CN103180271A - Pyrotechnic gas generator compounds - Google Patents
Pyrotechnic gas generator compounds Download PDFInfo
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- CN103180271A CN103180271A CN2011800515939A CN201180051593A CN103180271A CN 103180271 A CN103180271 A CN 103180271A CN 2011800515939 A CN2011800515939 A CN 2011800515939A CN 201180051593 A CN201180051593 A CN 201180051593A CN 103180271 A CN103180271 A CN 103180271A
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
- C06B23/007—Ballistic modifiers, burning rate catalysts, burning rate depressing agents, e.g. for gas generating
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
- C06B21/0033—Shaping the mixture
- C06B21/0066—Shaping the mixture by granulation, e.g. flaking
-
- 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
- C06B25/34—Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B29/00—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate
- C06B29/02—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate of an alkali metal
- C06B29/08—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate of an alkali metal with an organic non-explosive or an organic non-thermic component
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- 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
- C06D5/02—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by decompressing compressed, liquefied or solidified gases
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Air Bags (AREA)
- Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)
Abstract
The main subject of the present invention is a solid pyrotechnic gas generator compound, the composition of which contains, expressed as weight percentages: - from 60 to 70% of guanidine nitrate, - from 26 to 33%, advantageously 26 to 30%, of potassium perchlorate, - from 2.5 to 6% of at least one combustion modifier chosen from transition metal oxides, the precursors of such oxides and mixtures thereof, from 0 to 6% of at least one additive, and does not contain an explosive ingredient. Such a compound is particularly effective for the inflation of side airbags.
Description
Technical field
Theme of the present invention is gas-Generating Pyrotechnic Compounds, and this mixture is applicable to the vehicle passenger safeguard system, more specifically is applicable to airbag inflated, is applicable to the most specifically side airbag inflation (referring to following).
Background technology
In the past twenty years, the technical field that relates to the vehicle passenger protection has experienced very great development.The latest generation motor vehicle has been integrated the security system of some air bag types in passenger accommodation at present, and the operation of this security system is to complete by the combustion gases of pyrotechnics mixture.In air bag type system, mainly be divided into for the frontal airbag of head-on crash and the side airbag that is used for side collision.
Difference in side airbag system and frontal airbag system nature is air-bag deployment and needed time of location.Usually, this time shorter (be about 10ms-20ms, frontal airbag needs 40ms-50ms by contrast) of side airbag needs.For side airbag, the functional requirement of inflation makes that it need to (product ρ * n * Tc * Vc), described composition have sufficiently high rate of combustion (generally be equal to or greater than 30mm/s or even 35mm/s) under 20MPa in the whole working pressure range in the producer combustion chamber to obtain enough unit surface inflation rates by means of following pyrotechnic composition at short notice.In addition, turn round smoothly in order to guarantee this system, described pyrotechnic composition must also have good flammability characteristics.And the surface profile of considering the spice (ball type) that uses is convergent normally, and said composition should under low pressure have stable and sufficiently high rate of combustion in theory.In fact, what those skilled in the art knew is that the technical requirements that is used for side airbag is more stricter than the technical requirements that is used for frontal airbag.Certainly, any technical progress in described side airbag field also can be advantageously used in the frontal airbag field.
In this article, term " low pressure " is used for defining the pressure P that satisfies 0.1MPa≤P＜10MPa, and term " middle pressure " is used for defining the pressure P that satisfies 10MPa≤P＜30MPa, and term " high pressure " is used for defining the pressure P that satisfies P 〉=30MPa.
In addition, usually by by means of the spice that is comprised of the very little pill of size (pellets), the low rate of combustion of the pyrotechnics mixture that the existing producer gas generator for air bag is used compensates.Although because the tablets press tooling cost that yields poorly and produce by weight causes not having cost efficiency, yet this makes the deficiency that can partly overcome to a certain extent rate of combustion.Yet this solution has been given prominence to other two shortcomings:
-being difficult to ignite, this defective increases because the spice initial surface area is high, and requires to use the detonator that strengthens, or has added the auxiliary spice of relaying thing (relay) effect of igniting;
-the burning surface that causes because pellet size is little sharply reduces, and under low pressure produces long burning hangover (combustion tail).The burning hangover that this is under low pressure grown is the discharging source at the most toxic substances that exist for the gas that makes airbag aeration.
Therefore should be noted that, the pyrotechnics mixture of discussing (comprises under low pressure) increase of required rate of combustion thereby not only needs to strengthen the technical requirements that flow rate of gas postpones to reach inflation in whole pressure range, and needs to guarantee described the mixture not combustibility when using the relaying spice and the innocuousness of products of combustion.
