 ~ 6.9 %
- At 65C storage temperature, the following .
increase in weight was determined after 18 days:
Powder A Powder C Difference 8.0 % ~.9 ~
The results listed above clearly demonstrate the superiority of a propellant charge powder according to the invention over a conventional propellant charge powder with !
regard to the migration of the blasting oil into the casing material.
Finally r the additional advantage of comparatively slight erosion of the barrel of the weapon can be expected in the case of a propellant charge powder according to the invention owing to the precise adjustability of the - heat of explosion.
Four embodiments of the propellant charge powder according to the invention are described in more detail below.
-..... .
Example 1 A solvent-free diglycol dinitrate/nitroglycerine propellant charge powder was produced as follows:
148.8 kg Dry weight of a 30 ~ water-containing pulverulent raw mixture having the following composition, based on dry we1ght:
60 % Nitrocellulose having a degree of ,~ nitration of l3.0 ~ nitrogen 25 % Diglycol dinitrate 15 % Nitroglycerlne:
l.080 kg Akardit II
- 0.074 kg Magnesium oxide 0.075 kg Graphite are mixed together in a 400 l kneader of the type lS conventionally used in powder production.
After optimum thorough mixing in the kneader, the mixture is worked on ~ roller kneading mechanism at 85~C
to a thoroughly gelatinised sheet in the conventional way, then rolled into a press roll and pressed in a hydraulic press at 70~' to a 7~hole strand whose diameter and web width are adjusted to the requirements of the ammunition. A~ter cutting the strands to the required length, the powder is mixed after storage to ripen.
The finished powder has the following composition within the limits of tolerance:
.
.~, , ~ , .
~ 1 fi805Z
Nitrocellulose with 13.0 ~ nitrogen 59.5 ~ by weight Diglycol dinitrate 24.~ ~ by weight Nitroglycerine 14.9 ~ by weight Akardit II 0.7 ~ by weight 5 Graphite U.05 % by weight Magnesium oxide . 0.05 ~ by weiqht 100 . 00 96 by welght ~) . Its heat of explosion amounts to about 4,600 J/g.
The desirable ballistic behaviour described above 1~ was observed in the propellant charge powder.
Examp.le_2 .
A solvent~free butanetriol trinitrate/nitroglycerine propellant charge powder was produced as follows:
The kneading mixture is as follows:
148.8 kg Dry weight o~ a 30 ~ water-containing raw powder mixture haviny the following composition, based on dry weight:
64 ~ Nitrocellulose having a degree of nitration o~ 13~0 ~ nitrogen, 22 ~ 1,2,4-butanetriol trlnitrate, 14 ~ Nitroglycerine, 0.375 kg Centralit I
0.6~5 kg Akardit II
0.075 kg Magnesium oxide 25 0.075 kg Graphite.
.. ....... . .
The production corresponds to Example 1.
The finished powder has the following composition within the limits of tolerance:
Nitrocellulose with 13.0 ~ nitrogen Ç3.50 % by . weight 1,2,4-butanetriol trinitrate .21.70 ~ by weight Nitroglycerine . 14.00 ~ by -weight 10 Centralit I U.25 ~ by weight Akardit II 0.45 % by - weight Graphite . 0.05 % by weight Magnesium oxide O.U5 % by weiqht . 100.00 % by ~ :
. weight.
Its heat of explosion amounts to about 4950 JJg.
Example 3 A solvent-free diglycol dinitrate/nitroglycerine~
nitroguanidine propellant charge powder was produced as ~.
follows:
The kneading mixture is as follows: .
103.8 kg Dry weight of a 30 % water-containing pulverulent raw mixture analogous to E~ample 2, having diglycoI dinitrate instead of l,2,4 butanetriol trinitrate 1 1 6~3052 , ~45.0 kg Nitroguanidine - 0.300 kg Centralit I
0.750 kg Akardit II
0.075 kg Magnesium oxide 0.075 kg Graphite - The production corresponds to Example 1.
The finished powder has the following composition -j within the limlts of tolerance:
.~ J ~ .
Nitrocellylose with 13.0 ~ nitrogen 44.30.% by weight 10 Diglycol dinitrate L5 . OO % by weight Nitroglycerine .9.90 % by weight Nitroguanidine 30.00 %. by weight Centralit I 0.20 ~ by weight Akardit II O.S0 ~ by weight Magnesium oxide 0.05 % by weight GraphIte 0.05 % by weight . 100.00 % by weight ) Its heat of explosion amounts to about 4,100 J/g.
