DE1130343C2 - Process for generating pressurized gas, especially for jet propulsion, and a hypergolic system for carrying out this process - Google Patents

Description

The invention relates to a hypergolic system for generating pressurized gas by chemical means Reactions, especially of fuels with oxidizing agents, which are stable in themselves. In particular the systems according to the invention are suitable for generating pressurized gas for jet drives, e.g. B. for Missiles.

The term "oxidizing agent" used in the following description is to be used in the broadest sense understand and denote not only oxygen carriers, but also other substances that are associated with one or more corresponding other chemical substances react hypergolically with strong gas evolution be able. The term »Lithergol« used in the following describes the component of the corresponding System that is in a solid phase. "Fluid substances" include gaseous or liquid substances to understand.

It is the object of the invention to provide a hypergolic system, in particular for To create nozzle drives, through which the reactions are better than with previously known methods

ίο correspond to the needs of the practice and above all the reactions that occur can be easily controlled.

Hybrid hypergolic systems are from Zähringer, "Solid Propellant Rockets", 1958, and other references known.

The subject of the invention is a hypergolic system for the generation of pressurized gas by spontaneous reaction of a fluid, combustion-promoting phase, which consists of nitric acid, nitrogen dioxide, chlorine trifluoride and / or hydrogen peroxide, with a solid, non-porous shaped body, combustible phase with which the fluid , the combustion promoting phase is brought into contact in a gradually progressive manner, characterized in that the solid combustible phase consists of a mixture of a hypergolic component with the fluid, the combustion promoting phase and a non-hypergolic with the fluid, the combustion promoting phase reacting part, the hypergolic part of the solid combustible phase ayis lithium hydride, sodium hydride, potassium hydride, lithium amide, sodium amide, potassium borohydride, sodium borohydride, lithium aluminum hydride, paratoluidine, paraanisidine, paraphenylenediamine and / or naphthylenediamine (1.5) consists, the nic The hypergolic portion of the solid, combustible phase consists of polyesters, polyethylenes, polystyrene, polyamides, polyvinyl chloride and / or the elastomers of polyurethanes or rubber.

Among the amines mentioned, paratoluidine, which is advantageous from certain points of view, has a relatively low melting point, but organic amines are added in certain cases hypergolic character (compared to the above-mentioned substances that promote combustion) Preference that melts at a higher temperature, e.g. B. paraanisidin, paraphenylenediamine or the naphthylenediamine- (1.5).

These organic amines have, in particular, a hypergolic affinity for nitrogen dioxide, which can be present alone or in (for example 40%) solution in nitric acid, and for chlorine trifluoride (ClF ₃ ).

The hypergolic system according to the invention is used in that the chemical Substances that make up this are subdivided into at least two different masses, one of which is placed in a combustion chamber and is in the solid phase, while the other, which is gradually distributed into the chamber and supplied from a tight vessel, in which it is kept in stock, is in liquid or gaseous form, whereby the nature and the dimensions of these chemical bodies in these masses are chosen such that each Mass in itself is stable, while the two masses are components of a hypergolic one

3 4

System, i.e. can penetrate spontaneously and especially without solubility, so that the relationship

React energy supply from outside, z. B. without nis the components participating in the reaction,

External heat supply, if they are related to the unit of the surface of the solid

be brought by in this combustion chamber mass, which is from the liquid or gaseous mass by rinsing or wiping over a free (er 5 is rinsed, with a predetermined flow practically

accessible) surface that remains constant in the solid phase.

lowing mass with a 'preferably adjustable as well as the components of the system in the Flow of the two phases in liquid or gaseous form, i.e. when the phases present mass the two masses together consist of mixtures of different products, so to be brought. The solid phase io forms each of the constituent parts of the system; H. the The mass must be essentially dense (i.e. not solid and the liquid or gaseous mass, by itself or only slightly porous), it may with the liquid alone a stable component, z. B- as a result of it or gaseous form present mass not properties and / or due to the relative proportions be miscible or soluble in this, so that the remainder of its constituents (proportions that are sufficiently far from action between the two phases are removed in a limited 15 stoichiometric ratio) and / or th surface layer runs off by the mold due to the presence of a stabilizing agent the dimensions of the solid-phase means, while on the other hand for a spontaneous one the mass is determined. Course of the reaction, d. H. without it being necessary

For example, the invention provides that energy is supplied from the outside must be 20 in the following on the basis of the drawing, if the liquid or gaseous Described, in the constituent the free surface of the solid constituent

1 in an axial section a dismountable connection.

represents combustion chamber for a nozzle From the above it can be seen that drive is determined and, according to the invention, a multitude of hypergolic systems in this chamber can be envisaged with a device 25 fitted within the framework of the basic so that the solid phase (Lithergol) fall within the scope of the present invention, of the hypergolic system housed inside To explain the above, in can be; a number of examples are given below.

