DE1964537C - Explosives and method of making the same - Google Patents

Description

a) a first, non-explosive, liquid component in the form of hydrazine or of Hydrazine with a non-explosive amount of one or more oxidizing agents dissolved in it Produces salts,

b) Manufactures a second, normally non-explosive, solid component which is at least predominantly from one or more oxidizing clay Salts in particulate form,

c) the components a) and b), optionally with the addition of a thickener and / or Gelling agent, under solution at least

lih Til d Btdtil b)

Hyr _5ü ³ C aufwe st. In which

staring point of about ju ^ «> ^. ^ ^ ^ ^

^^ ⁿ _ß f ° f _ch ^g ^ ^äß _Ve S _a ltnis von '^ drazin zu Hvdrabem. can be found there Vernal ⁿ j / _{under detn Ge} .

"l ^1?" ™ - ™ ^ ¹ ^^ the solidification point, "chKpunkt ^the ™ _m - ^B _G ^ _{maybe point} the stöchionicht.aber _imum under the _m ^ Performance Metric balance sheet or ae _{ther is}

fah.gkejt as explosive on ^ J _{of the maximaIe}

merbei the ^ m ms ch e »η _{consideration}

Le.stungsfah '£'"[£de" ^ _{Hvdrazin and} Hydra Attracted that the <^ ^{m 'su'} ^ _{1 a} f _re ien Me

^ '^ - ^ "^^^ used tall like Alum.nium al, Keflu _heht .

will, as it is> rnι case of the brM K ^ ^^ ^

« ^{Sina au} <;"" _{with a} hydrogen

Ammonium nitrate zuJJ ^m ™ ⁿ ™ _{wig liquid}

J £ ^^ _επ AmmoniumnitratlösTgen and with a metallic fuel such as _A i i _{u min u 'm} -, or contain magnesium, as ^'"deTuSA. Patentschnft-3 124493 described _djesen explosives W ammonia _ther solvent for the ammonium ££ Amounts of about 2 to 35 percent by weight _before while the ammonium nitrate in amounts v _{0 ;. About 10 to} g ₃ percent by weight and the meta ι, amounts of about 15 to € 0 percent by weight vori.eg.

_The explosives according to the USA.-Patentscn, 3,124,495 is the Te.lchengröße of metahs ^ tI, -größer mm than 0.84, the blasting off ^ P ^ Hch dam.t enough. premature Uetona ™ ·. Avoid fiddling. In JeMJiA. ™ ^ n

^25th

Gelling agent, une g

to avoid handling an essential part of component b). In the component a) and formation of an explosive 35 3 124 495, the general ne ^ sive mixture is found mixed and that the hydrogen ^ & ^^ wj ^ _An,.

d) fine-particle aluminum in the mixture can be % ™ Nahrungsmittel ££ ! ^ hydrazine "(i'n de distributed.

ger solution used as solvent), the PaiLn.-

font does not distinguish between different,

which solvents and does not contain any Hm

point out that you can use special combinations

The invention relates to an explosive with hydra- von Hyd ^^^ zonium mononitrate as an oxidizer and finely divided medium with an intestine Aluminum as fuel and possibly with P ^ f ^^ S a content of ammonia and / or ammonium nitrate and possibly with additions of thickening and / or gelling agents. and a method for producing the same.

Explosives and propellants containing mixtures of hydrazine and hydrazonium mononitrate, are z. From U.S. Patents 2,704,706 and 2,943,927 known. U.S. Patent 2,704,706 describes mu hydrazonium mononitrate Kn.ib.h- 55 ammonium nitrate for use with known explosives such as nitrotoluene, wherein the nitrates are in solid form and no free hydrazine is present. In the U.S. Patent 2,943,927 it is stated that explosives are 60 "^ h g

based on hydrazine and Hydrazonium- 3 "> / fre.es Hyd ^ mononitrate a characteristically low solidification P ^he J'H

have rungspunkt and as fuels to ^

Together with conventional oxidizing agents such as hydrogen peroxide, fuming nitric acid or liquid 6 ₅ 3 to 77 oxygen, the mixture of hydrazine and hydrazonium mononitrate in this case at least about 18 percent by weight hydrazine and im

_{by Aluminiunv}

P ^ f ^ Sche particularly advantageous physi- te, chen irg " ^d ™ _e f ^ _1εη could. The USA, ^ chen E gensd ^ η « z £ ^^ ^, ^^

