EP3687962A1 - Composition generatrice de gaz - Google Patents
Composition generatrice de gazInfo
- Publication number
- EP3687962A1 EP3687962A1 EP18792970.8A EP18792970A EP3687962A1 EP 3687962 A1 EP3687962 A1 EP 3687962A1 EP 18792970 A EP18792970 A EP 18792970A EP 3687962 A1 EP3687962 A1 EP 3687962A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- nitrate
- composition according
- weight
- advantageously
- group
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
- C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
- C06D5/06—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
- C06B45/04—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive
- C06B45/06—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component
- C06B45/10—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component the organic component containing a resin
Definitions
- the present invention relates to solid gas generating compositions for emergency deballasting in submarines.
- the submarine Under normal conditions of use, to surface, the submarine must partially empty the ballasts of their water with gas and regain positive buoyancy. It is said that it "ballast hunt”.
- compositions generating gas For emergency deballasting, it is advantageous to use solid compositions generating gas.
- Such compositions based on glycidyl polyazide (PAG) and alkaline or alkaline earth nitrate are thus described in the DE19821010 application.
- PAG glycidyl polyazide
- alkaline or alkaline earth nitrate are thus described in the DE19821010 application.
- the advantage of these compositions is that they deliver a large amount of nitrogen, carbon dioxide and oxygen, which ensures the deballasting function, and that the products of combustion are without hydrogen and without monoxide carbon, prohibited gases because toxic and dangerous.
- Combustion products contain a significant amount of solid residues that result from the oxidation of the alkaline or alkaline earth nitrate, for example strontium oxide (SrO), calcium oxide (CaO ) or sodium oxide (Na2O). Conventionally, these products are in the solid state at the combustion temperature. They can disrupt the ballistic operation of the combustion chamber, possibly with nozzle plugging. • The PAG polymer has a very high cost, a cost that affects the price of the load to the point of making marketing problematic.
- the PAG azide-based polymer with a polyester having a hydroxy-terminus or a polyether having a hydroxy-terminus, such as polyethylene glycol (PEG) or diethylene glycol polyadipate (PADEG).
- PEG polyethylene glycol
- PADEG diethylene glycol polyadipate
- alkaline or alkaline-earth nitrate by a mixture of ammonium perchlorate or ammonium chlorate with an alkaline or alkaline-earth nitrate selected from the group consisting of sodium nitrate, potassium nitrate, strontium nitrate and barium nitrate.
- such a composition makes it possible to avoid the formation of solid residues during the generation of gases while avoiding the formation of the acid gas HCl due to the presence of chlorate and perchlorate by the formation of salts of alkali or alkaline chlorides earthy.
- the present invention therefore relates to a solid gas-generating composition
- a solid gas-generating composition comprising (advantageously consisting essentially of, in particular consisting of):
- a binder comprising (advantageously consisting essentially of, in particular consisting of) (a1) a polymer selected from the group consisting of polyesters having a hydroxy terminus, polyethers having a hydroxy terminus and mixtures thereof and (a2) a system crosslinking;
- an oxidizing charge constituted by a mixture of (bl) ammonium perchlorate or ammonium chlorate or their mixture with (b2) an alkaline or alkaline-earth nitrate selected from the group consisting of sodium nitrate, potassium nitrate, strontium nitrate, barium nitrate and mixtures thereof.
- composition according to the present invention therefore comprises (a1) a polymer selected from the group consisting of polyesters having a hydroxy terminus, polyethers having a hydroxy terminus and mixtures thereof.
- the polymer (a1) is chosen from the group consisting of polybutylene oxide, polytetramethylene oxide, polyoxypropylene glycol, polyethylene glycol, diethylene glycol polyadipate and mixtures thereof, advantageously in the group consisting of polyethylene glycol, diethylene glycol polyadipate and their mixture, in particular it is diethylene glycol polyadipate (PADEG).
- the composition according to the invention further comprises (a2) a crosslinking system.