And, according to temperature of combustion, also exist constraint condition.
As a rule, described temperature of combustion can not too high (must keep below 2400K under bottom line, more preferably less than 2350K) so that the unlikely damage of the gas temperature in air bag occupant healthy.Low combustion temperature makes it possible to limit the thickness of air bag on the one hand, makes it possible on the other hand simplify by the existence that reduces producer gas generator Internal baffle and strainer the design of described producer.
Side airbag system may need the producer gas generator of two types: the producer gas generator of all-pyro type (providing uniquely gas to generate by the burning of pyrotechnics spice) is provided, and the producer gas generator that is called as " mixed type " (jointly producing gas by the burning of pyrotechnics spice and by the neutral gas (neutral gas) of storing of pressurizeing in sealed vessel).For " mixed type " producer, the temperature of combustion of pyrotechnics spice is necessary can not be too low, so just can make enough heat of combustion gases, reduced by the temperature that precompressed neutral gas volumetric expansion causes with compensation.Ideally, require temperature of combustion higher than 2000K.
Therefore, those skilled in the art are seeking the pyrotechnics mixture that is suitable for all-pyro type producer gas generator or mixed type producer, more particularly be intended to for side airbag, namely has simultaneously approximately 2000K-2400K, the more preferably moderate temperature of combustion of 2000K-2350K, and (comprise under low pressure) in the whole service pressure range and all have high combustion speed (particularly under 20MPa higher than 30mm/s, more preferably under 20MPa higher than 35mm/s).
In addition, the pyrotechnics mixture that is used for air bag also must be intended to meet simultaneously following requirement:
The gas that-pyrotechnics spice (comprising one or more compounds) burning produces must be nontoxic, namely has carbon monoxide, oxynitride and the chlorine-containing compound of low levels;
-gas yield (i.e. the amount of the gas that burning produces) must be high to produce high inflation power;
-solids that produce, can consist of the focus that can damage the substitute cyst wall must keep low amount by burning;
-pressure index especially must low as far as possible (as description of the prior art, generally lower than 0.35) under medium and high pressure, and under low pressure also must be low as far as possible.In fact low pressure index makes it possible to be reduced in very significantly the operation variability between low temperature extreme value (40 ℃ of left and right) and high temperature extreme value (90 ℃ of left and right), and this is also the requirement of application facet.Its result also advantageously reduces the size of described producer metal construction for improving operation repeatability;
-its cut-off combustion pressure (ultimate pressure of its burning) must be as far as possible near barometric point.
For the basal component of described mixture, it is very desirable equally that the viewpoint that occurs from pyrotechnics is not had danger.Advantageously avoid existing the composition that belongs to the explosive substance class, as nitroguanidine, hexogen (hexogen, RDX) or octogen (octogen, HMX).Term " blasting compound " refers to that classification belongs to the composition of risk grouping 1.1 (referring to UNO-Recommendations relating to the transport of dangerous goods-manual of tests and criteria according to standard NF T70-502, the 4th revised edition, ST/SG/AC.10/11/Rev.4, ISBN 92-1-239083-8ISSN 1014-7179 and STANAG 4488).The Guanidinium nitrate that uses separately and potassium perchlorate and non-categorical belong to the composition of this risk grouping.Especially within connotation of the present invention, they do not consist of blasting compound.
Even this stage should be pointed out that with extremely low-levelly mix the high energy blasting compound, as nitroguanidine, also can adversely impel the temperature of combustion of mixture to raise, exceed the cutoff threshold by the desired determined 2350K of technological improvement needs of contriver.Therefore, in the mixture technical requirements not according to the invention that is mainly formed by guanidine derivative (preferred Guanidinium nitrate), explosive nitrogenous compound (preferred nitroguanidine) and inorganic oxidizer (as ammoniumper chlorate or potassium perchlorate) described in patent US 6 893 517.These mixtures also comprise low-level impact catalyzer (ballistic catalyst) in it forms, described impact catalyzer is comprised of the oxygenatedchemicals of transition metal, preferably have high specific surface area, usually be used for improving the rate of combustion (this catalyzer accelerates the decomposition of oxidation spice) under medium and high pressure in propelling agent (propellant) field.By pulsing operation, require to have high rate of combustion at the micro gas generator that is used for safety belt tensioning device described in described patent US 6 893 517 (and priority application EP 1 275 629) under medium and high pressure.The mixture of discussing pressure index under low pressure is high and burning does not under atmospheric pressure occur not is problem, because in the situation that use described mixture, described pressure can be down to low-level before the pyrotechnics effect finishes again.For producer gas generator, this application that is used for safety belt tensioning device does not need as context (air bag of the present invention, especially side airbag) the high combustion speed under strict like this requirement, especially low pressure, cut-off combustion pressure threshold value reduce (as far as possible near normal atmosphere) and the low pressure index of (particularly under low pressure) in whole combustion range.
