This invention relates to reactive composite material structures (RCM structures), such as reactive multilayer foils, and in particular, to arrangements for protecting RCM structures from unwanted ignition as by electrostatic discharge (ESD). It also concerns applications of the thus-protected structures.
Reactive composite materials (RCMs) are nanostructured materials comprising two or more solid materials with large negative heats of mixing, such as nickel and aluminum, spaced in a controlled fashion throughout a composite in uniform layers, local layers, islands, or particles. These materials are ignitable to support self-propagating exothermic chemical reactions. The reactions typically travel along the RCMs at speeds ranging from about 0.1 m/s to about 100 m/s.
RCMs may be produced via vapor deposition, mechanical deformation, or electrodeposition. Methods of making and using RCM structures are disclosed in the U.S. Pat. No. 6,736,942 entitled “Freestanding Reactive Multilayer Foils” (“the '942 patent”), which is incorporated herein by reference and in U.S. provisional application 60/692,822 to Xun, et al. filed Jun. 22, 2005, entitled “Methods Of Making Reactive Composite Structures, Resulting Products And Applications Thereof”.
Self-propagating reactions in RCMs are driven by a reduction in chemical bond energy. Upon the application of a suitable stimulus to ignite, a local bond exchange between constituents of the RCM produces heat that is conducted through the RCM to drive the reaction. Recent developments in RCM technology have shown that it is possible to carefully control the ignition threshold and the heat and velocity of the reaction. For instance, it has been demonstrated that the velocities, heats, and/or temperatures of the reactions in an RCM can be controlled by varying the thicknesses or scale of the reactant regions and that the heats of reaction can be controlled by modifying the RCM composition or by low-temperature annealing of the RCM after fabrication.
These technological advances have widened the scope of potential applications of RCMs. Important applications include: (a) reactive multilayer joining (see, for example, U.S. patent application Ser. No. 10/843,352 filed May 12, 2004 which is incorporated herein by reference); (b) hermetic sealing (see, for example, U.S. patent application Ser. No. 10/814,243 filed Apr. 1, 2004, incorporated herein by reference); (c) structural elements that are capable of releasing energy; and (d) initiating secondary reactions, as in flares, detonators and propellant-based devices.
Several different approaches have been employed for igniting self-propagating reactions in RCMs. Such techniques are described in U.S. patent application Ser. No. 10/959,502 (the '502 application) filed Oct. 7, 2004 which is incorporated herein by reference. The stimuli include electric current, mechanical impact, friction, induction heating, microwave radiation, and laser radiation. It is desirable to protect RCMs from unwanted ignition from accidental exposure to such stimuli.
Applicants have discovered that accidental exposure to stimuli such as electrostatic discharge (ESD) may, in some circumstances, result in current densities sufficient to ignite unprotected reactive composite materials. They have further discovered that reactive composite material (RCM) can be protected from unwanted ignition without adversely affecting the desirable properties of the RCM by layers of conducting and/or insulating materials at appropriate locations on the RCM. Thus protected RCM structures can be designed for such sensitive applications as joining, ignition of propellants, generation of light bursts, and structural materials.
The advantages, nature, and various additional features of the invention will appear more fully upon consideration of the illustrative embodiments now to be described in detail in connection with the accompanying drawings. In the drawings
a schematically illustrates an RCM foil with a thick metal layer over the surfaces and an insulating coating around the edges;
b schematically illustrates an RCM foil with a thick metal layer over the surfaces and a conducting coating around the edges;
a schematically illustrates an RCM foil that is wrapped with metal foil or mesh;
b schematically illustrates an RCM foil that is sandwiched between a sheet of metal foil and a sheet of metal tape, wherein the edges of the foil and tape extend beyond the RCM.
This detailed discussion is divided into two parts. Part I discusses ESD protective layers for a variety of RCM applications, and Part II describes advantageous embodiments.
Applicants have discovered that electrostatic discharge (ESD) through an RCM may result in a current density high enough to ignite the RCM. The current density required to ignite an RCM depends on intrinsic properties of the RCM, including the spatial distribution, size and intermixing of the constituents of the RCM, their interdiffusion behaviors, and their electrical conductivities, as well as extrinsic properties, such as the shape of the RCM and the location of the current path through it. Applicants have further determined that the sensitivity of an RCM to ignition via ESD can be reduced without adversely affecting desirable behavior of the RCM by the application of insulative and/or conducting layers to various portions of the RCM. The layers are disposed to change, reduce, or eliminate the path of the ESD current through the RCM. The layers also reduce unwanted ignition by other stimuli.