Exam ` 20 A solvent-containing butanetriol trinitrate~
methriol trinitrate/diglycol dinitrate/nitroguanidine propellant charge powder was produced as follows:
172 kg of a 30 % alcohol-containing nitrocellulose with 12~8 ~ N2 t~ 110 kg nitrocellulose, converted into alcohol-free substance) ... .. .
I 1 6805~
40 kg Nitroguanidine 2 kg Akardlt II
are introduced into a 400 litre kneader~
- A mixture of the following blasting oils which has been desensitized with solvents is introduced into this premixed material:
16 kg 1,2,4-butanetriol trinitrate Methriol trinitrate 16 kg Diglycol dinitrate lo 40 kg Alcohol-ether mixture.
- After mixing in the kneader, the mixture is left to ripen for 10 days at about 25C, thoroughly kneaded again thereafter and subsequently pressed in the hydraulic press to single hole strands. After cutting, the powder lS is dried in a warm air stream, optionally under vacuum.
The finished powder has the following composition within the limits of tolerance:
Nitrocellulose with 12.8 % nitrogen 55.~0% by weight 1,2,4-butanetrioltrinitrate 8.00% by weight 20 Methriol trinitrate 8.00 ~ by weight Diglycol dinitrate 8.00 % by weight Nitroguanidine 20.00 ~ by weight Akardit II 1.00 % by weight 100.00 ~ by weight Its heat of explosion amounts to about 3960 J/g.
A different conventional propellant charge powder B has the following composition:.
: Nitrocellulose with 12.6 ~ N256.00 ~ by weight 10 Nitroglycerine .38.80 % by weight.
- Stabilisers 5.10 ~ by weight Magnesium oxide + Graphite0.10 ~_~y weiqht 100.00 % by weight The heat of explosion amounts to about 4,600 J~g.
A propellant charge powder C according to the invention has the following composition Nitrocellulose with 13.0 ~ N259.50 % by weight Diglycol dinitrate24.80 ~ by weight Nitroglycerine 14.90 ~ by weight 20 Stabilisers 0.70 ~ by weight Magnesium oxide + Graphite0.10 ~ by weight . 100.00 % by weight The heat of explosion again amounts to about 4l600 Joule~g.
The propellant charge powders A and B contain _ g _ l l 6gos2 a much higher proportion of stabilisers and plasticisers and of stabilisers, respectively, than necessary. The excess proportion serves only to consume the energy, ~y means of which the heat of explosion is adjusted to the value indicated. With the propellant charge powder C
according to the invention, however, the same explosion heat is obtained without special energy consumption by the incorporation of two blastlng oils in suitable proportions.
In order to compare the properties of the powders, o ~ the propellant charge powders B and C were inserted in a -105 mm calibre weapon~ In this process, it was found that the propellant charge powder C according to the invention has a much more ~avourable external temperature-pressure behaviour than the propellant charge powder B.
The propellant charge powder B demonstrated a rise in pressure which should be judged as critical at only -40C, but this did not occur under otherwise identical conditions with the propellant charge powder C.
The blasting properties of the propellant charge powders A and C were compared with a 120 mm calibre weapon. It was found that the propellar.t charge powder C according to the invention prod~ced blasting rates which were only achieved by the propellant charge powder A at pressures which were 100 to 200 bar higher.
The propellant charge powder according to the invention with several blasting oils is therefore of .....
_ _ .. .. .... .. . ..
1 1 ~gO52 clear ballistic superiority relative to conventional propellant charge powders.
The propellant charge powder according to the invention exhibits another advantageous property:
Combustible cartridge shells are being used more and more in modern weapon systems instead of the conventional metal cartridges. They consist, for example, ~` of a high proportion of nitrocelluloses and additional neutral fibres, a resin binder and a chemical stabiliser for the nitrocellulose. Owing to their material compositionr they can absorb softeners and blasting oils in contact with propellant charge powders. However, in - order to guarantee that ammunition with combustible casings can be stored for a long time, it is important that the propellant charge powder releases a minimum amount of blasting oil into the casing material.
