Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
  • B60R21/00—Arrangements or fittings on vehicles for protecting or preventing injuries to occupants or pedestrians in case of accidents or other traffic risks
  • B60R21/02—Occupant safety arrangements or fittings, e.g. crash pads
  • B60R21/16—Inflatable occupant restraints or confinements designed to inflate upon impact or impending impact, e.g. air bags
  • B60R21/26—Inflatable occupant restraints or confinements designed to inflate upon impact or impending impact, e.g. air bags characterised by the inflation fluid source or means to control inflation fluid flow
  • B60R21/264—Inflatable occupant restraints or confinements designed to inflate upon impact or impending impact, e.g. air bags characterised by the inflation fluid source or means to control inflation fluid flow using instantaneous generation of gas, e.g. pyrotechnic
  • B60R21/2644—Inflatable occupant restraints or confinements designed to inflate upon impact or impending impact, e.g. air bags characterised by the inflation fluid source or means to control inflation fluid flow using instantaneous generation of gas, e.g. pyrotechnic using only solid reacting substances, e.g. pellets, powder
• • 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
  • C06B23/02—Compositions characterised by non-explosive or non-thermic constituents for neutralising poisonous gases from explosives produced during blasting
• • 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

Definitions

• New gas generating compositions used for inflating occupant safety restraints in motor vehicles are disclosed herein. More specifically, disclosed herein are airbag inflators employing gas generants that have increased gas conversion, lower bad gas production at lower temperatures and pressures, than the prior art gas generants.
• the new gas generants produce combustion products having acceptable levels of undesirable substances, such as slag.
• the new gas generants facilitate smaller inflators, as less generant mass is required to inflate the airbag and the lower combustion temperatures lessen damage to the airbag.
• Inflatable occupant restraint devices for motor vehicles have been under development worldwide for many years. Gas generating compositions for inflating the occupant restraint devices have been under development for many years and numerous patents have been granted thereon. Because the inflating gases produced by the gas generants must meet strict toxicity requirements, most, if not all gas generants now in use, are based on alkali or alkaline earth metal azides. Sodium azides have been a preferred fuel for gas generant compositions as they react with oxidizing agents to form a relatively non-toxic gas consisting primarily of nitrogen; however there are problems with azide based generants.
• a major problem associated with azide based gas generants is the extreme toxicity of the azide itself.
• the toxicity of the azide based generants makes their use inherently difficult and relatively expensive.
• the potential hazard and disposal problems of unfired inflation devices containing azide based generants must be considered.
• non-azide based gas generants i.e., guanidine nitrate and 5-aminotetrazole
• the non-azide based gas generants heretofore known produce unacceptably high levels of noxious substances upon combustion.
• the most difficult undesirable gases to control are nitrous oxide and carbon monoxide.
• An additional problem associated with the prior art non-azide based gas generants is the significantly higher combustion temperature relative to the azide based generants.
• the relatively high levels of nitrous oxide and carbon monoxide produced by the prior art non-azide gas generants is due, in part, to the relatively high combustion temperatures typically exhibited by the non-azide gas generants.
• the combustion temperature of a sodium azide/iron oxide composition can range from about 1 ,200 to about 1 ,900 degrees Celsius (1 ,473 to 2,173 ° K), while the non-azide gas generants exhibit combustion temperatures as high as 2,800 degrees Celsius (3,073 ° K).
• the aforementioned problems are solved by the new gas generant fuel systems that contain primary and secondary fuel components, mica and a limitation on the amount of the secondary fuel.
• the fuel system can be from about 40 to 70% by weight of the total gas generant.
• the primary fuel is selected from the group consisting of guanidine compounds.
• the secondary fuel is selected from tetrazole and/or triazole compounds.
• the new gas generant contains an oxidizer system that consists of at least one and preferably at least two components selected from the group consisting of transition metal oxides, alkali metal nitrates and alkaline earth metal nitrates.
• the new gas generant may contain excipients, processing aides and other compatible additives. In a most preferred embodiment the gas generant contains from 1 to about 5 % by weight of the total fuel composition is mica.