One measure of ESD protection is provided by testing with the Human Body Model as described in ANSI standard ANSI-STM5.1-2001. Applicants believe that the embodiments described herein can provide protected RCMs that are self-propagating and classifiable as class 3B or better when so tested under the ANSI standard.
A typical RCM structure is in the form of a thin reactive multilayer foil or a thicker three dimensional structure. In a thin RCM foil, the two major surfaces and the edges are the most pertinent geometric zones for ESD control. In a thicker, three-dimensional RCM structure, such as a cube, the faces, edges, and corners are the most pertinent zones. It is convenient to treat the zones separately, as the likelihood of ignition can vary based on which zone an ESD pulse hits.
In a thin foil, the edges are typically more sensitive than the surfaces, due to both the orientation of the layers and the thinness of the edges. If an ESD arc impinges on an edge, the arc is constrained to the thickness of the foil, whereas if the arc impinges on a surface, it may spread in two dimensions. Thus for a given ESD voltage, the ESD arc current density at the edge is higher than on a surface. The layer orientation also affects ignition sensitivity because the electrical resistance in the foil parallel to the plane of the layers is lower than the electrical resistance perpendicular to the plane. For a given voltage, lower resistance allows more current to flow, which produces more heat. Thus, a voltage imposed from an electrode to the edge of a foil generates more heat than the same voltage imposed from the electrode to the surface of the foil.
Applicants have developed strategies for protecting RCMs from ESD without impeding the use of the RCM for specific applications. In various applications, the surfaces, edges, or corners of an RCM must be exposed. For example, they typically need to be exposed for ignition of the RCM, for heat transfer from the RCM to its surroundings in such applications as heaters and igniters, for wetting with molten solder or braze layers in joining applications, or for light transmission in such applications as flares and non-lethal confusion blasts. ESD protection tailored for such applications may be achieved by protecting different zones using insulating or conducting layers.
Partially covering or wrapping an RCM can reduce its ESD sensitivity by modifying the current path. Sensitivity can be reduced by three mechanisms: 1) an alternate path for the ESD current is provided, reducing the amount of current that passes through the RCM; or 2) the ESD current is spread so that the current density is not high enough to ignite the RCM; or 3) the threshold for an ESD arc is raised beyond practical limits so that no arc forms.
Insulating or conducting layers may be advantageously applied to 1) the surfaces, 2) the edges, 3) a combination of surfaces and edges, or 4) the entire RCM. Different combinations of zones and layers provide respectively different levels of ESD protection appropriate for respectively different RCM applications.
Reducing the sensitivity of an RCM typically requires protection of the most sensitive zone. For instance, an insulating layer on only the surfaces of the RCM can reduce sensitivity if the surfaces are more subject to ignition than other zones. An insulating layer over the edges of a reactive foil can prevent arcing through the edge of the foil or can spread the arc to many points, reducing the current density at each point. An insulating layer covering one surface and the edges (or the entire foil) would have to undergo dielectric breakdown before current could travel to ground. The insulating layers should be between the RCM and the voltage source or ground, but they need not be in contact with the RCM to be effective. Thus, both insulating coatings and sheets can be effective insulating layers.
A conducting layer over the surfaces but not the edges of an RCM multilayer allows EDS current to spread before passing through the multilayer, thereby lowering the ESD current density. A conducting layer over the edges of a RCM allows an ESD arc at the edge to spread before the current travels through the multilayer. A conducting layer surrounding a multilayer foil provides a path for the current that can avoid the RCM multilayer entirely, or it can spread the current before it enters the multilayer. The surrounding conductor acts as a Faraday cage, keeping charge and current on the outer skin of the conducting layer. The conducting layer typically has a thickness of excess of about a micrometer.
Combinations of insulating and conducting layers can be devised to provide ESD protection without interfering with RCM applications. Insulating the edges and one major surface of an RCM foil while applying a conducting layer to the other major surface reduces ESD sensitivity without significantly affecting other ignition or emission behaviors. With this arrangement, the conducting surface is more likely to attract an ESD arc than the other surfaces and edges. The conducting layer spreads any ESD current before it passes into the multilayer, and the insulating layers would have to undergo dielectric breakdown before current could travel to ground.
Another arrangement stacks a combination of insulator and conductor in the same place. As examples, a metal tape with insulating adhesive, a polymer film with a metal layer on one side, or a metallized ESD bag can provide a conducting path around an RCM while ensuring that any current path through the multilayer has a high resistance.
