CN110325492A - Generate the pyrotechnics solid objects of gas - Google Patents
Generate the pyrotechnics solid objects of gas Download PDFInfo
- Publication number
- CN110325492A CN110325492A CN201780087086.8A CN201780087086A CN110325492A CN 110325492 A CN110325492 A CN 110325492A CN 201780087086 A CN201780087086 A CN 201780087086A CN 110325492 A CN110325492 A CN 110325492A
- Authority
- CN
- China
- Prior art keywords
- composition
- oxalate
- inorganic
- titanate
- nitrate
- 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.)
- Pending
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
- 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
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
- C06B23/001—Fillers, gelling and thickening agents (e.g. fibres), absorbents for nitroglycerine
-
- 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
- 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
- C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Air Bags (AREA)
Abstract
The present invention relates to the pyrotechnics solid objects for generating gas, and in terms of weight percentage, its composition is free of adhesive and blasting compound, it includes: -35% to 50%, preferably 40% to 50% guanidine nitrate；- 35% to 50% basic copper nitrate；The compound of -0.5% to 6% at least one inorganic titanate selected from aluminium oxide and fusing point higher than 2100K；And -5% to 18% the inorganic oxalates of at least one, be selected from sodium oxalate, tin oxalate, strontium oxalate, ferric oxalate, cupric oxalate and its mixture.The object is preferably applied to frontal airbag.
Description
The present invention relates to a kind of pyrotechnics solid objects of novel generation gas.The novel object is in its ignition temperature
Aspect (is implemented) in the generation (a small amount of, in the form of aggregate) and its production of (low), its residue of combustion with readily dry approach
It is particularly advantageous.The object is suitble to use in the gas generator with optimization structure.The optimization specifically carries out below
Explanation.
The pyrotechnics solid objects for generating gas protect system especially suitable for vehicle passenger, are more particularly suited for just
The expansion of face air bag.
Relevant technical field is protected to experienced considerable development in past 20 years to vehicle passenger.Vehicle exists
The security system of multiple substitute bladder type is incorporated in its passenger carriage.In the security system of substitute bladder type, front (is driven
Member or passenger) air bag and side (curtain (curtain), chest protection) air bag is different.Frontal airbag with
Time needed for the difference of side airbag essentially consists in air-bag deployment and positioning.Typically for frontal airbag
For, the time is long (about 40-50 milliseconds, the 10-20 millisecond relative to side airbag).
Frontal airbag largely needs it is said that being entirely the gas generator of pyrotechnics comprising at least one pyrotechnics dress
Material, the pyrotechnical charge are made of at least one pyrotechnics solid objects.The design of the type needs at least one described pyrotechnics solid again
Body object meets multiple requirements simultaneously and (is related to its gas yield, the expansion rate of its per unit area, its flammable, its burning temperature
Degree and rate, its pressure index, the nontoxicity of the gas caused by its burning, the amount of the solid particle caused by its burning
And the pyrotechnics safety during its acquisition and use).
So far, for the pyrotechnics solid objects of the generation gas especially suitable for vehicle passenger protection system,
Through proposing the pyrotechnic composition of multiple types.
Patent US 6 361 630 is described in guanidine nitrate type (GN, 15 to 35 weight % charge as reduction)+strontium nitrate
(Sr(NO3)2, 30 to 50 weight %, as oxidation charge) alkali in, use the heat absorbent of relatively large amount (15-25 weight %)
(coolant), the heat absorbent are selected from alkali or alkaline earth metal formates, alkali or alkaline earth metal oxalates and its mixing
Object.The document is actually only illustrated using calcium formate in alkali, in addition to the guanidine nitrate (GN) and strontium nitrate (Sr (NO3)2)
Outside, the alkali also contains a kind of blasting compound (HMX type) and adhesive (polyethylene/butylene-for improving its burn rate
Polystyrene block copolymer type adhesive).The object is obtained by dry approach.
Patent US 6 602 365 describes the pyrotechnics solid objects for (at least partly) obtaining by wet approach and generating gas,
It has the composition comprising following component:
The complex compound of nitric acid dicyandiamidines and metal (such as Cu, Zn, Mn), such as the complex compound of formula CuGuN,
Oxidant (for example, basic copper nitrate (BCN)), and
Another reducing agent (such as guanidine nitrate (GN)).
Since, there are the complex compound of the low enthalpy of formation, the object has low combustion temperature in its composition.
Currently, for frontal airbag, it appears that provide the cigarette of optimal compromise in terms of meeting multiple requirements (seeing above)
Fiery solid matter contains in its composition makees guanidine nitrate (GN as main component；Charge as reduction) and basic copper nitrate
(BCN；It charges as oxidation).Therefore, composition (GN/BCN type) can also contain at least one additive, the Additive
In residue of combustion reunion and/or advantageously act on burn rate.