• the new gas generants produce inflation gases at a desired high burn rate while reducing the production of toxic and/or undesired gases.
• US 5 467 715 teaches a gas generant composition comprising between about 20 and about 40 wt. % of fuel, said fuel comprising a tetrazole and/or triazole compound at between about 50 and about 85 wt. % of said fuel and a water soluble fuel at between 15 and about 50 wt. % of said fuel.
• US 5 46 715 teaches that up to about 5 wt. %, typically 0.2 to 5 wt. % of a processing aid or binder is employed in the formation of pellets.
• This processing aid is selected from materials known to be useful for this purpose, including molybdenum disulfide, graphite, nitrocellulose, polyvinylpyrolidone, sodium silicate, zinc stearate, talc, mica, minerals and others known to those skilled in the art.
• US 5 139 588 discloses a gas generating composition
• a gas generating composition comprising: (1 ) a non-azide fuel; (2) an oxygen containing oxidizer; (3) an alkaline metal salt of an inorganic or organic acid such as 5-aminotetrazole; and (4) a low temperature slag forming material selected from clays, talcs and silica.
• the nonazide gas generant uses tetrazoles or tetrazole salts as the fuel and nitrogen source.
• US 5 139 588 discloses the use of oxidizers and additives resulting in solid combustion products which coalesce into easily filtered slag or clinkers.
• US 5 500 059 discloses gas generating compositions that contain anhydrous 5-amino tetrazole, its salts, its complexes, and mixtures thereof as the fuel.
• the oxidizer mixtures comprise a metal oxide or metal hydroxide, namely cupric oxide, and a supplemental oxidizer selected from the group of metal nitrates, metal nitrites, metal chlorates, metal perchlorates, metal peroxides, ammonium nitrate, ammonium perchlorate, and mixtures thereof. From the examples in this reference it is apparent that burning rates for these compositions varied greatly with the highest reported as being 2.465 cm per second (0.986 inches per second) @ 79.08 Kg per sq.
• the new compositions disclosed herein have higher burning rates and gas yields with guanidine nitrate being the preferred primary fuel and 5-amino tetrazole being the preferred secondary fuel.
• Cupric oxide is utilized as an oxidizer at between 2 to 10% by weight of the total gas generating composition, while the major oxidizer comprising a mixture of strontium and potassium nitrates.
• Burning rates for the new gas generants are about 2.59 cm per second (1.02 inches per second) @ 70.8 Kg per sq. cm (1000 pounds per square inch) and the combustion chamber temperature is around 2100 0 K. Gas conversions for the new gas generants are above 73 wt %. Gas yields are in excess of 2.85 moles/10Og generant.
• US 6 132 537 discloses gas generant compositions comprising a co-fuel system of guanidine nitrate and a heterocyclic organic acid, namely cyanuric acid.
• the oxidizer system comprises a mixture of cupric oxide, basic copper nitrate, and potassium perchlorate with at least 20% by wt. being one or more transition metal oxides.
• Burning rates for the compositions disclosed in US 6 132 537 were not revealed. Combustion chamber temperatures were calculated to be 1683°K.
• Theoretical gas yield for the compositions disclosed in US 6 132 537 using the June, 1988 version of PEP (Propellant Evaluation Program) was calculated to be only 2.34 moles/ 100g generant.
• a preferred embodiment of the new gas generant has a fuel system of guanidine nitrate and 5-amino tetrazole.
• the preferred oxidizer system comprises at least one and preferably at least two compounds selected from the group consisting of cupric oxide, alkali metal nitrates and alkaline-earth metal nitrates.
• the alkali metal nitrates and alkaline-earth metal nitrates do not produce undesirable chloride salts, as does the potassium perchlorate found in the prior art compositions.
• US 6 893 517 discloses gas generating compositions that comprise at least one nitrogen-containing organic fuel, namely guanidine nitrate and a further fuel, nitroguanidine.
• the oxidizer is potassium perchlorate and the composition incorporates a combustion moderator selected from the transition metal oxides, namely cupric oxide.