Examination of the propellant charge powder according to the invention in this respect surprisingly revealed that it releases considerably less polyalcohol nitrate into combustible casing material than conventional propellant charge powders.
In particular, an investigation was carried out with the above-mentioned propellan~ charge powders A and C by pressing propellant charge powder between two pieces ~ combustible casing material and storing it in well sealed bottles at 65C and 80C. 'l'he increase in the .
- -- 11 -- .
.. . . . . .....
1 1 6~3052 weight of the combustible casing material was followed over a period of time.
At 80C storage temperature, the following increases in weight were determined.
Powder A Powder C Difference After one week 9.0 ~ 7.3 ~ 1.7 %
After three weeks 16.7 ~ 12.0 ~ 4.7 ~
~j After six weeks 21.4 % 14.5 ~ 6.9 %
- At 65C storage temperature, the following .
increase in weight was determined after 18 days:
Powder A Powder C Difference 8.0 % ~.9 ~
The results listed above clearly demonstrate the superiority of a propellant charge powder according to the invention over a conventional propellant charge powder with !
regard to the migration of the blasting oil into the casing material.
Finally r the additional advantage of comparatively slight erosion of the barrel of the weapon can be expected in the case of a propellant charge powder according to the invention owing to the precise adjustability of the - heat of explosion.
Four embodiments of the propellant charge powder according to the invention are described in more detail below.
-..... .
Example 1 A solvent-free diglycol dinitrate/nitroglycerine propellant charge powder was produced as follows:
148.8 kg Dry weight of a 30 ~ water-containing pulverulent raw mixture having the following composition, based on dry we1ght:
60 % Nitrocellulose having a degree of ,~ nitration of l3.0 ~ nitrogen 25 % Diglycol dinitrate 15 % Nitroglycerlne:
l.080 kg Akardit II
- 0.074 kg Magnesium oxide 0.075 kg Graphite are mixed together in a 400 l kneader of the type lS conventionally used in powder production.
After optimum thorough mixing in the kneader, the mixture is worked on ~ roller kneading mechanism at 85~C
to a thoroughly gelatinised sheet in the conventional way, then rolled into a press roll and pressed in a hydraulic press at 70~' to a 7~hole strand whose diameter and web width are adjusted to the requirements of the ammunition. A~ter cutting the strands to the required length, the powder is mixed after storage to ripen.
The finished powder has the following composition within the limits of tolerance:
.
.~, , ~ , .
~ 1 fi805Z
Nitrocellulose with 13.0 ~ nitrogen 59.5 ~ by weight Diglycol dinitrate 24.~ ~ by weight Nitroglycerine 14.9 ~ by weight Akardit II 0.7 ~ by weight 5 Graphite U.05 % by weight Magnesium oxide . 0.05 ~ by weiqht 100 . 00 96 by welght ~) . Its heat of explosion amounts to about 4,600 J/g.
The desirable ballistic behaviour described above 1~ was observed in the propellant charge powder.
Examp.le_2 .
A solvent~free butanetriol trinitrate/nitroglycerine propellant charge powder was produced as follows:
The kneading mixture is as follows:
148.8 kg Dry weight o~ a 30 ~ water-containing raw powder mixture haviny the following composition, based on dry weight:
64 ~ Nitrocellulose having a degree of nitration o~ 13~0 ~ nitrogen, 22 ~ 1,2,4-butanetriol trlnitrate, 14 ~ Nitroglycerine, 0.375 kg Centralit I
0.6~5 kg Akardit II
0.075 kg Magnesium oxide 25 0.075 kg Graphite.
.. ....... . .
The production corresponds to Example 1.
The finished powder has the following composition within the limits of tolerance:
Nitrocellulose with 13.0 ~ nitrogen Ç3.50 % by . weight 1,2,4-butanetriol trinitrate .21.70 ~ by weight Nitroglycerine . 14.00 ~ by -weight 10 Centralit I U.25 ~ by weight Akardit II 0.45 % by - weight Graphite . 0.05 % by weight Magnesium oxide O.U5 % by weiqht . 100.00 % by ~ :
. weight.
Its heat of explosion amounts to about 4950 JJg.
Example 3 A solvent-free diglycol dinitrate/nitroglycerine~
nitroguanidine propellant charge powder was produced as ~.
follows:
The kneading mixture is as follows: .