At present, for frontal airbag, the pyrotechnics mixture that good compromise is provided aspect gas temperature, gas yield, emitted particle level and toxicity comprise as the Guanidinium nitrate (GN) of reduction spice and as the basic copper nitrate (BCN) of oxidation spice as main component.Patent US 5 608 183 and US 6 143 102 have described this mixture.
Yet these mixtures have relatively low rate of combustion, less than or equal to 20mm/s, but also have low gas yield under 20MPa.And they also are difficult to ignite.
From improving the flammable angle of this class mixture, propose in the prior art based on adding perchlorate in the composition of Guanidinium nitrate (GN) and basic copper nitrate (BCN) to it.Therefore, patent application EP 1 526 121 has described a small amount of (being less than 5wt%) interpolation perchlorate (particularly potassium perchlorate) to improve igniting of these mixtures.Yet, mix perchlorate with low amount like this and can not fully improve the rate of combustion of described mixture to use at the producer gas generator that is used for side airbag satisfactorily.
Patent application WO 2007/042735 and WO 2009/126702 have described the mixture of same-type, its composition comprises as the Guanidinium nitrate (GN) of reduction spice, as the basic copper nitrate (BCN) of main oxidation spice and the second extra oxidation spice, and described the second oxidation spice is preferably by potassium perchlorate (KClO
4) form.These files are the high combustion speed under the superperformance of described mixture, particularly high pressure, are associated (described technique comprises for the dry method rolling of WO 2007/042735 (dry roller compacting) step and is used for the spray-drying of WO 2009/126702 and compresses this two consecutive steps) with its composition and for the production of the special process of described mixture.
From improving the angle of gas yield and rate of combustion, the mixture of uniting with perchlorate type strong oxidizer based on the one (or more) nitrogenous reducing agent also proposes according to prior art.
Patent application US 2006/0137785 has described the mixture of guanidine type reductive agent (nitroguanidine or Guanidinium nitrate) and ammoniumper chlorate, and ammoniumper chlorate must mix with significantly a large amount of (30wt% to 60wt%).The ammoniumper chlorate that mixes high-content like this causes two main shortcomings: the first, and temperature of combustion significantly improves (higher than 2800K); The second, produce hydrogenchloride (poisonous and gas that corrodibility is very strong), described hydrogenchloride is present in gaseous effluent subsequently.In order to overcome this problem, described patent has been described and need to have been added the iron oxide type metallic compound in guanidine+ammoniumper chlorate type mixture, thereby neutralization is present in the hydrochloric acid in combustion gases, causes the gas yield of described mixture to descend.
Mixing potassium perchlorate replaces ammoniumper chlorate to have advantages of making forming Repone K (KCl) rather than hydrogenchloride (HCl) (but the shortcoming that reduces gas yield is also arranged).Under any circumstance, mix the KClO of high-content like this
4(upper to 60wt%) will make temperature of combustion raise, and this is fully unacceptable under the background that expection is used.
Therefore in logical mode, those skilled in the art turn to the mixture by compositions of mixtures, described mixture comprises the potassium perchlorate (KClO of Guanidinium nitrate (GN uses separately or unites with co-conducer) and moderate (approximately 25wt% to 45wt%)
4), as the description in patent application WO 95/25709 and patent US 5 854 442 and US 5 997 666, described mixture make can obtain part meet the present invention for the mixture of the necessary demand of Application Areas, that is:
-good gas yield;
-moderate temperature of combustion;
-particulate emissions is nontoxicity in itself; And
-compare slightly with the composition of preparing based on Guanidinium nitrate (GN) and basic copper nitrate (BCN) in the rate of combustion of about 20MPa and be improved, but still be not enough to for side airbag.
The thermodynamic behaviour of this mixture (reference mixture 1) and impact characteristics (ballistic characteristics) provide in table 1 hereinafter, and (" binary ") of described mixture forms and only comprise Guanidinium nitrate (GN) and potassium perchlorate (KClO
4).
Table 1
(1) value that provides is relative pressure, the corresponding normal atmosphere of the null value of cut-off combustion pressure.
Among the desired advantage of mixture that is used for airbag system generation gas, reference mixture 1 shows many advantages.Basal component simply ready-made, not expensive, very safe aspect pyrotechnics (not containing the composition that belongs to the explosive compound class) and nontoxic.Thermomechanical property (gas yield, fraction of particle) is good, and the temperature of combustion maintenance is moderate, is therefore acceptable.The particulate of being emitted by burning is nontoxic (being essentially KCl).