• Burning rates referenced in Table 2 of the patent range from 30.8 to 46.2 mm/s @ 200 bar. Using the provided pressure exponent referenced in the same table, this translates to a burning rate of 0.82 to 1.40 in/s @ 1000 psi.
• Theoretical combustion temperatures for these compositions, also referenced in Table 2, range from 2377 to 2462°K. This is quite high for gas generator compositions used in airbags as such temperatures can damage the fabric of the air bag.
• Theoretical gas conversions are found in Table 2 and range from 78.44 to 81.32%.
• US 5 756 929 discloses a gas generant composition containing at least one high nitrogen non-azide fuel selected from the group consisting of guanidine nitrate, aminoguanidine nitrate, guanidine perchlorate, and guanidine picrate; and a secondary fuel of diammonium bitetrazole.
• the new gas generant fuel system contains primary and secondary fuel components.
• the fuel system can be from about 40 to 70% by weight of the total gas generant.
• the primary fuel is selected from the group consisting of guanidine compounds.
• the secondary fuel is selected from tetrazole and/or triazole compounds.
• the new gas generant contains an oxidizer system consisting of at least one and preferably at least two components selected from the group consisting of transition metal oxides, alkali metal nitrates, alkaline earth metal nitrates.
• the new gas generant preferably contains excipients, processing aides and other compatible additives. The most preferred excipient is mica.
• the new gas generants produce inflation gases at a desired high burn rate while reducing the production of toxic and/or undesired gases.
• US 5 765 866 discloses a gas generating compositions having a fuel, one or more oxidizers and mica.
• the mica content is greater than 5 and less than 25 wt. % of the total gas generating composition.
• US 5 765 866 provides a good discussion of mica and the testing procedures used for gas generating compositions.
• US 5 765 866 discloses the gas generant composition is incorporated into an airbag inflator.
• a gas generant comprising a fuel system, in a preferred embodiment, comprising guanidine nitrate and 5-amino tetrazole.
• the oxidizer system in a preferred embodiment, comprises a transition metal oxide, namely cupric oxide in the range of 2 to 10% by weight of the oxidizer system and the balance is comprised of alkali metal nitrates and/or alkaline-earth metal nitrates.
• the gas generant contains mica.
• the alkali metal nitrates and alkaline-earth metal nitrates do not produce the undesirable chloride salts in the gas generated, as does the perchlorates of the prior art compositions.
• Burning rates for the new gas generants are typically about 1.02 in/s @ 1000 psi and the combustion chamber temperatures are about 2100 0 K.
• Gas conversions for the new gas generants are unexpectedly high, generally above about 73 wt. %.
• a primary advantage of the new gas generant compositions is that reduced levels of toxic and/or undesirable gases are produced.
• An airbag inflator charged with the new gas generant can be of reduced weight and size.
• an airbag inflator comprising: (a) a metal housing; and (b) a gas generant inside the metal housing, the gas generant comprising: (i) greater than 1 and less than 5 wt. % mica; (ii) a primary fuel selected from the group consisting of guanidine compounds; (Hi) a secondary fuel at levels of less than 5 % by weight selected from the group consisting of tetrazoles, triazoles and mixtures thereof; (iv) an oxidizer system comprising at least two compounds selected from the group consisting of transition metal oxides, alkali metal nitrates and alkaline earth metal nitrates.
• the airbag inflator may contain a gas generant that comprises guanidine nitrate as the primary fuel and at least one compound selected from the group consisting of 5-amino tetrazole, bitetrazole, 3-nitro-1 , 2, 4- tiazol-5-one and mixtures thereof as the secondary fuel.
• a gas generant that comprises guanidine nitrate as the primary fuel and at least one compound selected from the group consisting of 5-amino tetrazole, bitetrazole, 3-nitro-1 , 2, 4- tiazol-5-one and mixtures thereof as the secondary fuel.
• the new gas generant composition consists of: (a) 45 to 55 weight % guanidine nitrate; (b) 30 to 35 weight % strontium nitrate; (c) 2 to 10 weight % cupric oxide; (d) 2 to 10 weight % potassium nitrate; (e) 1 to 5 weight % 5-amino tetrazole; (f) 1 to 5 weight % boron nitride; (g) 1 to 5 weight % mica; and (h) processing aids selected from the group consisting of tetrazoles, triazoles and mixtures thereof; (iv) an oxidizer system comprising at least two compounds selected from the group consisting of transition metal oxides, alkali metal nitrates and alkaline earth metal nitrates.