Insulating layers for ESD protection of RCMs include but are not limited to ceramic coatings and insulating polymer films and coatings. Advantageous ceramics include oxides, nitrides, and carbides. Insulating ceramics or polymers can serve as substrates for the sputter deposition of RCM foils, or the insulating materials can be deposited on RCM foils during manufacture, via vapor deposition or any other suitable method. Aluminum oxide can be anodized on an aluminum layer on the surface of an RCM. Advantageous thicknesses are about a micrometer or more. Other ceramic layers may be grown thermally, chemically, or electrochemically, or by similar methods. Advantageous insulating polymers include PET, PTFE, PEN, insulating epoxies and insulating commercial anti-static coatings (OhmShield™ from Static Solutions, Inc., Sanpro Silver Lining™, Sprayon™ S00610 and Zero-charge Anti-Stat™ from Techspray). Such insulating polymers can be applied by spraying or painting. Other useful insulating layers include polymer tape (e.g. Kapton and ESD tape), castable ceramics, chemically applied insulators and even wood or paper.
Conducting layers for ESD protection of RCMs include but are not limited to films or coatings of metal such as aluminum, nickel, copper, indium, and lead-tin alloy. In addition, some commercial anti-static coatings are conducting. The conducting coatings can be applied to RCMs by any of a variety of processes including sputtering (aluminum or nickel), attachment (copper cladding, aluminum foil folded around the RCM), electro-chemical deposition (nickel), rolling or pressing (solder or braze alloys such as indium or tin-lead), and even by spraying or painting (commercial conducting coatings such as Nickel, Silver, and Gold Print). Also useful are metal tapes with conducting adhesive such as Saint Gobain Performance Plastics tapes. The conducting protective layer need not be continuous. A metal screen or mesh can be effective provided the mesh thickness and openings are scaled to divert an arc from the RCM to ground.
Combinations of insulating and conducting materials for ESD protection of RCMs include films and tapes that have both conducting and insulated surfaces. Examples include ESD bags that comprise an insulating polymer lining with a metal exterior and metal tape with an insulating adhesive. Tapes can also have insulating polymer outer surfaces and conducting adhesives or tapes can be wholly conducting or wholly insulating layers.
One advantageous approach involves insulating a portion of the RCM but leaving at least one RCM surface uninsulated. This arrangement allows deliberate ignition of the RCM at the uninsulated surface using heat, laser, or other technique that would be difficult with a thick insulating layer in place. A thick insulating layer may also prevent transmission of light signals or heat from the RCM to the surroundings, impeding the usefulness of the RCM. In many cases, reducing the sensitivity of only the edges may provide adequate ESD protection, leaving the surfaces free to function as desired. A conducting layer on the uninsulated surface, such as a thick layer (greater than about one micrometer) of sputtered metal, impedes deliberate ignition much less than an insulating layer does. Thus, protecting the uninsulated surface with a thick conducting layer is a second advantageous approach.
Another advantageous approach—especially useful for RCMs disposed on conducting polymer backings—is to apply a conducting layer around the edges. If the polymer backing layer is metallized on the side distal the RCM, then a spark from the metallized polymer could jump to an unprotected RCM edge causing undesired ignition. Even coating the edge with insulating material might not prevent this occurrence. But a conducting layer, such as aluminum foil or metal tape with conducting adhesive, that is disposed around the edges provides a conducting path from the top surface of the RCM to the bottom metallized polymer. This path significantly reduces ESD risk.
In a first advantageous embodiment, shown in
As an example of the
In a second embodiment, shown in
As an example of the
In a third embodiment (
As an example of the
In another embodiment (
In a fifth embodiment (
In a variation of the fifth embodiment, (
As an example of the fifth embodiment, copper tape was clamped around the edges of a mechanically formed Pd—Al multilayer foil 40 μm thick with a 200 nm (weighted average) bilayer in such a way that the edges of the multilayer were entirely covered by the tape. The ignition threshold of the resulting samples was larger than 6 mJ, compared to 2 mJ for the multilayer without tape around the edges.
In a sixth embodiment (
For example, a Ni—Al multilayer foil 30 um thick with a 50 nm bilayer was wrapped with a 12 μm layer of aluminum foil. The energy required to ignite it was increased from 2 mJ to over 225 mJ. This structure can also be used to protect the multilayer foil from external radio frequency electromagnetic radiation.