Applicant more particularly describes (GN/BCN) the type object in patent application WO2012/153062, in its group
It is higher than at least one inorganic titanate of 2100K containing fusing point in.At least one of low weight content (≤5%) is inorganic
Titanate has dual function:
Its play the role of " slagging " agent or agglomerator (at least one inorganic titanate is a kind of fire resistant compound,
Its fusing point (seeing above) is apparently higher than the ignition temperature of (GN/BCN) alkali that the inorganic titanate is contained therein.Therefore, exist
Its powdery solid physical state (obviously participating in this manner) is kept under ignition temperature, this is to obtain that liquid copper residue is made to reunite
The essential feature of effect (for increasing the viscosity for the condensed phase being made of liquid copper).Thereby facilitate the filtering of residue of combustion
Property, it is possible to reduce generate the filtration system of gas)；And
It has a positive effect to burn rate, and (object in its composition containing at least one inorganic titanate is same
When with high burn rate (at 20MPa>=20mm/s) and medium ignition temperature (<2200K), have low-pressure index with
And the non-zero self-sustaining burning under atmospheric pressure).
Applicant actually already have accounted for space requirement and the gas with the pyrotechnics charge solids operation for generating gas
The technical issues of in terms of the weight (and therefore cost) of generator.Be expected that by make in the structure of the generator filtering and
The volume and weight of device needed for burning gases caused by cooling minimizes to optimize the structure of the generator.As saying
It is bright, it can be noted that: for the composition for the generation gas that ignition temperature is 1900K, the weight of the filter device used is usual etc.
In the weight for the charging for generating gas.For all actual purposes, cooling device (its can be constituted with given filter device itself
It is combined with the cooling effect of cooling effect and cooling device).
From the point of view of this viewpoint for optimizing the generator architecture, applicant proposed can have by what dry approach obtained
The pyrotechnics solid objects (but adhesive is not present in its composition) of the novel generation gas of GN/BCN type composition, combustion
Burn ignition temperature (be lower than 2200K) of the temperature (being lower than 1800K) lower than object described in patent application WO2012/153062.It is logical
The specific coolant (seeing below) of at least one that is present in the composition of object is crossed to reduce the ignition temperature；In specific alkali
Relatively limited amount (≤18 weight %, especially≤15 weight %, even≤13 weight in (see below its described composition)
Amount %) the presence of at least one specific coolant be effective (therefore ignition temperature decline), while only to other ginsengs
Number [burn rate (presence for not needing blasting compound), gas yield and the temperature stability of such as involved object] generates limited
Influence.
Therefore, according to its first theme, the present invention relates to a kind of pyrotechnics solid objects for generating gas.In particular, with weight
Measuring percentage indicates that the composition of the object includes:
- 35% to 50%, preferably 40% to 50% guanidine nitrate (GN)；
- 35% to 50% basic copper nitrate (BCN)；
- 0.5% to 6% at least one compound selected from the following: aluminium oxide (Al2O3), fusing point is higher than the nothing of 2100K
Machine titanate and their mixture；And
- 5% to the 18% inorganic oxalates of at least one, is selected from sodium oxalate (Na2C2O4), tin oxalate (SnC2O4), grass
Sour strontium (SrC2O4), ferric oxalate (FeC2O4), cupric oxalate (CuC2O4) and its mixture；
In addition, the composition is free of adhesive and blasting compound.
Therefore, the composition is GN (reduction charging)/BCN (oxidation charging) type.
Guanidine nitrate (GN) is used as reducing agent, especially because its ability, its rheological behaviour for generating bulk gas are suitable for
(especially it, which exists, can be realized starting powdery cigarette for the compacting for implementing (direct) pelletization stage or dry approach technique and pelletization stage
The good densification of fiery composition, while limiting applied compression stress: see below) and pyrotechnics security reason.The present invention
Pyrotechnics object composition include 35 weight % to 50 weight % guanidine nitrate (GN), preferably 40 weight % are to 50 weight %'s
Guanidine nitrate (GN).
Basic copper nitrate (BCN) be used as oxidant, this especially because its influence to burn rate, its ductility and its
" slagging " acts on (presence of copper).The amount of the basic copper nitrate is 35 weight % to 50 weight %, and usual ratio is 35
Weight % to 45 weight %.
Therefore, in GN/BCN type (as described above, especially with regard to required oxygen balance value, close to -3%) alkali, described group
It closes object and contains a small amount of (0.5 weight % to 6 weight %, usually 1 weight % to 6 weight %, preferably 3 weight % to 5 weight %)
At least one compound, be selected from aluminium oxide (Al2O3), fusing point be higher than 2100K inorganic titanate and its mixture.It is described
The presence of at least one compound for residue of combustion reunion (for all actual purposes, it could here be noted that oxidation
" slagging " ability of aluminium be greater than titanate) and burn rate for be suitable.The composition preferably comprises as described above
Aluminium oxide (Al2O3) or at least one titanate.Very preferably, containing aluminium oxide (Al2O3) or the titanate.
Other than at least one inorganic titanate and/or aluminium oxide, in GN/BCN type alkali as described above, this
The composition of invention object contain relatively limited amount (5 weight % to 18 weight %, especially 5 weight % to 15 weight %,
It is preferred that the specific coolant of at least one of 5 weight % to 13 weight %, highly preferred 7 weight % to 13 weight %), that is, choosing
From the inorganic oxalates of at least one of the following group: sodium oxalate (Na2C2O4), tin oxalate (SnC2O4), strontium oxalate (SrC2O4), ferric oxalate
(FeC2O4), cupric oxalate (CuC2O4) and its mixture.As described above, (containing at least one nothing in specific GN/BCN alkali
Machine titanate and/or aluminium oxide) in, the presence of at least one oxalates of the pointed relatively limited amount is proved
Reduce object ignition temperature without to the object other parameters (such as burn rate (presence for not needing blasting compound),
Gas yield (oxalates be better than formates) and stability (selected oxalates is not very moisture absorption) over time and
(not less than 200 DEG C, (those skilled in the art have understood the fusing point and/or decomposition temperature of oxalates used temperature stability, used
Oxalates be anhydrous form)) to make a significant impact be suitable.Selected oxalates or nontoxic and cost
Rationally.