Fig. 2 shows schematically the essential elements one according to the invention formed 30 examples first row Jet propulsion.

In the following explanation, reference is made to the liquid or gaseous component

game of the application of a hypergolic system of any of the named, which promotes combustion

Reference is made to a nozzle drive, but the substances are made.

the invention does not apply to this application. , components can consist of one or more of the other

A fuel run as described above hypergolic system exist, z. B. made of lithium extremely reliable because the reaction hydride.

between its components exclusively in the case of the non-hypergolic part of the solid, combustible

contact can occur between a component that can be exposed, in particular from poly-

excluded the surface of the solid mass and the fluids, polystyrene, polyamides or even

liquid or gaseous mass take place, which in the mixtures of several of the

Combustion chamber is initiated. The seized substances.

In other words, unity is based on the fact that the internal parts of the hypergolic

ren layers of the solid mass so long not with the 45 part and the non-hypergolic part, which the

liquid or gaseous mass can react, form a solid combustible component, one can e.g.

as long as they do not choose between the following limits by destroying the upper limit:

surface layer are exposed so that automatically

there is a self-limitation of the reaction. Hypergolic part;. 10 to 60%

In addition, by regulating the 50 non-hypergolic part ... 90 to 40% guiding the liquid or gaseous mass into the

Combustion chamber, e.g. through a change For the Lithergole, some the pressure and / or the cross section of the feed. Examples brought: line and / or the injection process, the amount of liquid or gaseous mass supplied 55 1. Paraanisidine (80%) and plasticized poly changed be so that that in the combustion, vinyl chloride (20%), the latter loading. Chamber pressure noticeably changed component to 45% from polyvinyl chloride and to and thus ultimately the recoil can be 55% from a plasticizer such as e.g. can be adjusted, which simply consists of a re-butyl phthalate.

regulation of the supply of liquid or gas-conveying 60 2. Paraphenylenediamine (85%) and plasticized

moderate mass is achieved. Polyvinyl chloride (15%), the latter being the latter

The combustion always takes place with a large stabilizing component made up of 30% polyvinyl chloride and too did take place even if slight differences between 70% from a plasticizer, e.g. B. off the injection pressure of the gaseous or liquid butyl phthalate, if necessary under ZuMasse and the mean pressure exist which would add a soluble amine to the plasticizer the combustion chamber prevails, this providing means; e.g. with paratoluidine (e.g. 30% high stability is based on the fact that the two polyvinyl chloride, 30% plasticizer and Phases not due to porosity, miscibility or 40% paratoluidine).

3. Polyurethane (20%) and paraphenylenediamine

(80%).
4. Polyurethane (10%) and paraphenylenediamine (90%).

5. Polyurethane (20%) and naphthylenediamine (1.5) (80%).

6. Polyurethane (10%) and naphthylenediamine (1.5) (90%).

Examples second row

This example concerns the case where the liquid or gaseous component consists of several, the combustion conveying substances and the solid component consists of several combustible substances, whereby at least one of these components, considered in isolation, does not have a hypergolic character having the liquid or gaseous component. .

The liquid or gaseous component can e.g. B. have the following composition:

85 »/ ο nitric acid (d = 1.52) with an addition of 15 "/" nitrogen dioxide.

If the liquid or gaseous component is a component of the nitric acid-nitrogen dioxide type is used then one could generally increase the density of the mixture and as a result to reduce the size and weight of the reservoir for this component increase the proportion of nitrogen dioxide and in particular a proportion of 40% of this latter component provide, whereby one obtains the greatest density for the liquid or gaseous component.

The solid combustible component can consist of the substances given in the first row of the examples are.

The examples given above are only intended to illustrate the great variety of possible combinations serve, which fall within the scope of the invention.

In each individual case the most favorable proportions of the different constituents must be determined before the liquid or gaseous and the solid Gathering crowds, and there must also be the most expedient and effective working conditions can be determined under which the relevant masses can be produced.

For example, the liquid or gaseous, the combustion-promoting substance consists of nitric acid and the solid, hypergolic fuels made of lithium hydride and sodium borohydride, and the solid, non-hypergolic fuels are common Polyester.

In detail one uses z. B. two parts of a phthalic acid ester and one part maleic acid ester in solution in styrene, the esters making up 64 ^fl / o of the total mass and styrene making up 36%. The liquid polymerizes easily in the cold or warm in the presence of an oxidizing catalyst.

The addition of flammable hypergolic material to the polyesters must be done with a certain amount of caution, since chemical reactions with the esters or the styrene may occur.