^P ^ ^ntsc ,, '"V _a sis of ammonia, ammonium nitrate 5» substances on de, ^' ^ "^^ i ^, ' _da hydrazine and

™ * "™haben Z ^ lX '* in and a spontaneous magnesium failure

flammable mass ^ can ^^

eratur liquid

^^^^ "S ^ oBtret, Feinteil". ^{s Pren} f? J ° "'' ^a " ^s "vdrazin and possibly Am-

ß ^em . ^{A. lum} ' ⁿ ' ^u ! "· _Amm o _niu mmtrat « stops when you step moniak "nd / otoAmm ⁰ lumn e.

the ^Ζ ™ »™ Ε! ¹ light weight at least ionic g

f identifies the _substance

by having 21 to 95% ^ Ä «· /. Aluminum and contains, with the possible ^^ ammonium nitrate so and ο _setting

between ammonium and hydrazine twines

jonium ions has a free hydrazine content of at least 3%.

In contrast to the explosives according to U.S. Pat. No. 3,124,495 contain those according to the invention Explosives based on Hvdrazoniummononitrat, Hydrazine and aluminum are free = hydrazine, which even if it is present in excess is. is particularly harmless for the explosive reaction, since it becomes too gaseous even when there is a loss of energy. Products decompose, while that consisting of ammonia or ammonia and water liquid component of the explosives according to the USA patent 3 124 495 requires the supply of energy for decomposition and therefore that which is set free Explosion energy reduced. Furthermore, the fact must be taken into account that the hydrazine in the Explosives mixture according to the invention is much more aK a simple solvent. The hydrazine in fact also act as a particularly effective one ArK !! - liquid in the presence of the explosive gemi ^ nes. by adding more energy to the mixture, since it forms gaseous end products re.i.- --τι and therefore to a considerably higher gassing depending on the initial weight unit of the explosive • leads. Of perhaps the greatest importance in cieich the ammonia, ammonium nitrate and aluminum : explosives containing or containing magnesium <3 of US Pat. No. 3,124,495 with the irazine, hydrazonium mononitrate and aluminum ■ itenden explosives according to the invention the consideration that the "liquid" (the r. -e liquid part of the explosive, as. the ammonia dissolved in the alkaline aqueous solution , -imtrate) in the absence of the metal not detonable ..- :> t. while the "liquid" is with explosives According to the invention (e.g. the solution of ammonia mnitrates in the hydrazine, which result from solvolytic Effect an ion equilibrium of HydrazontumiT.i Ammonium cations and nitrate anions as well as considerable amounts of free hydrazine and also free Contains ammonia) is explosive even without the addition of aluminum powder. It is believed that the explosives according to the invention lead to a two-stage explosion, with the initial Explosive shock wave primarily due to the rapid reaction of the oxidizing agent with the hydrazine while the reaction of the metal appears to be in two stages and a post-surge generated. As a result of this two-step reaction of the

The beneficial compositions of the explosives according to the invention have been shown to provide aluminum about twice the air pressure surge as trinitrotoluene, while the air pressure surge power of explosives according to U.S. Patent 3,124,495 is about the same as that of trinitrotoluene.

Aluminum nitride, a special characteristic of explosives, may be formed as an intermediate product according to the invention, and this is perhaps a further explanation for the increased blasting effect.

It should also be noted that from the documents of the German patent application published on June 16, 54 F 10935 an explosive is known which consists exclusively of hydrazonium mononitrate, but also up to 25% ammonium nitrate and optionally up to 10% aluminum powder may contain. In contrast to the explosive according to the invention, this is one at Room temperature solid explosive that contains neither free hydrazine nor free ammonia and does not exhibits the effectiveness of the explosives according to the invention.

The invention further comprises a process for the manufacture of the explosives defined above, which is characterized in that one

a) a first, non-explosive, liquid component in the form of hydrazine or hydrazine with a non-explosive amount of one or more oxidizing salts dissolved therein manufactures,

b) Manufactures a second, normally non-explosive, solid component which is at least predominantly consists of one or more oxidizing salts in particulate form,

c) the components a) and b), optionally with the addition of a thickening and / or gelling agent, dissolving at least a substantial part of component b) in the component a) and forming an explosive mixture mixed and

d) finely divided aluminum evenly distributed in the mixture.

