1. Field of the Invention
Embodiments of the invention include a method of simulating an ignition of a reactive multilayer foil. Other embodiments include various methods of igniting a reactive multilayer foil by transferring energy from an energy source to a reactive multilayer foil.
2. Background of the Invention
Reactive multilayer foils are nanostructured materials typically fabricated by vapor depositing hundreds of nanoscale layers that alternate between elements with large, negative heats of mixing such as Ni and Al. These ignitable materials support self-propagating reactions (e.g., chemical transformations) that travel along the foils at speeds ranging from about 1 m/s to about 30 m/s. Various implementations of these materials and related methods are disclosed in the following, the entirety of all of which are incorporated herein by reference: U.S. Pat. Nos. 5,381,944, 5,538,795, 5,547,715, and 6,534,194; U.S. patent application Ser. No. 09/846,486 filed May 1, 2001 and entitled “Free Standing Reactive Multilayer Foils” (“the '486 application); U.S. Provisional Patent Application No. 60/201,292 filed on May 2, 2000 and entitled “Free Standing Reactive Multilayer Foils” (“the '292 application”); an article by Besnoin et al. entitled “Effect of Reactant and Product Melting on Self-Propagating Reactions in Multilayer Foils” published in the Journal of Applied Physics, Vol. 92(9), pages 5474-5481 on Nov. 1, 2002 (“Besnoin”); an article by Blobaum et al. entitled “Deposition and Characterization of a Self-Propagating CuOx/Al Thermite Reaction in a Multilayer Foil Geometry” published in the Journal of Applied Physics, Vol. 94(5), pages 2915-2922 on Sep. 1, 2003; a chapter entitled “Self-Propagating Reactions in Multilayer Materials” published in the 1998 edition of the Handbook of Thin Film Process Technology edited by D. A. Glocker and S. I. Shah (“Glocker”); and an article entitled “Self-Propagating Exothermic Reactions in Nanoscale Multilayer Materials” that was presented at The Minerals, Metals, and Materials Society (TMS) Proceeding on Nanostructures in February of 1997 (“TMS”).
Self-propagating reactions (e.g., chemical transformations) in reactive multilayer foils are driven by a reduction in chemical bond energy, examples of which are disclosed in Glocker and an article by Gavens et al. entitled “Effects of Intermixing on Self-Propagating Exothermic Reactions in Al/Ni Nanolaminate Nanofoils” published in the Journal of Applied Physics, Vol. 87(3), pages 1255-1263 on Feb. 1, 2000 (“Gavens”), the entirety of both of which are incorporated herein by reference. Upon the application of a suitable stimulus (e.g., ignition or initiation of the chemical transformation), a local bond exchange between constituents of alternating layers produces large quantities of heat that are conducted down the foil and sustain the reaction. Recent developments in reactive multilayer foil technology have shown that it is possible to carefully control both the heat of the reaction as well as the reaction velocity, and have also provided alternative means for fabricating nanostructured multilayer foils. For instance, it has been demonstrated that the velocities, heats, and/or temperatures of the reactions can be controlled by varying the thicknesses of the alternating layers, as shown in U.S. Pat. No. 5,538,795; an article entitled “The Combustion Synthesis of Multilayer NiAl Systems” published in Scripta Metallurgica et Materialia, Vol. 30(10), pages 1281-1286 in 1994; Gavens; the '486 application; and the '292 application, the entirety of each of which are incorporated herein by reference. It has also been shown that the heats of reaction can be controlled by modifying the foil composition, or by low-temperature annealing of the reactive multilayers after their fabrication, for example, as shown in Gavens. Alternative methods for fabricating nanostructured reactive multilayers include: (i) mechanical processing, which is described in detail by U.S. Pat. No. 6,534,194, and (ii) electrochemical deposition.