The composition of object of the present invention is free of adhesive.Specifically, the nitre largely mixed in the composition
The rheology plastic behavior of sour guanidine (GN) makes the presence of any adhesive all be extra (especially by the acquisition forming of dry approach
Pyrotechnics object, particle, pellet and the monolith block of compression (seeing below)).It will be appreciated by those skilled in the art that can be obtained by dry approach
Object of the invention the advantages of, and this does not have the participation of adhesive (it will have significant shadow to the oxygen balance of composition
It rings)；In addition, there is no any adhesives particularly suitable for the low combustion temperature of the object and the target of high gas yield.
The composition of object of the present invention is free of blasting compound.Therefore it is both free of nitroguanidine, is also free of hexogen
(RDX), also without octogen (HMX) etc..Blasting compound is current and is traditionally interpreted as according to standard NF T 70-502 (ginseng
See " suggestion of the United Nations about Dangerous Goods Transport --- test and standard manual (UN Recommendations on the
Transport of Dangerous Goods-Manual of Tests and Criteria) ", the 4th revised edition, ST/SG/
AC.10/11/ revises 4, ISBN92-1-239083-8ISSN 1014-7179 and STANAG 4488) it is classified as risk class 1.1
Ingredient.For all actual purposes, it is worth mentioning at this point that guanidine nitrate (GN) is not the ingredient being included under the risk divides.?
It is especially suitable in the safety and ignition temperature of the object that there is no any blasting compounds in the composition of object of the present invention.
Incidentally need low combustion temperature.
Therefore, the object of the present invention with above-mentioned composition is proved to be particularly advantageous in the following areas:
1) its ignition temperature is (low: to be lower than 1800K；The low combustion temperature still be more than under 20MPa 15mm/s burning speed
Rate is related (to refer to the burn rate, it is already possible to show that it is suitable by using appropriate fine-grained ingredient (seeing below) herein
Shi Zengjia)),
2) its residue of combustion generated (a small amount of, in the form of aggregate), and
3) it obtains (simple dry approach is implemented).
It is present in the inorganic oxalates of at least one of object composition of the present invention to be preferably selected from: sodium oxalate (Na2C2O4)、
Strontium oxalate (SrC2O4) and cupric oxalate (CuC2O4)。
It is optionally present in inorganic titanate of at least one of the composition of the object of the present invention fusing point higher than 2100K (out
In all actual purposes, it is worth mentioning at this point that the composition contains 0.5% to 6%, be usually 1% to 6%, preferably 3% to
5% be selected from aluminium oxide (Al2O3), fusing point higher than 2100K inorganic titanate and its mixture at least one compound) it is excellent
Choosing is selected from metal titanate, titanates of alkali-earth metals and its mixture.It is much preferred that it is by metal titanate or alkaline earth gold
Belong to titanate composition.Preferably, the composition of the object of the present invention containing at least one titanate contains strontium titanates
(SrTiO3) and/or calcium titanate (CaTiO3) and/or aluminium titanates (Al2TiO5).It is particularly preferred that it contains strontium titanates
((SrTiO3), calcium titanate (CaTiO3) or aluminium titanates (Al2TiO5).The fusing point of these titanates be respectively 2353K, 2248K and
2133K, that is, (specifically, fusing point is significantly higher than the ignition temperature of the in addition GN/BCN alkali containing at least one inorganic oxalates
The ignition temperature of any GN/BCN alkali is always lower than 1950K).
In the context of its first theme, the present invention relates to the subtribes for the pyrotechnics solid objects for generating gas, with weight
Percentage indicates that its composition includes:
- 35% to 50%, preferably 40% to 50% guanidine nitrate (GN)；
- 35% to 45% basic copper nitrate (BCN)；
- 1% to 6%, preferably 3% to 5% at least one compound selected from the following: aluminium oxide (Al2O3), fusing point it is high
In the inorganic titanate and its mixture of 2100K；And
- 5% to 15%, preferably 5% to 13%, highly preferred 7% to the 13% inorganic oxalates of at least one, is selected from
Sodium oxalate (Na2C2O4), tin oxalate (SnC2O4) and its mixture；
In addition, the composition is free of adhesive and blasting compound.
In the object composition of the subtribe, at least one inorganic oxalates is preferably made of sodium oxalate.
About the object of the subtribe, content that is above-mentioned and being clearly suitable for the subtribe can be repeated.