In a variation on the sixth embodiment (
For example, a Ni—Al multilayer foil 30 μm thick with a 50 nm thick bilayer that was sputter-deposited on a 125 micron thick non-metallized PET substrate was placed on a sheet of Saint Gobain Performance Plastics aluminum tape with conducting adhesive, PET against adhesive. A sheet of aluminum foil 12.5 μm thick of size equal to that of the aluminum tape was placed over the multilayer foil and the margins were pressed against the aluminum tape. When an ESD arc of 450 mJ was discharged directly into the edge of the sandwich, a margin 1/16″ wide did not prevent ignition while a margin ⅛″ wide prevented ignition. Advantageously, this geometry is effective for heating and for igniting solid rocket propellant.
In yet another embodiment (
As a second example, a mechanically formed Ni—Al reactive multilayer foil 40 μm thick with a 200 nm thick bilayer (weighted average) was completely covered with about 0.5 mm of a dried commercial ESD liquid coating OhmShield™ AF 6500. The covered sample was less sensitive to ESD, requiring over 150 mJ for ignition versus 6 mJ for the same foil without the AF 6500 coating.
In another advantageous embodiment (
In another embodiment (
As a hypothetical example of the
It can now be seen that in one aspect, the invention comprises a body of reactive composite material subject to ignition having one or more edges, surfaces or corners protected from unwanted ignition by a layer of electrically insulating material, electrically conducting material or a combination of electrically insulating material and electrically conducting material. The layer can be chosen and configured to provide an alternative path to ESD current that does not pass through the body. Alternatively, the layer can be chosen and configured to spread ESD current before the current reaches the body and thus reduce ESD current density in the body, or the layer can be chosen and configured to increase the threshold for ESD arcing so that no ESD arc forms.
The layer can comprise insulating material that overlies one or more surfaces of the body, overlies one or more edges of the body, overlies at least one surface and at least one edge, overlies at least one surface, at least one edge and at least one corner or overlies substantially the entire body. Alternatively, the layer can comprise conducting material that overlies at least one surface of the body, at least one edge of the body, at least one surface and at least one edge of the body, overlies at least one surface, at least one edge and at least one corner of the body or overlies substantially the entire body. The layer can also alternatively comprise a combination of insulating material and conducting material.
In another aspect, the invention comprises a body of reactive composite material subject to ignition having first and second surfaces and edges between the first and second surfaces wherein the body is protected from unwanted ignition by a layer of conducting material overlying the first surface, a layer of conducting material overlying the second surface and a layer of conducting material overlying the edges. The conducting layer can be metal or conducting tape. Advantageously, the conducting material overlying the edges extends from the layer overlying the first surface to the layer overlying the second surface.
In a third aspect, the invention comprises a body of reactive composite material subject to ignition having first and second surfaces and edges between the surfaces wherein the body is protected from unwanted ignition by a layer of conducting material overlying the first surface and an insulating layer overlying the second surface. A layer of conducting material can be wrapped around the edges and partially or completely cover the insulating layer. Alternatively, a layer of insulating material can extend around the edges.
In another aspect, the invention comprises a body of reactive composite material subject to ignition having first and second surfaces and edges between the surfaces wherein the body is protected from unwanted ignition by covering the first surface, the edges and only a portion of the second surface with one or more insulating layers.
Yet another aspect of the invention is a method of protecting from unwanted ignition a body of reactive composite material subject to ignition by providing a body of reactive composite material having one or more edges, surfaces and corners and disposing on one or more of the edges, surfaces or corners at least one layer of insulating material, conducting material or a combination of insulating material and conducting material.
It is to be understood that the above-described embodiments illustrate only a few of the many possible arrangements that can be devised using the principles of the invention. Those skilled in the art can make many variations and modifications without departing from the spirit and scope of the invention.
The present application claims the benefit of U.S. Provisional Patent Application Ser. No. 60/781,671 filed on Mar. 13, 2006, U.S. Provisional Patent Application Ser. No. 60/692,857 filed on Jun. 22, 2005, and U.S. Provisional Patent Application Ser. No. 60/692,822 filed Jun. 22, 2005, all of which are herein incorporated by reference.
The United States Government has certain rights in this invention pursuant to Award 70NANB3H3045 supported by NIST.
Number | Date | Country | |
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60781671 | Mar 2006 | US | |
60692857 | Jun 2005 | US | |
60692822 | Jun 2005 | US |