Yet this mixture does not show whole expectation performances, particularly for side airbag is used.At first, under 20MPa approximately the rate of combustion of 26mm/s with compare with the mixture of basic copper nitrate (BCN) based on Guanidinium nitrate (GN), only promoted 20% to 30%, and still lower with respect to the technical requirements of setting.Secondly, carrying out test period with this reference formula, although find with potassium perchlorate (KClO
4) when all replacing basic copper nitrate (BCN) oxygenant and making it possible to improve higher than 5MPa rate of combustion and therefore improve flammable, but highly adversely cause on the contrary having very high pressure index under low pressure (in the scope of 6MPa to 10MPa greater than 0.55), and can not burn under atmospheric pressure that (extra test shows that the cut-off operating pressure is the 1.7MPa left and right; And advantageously under atmospheric pressure have non-zero burning (nonzero combustion) based on the mixture of Guanidinium nitrate (GN) and basic copper nitrate (BCN) preparation).
Summary of the invention
By Guanidinium nitrate (GN)/potassium perchlorate (KClO
4) known performance of mixture sets out, the contriver wishes the gas-Generating Pyrotechnic Compounds that proposes to improve, described mixture especially is suitable for side airbag.These mixtures make especially and himself significantly improve the target of following 3 when keeping or improving other features:
-cut-off combustion pressure reduces;
-from 6MPa, pressure index reduces (＜0.26), and preferred a large amount of reduce (≤0.2) are very preferably to reduce very in a large number (≤0.1);
-in whole pressure range, particularly under low pressure, rate of combustion improves.
fully unexpectedly prove, exist a kind of oxygen transistion metal compound (precursor compound of transition metal oxide or this monoxide) that contains of (at least) of low levels also to be improved (namely in the composition of mixture of the present invention at desired above-mentioned 3, rate of combustion under low pressure also improves, the cut-off combustion pressure reduces and reduces at whole pressure range internal pressure index) have a main effect, described contain the oxygen transistion metal compound preferably have high specific surface area (usually in the propelling agent field as impacting catalyzer, be used under high pressure promoting rate of combustion (decomposition by the accelerated oxidation spice realizes)).
The composition of gas-Generating Pyrotechnic Compounds of the present invention (be particularly suitable for airbag applications, especially side airbag is used) comprises:
-Guanidinium nitrate, and
-potassium perchlorate.
It is characterized in that, described composition comprises by weight percentage:
-60% to 70% Guanidinium nitrate;
-26% to 33%, preferred 26% to 30% potassium perchlorate;
-2.5% to 6% at least a combustion modifiers, described combustion modifiers are selected from the precursor of transition metal oxide, this type oxide and the mixture of above-mentioned substance;
-0 to 6% at least a additive; And
Do not comprise blasting compound.
According to a modification, the composition of mixture of the present invention (only) forms (GN+KClO by mentioned component
4+ at least a combustion modifiers+optional at least a additive), select the above-mentioned content of mentioning.
The composition of above-mentioned first three types (Guanidinium nitrate, potassium perchlorate and concrete combustion modifiers) is usually above the 90wt% of mixture of the present invention (composition) gross weight, very as a rule is 94wt% at least, or even higher than 98wt%.Be susceptible to clearly and optional have additive, as making auxiliary material (for example calcium stearate, silicon-dioxide).The composition of above-mentioned three types can account for the 100wt% of mixture gross weight of the present invention fully.
In addition, the Guanidinium nitrate that accounts for gross weight 60% to 70% due to the pyrotechnics security reason with and rheology plasticity (rheoplastic) performance select, described rheology plasticity is suitable for carrying out the packing stage of dry way process and optional one-tenth ball stage (vide infra), guaranteed the excellent sealing of initial powdery pyrotechnics composition has been limited institute's applied pressure load simultaneously.Make described mixture through dry way process and comprise 4 key steps (vide infra) at the most, existing special description the in patent application WO 2006/134311.
In the composition of mixture of the present invention, there be (by 26wt% to 33wt%, preferably by 26wt% to 30wt%) particularly according to temperature of combustion, " combustibility " and the rate of combustion under the target high pressure in potassium perchlorate with moderate intermediate amounts.
At GN+KClO
4In mixture, the combustion modifiers of being selected by the inventor manifests according to desired 3 improves (referring to above-mentioned) particularly advantageous (unforeseeable) performance.