Above-mentioned four constituents (such as described guanidine nitrate (GN), basic copper nitrate (BCN), aluminium oxide and/or inorganic titanate
(fusing point be higher than 2100K) and inorganic oxalates) (composition of the conventional constituent of object of the present invention, particularly above-mentioned subtribe at
Point) usually account at least the 98% of pyrotechnics object composition weight of the present invention.Above-mentioned four constituents can represent object of the present invention completely
At least 99.5 weight % of total weight, or even 100 weight %.For example, it is expressly contemplated that (especially hard selected from such as processing aid
Resin acid calcium, graphite, silica) at least one " other " additive (aluminium oxide and/or at least one inorganic being optionally present
Titanate and at least one inorganic oxalates are fully able to analogy additive), content is less than or equal to 2 weight %.Ying Li
Solution, in view of the above description, which cannot be made of in any way adhesive or explosive component.
(main) constituent of object of the present invention --- guanidine nitrate+basic copper nitrate+aluminium oxide and/or at least one spy
The specific inorganic oxalates of fixed inorganic titanate+at least one --- it is known product.They are powder type, granularity
Narrowly distributing (surrounds its median diameter (d50)).It is entire herein (including in embodiment), shown in median diameter be with body
The median diameter of product meter.
Especially with respect to the burn rate for obtaining the object and the object by dry approach, object of the present invention
(main) constituent preferably has thin or even very thin granularity.Its median diameter (d50) value usually less than or wait
In 20 μm.
In order to which the perfection of GN/BCN ground caustic last (main constituents of object of the present invention, usually participated in powdery state) is mixed
Close, it is proposed that the median diameter of one of the guanidine nitrate (GN) and basic copper nitrate (BCN) be substantially higher than the guanidine nitrate (GN) and
The median diameter of another in basic copper nitrate (BCN), described basic (significant) higher median diameter generally remain be less than or
Equal to 20 μm (seeing above).Statement " substantially higher " is understood to mean that " being at least 1.8 times of height ", preferably " is at least twice
It is high ", highly preferred " being at least 5 times of height ", or even " being at least 10 times of height ".The GN powder for being 12 μm especially with median diameter
End and BCN powder of the median diameter less than 6 μm obtain highly preferred result.According to a preferred variants, the guanidine nitrate
It is less than or equal to 1 μm with the median diameter (such as median diameter of the basic copper nitrate) of one of basic copper nitrate, and it is described
The median diameter median diameter of the guanidine nitrate (therefore for example) of another in guanidine nitrate and basic copper nitrate is to be at least 5 μ
M, more preferably at least 10 μm (while generally remaining less than or equal to 20 μm (seeing above)).It is 10 especially with median diameter
μm to 14 μm of GN powder and median diameter be that 1 μm of BCN powder obtains highly preferred result.Ad hoc proposal is using very
Thin powder (d50≤ 1 μm) and " substantially rougher " powder, to generate perfect mixture and to obtain high burn rate.It is suitable
When utilizing granularity to influence this (front) of burn rate, to compensate limited shadow of the presence to the burn rate of oxalates
It rings.
When there are aluminium oxide (it is also participated in powdery state), preferably deposited with thin or even very thin granularity
?；Then its specific surface area is high, even very high.For repertoire, it has been mentioned that the value of median diameter is usually less than
Or it is equal to 20 μm.For aluminium oxide, it can propose that the value of median diameter is typically less than or equal to 10 μm, preferably lower than or equal to 5 μ
M, highly preferably less than or equal to 1 μm, or even as low as 100nm or even 10nm.
When there is at least one inorganic titanate (it is also participated in powdery state), it is also preferred that with grain as small as possible
Degree exists.It is therefore advantageous that existing at least one inorganic titanate is the thin of micron-scale or even nano-scale
Powder-form, i.e. median diameter (d50) less than 6 μm, or even less than 1 μm (in the context of the preferred variants usually are as follows:
0.5μm≤d50≤6μm).The specific surface area of existing at least one inorganic titanate is preferably greater than 1m2/ g is (very preferably
Greater than 5m2/ g or bigger).
About the granularity of at least one inorganic oxalates, itself is also suitably thin as much as possible.However, with " coarseness "
Commercial product, particularly median diameter be greater than 40 μm (especially 60 μm) sodium oxalate have been obtained for good result.In the least
Without query, obtained with (at least) a kind of thinner oxalates (especially less than 20 μm of median diameter (seeing above)) of the invention
The good result obtained will be more preferable.
Object of the invention more particularly to the pyrotechnics object of forming, particle, pellet or (compression) monolith block (under
Text) form exist.
The manufacture of pyrotechnics solid objects of the invention will now be described.Related manufacturing method similarly relates to dry approach
Or wet approach and means, preferably dry approach and means.
Dry approach
Pyrotechnics solid objects of the invention (can pass through dry approach) by the powder obtained by mixing its constituent
Last mixture is pelletized (compression) simply to manufacture (it should be understood that the ingredient is relatively thin, as thin (referring to upper as possible to have
Text) the powdery state of granularity use, and it is substantially or even entirely the GN, BCN, aluminium oxide and/or inorganic
Titanate and the oxalates).
Pyrotechnics object of the invention can also be according to the method that can include up to four key steps (by dry approach)
Manufacture.This method is known to those skilled in the art.It is specifically described in patent application WO2006/134311.