It has been found that the explosives according to the invention approximate the following ingredients should contain the following weight ratios:

component

Continue
Area

Preferred
Area

Most favorable composition

aluminum

NH ₃ and NHi

N ₁ H ₄ and N ₁ Hi

NO7 or equivalent

In the above compositions, the nitrate ion or its equivalent may be in the form of one or more compounds, namely in the form of nitrates or mixtures thereof with small amounts of perchlorates. May optionally contain small amounts of one or more other oxidizing salts, the oxidising salt, the certain instead of consisting of hydrogen and nitrogen cations metal cations up 2 to 45

0 to 18

6 to 75

14 to 70

20 to 35

0 to 10

15 to 30

25 to 55

33 10 19 38

point. In this sense, small amounts of alkali nitrates, Calcium nitrate, aluminum nitrate, hydrazonium perchlorate, alkali perchlorate, calcium perchlorate or Use a mixture of these. In normal use of the explosives, however, the presence of small amounts of metal cations does not provide any particular advantage and even affects the explosive effect of the

Explosives because the metal cations do not form a gaseous but a solid reaction product. Under In some circumstances, however, small amounts of metal cations in the oxidizing salts are favorable because they suppress the foaming of the mass during manufacture or give the explosives a longer shelf life or impart other desired physical properties.

The explosives according to the invention can be manufactured. either by mixing ammonium nitrate and hydrazine and then adding the aluminum particles, or by mixing hydrazonium mononitrate with hydrazine and then adding aluminum particles. In the first case, the nitrate in the finished explosive is in the form of hydrazonium mononitrate and ammonium nitrate in an unstable equilibrium with hydrazine and ammonia. In the second case, the nitrate ions are essentially in the form of hydrazonium mononitrate without substantial amounts of ammonium nitrate. In a modified manner, in order to obtain an explosive in which the nitrate is present as completely as possible as hydrazonium mononitrate and not as ammonium nitrate, the first-mentioned production process can be carried out in such a way that the ammonium nitrate and the hydrazine are mixed at elevated temperatures and / or in a vacuum the evolving gaseous :: to remove ammonia. The explosive obtained according to the first of the two manufacturing processes described above, that is, the one which contains a mixture of hydrazonium mononitrate and ammonium nitrate in an unstable equilibrium with hydrazine and ammonia, is produced from the following components in ό: η in percent by weight: η :

component Continue
Area Preferred
Area best
Put together! aluminum 2 to 45
■ 18 to 92
6 to 75 20 to 35
32 to 70
15 to 30 33
48
19th NH ₄ NO ₃ . ... N ₂ H ₄

If an explosive is to be produced, with hydrazine mononitrate and hydrazine in the fo '· the nitrate ions practically exclusively in the form of weight percentages with one another of hydrazonium mononitrate are available, you can mix 30:

component N ₂ H ₅ NO, Continue
Area Preferred
Area best
composition N ₂ H ₄ 21 to 95
3 to 77 38 to 83
7 to 30 57
10

When measuring the relative proportions of the constituents, the conventional thickeners are also used and / or gelling agents to be considered. Such agents can, based on the total amount by weight of the explosive, within a wide range of about 0 to 20 percent by weight, are added within a preferred range of about 1 to 5 percent by weight, while the the cheapest amount is about 3 percent by weight.

Thickening and / or gelling agents usually become the explosives according to the invention lugesetzt in order to ztx the finely divided aluminum in the explosive in as evenly a distribution as possible hold, since the explosive without the addition of thickening and / or gelling agent η a liquid Slurry is because the hydrazine-containing solvent and the dissolved oxidant are in shape a liquid or a liquid slurry. The thickening or gelling of the explosive can by adding a wide variety of agents known per se in amounts of up to about 20 percent by weight respectively. Typical thickening and gelling agents are finely divided silicas, which are usually found in Amounts up to about 10 weight percent is added, and a crosslinking gelling agent which is usually is added in amounts up to about 5 percent by weight. The gelling agents are usually used in Supplied in powder form and such a powder can be added to the liquid mixture or a liquid component be added to the same prior to the addition of other components of the explosive. So you can z. B. add the gelling agent to the hydrazine and also with solid ammonium nitrate mix before mixing it with the hydrazine. The addition of certain gelling agents to the Explosives can have the further advantage of making the explosives "water-insensitive" for many uses to make, e.g. B. for use on the floor or in the floor, w> Otherwise the explosives could become insensitive to water absorption from the environment. There is soot too an effective thickener, but has no gelling effect.