• the new airbag inflator may contain a gas generant that is (a) 40-70 wt. % of said primary and secondary fuels; and (b) 30-70 wt. % of said oxidizer system.
• the primary fuel is selected from the group consisting of guanidine nitrate, nitroguanidine, aminoguanidine nitrate, diaminoguanidine nitrate, triaminoguanidine nitrate and mixtures thereof.
• the primary fuel is guanidine nitrate and the secondary fuel is 5-amino tetrazole and the oxidizer system comprises potassium nitrate, copper oxide and strontium nitrate.
• the potassium nitrate is 5-10 wt. % of said generant and the strontium nitrate is 40-50 wt. % of said generant.
• Mica is preferably present at from about 1 to about 5 wt. % of the total gas generant.
• the gas generant may contain processing aids known to those of skill in the art. Boron nitride is a preferred processing aid.
• the new gas generant composition comprises: (a) a primary and secondary fuel, said primary fuel is a guanidine compound ranging from about 40 to 60% by weight, more preferably from 45 to 55% by wt. of the total gas generant composition and said secondary fuel is a tetrazole or triazole ranging from about 2 to 15% by weight, more preferably from 2 to 10 % by wt. of the gas generant composition; (b) an oxidizer system comprising at least two components, said oxidizer system ranging from about 30 to 70% by weight of said gas generant composition, wherein said oxidizer system consists of (i) a transition-metal oxide ranging from about 2 to 15% by weight, more preferably from 2 to 10 % by wt.
• the gas generant composition and (ii) an alkali metal nitrate, an alkaline-earth metal nitrate, or mixtures thereof, wherein said alkali metal nitrate, alkaline-earth metal nitrate or mixtures thereof range from about 30 to 50% by weight of the gas generant composition; (c) from 1 to 5 wt. % mica; and d) from 0 to 5% by weight of the gas generant composition of a processing additive.
• the processing aid is boron nitride
• the transition- metal oxide is cupric oxide
• the alkali metal nitrate is potassium nitrate
• the alkaline-earth metal nitrate is strontium nitrate.
• the secondary fuel is selected from the group consisting of 5-amino tetrazole, bitetrazole, 3-nitro-1 , 2, 4-triazol-5- one, and mixtures thereof. Most preferred is 5-amino tetrazole.
• the primary fuel is selected from the group consisting of guanidine nitrate, nitroguanidine, aminoguanidine nitrate, diaminoguanidine nitrate, triaminoguanidine nitrate, and mixtures thereof. The most preferred primary fuel is guanidine nitrate.
• gas generant composition comprising: (a) 45 to 55 weight % guanidine nitrate; (b) 30 to 35 weight % strontium nitrate; (c) 2 to 10 weight % cupric oxide; (d) 2 to 10 weight % potassium nitrate; (e) 2 to 10 weight % 5-amino tetrazole; (f) 0 to 5 weight % boron nitride; and (g) 1 to 5 weight % mica; and (h) processing aids.
• the new gas generant composition assists in the production of a gas that is low in particulate matter after filtration and toxic and/or undesirable gases.
• the new generant compositions and the new airbag inflators are easily prepared.
• Fig. 1 is a side view of an exemplary airbag inflator useful with the new gas generant compositions.
• Fig. 2 is a cross section of the airbag inflator of Fig. 1 taken along line 2-2.
• Processing aids such as silicon dioxide, may be used in the new gas generant.
• processing aids such as silicon dioxide
• Those skilled in the art understand that depending upon the particular oxidizers and fuels utilized, certain processing aids have beneficial properties over others.
• Representative of processing aids useful in the new gas generants is silica TS-530 made by the Cabot Corporation of Tuscola, III., U.S.A.