When manufacturing process starts, aluminium oxide or (and) at least one inorganic titanate (its fusing point is higher than 2100K) and extremely
A kind of few inorganic oxalates (being selected from sodium oxalate, tin oxalate, strontium oxalate, ferric oxalate, cupric oxalate and its mixture) preferably with it is other
Constituent (predominantly GN+BCN, or even all GN+BCN) blending.However, in the method for manufacturing object of the present invention,
Can downstream be added the aluminium oxide or (and) at least one inorganic titanate (its fusing point is higher than 2100K) or (and) institute
At least one inorganic oxalates (selected from sodium oxalate, tin oxalate, strontium oxalate, ferric oxalate, cupric oxalate and its mixture) is stated, especially
The inorganic oxalates of at least one.It should be understood that there are several alternative solutions.In passing, it may be noted that in the method mistake
Cheng Zhong, however not excluded that the aluminium oxide involved in multiple processes, at least one inorganic titanate and at least one inorganic oxalates
One of and/or it is another.
Preferred dry approach and means for manufacturing (preparation) pyrotechnics object of the invention include the following steps: to make the object
Powdery constituent (optionally, other than the inorganic oxalates of at least one that can be added later) mixture into
The compacting of row dry type.Dry type compacting is usually in a way known in roller type press with 108To 6.108Pa(108Pa≤p≤
6.108Pa compaction pressure (p)) carries out.It can be according to different variant (characterization step with " simple " compacting, then
It is at least one additional step, or the characterization step with the compacting in conjunction with forming step) it carries out.
Therefore, pyrotechnics solid objects of the invention can exist in a variety of manners and (especially generate during manufacturing process
Final object):
Terminate in the dry type compacting (by using at least one compression roll, outer surface has cavity) combined with forming
When, the sheet material with embossing pattern is obtained, it can the broken pyrotechnics object to directly obtain forming；
At the end of dry type compacting (generating " simple " compacting of flat sheet), then pelletizing, particle is obtained；
In dry type compacting (" simple " compacting of generation flat sheet), then granulation (granulation), then granulation
At the end of (dry type compression), pellet or (compression) monolith block are obtained.
------------------------------
Obtained at the end of one or the other in above-mentioned steps --- the pyrotechnics object of forming, particle, pellet and
Monolith block --- object of the present invention is particularly preferred, it should be appreciated that pellet can also be by being directly granulated (pelletizing)
It obtains (seeing above).
Wet approach
Pyrotechnics solid objects of the invention can also be obtained by wet approach technique.This method comprises the following steps: 1) will
All or (usually quite) some main components are placed in aqueous solution that (step being placed in aqueous solution generally includes to make
At least one main component dissolution (more specifically dissolving guanidine nitrate (GN)))；2) powder is obtained by spray drying；It 3) will not
The ingredient in solution is placed in be added in gained powder；Then the pulverulent mixture 4) made by the dry approach technique of standard at
Shape (in the form of object).
Object of the invention exists preferably in the form of particle, pellet or monolith block.
In a non-limiting manner, here it can be pointed out that:
Common median diameter (the d of particle of the invention50) be 200-1000 μm (and bulk density is 0.8-1.2g/
cm3)；With
The thickness of pellet of the invention is usually 1 to 6mm, and diameter is 3mm to 15mm.
The particle and pellet are very suitable for main target and apply (frontal airbag, in motor vehicle safety field).
The pyrotechnics object and monolith block of forming are used for other purposes.
According to its another theme, it to be object of the present invention that the present invention relates to powder composition (mixtures of powder)
Precursor, therefore its composition corresponds to the composition (seeing above) of object of the present invention.
According to its another theme, the present invention relates to the gas generators containing the pyrotechnics charge solids for generating gas；It is described
Charging contains at least one pyrotechnics solid objects of the invention.Especially the generator equipped with pellet of the invention is very suitable
For air bag, especially frontal airbag (seeing above).
Explanation of the invention is provided in a non limiting manner now.
By following component by be directly compacted dry approach technique (=45 × 106It is carried out under the pressure of Pa (450 bars) simple
It is granulated) prepare pellet (diameter 11mm, the pellet with a thickness of 3mm):
- GN (is sold, 10-14 μm of grade) by German Ali's chemical groups (Alzchem AG (DE)), (d5012 μm of ≈),
- BCN (is sold, 4-6 μm by Xie Pode chemical company, the U.S. (Shepherd Chemical Company (US))
Grade), (d505 μm of ≈),
-BCN(d501 μm of ≈),
-SrTiO3(by temperature gradient processing technology company, the U.S. (Thermograde Process Technology Ltd
(US)) sell, 4-6 μm of grade), (d505.5 μm of ≈),
-Al2O3(being sold by German Ying Chuan industrial group (Evonik Industries AG (DE)), 10-100nm grades),
(specific surface area: 100m2/ g),
-Na2C2O4(being sold by Alpha's AlfaAesar group, the U.S. (Alfa Aesar (US)), 40-70 μm of grade), (d50≈
55 μm),
-SrC2O4It (is sold by French Yi Satisi company (Isaltis (FR)), (d504 μm of ≈),
-CuC2O4(being sold by French Claude Bernard enlightening company (Bernardy (FR))), (d50≈5μm)。
The following table 1 gives five embodiments (embodiment 1, embodiment 2, the reality of the composition of object of the invention (pellet)
Apply example 3, embodiment 4 and embodiment 5) and object (pellet) (comparative example 1, according to patent application WO2012/ with the prior art
153062) feature (performance for calculating or measuring) for the object (pellet) compared；As described above, the present invention and the prior art
The object (pellet) manufactured by mentioned component.
