The invention relates in general to heat generating structures, and more particularly to a heat generating structure that provides heat for various purposes, including pyrolysis of various materials or compounds impregnated or located within the structure to generate a desired or target gas.
Fuel cells require hydrogen for proper operation. One proposed source of hydrogen is through the pyrolysis of ammonia borane using a heat source in pellet form. This net exothermic process involving ammonia borane is useful as a source of hydrogen because of its relatively high hydrogen content—ammonia borane is approximately twenty percent by weight hydrogen. Typically, heating of the ammonia borane occurs at a steady rate to achieve the desired pyrolytic decomposition temperature of several hundred degrees Centigrade. Practical commercial applications of such technology require both high utilization efficiency and economic efficiency (relatively high ammonia borane content per system). Efforts to pyrolyze ammonia borane contained within pressed pellets, in which ammonia borane is mixed with a type of pyrotechnic composition or thermite composed of, for example, aluminum, boron and ferric oxide powders. At high thermite content (e.g., 80%) of the pellet, gravimetric hydrogen generation is relatively low because of the correspondingly low ammonia borane pellet content (e.g., 20%). In contrast, at relatively high ammonia borane content, the resulting amount of hydrogen generated is also low because the driving thermite reaction cannot be sustained and the exothermicity of the ammonia borane pyrolysis is insufficient to continue its own decomposition—that is, the thermite concentration in the pellet is too “dilute” to completely propagate throughout the pellet Also, the thermite is typically of a particulate nature which may lead to propagation problems irrespective of its content (i.e., discontinuous or shorter than desired propagation duration, particle size variations, mixing inconsistencies and/or compaction variations) because the thermite is not physically continuous.
What is needed is a continuous heat generating structure composed, for example, of two dissimilar materials, such as metals, that provide sufficient heat for various purposes, including the complete pyrolysis of a compound (e.g., ammonia borane) impregnated or located within the structure, where the structure has a relatively high content of the compound for the generation of a correspondingly high amount of a target gas (e.g., hydrogen from pyrolysis of ammonia borane), where the exothermic alloying reaction occurring within the dissimilar metals of the heat generating structure propagates largely independent of the compound in contact with the structure, and where the only gases given off are those of the pyrolysis reaction products, for example, hydrogen.
Briefly, according to as aspect of the present invention, a heat generating structure includes a substrate comprised of a first material and a second material coating at least a portion and preferably all of the first material, where the second material is different from the first material. The structure also includes a material or compound such as ammonia borane that is impregnated or located within the structure. When the structure is thermally energized, the first and second materials react with each other in an exothermic and self-sustaining reaction that pyrolyzes the impregnated compound to create a target gas, for example, hydrogen from the ammonia borane. An additional material, for example, a thermite, may be interposed between the structure and the ammonia borane to facilitate the ignition of the ammonia borane.
These and other objects, features and advantages of the present invention will become more apparent in light of the following detailed description of preferred embodiments thereof, as illustrated in the accompanying drawings.
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In a preferred embodiment, the coating 16 comprises nickel that is applied onto the outer surface of each of the wires 14 of the aluminum metal mesh substrate 12 by, for example, electroplating or other methods such as vacuum sputtering or through an electroless process. The nickel coating 16 may include other materials including boron, phosphorus and/or palladium. Also, if aluminum is utilized as the mesh substrate material, any aluminum oxide that is present on the outer surface of the aluminum wires 14 may be removed and a coating of zinc may be applied to the outer surface of the wires 14. The zinc may allow initiation or ignition of the structure 10 at a lower temperature than if the zinc were not present. In the alternative, the zinc coating may be removed if an electroless process is used to coat the nickel onto the aluminum wire 14. The amount of nickel that is coated onto the aluminum mesh wires 14 may be in a one to one ratio with the underlying aluminum wires 14; that is, the nickel may be in an equivalent molar content as that of the aluminum. Such a ratio of nickel to aluminum allows for the continuous self propagation in an exothermic heat evolution reaction when the mesh substrate 12 is ignited, as described in detail hereinafter. The heat generating structure 10 may be considered to be a reactive multilayer laminate comprising the substrate 12 and the coating 16, with both the substrate 12 and the coating 16 comprising reactive metals in a preferred embodiment.