Described at least a combustion modifiers is selected from the precursor of transition metal oxide, this type oxide and the mixture of above-mentioned substance.The precursor of this type oxide makes and forms this type oxide (producing this type oxide) when decomposing at its temperature between pyrotechnics mixture main combustion period.Therefore, basic copper nitrate (Cu (NO
3)
23Cu (OH)
2) be decomposed into cupric oxide (CuO) (referring to following).
Described at least a combustion modifiers with the amount that is enough to onset (〉=2.5wt%) have (according to above-mentioned 3 improvement), and inexcessive (thereby≤6wt%) be unlikely to damage gas yield.Usually there is a kind of this type of combustion modifiers, has at least two kinds of examples of such additives yet also clearly imagined within the scope of the invention.
Preferably, described at least a combustion modifiers is selected from zinc oxide (ZnO), ferric oxide (Fe
2O
3), chromic oxide (Cr
2O
3), Manganse Dioxide (MnO
2), cupric oxide (CuO), basic copper nitrate (Cu (NO
3)
23Cu (OH)
2) and the mixture of above-mentioned substance.The precursor basic copper nitrate of cupric oxide and described cupric oxide (producing with regard to the meaning that forms cupric oxide when decomposing at a certain temperature with regard to BCN) is effective especially.Therefore particularly preferably be, mixture of the present invention comprises as the cupric oxide of combustion modifiers and/or basic copper nitrate.Use these combustion modifiers to make and to obtain to be less than or equal to 0.1 mixture of the present invention in pressure range 6MPa-52MPa internal pressure index value.
Preferably, at least a combustion modifiers according to the present invention has greater than 3m
2/ g, be preferably greater than 10m
2/ g, very preferably greater than 25m
2The specific surface area of/g.
Be understandable that, the described at least a concrete effect of combustion modifiers (being selected from the mixture of transition metal oxide, its precursor and above-mentioned substance) in the composition of mixture of the present invention is not only as improving rate of combustion in prior art (especially referring to patent US 6 893 517 mentioned above instruction) under high and medium voltage, and unexpectedly gives described pyrotechnics mixture following character:
-under low pressure (or even equaling under atmospheric pressure actual) stable and self-sustained burning;
-compare higher rate of combustion under low pressure with prior art compositions;
-low pressure, medium and high pressure overdraft index is low or even actual be zero, this compares remarkable reduction with the composition of prior art, and this does not produce the temperature of combustion about too much solid particulate and 2300K when making described mixture have " good combustibility ", burning.
What can mention is that the mixture of the present invention that its composition more than has been described in detail in detail has herein:
-lower than the temperature of combustion of 2350K;
-be less than or equal to 1.5MPa, preferably less than 0.2Mpa, very preferably equal the cut-off combustion pressure (relative value is namely take normal atmosphere as benchmark) of 0.1MPa;
-for the pressure at 6MPa to 52MPa, be less than or equal to 0.25, preferably be less than or equal to 0.2, very preferably be less than or equal to 0.1 pressure index;
-following rate of combustion:
Greater than 24mm/s, be preferably greater than 36mm/s under+low pressure,
+ in depress greater than 30mm/s, be preferably greater than 35mm/s,
Greater than 37mm/s, be preferably greater than 45mm/s under+high pressure.
It must be emphasized that, mixture of the present invention has low or even low-down pressure index herein.
The above-mentioned optimal result of mentioning (preferred modification and modification very preferably) uses cupric oxide and basic copper nitrate as combustion modifiers to obtain especially.In order to support this conclusion, can be with reference to embodiment hereinafter.
So in the context of the present invention, oxide compound and the original purposes (especially take above-mentioned parameter as benchmark) (described purposes with respect to impact catalyzer in difference form known conventional use be original) of oxide precursor in the composition of mixture of the present invention discussed have been proposed.
At mentioned component (GN+KClO
4The combustion modifiers of+at least a particular type) outside, pyrotechnics mixture of the present invention also can comprise low levels and (be less than or equal to 6wt%, usually at least a additive 0.1wt% at least), particularly: at least a additive (the moulding effect in procurement process) that obtains described mixture, for example calcium stearate or Magnesium Stearate, the graphite of impelling; And/or the additive of the cohesion the during burning of the described solid phase prod of at least a improvement, be selected from refractory oxide with the softening temperature that adapts with described composition or fusing point, as silicon-dioxide or aluminum oxide.This refractory oxide is preferably silicon-dioxide, usually (is preferably 100m so that specific surface area is high
2More than/g) the finely powdered form (be preferably the micron order size, be very preferably nano-grade size) introduce, or introduce take minor diameter (1 micron to 20 microns), length as the form of the silica fiber of tens of microns or hundreds of microns (20 microns to 500 microns).Proof unexpectedly, the situation for silicon-dioxide exists with the content of 0.5wt% to 6wt%, preferred 0.5wt% to 3.5wt% in pyrotechnics mixture of the present invention has the effect of the reduction cut-off combustion pressure of highly significant equally.