These technological advancements set forth above—including the control of reaction heats, velocities, and temperatures, as well as alternative multilayer foil fabrication methods—have widened the scope of potential applications of reactive multilayer foils to include: (a) reactive multilayer joining (examples of which are disclosed in U.S. Provisional Patent Application No. 60/469,841 filed May 13, 2003 (“the 841 application) and U.S. patent application Ser. No.10/843,352 filed May 12, 2004 (“the 352 application), the entirety of both of which are incorporated herein by reference), (b) hermetic sealing (examples of which are disclosed in U.S. Provisional Patent Application No. 60/461,196 filed Apr. 9, 2003 and U.S. patent application Ser. No. 10/814,243 filed Apr. 1, 2004, the entirety of both of which are incorporated herein by reference), (c) structural energetics, and (d) the use of reactive multilayer foils for initiating secondary reactions, e.g. in fuses and detonators.
Several different means have been employed for igniting self-propagating reactions (e.g., initiating the chemical transformation) in nanoscale multilayer foils. In some methods, impact of a sharp stylus initiates ignition, and in other ignition is started with a spark from an electrical source (examples of which are disclosed in an article by Ma et al. entitled “Self-propagating Explosive Reactions in Al/Ni Multilayer Thin Films” published in Applied Physics Letters, Volume 57, page 1262 in 1990 (“Ma”); an article by Reiss et al. entitled “Self-propagating Formation Reactions in Nb/Si Multilayers” published in Mat. Sci. and Eng. A., Volume A261, pages 217-222 in 1999; an article by van Heerden et al. entitled “Metastable Phase Formation and Microstructural Evolution during Self-Propagating Reactions in Al/Ni and Al/Monel Multilayers” published in Mat. Res. Soc. Symp. Proceedings, Volume 481, pages 533-8 in the Fall of 1997; and TMS, the entirety of all of which are incorporated herein by reference). Alternatively, the heat from a filament (examples of which are disclosed in an article by Anselmi-Tamburni et al. entltied “The Propagation of a Solid-State Combustion Wave in Ni-Al Foils” published in the Journal of Applied Physics, Volume 66, page 5039 in 1989; and an article by Dyer et al. entitled “The Combustion Synthesis of Multilayer NiAl Systems” published in Scripta Metallurgica et Materialia, Volume 30, page 1281 in 1994, the entirety of both of which are incorporated herein by reference), or laser radiation (examples of which are disclosed in an article by Wickersham et al. entitled “Explosive Crystallization in Zirconium/Silicon Multilayers” published in the J. Vac. Sci. Technol. A, Volume 6, page 1699 in 1988 (“Wickersham”), the entirety of which is incorporated herein by reference) may be used to start ignition. To begin to understand what power or energy is needed to ignite a reaction, Ma investigated the effect of the period of a multilayer foil has on the reaction process using Ni/Al multilayer foils and an electrical stimulus. Results disclosed in Ma suggest that reactions in films with larger periods require more power for ignition than reactions in films with smaller periods. The results also suggest that power requirements decrease as the initial sample temperature increases. Wickersham conducted an ignition study on Zr/Si multilayer films using the impact from a tungsten-carbide (WC) tip to start the reaction. According to Wickersham, thicker films were ignited at lower sample temperatures for a given period of a multilayer foil. These two studies suggest that ignition depends on bilayer thickness (e.g., period), initial sample temperature, and overall foil thickness.
Prior knowledge regarding ignition of reactive multilayer foils is, however, limited, in large part because several essential factors controlling ignition requirements have not been clearly investigated and the extent of their impact is consequently unknown, although some material is disclosed, for example, in U.S. Pat. No. 5,606,146. These include such features as intermixing between layers (examples of which are disclosed in Gavens and Glocker), the duration of the stimulus, and the energy or power density of the ignition source. This lack of knowledge regarding key properties of the ignition source constitutes an obstacle to the design of effective ignition systems and devices.