In a variation of the substrate 12 of the heat generating structure 10 of the present invention, the substrate 12 may simply comprise a single wire 14 comprising one material that is coated with a second material.
The materials (e.g., metals) comprising the substrate 12 and the coating 16 are selected based on their individual characteristics, such as melting point and density, and in combination for enthalpy of alloying. For any bimetallic structure comprising a substrate of a first metal coated with a second, different metal to propagate, the formation of alloys from the individual metal constituent components must be exothermic. This heat evolved warms not only the surrounding environment, but also the continuous metal structure. After a source of ignition (e.g., a match or a heating element such as a semiconductor bridge) is applied to the structure 10 of the present invention, the alloying temperature of the metals (typically close to the melt point of the aluminum wire 14 first) is eventually achieved and the materials are thermally energized and react with each other such that further alloying between the two metals is induced. Accordingly, heat is liberated with resulting propagation in a self-sustaining manner throughout the entire continuous heat generating structure 10 from a first or starting point within the structure 10 and along a travel path to a second or ending or discharge point within the structure 10, and preferably in a controlled and repeatably manufacturable manner. The starting and ending points are typically spaced from each other with the travel path in between.
For example, if the structure 10 is of a three-dimensional, rectangular-shape, once ignited at a first or starting end of the structure 10, the thermal energization of the reactive materials comprising the structure 10 will cause the propagation to continue through to the second or discharge end at a consistent timed rate depending on the intermetallic or bimetallic (or non-metallic) composition of the structure 10 as well as on the geometric configuration (e.g., thickness of wires 14, wire crossing frequency) of the structure 10. Thus, by controlling the composition and the configuration of the reactive materials comprising the heat generating structure 10, the burn or propagation rate can be controlled (that is, the reaction rate or time period for propagation from the first end to the second end along the travel path of the reactive material can be selected).
More specifically, the exothermic reaction between the dissimilar materials comprising the heat generating structure 10 can be made to occur at a relatively slower propagation or burn rate than prior art devices in part not only due to the composition of the dissimilar materials selected but also due to the three-dimensional characteristics of the substrate portion 12 of the structure 10; in particular, to a non-uniform and varying distribution of the mass of the substrate and corresponding coating along the direction of the primary propagation or burn path. For example, if the coated mesh structure 10 of
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Depending upon the compound selected to be pyrolyzed to generate a target gas, the thermite layers 26 may or may not be needed. For example, the thermite layers 26 are required when ammonia borane is used to generate hydrogen since the propagation of the coated mesh substrates 12 forming the multilayer laminate 24 will not propagate through the ammonia borane without the thermite layers 26 located therebetween. As such, the thermite layers 26 may be considered to be an additional heat generating source, where the thermite and the coated metal mesh together pyrolyze the ammonia borane. That is, when the coated metal mesh substrates 12 are ignited and begin to propagate in a self sustaining exothermic reaction, the resulting heat generated ignites the thermite layers 26, which provide additional heat to pyrolyze the ammonia borane. If the thermite layers 26 are not utilized, then the layers 28 of the compound to be pyrolyzed may be located next to and/or within the voids of the substrate 12. Located next to each layer 28 of ammonia borane is a layer 30 of carbon foam. The carbon foam may be formed as part of the layered structure 22 such that it encases all or part of the remaining layers 24-28 of the layered structure 22, with perhaps an opening in the carbon foam for an initiation device (not shown) used to ignite the coated metal mesh substrates 12 forming the multilayer laminate 24.