What therefore give the credit to equally the contriver is to have proved that silicon-dioxide is at GN+KClO
4Effect (table 3 vide infra) during type forms and therefore at composition (GN+KClO of the present invention
4+ at least a combustion modifiers) effect in, wherein said effect have been taken into account the effect (having contained the effect that reduces the cut-off combustion pressure) when having at least a combustion modifiers.
Described at least a additive participates in moiety (GN, KClO
4The combustion modifiers of+at least a the above-mentioned type) (when beginning in manufacturing process), or further add in the follow-up phase of the operation of making mixture of the present invention.
The composition of having stated mixture of the present invention does not comprise blasting compound (referring to the above-mentioned NF standard that provides and UNO suggestion), and this point is special in following parameter: pyrotechnics security and temperature of combustion.Notice in addition, the weight of the pyrotechnics mixture that air bag, especially side airbag inflation are required is greater than inflating required weight (described inflation does not belong to same type: inflationtime is higher than the 10ms-20ms/ pulse) according to safety belt tensioning device in patent US 6 893 517.
Pyrotechnics mixture of the present invention can obtain according to the wet method operation.According to a modification, described operation comprises extrudes the mashed prod that comprises the component of described mixture.According to another modification, described operation comprises the following steps: will own (or part) main ingredient and be placed in the aqueous solution, comprise at least a (oxygenant and/or the reductive agent) solubilising in described main component, and produce powder, add the component of not inserting solution in the powder that produces, and be object form by common dry method operation with described powder compacting subsequently by spraying drying subsequently.
Pyrotechnics mixture of the present invention also can obtain by the dry method operation, for example by becoming simply ball to obtain by the powder that mixes its component acquisition.
Comprise for the preferable process that obtains pyrotechnics mixture of the present invention the step that described mixture is in mixture (except the described at least a additive that can add) the dry method compacting of the moiety of powder type during operation.The dry method compacting is usually in a manner known way in roll squeezer, 10
8Pa to 6 * 10
8Carry out under compaction pressure between Pa.It can carry out according to different modification (characterization step with " simply " compacting continues with at least one extra step, and this extra step is carried out the characterization step of compacting for combining with forming step).Therefore, can there be (especially producing resulting composite according to manufacturing process) in a variety of forms in pyrotechnics mixture of the present invention:
-combine with the moulding effect and carry out dry method compacting (by using at least one compression roll, its outside surface has cavity), obtain to have the plate-like product of protruding pattern when finishing, can be with the pyrotechnics product of its fragmentation with direct acquisition moulding;
Granulation is carried out in the compacting of-dry method again, obtains particle when finishing;
Granulation is carried out in the compacting of-dry method again, becomes subsequently ball (dry method compression), obtains pill when finishing;
Granulation is carried out in the compacting of-dry method again, subsequently resulting particle is mixed with extrudable tackiness agent, and the described tackiness agent that is loaded with described particle is extruded, obtain the monoblock (monolithic blocks) (being loaded with described particle) of extruding when finishing.
Therefore, pyrotechnics mixture of the present invention especially can exist with the product form of following type:
-particle;
-pill;
-monoblock.
On nonrestrictive meaning, can propose at this:
The particle diameter (median diameter) that-particle of the present invention has 200 μ m to 1400 μ m usually (and has 0.8cm
3/ g to 1.2cm
3The apparent density of/g);
-pill of the present invention has the thickness of 1mm to 3mm usually.
When obtaining mixture of the present invention by the dry method operation, the moiety of mixture of the present invention preferably has thin particle diameter, is less than or equal to 20 μ m.Described particle diameter (median diameter) is generally 3 μ m to 20 μ m.If pass through the dry method operation by the KClO of median particle diameter at 10 μ m to 20 μ m
4Guanidinium nitrate powder between powder and 5 μ m to 15 μ m obtains mixture of the present invention, and this mixture shows its whole potentiality (potential).
According to another theme, the present invention relates to powder composition (mixture of powder), described composition is the precursor of mixture of the present invention, therefore the composition of described precursor is corresponding to the composition (referring to above-mentioned) of mixture of the present invention.
According to another theme, the present invention relates to comprise the producer gas generator of at least a mixture of the present invention.Described producer is applicable to air bag fully, especially side airbag (referring to above-mentioned).
Next in unrestriced mode, the present invention is described in detail.