The following table 1 give the composition of pellet other two embodiment (embodiment A and comparative example 2) and the ball
The performance (obtaining in a similar manner) of grain.These embodiments highlight using with very thin granularity BCN (and have show
Write the GN of higher granularity) the advantages of.
Object (pellet) is assessed by calculation of thermodynamics and the physical measurement by therefore carrying out to pellet.In pressure measuring chamber
(volume 40cm3) in igniting several times after obtain the burn rate and pressure index of the pellet.Therefore, shown numerical value is flat
Mean value.
Contain the guanidine nitrate of shown weight percent in its composition with reference to the pellet (comparative example 1) of the prior art
(GN), basic copper nitrate (BCN) and strontium titanates (SrTiO3)。
For Examples 1 and 2, three kinds of ingredients are guanidine nitrate (GN), basic copper nitrate (BCN) and strontium titanates (SrTiO3),
For embodiment 3,4 and 5, three kinds of ingredients are guanidine nitrate (GN), basic copper nitrate (BCN) and aluminium oxide, in addition to these three ingredients
Outside, the pellet of embodiment 1 to 5 (embodiment 1, embodiment 2, embodiment 3, embodiment 4 and embodiment 5) also contains in its composition
Having () () () according to the present invention reduces the reagent of ignition temperature: being sodium oxalate (Na for embodiment 1-32C2O4), for implementing
Example 4 is strontium oxalate (SrC2O4), it is cupric oxalate (CuC for embodiment 52O4).These four ingredients exist with shown weight percent
In composition.
The feature (performance) of the composition (object) of Examples 1 and 2 is shown: by sodium oxalate (Na2C2O4) with variable
(weight content is respectively 7.5 and 10%) is added in the composition (comparative example 1) of the type of comparative example 1, causes ignition temperature aobvious
Writing reduces (respectively -144 DEG C and -190 DEG C).For target application (frontal airbag), the value of pressure index is still can
Receive.
The feature (performance) of the composition (object) of embodiment 3 is shown: the presence of aluminium oxide helps to obtain good
(ignition temperature reduces and (reduces -155 DEG C compared with comparative example 1) performance, and the burn rate under 20MPa compared with Example 2
Value increases, and the reunion quality of residue of combustion increases in parallel compared with Example 2).
The feature (performance) of the composition (object) of embodiment 4 is shown: by aluminium oxide and strontium oxalate (SrC2O4) combination add
It adds in the composition (comparative example 1) of the type of comparative example 1, ignition temperature is caused to significantly reduce (for -156 DEG C).For target
Using (frontal airbag), the value of pressure index is still acceptable.It must be emphasized that the group of extraordinary residue of combustion
Poly- quality.
The feature (performance) of the composition (object) of embodiment 5 is shown: by aluminium oxide and cupric oxalate (CuC2O4) combination add
It adds in the composition (comparative example 1) of the type of comparative example 1, ignition temperature is caused to significantly reduce (for -146 DEG C).
Therefore, the embodiment A that considers parallel with comparative example 2 (comparative example 2) is shown: oxalates is being not present (more
Especially sodium oxalate, strontium oxalate and cupric oxalate) in the case where, thin rank (d50=1 μm) basic copper nitrate (BCN) participate in GN
Type (granularity is considerably higher)+BCN+Al2O3(2.7%) in composition.Influence to burn rate is significant: being increased above
20% (compared with the burn rate of the pellet of comparative example 2 (comparative example 2)).Therefore, it was confirmed that within the scope of the invention,
Ignition temperature can be reduced by existing small grain size BCN, at the same optimize burn rate (in fact, by make form GN or
One of BCN has small grain size, then the another kind in the composition can have significant bigger granularity).
Table 1
Claims (14)
1. a kind of pyrotechnics solid objects for generating gas, in terms of weight percentage, the composition of the object includes:
- 35% to 50%, preferably 40% to 50% guanidine nitrate；
- 35% to 50% basic copper nitrate；
The compound of -0.5% to 6% at least one inorganic titanate selected from aluminium oxide and fusing point higher than 2100K；And
- 5% to the 18% inorganic oxalates of at least one, selected from sodium oxalate, tin oxalate, strontium oxalate, ferric oxalate, cupric oxalate and
Its mixture；
The composition is free of adhesive and blasting compound.
2. object as described in claim 1, which is characterized in that the inorganic oxalates of at least one by sodium oxalate, strontium oxalate,
Or cupric oxalate composition.
3. object as claimed in claim 1 or 2, in terms of weight percentage, the composition of the object includes:
- 35% to 50%, preferably 40% to 50% guanidine nitrate；
- 35% to 45% basic copper nitrate；
The change of -1% to 6%, preferably 3% to 5% at least one inorganic titanate selected from aluminium oxide and fusing point higher than 2100K
Close object；And
- 5% to 15%, preferably 5% to 13%, highly preferred 7% to the 13% inorganic oxalates of at least one, is selected from oxalic acid
Sodium, tin oxalate and its mixture.
4. object as claimed any one in claims 1 to 3, which is characterized in that the composition of object includes selected from the group below
At least one inorganic titanate: strontium titanates, calcium titanate, aluminium titanates and their mixture.