103.8 kg Dry weight of a 30 % water-containing pulverulent raw mixture analogous to E~ample 2, having diglycoI dinitrate instead of l,2,4 butanetriol trinitrate 1 1 6~3052 , ~45.0 kg Nitroguanidine - 0.300 kg Centralit I
0.750 kg Akardit II
0.075 kg Magnesium oxide 0.075 kg Graphite - The production corresponds to Example 1.
The finished powder has the following composition -j within the limlts of tolerance:
.~ J ~ .
Nitrocellylose with 13.0 ~ nitrogen 44.30.% by weight 10 Diglycol dinitrate L5 . OO % by weight Nitroglycerine .9.90 % by weight Nitroguanidine 30.00 %. by weight Centralit I 0.20 ~ by weight Akardit II O.S0 ~ by weight Magnesium oxide 0.05 % by weight GraphIte 0.05 % by weight . 100.00 % by weight ) Its heat of explosion amounts to about 4,100 J/g.
Exam ` 20 A solvent-containing butanetriol trinitrate~
methriol trinitrate/diglycol dinitrate/nitroguanidine propellant charge powder was produced as follows:
172 kg of a 30 % alcohol-containing nitrocellulose with 12~8 ~ N2 t~ 110 kg nitrocellulose, converted into alcohol-free substance) ... .. .
I 1 6805~
40 kg Nitroguanidine 2 kg Akardlt II
are introduced into a 400 litre kneader~
- A mixture of the following blasting oils which has been desensitized with solvents is introduced into this premixed material:
16 kg 1,2,4-butanetriol trinitrate Methriol trinitrate 16 kg Diglycol dinitrate lo 40 kg Alcohol-ether mixture.
- After mixing in the kneader, the mixture is left to ripen for 10 days at about 25C, thoroughly kneaded again thereafter and subsequently pressed in the hydraulic press to single hole strands. After cutting, the powder lS is dried in a warm air stream, optionally under vacuum.
The finished powder has the following composition within the limits of tolerance:
Nitrocellulose with 12.8 % nitrogen 55.~0% by weight 1,2,4-butanetrioltrinitrate 8.00% by weight 20 Methriol trinitrate 8.00 ~ by weight Diglycol dinitrate 8.00 % by weight Nitroguanidine 20.00 ~ by weight Akardit II 1.00 % by weight 100.00 ~ by weight Its heat of explosion amounts to about 3960 J/g.
Claims (8)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A multi-base propellant charge powder for tubular weapons and missiles having a specific, predetermined heat of explo-sion, comprising nitrocellulose and at least two different blasting oils selected from the group consisting of nitrogly-cerine, diglycol dinitrate, methriol trinitrate and 1,2,4-butane-triol trinitrate, wherein:
(a) said propellant charge powder is made in a production process without the use of solvents and the total blasting oil content is determined with regard to optimum homogenization and gelatination in the production process, said total blasting oil content amounting at most to 100% by weight, based on the content of nitrocellulose; and wherein (b) the proportion of higher calorific blasting oils in the total blasting oil content is chosen to produce said specific, predetermined heat of explosion.
(a) said propellant charge powder is made in a production process without the use of solvents and the total blasting oil content is determined with regard to optimum homogenization and gelatination in the production process, said total blasting oil content amounting at most to 100% by weight, based on the content of nitrocellulose; and wherein (b) the proportion of higher calorific blasting oils in the total blasting oil content is chosen to produce said specific, predetermined heat of explosion.
2. A propellant charge powder according to claim 1, contain-ing the blasting oils: nitroglycerine and diglycol dinitrate.
3. A propellant charge powder according to claim 1, in which the total blasting oil content, based on the content of nitro-cellulose, amounts to between 54% by weight and 82% by weight.
4. A propellant charge powder according to claim 1, claim 2 or claim 3, further comprising at least one other nitro com-pound as energy carrier, selected from the group consisting of nitroguanidine and nitramines.
- Page 1 of Claims -
- Page 1 of Claims -
5. A propellant charge powder according to Claim 1, in which the powder contains 33-52% by weight of diglycol dinitrate and 21-30% by weight of nitroglycerine, based on the content of nitrocellulose.
6. A propellant charge powder according to Claim 1, in which the powder contains 41-43% by weight of diglycol dinitrate and 24-26% by weight of nitroglycerine, based on the content of nitrocellulose.