Another limitation arises in situations where direct access to the foil is not available when the reaction must be initiated. A case-in-point concerns bonding or joining applications where the reactive foil is sandwiched between two solder or braze layers (e.g., lead, tin, silver, zinc, gold, and/or antimony) and two components (examples of which are disclosed in U.S. Pat. No. 5,381,944, the '841 application, and the '352 application). In many cases, (e.g., the mounting of heat sinks onto chips or chip packages or bonding of microelectronic components) a direct-access method of ignition may not be practical because the foil is “shielded” by the components. Thus, in these situations methods of ignition are needed that effectively address this problem.
In order to overcome the limitations above, aspects of the invention introduces a new methodology for the ignition of reactive multilayer foils. Some of these aspects of the present invention include:
Application of a multi-dimensional computational code for the determination of energy requirements of ignition sources. The code may be based on a multi-dimensional transient formulation of the evolution equations of energy and composition;
Methods for the ignition of reactive multilayer foils; and
Methods for overcoming accessibility limitations.
These and other aspects of the invention are described in detail in various exemplary embodiments set forth herein.
An embodiment of the invention includes a method for simulating an initiation and properties of a self-propagating reaction in a reactive multilayer foil. The method includes providing an atomic concentration evolution equation, providing an energy evolution equation including energy source terms associated with (i) a thermal diffusion of the reactive multilayer foil, (ii) a heat of mixing of the reactive multilayer foil, and (iii) a stimulus configured to initiate a chemical transformation of the reactive multilayer foil, discretizing the atomic concentration evolution equation and the energy evolution equation to form a discretized system of equations, and determining the behavior of an atomic concentration and energy fields of the reactive multilayer foil by integrating the discretized system of equations using parameters associated with the reactive multilayer foil.
Another embodiment of the invention includes a program storage device readable by a machine, tangibly embodying a program of instructions executable by the machine to perform method steps for simulating an initiation and properties of a self-propagating reaction in a reactive multilayer foil. The method includes the steps of providing an atomic concentration evolution equation, providing an energy evolution equation including energy source terms associated with (i) a thermal diffusion of the reactive multilayer foil, (ii) a heat of mixing of the reactive multilayer foil, and (iii) a stimulus configured to initiate a chemical transformation of the reactive multilayer foil, discretizing the atomic concentration evolution equation and the energy evolution equation to form a discretized system of equations, and determining the behavior of an atomic concentration and energy fields of the reactive multilayer foil by integrating the discretized system of equations using parameters associated with the reactive multilayer foil.
In various embodiments, the invention may include one or more of the following aspects: the atomic concentration evolution equation may be
wherein C is atomic concentration and D is atomic diffusivity of the reactive multilayer foil; the energy evolution equation may be
wherein H is enthalpy, k is thermal conductivity, t is time, T is temperature, and Q is heat of reaction of the reactive multilayer foil; the energy evolution equation may be
wherein H is enthalpy, k is thermal conductivity, t is time, T is temperature, and Q is heat of reaction of the reactive multilayer foil, wherein qm is rate of energy generation associated with the stimulus; the discretization of the atomic concentration evolution equation and the energy evolution equation may be based on a finite-difference method, a finite-element method, a finite-volume method, a spectral-element method, or a collocation method; the parameters associated with the reactive multilayer foil may include at least one of length, width, thickness, density, heat capacity, thermal conductivity, heat of fusion, melting temperature, heat of reaction, atomic weight, atomic diffusivity, and activation energy; the stimulus may be associated with one or more of an electrical source, a thermal source, a source of mechanical action, a sound source, an ultrasound source, a microwave source, a chemical source, an RF source, and an electromagnetic source; the energy source term associated with the stimulus may be a volumetric source term, a surface source term, or a combination of the volumetric and surface source terms; varying parameters of the stimulus; and the parameters associated with the stimulus may include one or more of a position of the stimulus relative to the reactive multilayer foil, potential energy, kinetic energy, electrical potential, current voltage, pulse duration, contact area, power, wavelength, spot size, and pulse energy.
