Gas generants containing a transition metal complex of...

Explosive and thermic compositions or charges – Containing hydrazine or hydrazine derivative

Reexamination Certificate

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Details

C149S045000

Reexamination Certificate

active

06689237

ABSTRACT:

BACKGROUND OF THE INVENTION
This invention relates generally to gas generant materials such as are used to inflate automotive inflatable restraint airbag cushions and, more particularly, to the enhancement of the rate at which such materials burn or otherwise react.
Gas generating materials are useful in a variety of different contexts. One significant use for such compositions is in the operation of automotive vehicle occupant restraints. For example, it is well known to protect a vehicle occupant using a cushion or bag, e.g., an “airbag cushion,” that is inflated or expanded with gas when the vehicle encounters sudden deceleration, such as in the event of a collision. In such systems, the airbag cushion is normally housed in an uninflated and folded condition to minimize space requirements. Such systems typically also include one or more crash sensors mounted on or to the frame or body of the vehicle to detect sudden decelerations of the vehicle and to electronically trigger activation of the system. Upon actuation of the system, the cushion begins to be inflated in a matter of no more than a few milliseconds with gas produced or supplied by a device commonly referred to as an “inflator.” In practice, such an airbag cushion is desirably deployed into a location within the vehicle between the occupant and certain parts of the vehicle interior, such as a door, steering wheel, instrument panel or the like, to prevent or avoid the occupant from forcibly striking such part(s) of the vehicle interior.
Gas generant compositions commonly utilized in the inflation of automotive inflatable restraint airbag cushions have previously most typically employed or been based on sodium azide. Such sodium azide-based compositions, upon initiation, normally produce or form nitrogen gas. While the use of sodium azide and certain other azide-based gas generant materials meets current industry specifications, guidelines and standards, such use may involve or raise potential concerns such as relating to the safe and effective handling, supply and disposal of such gas generant materials.
In view thereof, significant efforts have been directed to minimizing or avoiding the use of sodium azide in automotive airbag inflators. Through such efforts, various combinations of non-azide fuels and oxidizers have been proposed for use in gas generant compositions. These non-azide fuels are generally desirably less toxic to make and use, as compared to sodium azide, and may therefore be easier to dispose of and thus, at least in part, found more acceptable by the general public. Further, non-azide fuels composed of carbon, hydrogen, nitrogen and oxygen atoms typically yield all gaseous products upon combustion. As will be appreciated by those skilled in the art, fuels with high nitrogen and hydrogen contents and a low carbon content are generally attractive for use in such inflatable restraint applications due to their relatively high gas outputs (such as measured in terms of moles of gas produced per 100 grams of gas generant material).
Most oxidizers known in the art and commonly employed in such gas generant compositions are metal salts of oxygen-bearing anions (such as nitrates, chlorates and perchlorates, for example) or metal oxides. Unfortunately, upon combustion, the metallic components of such oxidizers typically end up as a solid compound, such as an oxide, and thus reduce the relative gas yields realizable therefrom. Consequently, the amounts of such oxidizers in a particular formulation typically affect the gas output or yield from the formulation. If oxygen is incorporated into the fuel material, however, less of such an oxidizer may be required and the gas output of the formulation can be increased.
In addition to low toxicity and high gas outputs, gas generant materials desirably are relatively inexpensive, thermally stable (i.e., desirably decompose only at temperatures greater than about 160° C.), and have a low affinity for moisture.
In addition to the above-identified desirable properties and characteristics, gas generant materials for use in automotive inflatable restraint applications must be sufficiently reactive such that upon the proper initiation of the reaction thereof, the resulting gas producing or generating reaction occurs sufficiently rapidly such that a corresponding inflatable airbag cushion is properly inflated so as to provide desired impact protection to an associated vehicle occupant. In general, the burn rate for a gas generant composition can be represented by the equation (1), below:
r
b
=k
(
P
)
n
  (1)
where,
r
b
=
burn rate (linear)
k =
constant
P =
pressure
n =
pressure exponent, where the pressure exponent is the
slope of a linear regression line drawn through a log-log
plot of burn rate versus pressure.
Guanidine nitrate (CH
6
N
4
O
3
) is a non-azide fuel with many of the above-identified desirable fuel properties. For example, guanidine nitrate is commercially available, relatively low cost, non-toxic, provides excellent gas output due to a high content of nitrogen, hydrogen and oxygen and a low carbon content and has sufficient thermal stability to permit spray-dry processing. In view thereof, guanidine nitrate has found wide utilized in the automotive airbag industry.
Unfortunately, guanidine nitrate suffers from a lower burn rate than may be desired in many applications. Thus, there remains a need and a demand for an azide-free gas generant material that may more effectively overcome one or more of the problems or shortcomings described above.
Commonly assigned U.S. patent application, Ser. No. 09/715,459, filed Nov. 17, 2000, relates generally to gas generant compositions which desirably include or contain guanylurea nitrate (also known as dicyandiamidine and amidinourea). In particular, guanylurea nitrate advantageously has a relatively high theoretical density such as to permit a relatively high loading density for a gas generant material that contains such a fuel component. Further, guanylurea nitrate exhibits excellent thermal stability, as evidenced by guanylurea nitrate having a thermal decomposition temperature of 216° C. In addition, guanylurea nitrate has a large negative heat of formation (i.e., −880 cal/gram) such as results in a cooler burning gas generant composition, as compared to an otherwise similar gas generant containing guanidine nitrate.
While the inclusion or use of guanylurea nitrate in gas generant materials can serve to avoid reliance on the inclusion or use of sodium azide or other similar azide materials while providing improved burn rates and overcoming one or more of the problems, shortcomings or limitations such as relating to cost, commercial availability, low toxicity, thermal stability and low affinity for moisture, even further improvement in the burn rate of gas generant formulations may be desired or required for particular applications.
For some inflator applications, a low gas generant formulation burn rate can be at least partially compensated for by reducing the size of the shape or form of the gas generant material such as to provide the gas generant material in a shape or form having a relatively larger reactive surface area. In practice, however, there are practical limits to the minimum size of the shape or form, such as a tablet, for example, to which gas generant materials can reproducibly be manufactured, and increased burn rates may be needed for particular applications which require a higher inflator performance.
The above-identified, co-pending, commonly assigned, U.S. patent application Ser. No. 09/998,122 filed on Nov. 30, 2001 teaches burn rate enhancement via the incorporation or use of a transition metal complex of diammonium bitetrazole. These compounds, when used as a part of a gas generant formulation, in conjunction with a primary fuel, such as guanidine nitrate, enhance burn rate. While such inclusion of a transition metal complex of diammonium bitetrazole may desirably serve to enhance the burn rate of a formulation, these compounds are relatively

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