Following table 2 has provided the example of the composition of mixture of the present invention, and the prior art mixture 1 of described mixture and the reference performance of comparing.Described mixture utilizes calculation of thermodynamics or based on particle or pill are carried out physical measurement and estimated, by composition through mixed powder-compacting-granulation-and the dry method operation of choosing into ball wantonly make described particle or pill.
The prior art mixture 1 of reference (referring to above-mentioned table 1) comprises Guanidinium nitrate and potassium perchlorate, and does not comprise any combustion modifiers within implication of the present invention.The mixture of embodiment 1 to embodiment 7 except two kinds of compositions of reference mixture 1, also comprises this type of combustion modifiers in it forms.
The amount of having adjusted main component to be keeping oxygen balance value to approach-3%, thus the direct performance of the mixture of comparison sheet 1.
As the expection according to the instruction of prior art (instruction in patent US 6 893 517 and propelling agent field), the result of table 2 shows that the combustion modifiers of adding in the composition of the type of reference mixture 1 within implication of the present invention makes that rate of combustion increases under medium and high pressure, and temperature of combustion does not have any remarkable change.
Beat allly be, described interpolation makes pressure index and cut-off combustion pressure reduce simultaneously very largely, and in whole working pressure range (greater than 6MPa) is all very low for described pressure index, and under low pressure, rate of combustion increases considerably.
CuO is for providing the compound (referring to embodiment 2) that significantly improves when being added into reference composition 1.Pressure index is actual in whole working range is zero, the actual normal atmosphere that equals of cut-off operating pressure.
Metal composite, decompose during the heat release combustion reactions as BCN, original position produces the CuO (through experiment confirm) with high-specific surface area, therefore in this scope, available BCN replaces CuO as combustion modifiers, has the result (referring to embodiment 7) that is equal to CuO.
When take low amount (in an embodiment as 5%) when mixing, CuO and BCN make the gas yield value that can keep favourable (＞32g/mol), and finally make the inflation rate of per unit area and the GN/KClO of reference mixture 1
4Reference forms compares remarkable improvement the (surpassing 40%).
Following table 3 demonstrates second beat all effect of inventor proof, that is: when mixing silicon-dioxide with moderate contents in the composition of mixture of the present invention, the cut-off combustion pressure reduces (measuring with particle) very significantly.Be not sufficient to make us becoming interested with another refractory metal oxide, this effect of obtaining as aluminum oxide.
Table 3
Claims (13)
1. solid gas-Generating Pyrotechnic Compounds, the composition of described mixture comprises:
-Guanidinium nitrate; And
-potassium perchlorate;
It is characterized in that, the composition of described mixture comprises by weight percentage:
-60% to 70% Guanidinium nitrate;
-26% to 33%, preferred 26% to 30% potassium perchlorate;
-2.5% to 6% at least a combustion modifiers, described combustion modifiers are selected from the precursor of transition metal oxide, described oxide compound and the mixture of above-mentioned substance;
-0 to 6% at least a additive; And
Do not comprise blasting compound.
2. mixture as claimed in claim 1, is characterized in that, the composition of described mixture is comprised of described Guanidinium nitrate, potassium perchlorate, at least a combustion modifiers and optional at least a additive.
3. mixture as claimed in claim 1 or 2, is characterized in that, the composition of described mixture have at least 94wt%, preferably at least 98wt% or even 100wt% consisted of by described Guanidinium nitrate, potassium perchlorate and at least a combustion modifiers.
4. mixture as described in any one in claims 1 to 3, is characterized in that, described at least a combustion modifiers is selected from zinc oxide (ZnO), ferric oxide (Fe
2O
3), chromic oxide (Cr
2O
3), Manganse Dioxide (MnO
2), cupric oxide (CuO), basic copper nitrate (Cu (NO
3)
23Cu (OH)
2) and the mixture of above-mentioned substance.
5. mixture as described in any one in claim 1 to 4, is characterized in that, described at least a combustion modifiers is comprised of cupric oxide and/or basic copper nitrate.
6. mixture as claimed in claim 5, is characterized in that, described mixture has under the pressure of 6MPa to 52MPa and is less than or equal to 0.1 pressure index.
7. mixture as described in any one in claim 1 to 6, is characterized in that, described at least a combustion modifiers has greater than 3m
2/ g, be preferably greater than 10m
2/ g, very preferably greater than 25m
2The specific surface area of/g.
8. mixture as described in any one in claim 1 to 7, is characterized in that, the composition of described mixture comprises silicon-dioxide as additive.
9. mixture as claimed in claim 8, is characterized in that, described silicon-dioxide is in powder-form, has preferred 100m
2The high-specific surface area that/g is above, and have micron order size, preferred nano-grade size; Perhaps described silicon-dioxide is in the form of silica fiber, and described silica fiber diameter is that 1 micron to 20 microns, length are 20 microns to 500 microns.