- the crosslinking system that can be used in the composition according to the present invention is advantageously liquid and in particular chosen from polyisocyanates such as toluene diisocyanate, in particular alicyclic polyisocyanates, such as dicyclohexylmethylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate or biuret triisocyanate.
- the crosslinking system is generally present in the composition in a content of between 0.4 and 5% by weight relative to the total weight of the composition.
- composition according to the present invention further comprises (b1) ammonium perchlorate or ammonium chlorate or a mixture thereof.
- ammonium perchlorate is preferred.
- the composition according to the present invention furthermore comprises a nitrate (b2) chosen from the group consisting of sodium nitrate, potassium nitrate, strontium nitrate, barium nitrate and their mixtures, advantageously in the group consisting of sodium nitrate, potassium nitrate and their mixture, still more advantageously, it is sodium nitrate.
- composition according to the present invention comprises (advantageously essentially consists of, in particular is constituted by):
- a binder comprising (advantageously consisting essentially of, in particular consisting of) (a1) PADEG and (a2) an isocyanate crosslinking system;
- an oxidizing charge consisting of a mixture of (bl) ammonium perchlorate with (b2) sodium nitrate.
- the nitrate content (b2) is such that the neutralization of the alkaline by the chlorine of ammonium perchlorate or ammonium chlorate is complete.
- it is between 40 and 57% by weight relative to the total weight of the filler (b), advantageously between 42 and 56.3% by weight.
- the nitrate content (b2) is between 44 and 57% by weight relative to the total weight of the filler (b), advantageously between 45.degree. , 6 and 56.3% by weight.
- the component (b1) is ammonium perchlorate and the nitrate content (b2) is between 40 and 55% by weight relative to the total weight of the filler (b), advantageously between 42 and 52.7% by weight.
- Table 1 below gives the precise mixtures allowing the neutralization of the alkaline by chlorine.
- the binder content (a) is sufficient to allow the composition according to the invention to be manufactured, more advantageously castable.
- this content is at least 10% by weight relative to the total weight of the composition according to the invention.
- the binder content (a) is not too important to avoid the appearance of carbon monoxide and hydrogen.
- the binder content (a) is between 10 and 20% by weight, more preferably between 12 and 18% by weight, relative to the total weight of the composition according to the invention.
- the binder (a) according to the invention is PEG
- its content is between 11 and 18% by weight, advantageously between 12 and 17% by weight relative to the total weight of the composition according to the invention. 'invention.
- binder (a) according to the invention is PADEG
- its content is between 12 and 19% by weight, advantageously between 13 and 18% by weight relative to the total weight of the composition according to the invention.
- the content of binder (a) is between 11 and 17% by weight, advantageously between 12 and 16% by weight. weight relative to the total weight of the composition according to the invention.
- the content of binder (a) is between 14 and 19% by weight, advantageously between 15 and 18%. by weight relative to the total weight of the composition according to the invention.
- Table 2 below gives examples of binder content according to the composition according to the invention.
- composition according to the present invention may further comprise additives such as, for example, antioxidants, wetting agents, manufacturing additives, chain extenders, polymerization catalysts, combustion modifiers (accelerators or retarders), ballistic additives (eg cooling such as copper or bismuth salt, iron oxide), adhesion agents binder-loads and bridges.
- additives such as, for example, antioxidants, wetting agents, manufacturing additives, chain extenders, polymerization catalysts, combustion modifiers (accelerators or retarders), ballistic additives (eg cooling such as copper or bismuth salt, iron oxide), adhesion agents binder-loads and bridges.
- additives are generally present in the binder (a).
- the additives, if present, are generally present in the composition in a content of between 0.1 and 10% by weight relative to the total weight of the composition.
- composition according to the present invention advantageously does not comprise aluminum, in particular in the form of powder.
- nitric esters such as nitroglycerin, BTTN or TMETN.
- the present invention further relates to a pyrotechnic charge characterized in that it comprises the composition according to the present invention in a structure.