A further embodiment of the invention includes a method of initiating a chemical transformation of a reactive multilayer foil. The method includes providing an electrical energy source and the reactive multilayer foil, and initiating the chemical transformation of the reactive multilayer foil by providing an arc-free discharge from the electrical energy source to the reactive multilayer foil.
In various embodiments, the invention may include one or more of the following aspects: the electrical energy source may include one or more of a voltage source, a current source, a charged capacitor, a piezoelectric device, a thermoelectric device, and a ferroelectric device; the electrical energy source may have a potential less than or equal to about 10 V; the electrical energy source may have a potential less than or equal to about 5V; the electrical energy source may have a potential less than or equal to about 1V; the arc-free discharge may have a duration less than or equal to about 1 ms, an electrical lead may be operatively connected to the electrical energy source and placed in contact with the reactive multilayer material; a contact area between the electrical lead and the reactive multilayer foil may have a diameter less than or equal to about 1 mm; the arc-free discharge may be provided to the reactive multilayer material at a contact area less than or equal to about 1 mm; and the arc-free discharge may have an energy less than or equal to about 40 mJ.
Still another embodiment of the invention includes a method of initiating a chemical transformation of a reactive multilayer foil. The method includes providing a laser source and the reactive multilayer foil, and initiating the chemical transformation of the reactive multilayer foil by transferring energy from the laser source to the reactive multilayer material. The energy from the laser source impinges on a spot on the reactive multilayer foil having an area less than or equal to about 1 mm.
A still further embodiment of the invention includes a method of initiating a chemical transformation of a reactive multilayer foil. The method includes providing a laser source and the reactive multilayer foil, and initiating the chemical transformation of the reactive multilayer foil by transferring energy from the laser source to the reactive multilayer material. The laser source has a power output less than or equal to about 300 W.
Yet another embodiment of the invention includes a method of initiating a chemical transformation of a reactive multilayer foil. The method includes providing a laser source and the reactive multilayer foil, and initiating the chemical transformation of the reactive multilayer foil by transferring energy from the laser source to the reactive multilayer material. The energy transferred is less than or equal to about 40 mJ.
A yet further embodiment of the invention includes a method of initiating a chemical transformation of a reactive multilayer foil. The method includes providing a laser source and the reactive multilayer foil, and initiating the chemical transformation of the reactive multilayer foil by transferring energy from the laser source to the reactive multilayer material. The energy is transferred at a wavelength between about 300 nm and about 2 microns.
Another embodiment of the invention includes a method of initiating a chemical transformation of a reactive multilayer foil. The method includes providing a laser source and the reactive multilayer foil, and initiating the chemical transformation of the reactive multilayer foil by transferring energy from the laser source to the reactive multilayer material. The reactive multilayer foil includes at least one layer of solder or braze.
In various embodiments, the at least one layer of solder or braze may include one or more of indium, lead, tin, silver, zinc, gold, and antimony.
A further embodiment of the invention includes a method of initiating a chemical transformation of a reactive multilayer foil. The method includes providing a laser source and the reactive multilayer foil, providing a component to be joined to another component by the chemical transformation of the reactive multilayer foil, the component including an optical path configured to allow the energy from the laser source to be transferred to the reactive multilayer foil via the optical path, and initiating the chemical transformation of the reactive multilayer foil by transferring energy from the laser source to the reactive multilayer foil through the optical path.
Still another embodiment of the invention includes a method of initiating a chemical transformation of a reactive multilayer foil. The method includes providing a laser source and the reactive multilayer foil, and initiating the chemical transformation of the reactive multilayer foil by transferring energy from the laser source to the reactive multilayer material. The energy from the laser source is redirected prior to being transferred to the reactive multilayer foil.
In various embodiments, the invention may include providing an optical system and redirecting the energy via the optical system.