• the oxidizer system useful in the composition of the new gas generant consists of at least two components, ranging from 30 to 70% by weight of the total gas generant, wherein said oxidizer system consists of a transition metal oxide; and alkali metal nitrates, alkaline earth metal nitrates and mixtures thereof.
• Representatives of the alkaline earth metal nitrates useful in the new gas generants include strontium nitrate.
• the preferred oxidizer system of the new gas generant is a mixture of strontium nitrate, potassium nitrate and cupric oxide.
• Mica is useful in the new gas generant compositions.
• Mica is a name for a group of complex crystalline hydrous aluminum silicate minerals constructed of extremely thin cleavage flakes and characterized by near perfect basal cleavage, and a high degree of flexibility, elasticity, and toughness.
• the various micas although structurally similar, vary in chemical composition. The properties of mica derive from the periodicity of weak chemical bonding alternating with strong bonding. Representative of the minerals of the mica group are muscovite, phlogopite, biotite, lepidolite and others such as fluorophlogopite.
• the silicon to aluminum ratio is about 3:1. Any naturally occurring mica is useful in the new gas generant composition.
• the mica useful in the composition employed with the new airbag inflators is typically ground mica having a particle size ranging from 2 to 100 microns. This ground mica is often referred to as flake mica. In the new gas generant mica with a particle size in the range of 2-25 microns is preferred.
• the new gas generant composition may optionally contain up to about 3 wt. %, typically between about 1 and about 2 wt. %, of a catalyst. Those of skill in the art are aware of the catalysts that are useful in gas generant compositions.
• the gas generant is ignited by heat generated by a booster composition and the resulting chemical reaction generates gas which passes through a knitted wire annular filter and then through a perforated annular tube.
• a knitted wire cushion is used to protect the gas generant pellets.
• An autoignition substance is in close proximity to the booster composition.
• An autoignition substance is a composition that will spontaneously ignite at a preselected temperature and thereby ignite the booster composition that will then ignite the gas generate.
• a one Kg batch of each of seven gas generant compositions was formulated according to Table I below.
• the compositions were prepared by initially mixing all the components, except for the 5-aminotetrazole (5-AT), in a batch-type vibratory grinder (Sweco) for 120 minutes.
• the mica used was Micro Mica 3000 (muscovite) obtained from the Charles B. Crystal Co., Inc. of New York, N.Y., U.S.A. It was finely divided mica having a bulk density of about 12.4 lbs/cubic foot and a specific gravity of about 2.8.
• the 5-AT was then added to the grinder and the mixture was ground for an additional 120 minutes.
• the mixture was then placed in a plough-type mixer and about 15% by wt. water was added to form agglomerate that was then passed through a granulator with an 8 mesh screen.
• the granules were placed on a tray and dried at 120 0 C in an explosion proof oven for about 3 hours. The water content after drying was between 0.5 and 1 % by weight. The dried granules were then passed through the granulator using a 20 mesh screen. The samples were then pelletized with a rotary pellet press. The pellets were about 5 mm in diameter, 1.2 mm high, weighed about 51 to 53 mg each.
• the assembled inflators containing the various gas generants were evaluated in a 2.83 cubic meter (100 cubic foot) test tank fitted with equipment to record the pressure and time profile of the combustion and to analyze the gases exiting the inflator.
• the 2.83 cubic meter (100 cubic foot) test is designed to simulate the interior volume of the standard automobile. Gas analysis and particulate analysis is also possible using this test.
• the test equipment consisted of a 2.83 cubic meter (100 cubic foot) steel chamber containing a steering wheel simulator. To the chamber was attached a vacuum pump, a bubble flow meter, filters and a FT/I R gas analyzer (spectrophotometer).
• the inflator was attached to the simulated steering wheel assembly within the chamber, the chamber was sealed and the gas generant ignited. Gas samples were analyzed using an FTIR spectrometer at zero time and at 1 , 5, 10, 15 and 20 minute intervals from ignition. Airborne particulate production can be measured using the 2.83 cubic meter (100 cubic foot) test chamber by filtering post-ignition air from the chamber through a fine filter and measuring the weight gained by the filter.
• Table II sets forth the data collected for Formulations 1 through 7.