7. A propellant charge powder according to Claim 5 or Claim 6, further comprising at least one other nitro compound as energy carrier, selected from the group consist-ing of nitroguanidine and nitramines.
8. A method of producing a multi-base propellant charge powder for tubular weapons and missiles having a specific, predetermined heat of explosion, comprising the steps of:
(a) mixing together the components of a raw mixture comprising nitrocellulose and at least two different blasting oils selected from the group consisting of nitroglycerine, diglycol dinitrate, methriol trinitrate and 1,2,4-butane-triol trinitrate, the total blasting oil content being determined with regard to optimum homogenization and gela-tination of the mixture and amounting at most to 100% by weight based on the nitrocellulose content, and the higher calorific blasting oils in the total blasting oil content being chosen to produce said specific heat of explosion;
- Page 2 of Claims -(b) pressing the gelatinized mixture through a die into strands of the desired diameter for use as a propellant charge in ammunition.
-Page 2a of Claims -
(a) mixing together the components of a raw mixture comprising nitrocellulose and at least two different blasting oils selected from the group consisting of nitroglycerine, diglycol dinitrate, methriol trinitrate and 1,2,4-butane-triol trinitrate, the total blasting oil content being determined with regard to optimum homogenization and gela-tination of the mixture and amounting at most to 100% by weight based on the nitrocellulose content, and the higher calorific blasting oils in the total blasting oil content being chosen to produce said specific heat of explosion;
- Page 2 of Claims -(b) pressing the gelatinized mixture through a die into strands of the desired diameter for use as a propellant charge in ammunition.
-Page 2a of Claims -
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2900020A DE2900020C2 (en) | 1979-01-02 | 1979-01-02 | Process for the production of a polybasic propellant charge powder |
| DEP2900020.2 | 1979-01-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1168052A true CA1168052A (en) | 1984-05-29 |
Family
ID=6059967
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000342521A Expired CA1168052A (en) | 1979-01-02 | 1979-12-21 | Poly-base propellant |
Country Status (15)
| Country | Link |
|---|---|
| JP (1) | JPS5595698A (en) |
| BE (1) | BE880961A (en) |
| CA (1) | CA1168052A (en) |
| CH (1) | CH644831A5 (en) |
| DE (1) | DE2900020C2 (en) |
| ES (1) | ES487140A1 (en) |
| FR (1) | FR2445823A1 (en) |
| GB (1) | GB2038796B (en) |
| GR (1) | GR71450B (en) |
| IT (1) | IT1127288B (en) |
| NL (1) | NL186807B (en) |
| NO (1) | NO151036C (en) |
| PT (1) | PT70653A (en) |
| SE (1) | SE449487B (en) |
| ZA (1) | ZA796889B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2258230B (en) * | 1982-06-25 | 1993-10-13 | Poudres & Explosifs Ste Nale | Production of double-base propergol propellant blocks |
| GB8409867D0 (en) * | 1984-04-16 | 1993-06-16 | Ici Plc | Nitrocellulose propellant composition |
| BR9006751A (en) * | 1989-05-11 | 1991-08-06 | Nitrochemie Gmbh | PROCESS AND MACHINE TO PREPARE TRIBASIC PROPULSE LOAD POS |
| CA2053832C (en) * | 1990-12-11 | 1999-09-07 | Edward H. Zeigler | Stable plasticizers for nitrocellulose/nitroguanidine-type compositions |
| US6309484B2 (en) * | 1997-02-08 | 2001-10-30 | Diehl Stiftung & Co. | Propellent charge powder for barrel-type weapons |
| RU2130446C1 (en) * | 1998-07-29 | 1999-05-20 | Научно-техническая фирма "Взрывтехнология" | Explosive powder composition and method of preparation thereof |