10. mixture as claimed in any one of claims 1-9 wherein, it is characterized in that, described mixture obtains by the dry method operation, and described dry method operation comprises following steps: mixture is carried out the step of compacting, described mixture comprises the moiety of the described mixture that is in powder type; Optional granulation step subsequently; And choose after granulation step step by becoming ball to carry out moulding wantonly.
11. mixture as described in any one in claim 1 to 10 is characterized in that described mixture is in the form of particle, pill or monoblock.
12. a powder composition, described composition are the precursors of the described mixture of any one in claim 1 to 11, the composition of described powder composition is corresponding to the composition of the described mixture of any one in claim 1 to 9.
13. a producer gas generator that is suitable for air bag is characterized in that, described producer gas generator comprises the described mixture of any one at least a claim 1 to 11.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1057353 | 2010-09-15 | ||
| FR1057353A FR2964656B1 (en) | 2010-09-15 | 2010-09-15 | PYROTECHNIC COMPOUNDS GENERATORS OF GAS |
| PCT/FR2011/052125 WO2012035271A2 (en) | 2010-09-15 | 2011-09-15 | Pyrotechnic gas generator compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103180271A true CN103180271A (en) | 2013-06-26 |
Family
ID=43927666
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011800515939A Pending CN103180271A (en) | 2010-09-15 | 2011-09-15 | Pyrotechnic gas generator compounds |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US20130228254A1 (en) |
| EP (1) | EP2616413B8 (en) |
| JP (1) | JP2013541487A (en) |
| KR (1) | KR20140135087A (en) |
| CN (1) | CN103180271A (en) |
| BR (1) | BR112013006065A2 (en) |
| FR (1) | FR2964656B1 (en) |
| MX (1) | MX2013002988A (en) |
| WO (1) | WO2012035271A2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106458784A (en) * | 2014-06-05 | 2017-02-22 | Tk控股公司 | Improved booster composition |
| CN107573199A (en) * | 2016-11-03 | 2018-01-12 | 湖北航天化学技术研究所 | A kind of voltage-controlled heat production gas generating agent of high security |
| CN108752154A (en) * | 2018-06-08 | 2018-11-06 | 中国科学技术大学 | A kind of composite gas propellant and preparation method spreading incendiary effect with wheat |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3007659B1 (en) | 2013-06-28 | 2017-03-24 | Herakles | METHOD FOR DELIVERING A PRESSURIZED LIQUID FROM THE COMBUSTION GASES OF AT LEAST ONE PYROTECHNIC LOAD |
| US10214460B2 (en) * | 2014-06-05 | 2019-02-26 | Joyson Safety Systems Acquisition Llc | Booster composition |
| FR3037812B1 (en) | 2015-06-29 | 2017-08-04 | Herakles | FIRE EXTINGUISHER |
| FR3077989B1 (en) | 2018-02-20 | 2021-11-19 | Arianegroup Sas | FIRE EXTINGUISHER |
| CN110317120B (en) * | 2019-05-30 | 2020-10-20 | 湖北航鹏化学动力科技有限责任公司 | Ignition powder, preparation method and application thereof and safety airbag gas generator |
| JP2024037522A (en) * | 2022-09-07 | 2024-03-19 | 株式会社ダイセル | Gas-generating agent composition |
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- 2011-09-15 JP JP2013528747A patent/JP2013541487A/en active Pending
- 2011-09-15 US US13/821,525 patent/US20130228254A1/en not_active Abandoned
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| CN107573199A (en) * | 2016-11-03 | 2018-01-12 | 湖北航天化学技术研究所 | A kind of voltage-controlled heat production gas generating agent of high security |
| CN108752154A (en) * | 2018-06-08 | 2018-11-06 | 中国科学技术大学 | A kind of composite gas propellant and preparation method spreading incendiary effect with wheat |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20140135087A (en) | 2014-11-25 |
| JP2013541487A (en) | 2013-11-14 |
| WO2012035271A3 (en) | 2012-05-10 |
| MX2013002988A (en) | 2013-06-24 |
| US20130228254A1 (en) | 2013-09-05 |
| EP2616413B8 (en) | 2021-12-08 |
| FR2964656B1 (en) | 2012-10-12 |
| BR112013006065A2 (en) | 2016-06-07 |
| EP2616413B1 (en) | 2021-11-03 |
| FR2964656A1 (en) | 2012-03-16 |
| WO2012035271A2 (en) | 2012-03-22 |
| EP2616413A2 (en) | 2013-07-24 |
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Application publication date: 20130626 |