The polyester used should not contain any free acid groups due to the incorporation harmful hydrogen could be released into the hypergolic fuel,

The catalyst used is preferably a substance which, among other things, can have a hypergolic effect, which is the case, for example, with borohydrides and amides.

In two special embodiments, the following composition is chosen for the fuel

Lithium hydride 64.5% 34%

Borohydride 2% 2%

Polyester. 33 5% 64%

The solid mass can either be in a special shape or in the combustion chamber of the jet drive and one can proceed as it is explained below with reference to FIG is, in which a combustion chamber is shown.

It starts in that the three individual components of the solid component in a container ^mi f ^ht ™ ^{d the} mixture then Stickstoffatmo ^s Ph ^{are in de. r} temperature of the environment for so long

let rest until a paste is obtained that is practical has the consistency of mastic, which takes about 6 hours.

The paste prepared in this way is then brought into the combustion chamber, which consists of a cylindrical Sleeve 1 can exist, which can for example also consist of duralumin. This cylindrical Sleeve 1 is provided at one end with a base 2 through which a cylindrical core 3 is held which, together with the inner wall of the sleeve 1, defines an annular space that is connected to this Paste is filled.

When this paste is poured in, a thin layer is poured onto the inner surface of the base 2 pure polyester (at a height of about 5 mm) through which the injection nozzles during operation of the Drive unit are protected, this protection is made possible by the fact that pure polyester has no hypergolic character towards nitric acid. The paste will then as well as it will gradually is introduced, compressed in the furnace, and, when the cylindrical sleeve 1 is filled, it is with the help a second plate 4 kept under pressure, which is pressed against the core 3, which for example can be done by means of a screw 5. The whole arrangement is then at one temperature of about 60 ° C for 8 hours in a heating furnace, whereupon this whole arrangement is applied to the Temperature of the environment is cooled and the bottom 2 and the plate 4 and the central core 3 removed will.

The cylindrical sleeve 1 is thus internally provided with an annular lining (5, which consists of a solid mass that is hard, dense and free of cracks and foam and that is firmly attached to the inner wall this sleeve 1 is anchored. Removing the bottom 2 and plate 4 and pulling them out of the core 3 can be made easier that these elements with a non-adhesive special lacquer be coated.

In order to complete the drive unit, the cylindrical sleeve 1, as shown in FIG is to be provided only on the one hand at one end with a base 7, which carries an injection nozzle 8, the

7 8.

is supplied with pressurized nitrogen, which comes from a saline portion (10 to 25%), the hypergolic beeperic acid container, and on the other hand, on the component (30 to 60%) and the metal powder (5 to the other end with a tube 9 are provided , 50%). ■. ■
its preferably insertable neck from one. Advantageous results are obtained if one consists of the appropriate refractory material. 5 Proportions of the solid component within the following The production of the solid component, for example, selects limits, which in the following, for example, for a drive unit, could be given in a similar way:

Way also take place in such a way that as hypergolic loading polyvinyl chloride 11%

part of this solid component instead of phthalic acid butyl ester 18%

Lithium hydride sodium hydride or potassium hydride paratoluidine 51 ° /

Another example is the nutty one

or gaseous substance that promotes combustion If one generally has the smallest free surface

still from nitric acid, while the solid, does not want to decrease, which the combustible solid phase provides

hypergolic substance consists of polyethylenes, whose 15 tet, and thereby the dimensions of the solid body

chemical structure allows it to decrease in a great deal, then one could reduce the proportion of

divertic hypergolic fuels in the form of paratoluidins, and one therefore has a

be worked without chemical secondary Lithergol with 85% paratoluidine and 15% plastic

has to fear reactions. For this reason fiertem polyvinyl chloride produced, which is still up to

If you mix in particular polyethylene with a 20 to 130 ° C remains gelatinous.

or more of the following substances: lithium hydride, in order to produce such a solid component - sodium hydride, sodium amide, potassium borohydride or oil, phthalic acid butyl ester and lithium aluminum hydride are added to a mixer. which contains polyvinyl chloride in suspension. The polyethylenes are normally added as a powder, then paratoluidine and stirred until dissolved, and they are mixed with the selected 25 of this latter component, these working hypergolic fuels, which are also powder, preferably carried out as a fine process at about 40 ° C, and the powder thus obtained becomes. Aluminum powder is then added, and it is then poured into a mold similar to that shown in FIG. 1 is further stirred, and then the form provided is poured, whereupon the entire product obtained is placed in a closable form, the voltage is brought to a temperature which is then heated ^{to about 130 ° C. for 2 hours.} Melting point of the system employed corresponds, after cooling, a dark gray, for example, ⁰ to 160 C, and wherein the homogeneous during this work Lithergol sphere and does not change in the Atmostufe this powder compacted as much as possible.