• the combination of less than 5% by weight mica and 5% by weight or less of a tetrazole and/or triazole provides the advantages presently described. It is believed that the fuel component comprises a major portion of a guanidine compound in combination with a tetrazole and/or triazole fuel provides substantial benefits.
• a higher level of mica is used to demonstrate that the level of mica is important to the new multi-fuel gas generant.
• the level of components of Formulation 7 are used except that the level of guanidine nitrate is 50% by weight, the level of strontium nitrate is 31 % by weight and the level of mica is 7% by weight.
• Fig. 1 is a side view of an exemplary vehicle airbag inflator 10 that can employ the new gas generant compositions disclosed herein.
• a mounting plate 11 is used to attach the inflator to a steering wheel, instrument panel or other suitable location in the vehicle.
• a gas generant inside the airbag inflator is burned it generates gasses that exit the inflator via apertures 12 in the metal inflator housing 13.
• Fig. 2 is a cross section of the airbag inflator of Fig. 1 taken along line 2 - 2 of Fig. 1.
• the airbag inflator 10 is activated by a signal from a crash sensor if a crash of sufficient magnitude to require activation of the inflator 10 is sensed.
• the activation signal closes an electrical circuit or initiates a firing signal that activates an initiator such as a squib 24, which ignites a booster composition 15, which in turn ignites the new gas generating composition 16.
• the igniter assembly 22 comprising the squib 24 and two electrodes is attached to the inflator housing through any useful means and is preferably attached via a weld.
• a "squib” is understood to be an electrical device having two electrodes insulated from one another and connected by a bridge wire.
• the bridge wire is preferably embedded in one or more layers of a pyrotechnic composition that gives a flash of heat of sufficient intensity to ignite the booster composition 15.
• Any suitable booster composition 15 may be employed.
• the gas generant 16 is ignited by the heat generated by the booster composition 15 and the resulting chemical reaction generates gas, which passes through a knitted wire annular filter 26 and then through perforated annular tube 17.
• the knitted wire filter 26 and the perforated tube 17 are preferably made of stainless steel but low carbon steel may be employed.
• a knitted wire cushion 18 is used to protect the gas generant pellets.
• Backup ring 19 holds the wire cushion 18 and the wire filter 26 in places.
• An autoignition substance 21 is in close proximity to the booster composition 15.
• the autoignition substance 21 is a composition that will spontaneously ignite at a preselected temperature and thereby ignite the booster composition 15 which will then ignite the gas generate 16.
• the new gas generants may react in a much more violent manner if the ambient temperature is elevated, so it is desirable to ignite the gas generant before such a violent reaction can occur.
• An autoignition retainer 23 secures the autoignition substance 21 against the interior wall of the metal housing 13 to assure that proper heat transfer occurs for the ignition of the autoignition substance 21 at the desired temperature.
• the airbag inflator represented in the drawings and described herein is merely representative and that a new airbag inflator has a metal housing containing the gas generant disclosed herein.
• gas generants produce restricted levels of various reaction products.
• the new gas generants will be able to meet these standards.
• the automotive industry is constantly searching for gas generants that produce reduced levels of undesirable gases and provides for savings in the production of airbags.
• the automotive industry is also in need of gas generants that do not use azide based generants to avoid the problems associated with azide toxicity.
• the use of a dual non-azide fuel system and a dual oxidizer system, preferably with 1-5 weight % of mica, will address the needs of the industry and promote the use of non-azide fuels.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
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• Health & Medical Sciences (AREA)
• Toxicology (AREA)
• Physics & Mathematics (AREA)
• Fluid Mechanics (AREA)
• Mechanical Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Combustion & Propulsion (AREA)
• Air Bags (AREA)

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• 2007
  • 2007-07-16 US US11/778,222 patent/US20090020197A1/en not_active Abandoned
• 2008
  • 2008-07-07 EP EP08780007.4A patent/EP2164823A4/de not_active Withdrawn
  • 2008-07-07 CN CN200880022284.7A patent/CN101687722B/zh not_active Expired - Fee Related
  • 2008-07-07 WO PCT/US2008/008332 patent/WO2009011769A1/en active Application Filing

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