In operation, when the coated metal mesh substrates 12 are ignited, the adjacent thermite layers 26 also ignite. This causes the layers 28 of ammonia borane to pyrolyze with liberation of hydrogen gas. The hydrogen gas represents the desired or target gas and permeates through the layers 30 of carbon foam or other suitable similar material and is then collected and utilized in conjunction, for example, with a fuel cell. For example, if the heat generating structure 10 comprising an aluminum mesh substrate 12 coated with an equivalent molar content of nickel is impregnated and/or located next to the thermite layers 26 and ammonia borane layers 28, the overall structure 22 can hold by weight approximately 60% ammonia borane. Thus, the heat generating structures of the present invention expands the range of structures suitable for pyrolysis of ammonia borane or other compounds or materials. This ensures a higher amount of hydrogen generated by the alloying process of the ignited heat generating structure 10. The layered structure 22 may include the layers 28 of ammonia borane using a press or a solution-based process. Through proper selection of the metals comprising the wires 14 and the coating 16, the exothermic alloying reaction of the ignited heat generating structure 10 propagates largely independent of the ammonia borane. Thus, as can be seen from the foregoing, the multilayer laminate 24 comprising the heat generating structure of the embodiment of
The heat generating structure 10 of the present invention is not limited to pyrolyzing ammonia borane to generate hydrogen gas. Other materials or compounds may be disposed in a structure 22 similar to that of
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The three-dimensional characteristics of the heat generating structure of the present invention result in the transmission of heat into a structure comprising a substrate with a network of many different burn or propagation directions at one or more instants in time, in addition to the propagation direction along the desired burn path. This is particularly true with respect to the foam substrate 34 as compared to the mesh substrate 12 in terms of the number of different burn or propagation directions at one or more instants in time. Unlike systems based on compacted powder, the continuous nature of the mesh substrate 12 or foam substrate 34 and the intimate contact between the metal coating the substrates eliminates the pressure dependency required for intimate contact between layers. Thus, the burn rate of the structure is less dependent upon pressure. Failures are also reduced as a consequence of the many filaments and intersections inherent in the substrates 12, 34. In addition, consistency is enhanced since the exothermicity is controlled by the content of the metals, which content is, in turn, characterized by easily measurable and controllable weights and thicknesses (i.e., a composition and a configuration).
In general, any material that can be prepared or formed as a foam substrate 34, a mesh substrate 12, or other solid (
Also, metal particles such as aluminum, magnesium, boron, beryllium, zirconium, titanium, zinc may be used in combination with fluoropolymers such as polytetrafluoroethylene, fluoroelastomers, fluorosurfactants, or fluoroadditives. As such, the metals may be formed in finely divided particles within a matrix of one of the polymers and extruded to form a wire-like structure such as a filament which is then integrated into the structure of the substrate (e.g., the wire mesh substrate 12 of
Further, the following non-energetic polymers (i.e., non-energetic binders) can be combined with any of the above materials to form the substrate: hydroxy terminated polybutadiene, hydroxy terminated polyether, carboxy terminated polybutadiene, polyether, polycaprolactone, or polyvinyl chloride. Alternatively, such a combination of non-energetic polymers can be placed inside of an aluminum tube, where a plurality of such tubes comprises the substrate. In addition, there exist many powder-based reactions composed of a fuel and an oxidizer that constitute the bulk of pyrotechnic formulations, such as a thermite. Incorporating these into the heat generating structure of the present invention necessitates the use of a binder material, such as the energetic polymers and plasticizers listed above or the non-energetic polymers listed above, together with a non-reacting metal wire material. Thus, referring to
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The present invention has been described and illustrated herein in conjunction with various preferred embodiments as comprising a heat generating structure that is used to pyrolyze another material to produce a target gas. However, the present invention is not limited as such. The present invention may comprise a heat source that is used for to provide heat for various purposes or applications other than for the pyrolysis of another material or compound. For example, the present invention may be used to provide localized heat to certain areas in a relatively precise manner.
Although the present invention has been illustrated and described with respect to several preferred embodiments thereof, various changes, omissions and additions to the form and detail thereof, may be made therein, without departing from the spirit and scope of the invention.
This invention was made with Government support under contract W909MY-06-C-0041 awarded by the U.S. Army. The Government has certain rights in this invention.