is so that the density of the mixture as large as possible Triggering the hypergolic reaction of a

will. 35 such lithergols with nitric acid can thereby

After taking off the mold you get a speed that you can hit the surface

Body of the combustion chamber, which is filled with one of these Lithergols, on which the nitric acid

Lithergol is provided, which is perfectly smooth and splashed, a layer with a composition

is homogeneous. of a stronger hypergolic character,

In the following another embodiment 4 °, e.g. made of polyvinyl chloride (about 23%), phthalic acid

of the invention described, according to which the solid butyl ester (about 35%) and lithium hydride (about

part of the system on the one hand by a powder of 42%), or from a suspension of 10% lithium

at least one metal is added, for example hydride in paratoluidine (which can be made with a brush or with

made of aluminum, beryllium, magnesium, lithium, which can be applied to the spray gun) or also

has a higher energy content. 45 a layer of paraphenylenediamine that is not

According to a further embodiment of the invention changed and the other, also hyper-

dung is used as a liquid, combustion-promoting golic part of the solid component before changes.

Component nitric acid or a solution of rangen protects.

Nitric dioxide is used in nitric acid, while a Lithergol, which is treated with the first composition for the solid component of the system, can be used with a liquid substance: this component, which consists of nitric acid, can be used as a metal powder, aluminum powder with a characteristic speed on the order of magnitude of fineness of the order of 2 microns, ^now S. y ^on 1800 m / sec. obtained, which in the case of a thermoplastic component as a polyvinyl drive unit to a pressure in the chamber of ■ chloride that has been plasticized with esters, for example, 55 25 kg / cm *, whereby a speci. with Phthalsäurebutylester, especially the fish itself thrust on the order of 250 m seconding acquaintances mixtures of 45 to 55% poly ^de ". ^e ™ · ^old.".., "_ .. ■ _u.
vinyl chloride with butyl phthalate, octyl adipate or ^{Em in} this way manufactured jet drive octyl phthalate is extremely adaptable because as a hypergolic component a solid organic ^6o ** thrust through a change in the supply. nic amine, especially paratoluidine of the fuel can be regulated. It was thus- (melting point 50 ° C, sublimation point even possible without creating a dangerous overpressure of 200 ° C), or one of the above-mentioned others, to interrupt the combustion and initiate like amines by adding the fuel.

65 fes was interrupted and then continued again.

The proportions used are available - no matter which embodiment is chosen, preferably within the following limits: the actual one receives a nozzle drive unit, its host thermoplastic Proportion (5 to 20%) that is clearly evident from the description in terms of plasticization

and that, without having to go into further detail, has a large number of advantages, under to which only the following are listed:

Stable combustion in a very large one Pressure range of the chamber, continuous change in pressure in the

Chamber depending on the supply of the oxidizing agent,

Possibility of regulating or implementing a predetermined program, higher performance,

very high operational reliability.

1 sheet of drawings

Claims (5)

Patent claims: 1. Hypergolic system for the generation of pressurized gas through the spontaneous reaction of a fluid, the combustion promoting phase, which consists of nitric acid, nitrogen dioxide, chlorine trifluoride and / or hydrogen peroxide, with a solid, non-porous shaped body, combustible phase, with which the fluid phase promoting combustion gradually progresses Way is brought into contact, thereby characterized in that the solid combustible phase consists of a mixture of one with the fluid, the combustion promoting phase hypergolically reacting portion and one with the fluid, the combustion promoting phase is not hypergolically reacting portion, wherein the hypergolic portion of the solid combustible phase made of lithium hydride, sodium hydride, potassium hydride, Lithium amide, sodium amide, potassium borohydride, sodium borohydride, lithium aluminum hydride, Paratoluidine, Paraanisidin, Paraphenylenediamine and / or Naphthylenediamine (1.5) consists, the non-hypergolic part of the solid combustible phase made of polyesters, polyethylenes, polystyrene, Polyamides, polyvinyl chloride and / or the elastomers of polyurethanes or rubber consists. 2. Hypergolic system according to claim 1, characterized in that the solid component The system also includes aluminum, beryllium, magnesium or lithium in powder form contains. 3. Hypergolic system according to claim 2, characterized in that the grain size of the Metal powder is below 10 microns and especially below 2 microns. 4. Hypergolic system according to claim 1 to 3, characterized in that the non-hypergolic Part consists of polyvinyl chloride, which with esters, z. B. with butyl phthalate is plasticized. 5. Hypergolic system according to one of the preceding "previous claims, characterized in that that the exposed surface of the solid component with a mixture of polyvinyl chloride, Butyl phthalate and lithium hydride or with a suspension of lithium hydride in Paratoluidine or covered with paraphenylenediamine.