- the loadings can be full or channel, advantageously they are channel, especially central channel.
- the structures are conventional structures like propellant structure.
- the loading is possibly starred or slightly evolutive.
- the loads are generally incorporated in cylinders. They can have a weight ranging from 50 to 200 kg.
- the solid composition according to the invention is manufactured according to the methods conventionally used for this type of composition. For example by mixing in a kneader in which the various ingredients are introduced in an appropriate order and carefully and thoroughly kneaded under given pressure and temperature conditions. This mixture, which is in the form of a paste, is cast in a mold with shaping tools. The whole is baked to ensure the hardening of the dough.
- the present invention finally relates to the use of the composition or the pyrotechnic charge according to the invention for the generation of clean gas for the rapid flushing of submarine ballasts, that is to say for the emergency deballasting of vehicles. submarines.
- the generator consists of a combustion chamber in which is housed the loading, a sealed nozzle and an igniter.
- the pressure in the combustion chamber equilibrates around 10 MPa, the combustion flow rate (sensitive to the combustion rate and the combustion surface) evacuating through the neck of the nozzle initiated. After the nozzle exit, the gases are led into the ballast. The pressure rise in the ballast makes it possible to evacuate the water.
- the gases obtained do not have solid residues and only infinitesimal quantities of HCl.
- the gases obtained being nitrogen, carbon dioxide and oxygen.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Molecular Biology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Air Bags (AREA)
- Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1759146A FR3071831B1 (fr) | 2017-09-29 | 2017-09-29 | Composition generatrice de gaz |
| PCT/FR2018/052339 WO2019063923A1 (fr) | 2017-09-29 | 2018-09-24 | Composition generatrice de gaz |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP3687962A1 true EP3687962A1 (fr) | 2020-08-05 |
| EP3687962C0 EP3687962C0 (fr) | 2024-06-12 |
| EP3687962B1 EP3687962B1 (fr) | 2024-06-12 |
Family
ID=61521551
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP18792970.8A Active EP3687962B1 (fr) | 2017-09-29 | 2018-09-24 | Composition generatrice de gaz |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP3687962B1 (fr) |
| FR (1) | FR3071831B1 (fr) |
| WO (1) | WO2019063923A1 (fr) |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3215573A (en) * | 1963-04-22 | 1965-11-02 | Aerojet General Co | Polyurethane-base propellants containing unsaturated hydrocarbons |
| FR2709488B1 (fr) * | 1990-08-24 | 1996-04-26 | Hercules Inc | Propergol solide à liant contenant un polyéther non cristallin et un plastifiant énergétique. |
| DE19821010C1 (de) | 1998-05-11 | 1999-10-28 | Bayern Chemie Gmbh Flugchemie | Gasgenerator-Festtreibstoff und dessen Verwendung |
| US6835255B2 (en) * | 1998-06-01 | 2004-12-28 | Alliant Techsystems Inc. | Reduced energy binder for energetic compositions |
| FR2818636B1 (fr) * | 2000-12-22 | 2003-02-28 | Poudres & Explosifs Ste Nale | Compositions pyrotechniques generatrices de gaz a liant hydrocarbone et procede de fabrication en continu |
| FR2959508B1 (fr) * | 2010-04-29 | 2015-01-02 | Snpe Materiaux Energetiques | Compose pyrotechnique generateur de gaz; procede d'obtention |
-
2017
- 2017-09-29 FR FR1759146A patent/FR3071831B1/fr active Active
-
2018
- 2018-09-24 EP EP18792970.8A patent/EP3687962B1/fr active Active
- 2018-09-24 WO PCT/FR2018/052339 patent/WO2019063923A1/fr not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| EP3687962C0 (fr) | 2024-06-12 |
| FR3071831B1 (fr) | 2021-06-11 |
| WO2019063923A1 (fr) | 2019-04-04 |
| FR3071831A1 (fr) | 2019-04-05 |
| EP3687962B1 (fr) | 2024-06-12 |
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