5. object according to any one of claims 1 to 4, which is characterized in that the composition of object includes at least 98 weights
Measure the guanidine nitrate, basic copper nitrate, the aluminium oxide of % or even at least 99.5 weight % or even 100 weight %
And/or inorganic titanate and inorganic oxalates.
6. the object as described in any one of claims 1 to 5, which is characterized in that the guanidine nitrate, basic copper nitrate, oxidation
The median diameter of aluminium and/or inorganic titanate and inorganic oxalates is less than or equal to 20 μm.
7. such as object described in any one of claims 1 to 6, which is characterized in that one in the guanidine nitrate and basic copper nitrate
The median diameter of kind is noticeably greater than median diameter another in the guanidine nitrate and basic copper nitrate.
8. the object as described in any one of claims 1 to 7, which is characterized in that one in the guanidine nitrate and basic copper nitrate
The median diameter of kind is less than or equal to 1 μm, and median diameter another in the guanidine nitrate and basic copper nitrate is at least 5 μ
M, preferably at least 10 μm.
9. such as object described in any item of the claim 1 to 8, which is characterized in that the composition of object includes aluminium oxide, described
The median diameter of aluminium oxide is less than or equal to 5 μm.
10. object as claimed in any one of claims 1-9 wherein, which is characterized in that the composition of object includes at least one nothing
Machine titanate, the median diameter of at least one inorganic titanate is less than 6 μm, and preferably smaller than 1 μm.
11. the object as described in any one of claims 1 to 10, which is characterized in that the object is obtained by dry approach and means
, described method includes following steps: the step of pulverulent mixture of the powdery constituent containing the object is compacted；With
Optional granulation step afterwards；Then it is optional by being granulated to shape the step of.
12. the object as described in any one of claims 1 to 11, which is characterized in that object is particle, pellet or monolith block
Form.
13. a kind of powder composition is the precursor of the object as described in any one of claims 1 to 12, the composition
Composition corresponds to the composition of the object as described in any one of claims 1 to 10.
14. a kind of gas generator containing the pyrotechnics charge solids for generating gas, which is characterized in that the charging is containing as weighed
Benefit require any one of 1 to 12 described at least one object.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1663229A FR3061174B1 (en) | 2016-12-22 | 2016-12-22 | SOLID PYROTECHNIC OBJECTS GENERATORS OF GAS |
| FR1663229 | 2016-12-22 | ||
| PCT/FR2017/053727 WO2018115735A1 (en) | 2016-12-22 | 2017-12-20 | Gas-generating pyrotechnic solid objects |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110325492A true CN110325492A (en) | 2019-10-11 |
Family
ID=59296880
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780087086.8A Pending CN110325492A (en) | 2016-12-22 | 2017-12-20 | Generate the pyrotechnics solid objects of gas |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20200002243A1 (en) |
| EP (1) | EP3558900B8 (en) |
| JP (1) | JP2020514218A (en) |
| KR (1) | KR20190101995A (en) |
| CN (1) | CN110325492A (en) |
| FR (1) | FR3061174B1 (en) |
| WO (1) | WO2018115735A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116249682A (en) * | 2020-10-01 | 2023-06-09 | 株式会社大赛璐 | Gas generating agent composition |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111978136B (en) * | 2020-09-01 | 2021-11-23 | 湖北航天化学技术研究所 | Improved gas generating agent and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6361630B2 (en) * | 1999-08-17 | 2002-03-26 | Trw Inc. | Cool burning gas generating composition |
| US20030094225A1 (en) * | 2001-03-02 | 2003-05-22 | Knowlton Gregory D. | Low solids gas generant having a low flame temperature |
| CN1644574A (en) * | 2004-12-16 | 2005-07-27 | 中国航天科技集团公司第四研究院第四十二研究所 | Non-nitrine gas generating agent and production thereof |
| CN1918086A (en) * | 2004-02-10 | 2007-02-21 | Snpe巨能材料公司 | Gas-generating pyrotechnical compositions and pyrotechnical compounds for automotive safety |
| CN103517887A (en) * | 2011-05-09 | 2014-01-15 | 海瑞克里兹 | Pyrotechnic gas generator compounds |
| CN104744185A (en) * | 2013-12-30 | 2015-07-01 | 比亚迪股份有限公司 | Gas generating agent composition and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6602365B1 (en) | 2000-11-17 | 2003-08-05 | Autoliv Asp, Inc. | Gas generation via metal complexes of guanylurea nitrate |
| FR2887247B1 (en) | 2005-06-15 | 2007-10-12 | Snpe Materiaux Energetiques | PROCESS FOR MANUFACTURING GAS GENERATOR PELLETS COMPRISING A DRY GRANULATION STEP |
| JP5275862B2 (en) * | 2008-04-11 | 2013-08-28 | 株式会社ダイセル | Gas generant composition |
-
2016
- 2016-12-22 FR FR1663229A patent/FR3061174B1/en active Active
-