In many types of application of the explosives it is also expedient in the manufacture or use add a desensitizer to reduce the sensitivity of the explosive. Water is an effective desensitizer, but it also has a pronounced effect on the Energy development; Wisser can act as a desensitizer expediently added to certain mixtures in amounts of up to about 10 percent by weight will. Other effective desensitizers are glycerin, glycol, wax, and various Hydrocarbon oils, such as. B. heating oil. Fuel oil can be used as a desensitizer in amounts up to about 20%. based on the total weight of the explosive. When used as a desensitizer

a solid, fusible material such as wax is used, it is expediently heated and the mass added at a higher temperature. When it cools down, the wax solidifies and works at the same time as a thickener. In general, any non-volatile substance that is in admixture with the hydrazine and the hydrazine salt of the explosive is storage stable, act as desensitizers.

Some explosives according to the invention have freezing points near room temperature, so it is appropriate to add a freezing point depressant to them. An example of a compatible freezing point depressant for this purpose is hydrazonium monothine cyanate (N ₂ H ₆ SCN).

The above and other modifiers for the

physical properties of explosives are with reference to hydrazine and hydrazonium mononitrate Containing Explosives in U.S. Patent 3,419,443 discussed.

Various explosives according to the invention are shown in the table below.

o given components in the given proportions manufactured. Cast trinitrotoluene is used as a reference explosive.

Table I.

N, H, NH ₄ NO ₁ Composition, I. Other 4} Explosive funnel size diameter (cast Part by weight 4th
4 > finely divided silica (Loads of 454g each, SOcm tier in cm ■ Example Trinitro 4 y Dug in sand loam) 134.6 toluene) Al 4 finely divided silica depth 40 100 10 water cm X 40
40 100
100 83.8 203.2 70 80 190.5
185.4 40 100 68 180.3 1 47
36 101.6 213.3 2
3 54 91.4
94 4th 68 91.4 5 101.6

In Examples 1 to 5, a first, non-explosive liquid ingredient is first prepared by dissolving 5 parts of ammonium nitrate in the hydrazine at room temperature. Once a uniform solution has formed, the remainder of the ammonium nitrate and thickener are added with stirring, and the mixture is stirred until the nitrate in the hydrazine has gone virtually completely into solution. The aluminum powder is then gradually added (particle size predominantly in the range from 30 to 40 μ), stirring with a high-speed stirrer at 1750 rpm and stirring continued until the viscosity of the mixture has risen enough so that the aluminum particles do not separate sell more. Then three charges of 454 g each are produced from each batch, a conventional Boston round bottle made of polyethylene with a capacity of 473 cm ^{3 being} used as the container for the explosives according to Examples 1 to 5. All charges are amplified with 50 g of tetranitro-N-methylaniline and initiated with seismographic detonators (Dupont SSS EB), whereby the units of detonator and amplifier are packed in a polyethylene bag to prevent a reaction with the explosive, and the polyethylene bottle is attached to the Page is cut open above the contents of the explosives for inserting the bag containing the detonator and the amplifier and for leading out the detonator lines. All loads are then buried 50 cm deep in similar sand loam soil. All charges are inserted with the bottom of the container down and tamped into the blast holes, measuring the depth to the bottom of the explosive charge.

To determine the size of the funnel, the depth of the funnel is in the middle of the same up to to solid ground in centimeters and the mean diameter of the funnel as the mean of four diameters determined. The funnel sizes for Examples 1 to 5 and for Comparative Example X are given in the table above. Out These values result in the improvement in the size of the blasting funnel in all examples according to the invention compared to using cast trinitrotoluene (Example X). Furthermore, it follows from the Table that the amount of aluminum is not particularly critical (considering the 20% aluminum of the Example 3 compares with the 32% aluminum of Example 1) and that the presence of a considerable The amount of water (in example 5 about 5%) does not significantly affect the size of the funnel (comparison of Examples 1 and 5).