| FR2839715B1 (en) * | 2002-05-14 | 2005-02-04 | Poudres & Explosifs Ste Nale | PROPULSIVE POWDER COMPOSITIONS FOR HIGH-STRENGTH TUBE WEAPONS AND REDUCED EROSIVE EFFECT |
| JP5987446B2 (en) * | 2012-04-23 | 2016-09-07 | 日油株式会社 | Triple base propellant composition |
| JP2015105219A (en) * | 2013-12-02 | 2015-06-08 | 日油株式会社 | Triple based propellant composition |
| JP6402899B2 (en) * | 2014-06-19 | 2018-10-10 | 日油株式会社 | Triple base propellant composition |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR341911A (en) * | 1904-04-06 | 1904-08-23 | Anton Mikolajczak | Manufacturing process of explosives and powders |
| GB343107A (en) * | 1929-09-11 | 1931-02-11 | Arthur Hough | Improvements in the manufacture of smokeless powder propellants |
| DE548427C (en) * | 1931-01-10 | 1932-04-19 | Chemische Fabriken | Process for the production of solvent-free, low-smoke powders |
| US3951706A (en) * | 1962-07-03 | 1976-04-20 | Eldridge Judson B | Solid propellant mixtures and process of preparation |
| US3865659A (en) * | 1965-06-16 | 1975-02-11 | Dow Chemical Co | Nitrocellulose propellant composition containing metal and triaminoguanidinium hydrazinium diazide |
| US3867214A (en) * | 1967-09-18 | 1975-02-18 | Us Army | Nitrocellulose doublebase propellant containing ternary mixture of nitrate esters |
| FR2165093A5 (en) * | 1971-12-17 | 1973-08-03 | Poudres & Explosifs Ste Nale | |
| JPS5743556B2 (en) * | 1973-01-08 | 1982-09-16 | ||
| US4082583A (en) * | 1974-01-14 | 1978-04-04 | The United States Of America As Represented By The Secretary Of The Navy | Solventless double base propellants and method for plasticizing mtn nitrocellulose propellants without use of solvents |
| DE2603927A1 (en) * | 1976-02-03 | 1977-08-04 | Dynamit Nobel Ag | TEMPERATURE COMPENSATING DRIVE CHARGE |
-
1979
- 1979-01-02 DE DE2900020A patent/DE2900020C2/en not_active Expired
- 1979-12-04 CH CH1073779A patent/CH644831A5/en not_active IP Right Cessation
- 1979-12-17 GR GR60782A patent/GR71450B/el unknown
- 1979-12-18 IT IT28168/79A patent/IT1127288B/en active
- 1979-12-19 ZA ZA00796889A patent/ZA796889B/en unknown
- 1979-12-19 NL NLAANVRAGE7909134,A patent/NL186807B/en not_active Application Discontinuation
- 1979-12-20 NO NO794219A patent/NO151036C/en unknown
- 1979-12-20 ES ES487140A patent/ES487140A1/en not_active Expired
- 1979-12-20 FR FR7931290A patent/FR2445823A1/en active Granted
- 1979-12-21 CA CA000342521A patent/CA1168052A/en not_active Expired
- 1979-12-22 JP JP16748079A patent/JPS5595698A/en active Granted
- 1979-12-27 SE SE7910652A patent/SE449487B/en not_active IP Right Cessation
- 1979-12-28 BE BE0/198825A patent/BE880961A/en not_active IP Right Cessation
- 1979-12-31 GB GB7944658A patent/GB2038796B/en not_active Expired
-
1980
- 1980-01-02 PT PT70653A patent/PT70653A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| PT70653A (en) | 1980-02-01 |
| BE880961A (en) | 1980-04-16 |
| SE449487B (en) | 1987-05-04 |
| GB2038796A (en) | 1980-07-30 |
| GB2038796B (en) | 1982-11-17 |
| JPS5595698A (en) | 1980-07-21 |
| NL186807B (en) | 1990-10-01 |
| SE7910652L (en) | 1980-07-03 |
| CH644831A5 (en) | 1984-08-31 |
| NO151036B (en) | 1984-10-22 |
| IT1127288B (en) | 1986-05-21 |
| IT7928168A0 (en) | 1979-12-18 |
| ZA796889B (en) | 1980-12-31 |
| NL7909134A (en) | 1980-07-04 |
| FR2445823A1 (en) | 1980-08-01 |
| DE2900020A1 (en) | 1980-07-03 |
| DE2900020C2 (en) | 1982-12-09 |
| JPH0234914B2 (en) | 1990-08-07 |
| ES487140A1 (en) | 1980-09-16 |
| GR71450B (en) | 1983-05-18 |
| NO794219L (en) | 1980-07-03 |
| FR2445823B1 (en) | 1984-06-01 |
| NO151036C (en) | 1985-01-30 |
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