2017
- 2017-12-20 KR KR1020197019861A patent/KR20190101995A/en unknown
- 2017-12-20 CN CN201780087086.8A patent/CN110325492A/en active Pending
- 2017-12-20 WO PCT/FR2017/053727 patent/WO2018115735A1/en unknown
- 2017-12-20 JP JP2019534212A patent/JP2020514218A/en active Pending
- 2017-12-20 EP EP17829259.5A patent/EP3558900B8/en active Active
- 2017-12-20 US US16/472,297 patent/US20200002243A1/en not_active Abandoned
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6361630B2 (en) * | 1999-08-17 | 2002-03-26 | Trw Inc. | Cool burning gas generating composition |
| US20030094225A1 (en) * | 2001-03-02 | 2003-05-22 | Knowlton Gregory D. | Low solids gas generant having a low flame temperature |
| CN1918086A (en) * | 2004-02-10 | 2007-02-21 | Snpe巨能材料公司 | Gas-generating pyrotechnical compositions and pyrotechnical compounds for automotive safety |
| CN1644574A (en) * | 2004-12-16 | 2005-07-27 | 中国航天科技集团公司第四研究院第四十二研究所 | Non-nitrine gas generating agent and production thereof |
| CN103517887A (en) * | 2011-05-09 | 2014-01-15 | 海瑞克里兹 | Pyrotechnic gas generator compounds |
| CN104744185A (en) * | 2013-12-30 | 2015-07-01 | 比亚迪股份有限公司 | Gas generating agent composition and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 柴玉萍: "非叠氮燃气发生剂配方研制进展", 《宇航材料工艺》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116249682A (en) * | 2020-10-01 | 2023-06-09 | 株式会社大赛璐 | Gas generating agent composition |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20190101995A (en) | 2019-09-02 |
| WO2018115735A1 (en) | 2018-06-28 |
| FR3061174B1 (en) | 2019-05-31 |
| US20200002243A1 (en) | 2020-01-02 |
| FR3061174A1 (en) | 2018-06-29 |
| EP3558900A1 (en) | 2019-10-30 |
| JP2020514218A (en) | 2020-05-21 |
| EP3558900B8 (en) | 2021-12-29 |
| EP3558900B1 (en) | 2021-11-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2346797B1 (en) | Gas generating compositions having glass fibers | |
| DE69729881T2 (en) | AZIDFREE GAS-CREATING COMPOSITIONS | |
| KR101899028B1 (en) | pyrotechnic gas generator compounds | |
| EP2265562B1 (en) | High performance gas generating compositions | |
| CN105777460B (en) | Gas generant composition | |
| CN103180271A (en) | Pyrotechnic gas generator compounds | |
| WO1997012848A1 (en) | Gas generating agent for air bags | |
| JP2002512167A (en) | Pyrotechnic gas generant composition with high oxygen balance fuel | |
| CN110325492A (en) | Generate the pyrotechnics solid objects of gas | |
| JP2002187790A (en) | Gas generating agent composition and gas generator using the same | |
| CN100348554C (en) | Composite oxidant used for fireworks | |
| TW440556B (en) | Enhancings agent composition for inflator | |
| CN105358508A (en) | Gas generator having increased combustion rate and combustion gas amount | |
| EP4007746A1 (en) | Ignition booster composition | |
| JP4248254B2 (en) | Gas generant composition | |
| WO2020205068A1 (en) | Gas generant compositions comprising a thermally stable crystalline hydrate compound for cooling combustion flame temperature and improving ballistic performance | |
| JP2926321B2 (en) | Gas generator for airbag | |
| CN118900832A (en) | Pyrotechnic composition and method for preparing same | |
| US20230286881A1 (en) | Pyrotechnic compositions and methods of making the same | |
| DE112014002656T5 (en) | Nitroaromatically substituted metal hydroxide nitrates | |
| JPH11310489A (en) | Fuel for gas generating agent and gas generating agent composition | |
| JPH1077259A (en) | Finely powdery biscarbamoylhydrazine, granulated product thereof and gas generating agent for air bag | |
| DE102007025453A1 (en) | Composition useful in a gas generating system or vehicle occupant protection system comprises transitional metal complexes of 5-aminotetrazole as a first fuel and phase stabilized ammonium nitrate as a primary oxidizer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: French Ramiro Applicant after: ARIANEGROUP S.A.S. Address before: Paris France Applicant before: ARIANEGROUP S.A.S. |
|
| CB02 | Change of applicant information | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20221130 Address after: Room 3023, Zone 6, Cailian Commercial Plaza, No. 2900, Xiangcheng Avenue, Yangcheng Street, Xiangcheng District, Suzhou City, Jiangsu Province Applicant after: Shimaipaite (Suzhou) Technology Co.,Ltd. Address before: French Ramiro Applicant before: ARIANEGROUP S.A.S. |
|
| TA01 | Transfer of patent application right | ||
| CB02 | Change of applicant information |
Address after: Room 3023, Zone 6, Cailian Commercial Plaza, No. 2900, Xiangcheng Avenue, Chengyang Street, Economic and Technological Development Zone, Xiangcheng District, Suzhou City, Jiangsu Province, 215131 Applicant after: Shimaipaite (Suzhou) Technology Co.,Ltd. Address before: Room 3023, Zone 6, Cailian Commercial Plaza, No. 2900, Xiangcheng Avenue, Yangcheng Street, Xiangcheng District, Suzhou City, Jiangsu Province, 215131 Applicant before: Shimaipaite (Suzhou) Technology Co.,Ltd. |
|
| CB02 | Change of applicant information |