Example 6

To further characterize the properties of typical explosives, it is stated that the Explosives of Example 1, prepared as described above, a density of 1.61 at 2O.5X and a Has a sensitivity of 70 kg / cm. For comparison purposes, an explosive is made from the same components as in example! (but only with 3 parts of finely divided silica) produced, in this Trap the hydrazine preheated to 66 ° C and then slowly added to the ammonium nitrate with stirring whereupon the mixture is heated to 49 C to bring all the nitrate into solution and gaseous To develop ammonia. This gives an explosive with comparable sensitivity with a density of 1.752 at 20 "C.

Example 7

To the influence of a desensitizer; Pointing at the funnel size will be the explosives of Example I (but only with 3 parts of finely divided silica

309620/77

acid) compared with an explosive which, in addition to the components of the explosive according to Example 1, also contains 21 percent by weight of glycerol. Experiments show that this mixture is clearly dcsensitized, but can still be detached. The explosive of Example 1 gives a funnel 92.7 cm deep and 292 cm in diameter, while the desensitized explosive gives a funnel 66 cm deep and 172.7 cm in diameter. Changing the glycerin amount of 16 up to 22 ° / ₀ in similar experiments. in no case one obtains an explosive which is sensitive to detonators; However, all explosives are lined with rubber iron pipes sensitive bullets, wherein occur in glycerol levels of 20 ° / ₀ and less detonations of low magnitude.

Examples 8 and 9

IO

»5

ao

To further investigate the size of the blasting funnel, which is achieved with desensitized explosives, an explosive of the composition given in Example 1 with 5 percent by weight of heating oil is prepared according to Example 8 and an explosive of the same composition with 10% of heating oil according to Example 9. The explosive according to examples is sensitive to both rifle shot put (0.30-06) and; · ι; rh against detonators, while the sort c material according to example 9 is insensitive to rifle shot put and detonators. When fortified with 50 g of tetranitro-N-methylaniline, the explosives according to Examples 8 and 9 can both be detonated; the explosive according to Example 9 generates a Blasts funnel of 108 cm depth and 238.8 cm in diameter, while a Blasts judges IK S ₁ cm deep and 289.6 cm diameter obtained with the explosive according to Example 1

Example 10

If the explosive from Example 1 is mixed with 0.1 percent by weight of “Guartec 503” and 4 parts of finely divided silica, a mass of Cream-like consistency and a viscosity that sa low that the mass is like a thick syrup can be poured, but is so high that the aluminum does not settle. The combination of »Guartec 5O3 < and finely divided silica proves to be a particularly effective thickener for the pulp according to example 1.

Examples 11 and 12

In order to further investigate the funnel sizes that are obtained with the explosives according to the invention in comparison with known aluminum-containing explosives, a series of comparative tests are carried out with equal amounts of the explosives according to Example III (with 5 parts of fine-particle silica) and Example 2, these in the same soil can be compared with the same quantities of "Navy H-6" or "Tritonal". "H-6" consists of 60 percent by weight of cyclotrimethylene trinitramine and 40 percent by weight of trinitrotoluene and also contains 5 percent by weight of wax and 20 percent by weight of aluminum particles. "Tritonal" is a mixture of 80 percent by weight trinitrotoluene and 20 percent by weight aluminum particles. All cargoes are placed in steel cans, and in each case the amount of cargoes is 454 g and the cargoes are buried 50 cm in the ground. The charges CrZe ¹ J ⁰ IeR S ⁿ v ⁿ . ^a irichtergrößen become apparent from the following table.

Table II example

(with 5 parts finer Silica)

H-6 Tritonal

Size of the funnel

depth cm

92.7

91.4

78.11

83.19

Diameter cm

205.7

190.5 199.4 179.1

Claims (2)

Patent claims: 1. Explosives with hydrazonium mononitrate as oxidizer and finely divided aluminum as fuel and optionally with a content of ammonia and / or ammonium nitrate and optionally with additions of thickening and / or gelling agents, characterized in that it is 21 to 95 "/ _{e contains} hydrazonium mononitrate, 2 to 45% aluminum and 3 to 77% free hydrazine, the possible content of ammonia and / or ammonium nitrate being such that the explosive is released after the balance between ammonium and ₅ hydrazonium ions has a content of free hydrazine of at least 3 ⁰ Z ₀ . 2. A method for producing the explosive according to claim 1, characterized in that