A still further embodiment of the invention includes a method of initiating a chemical transformation of a reactive multilayer foil. The method includes providing a laser source, a fiber optic cable, and the reactive multilayer foil, and initiating the chemical transformation of the reactive multilayer foil by transferring energy from the laser source via the fiber optic cable to the reactive multilayer material. [030] Yet another embodiment of the invention includes a method of initiating a chemical transformation of a reactive multilayer foil. The method includes providing a laser source and the reactive multilayer foil, the reactive multilayer foil being partially coated with an energy absorbing material, and initiating the chemical transformation of the reactive multilayer foil by transferring energy from the laser source to the energy absorbing material.
In various embodiments, the invention may include one or more of the following aspects: the reactive multilayer foil may be partially coated with an energy reflecting material; the energy reflecting material may have a higher reflectivity than the reactive multilayer foil; the energy absorbing material may include carbon black or black ink; and the energy absorbing material may have a higher absorptivity than the reactive multilayer foil.
A yet further embodiment of the invention may include a method of initiating a chemical transformation of a reactive multilayer foil. The method includes providing a microwave source and the reactive multilayer foil, and initiating the chemical transformation of the reactive multilayer foil by transferring energy from the microwave source to the reactive multilayer foil.
Another embodiment of the invention includes a method of initiating a chemical transformation of a reactive multilayer foil. The method includes providing the reactive multilayer foil and a projectile, and penetrating the reactive multilayer foil with the projectile. The penetrating initiates the chemical transformation of the reactive multilayer material.
In various embodiments, the projectile may be spring-loaded.
A further embodiment of the invention includes a method of initiating a chemical transformation of a reactive multilayer foil. The method includes providing an ultrasound source and the reactive multilayer foil, and initiating the chemical transformation of the reactive multilayer foil by transferring energy from the ultrasound source to the reactive multilayer foil.
Still another embodiment of the invention includes a method of initiating a chemical transformation of a reactive multilayer foil. The method includes providing an induction heating source and the reactive multilayer foil, and initiating the chemical transformation of the reactive multilayer foil by transferring energy from the induction heating source to the reactive multilayer foil.
In various embodiments, the invention may include one or more of the following aspects: the reactive multilayer foil may include a magnetic element; the magnetic element may be Ni.
A still further embodiment of the invention includes a method of initiating a chemical transformation of a reactive multilayer foil. The method includes providing the reactive multilayer foil, and initiating the chemical transformation of the reactive multilayer foil by mechanically fracturing the reactive multilayer foil.
In various embodiments, the invention may include one or more of the following aspects: the reactive multilayer foil may include a recessed portion; the recessed portion may be configured to assist in the mechanical fracturing of the reactive multilayer foil; and the reactive multilayer foil may be configured to mechanically fracture at the recessed portion.
Yet another embodiment of the invention includes a method of initiating a chemical transformation of a reactive multilayer foil. The method includes providing the reactive multilayer foil, and initiating the chemical transformation of a reactive multilayer foil by generating friction on the reactive multilayer foil.
In various embodiments, the invention may include one or more of the following aspects: providing an object with an abrasive surface; generating friction may include placing the abrasive surface in contact with the reactive multilayer foil; generating friction may include rotating the object; generating friction may include sliding the object; the object may include a rotary tool bit; the object may include a diamond wheel.
A yet further embodiment of the invention includes a method of initiating a chemical transformation of a reactive multilayer foil. The method includes providing an electrical energy source, the reactive multilayer foil, and an electrical lead, and initiating the chemical transformation of the reactive multilayer foil by transferring energy from the electrical energy source to the reactive multilayer foil via the electrical lead.
In various embodiments, the invention may include one or more of the following aspects: providing a component to be joined to another component by the chemical transformation of the reactive multilayer foil; the component may include the electrical lead; the electrical energy source may include one or more of a voltage source, a current source, a charged capacitor, a piezoelectric device, a thermoelectric device, and a ferroelectric device.
Another embodiment of the invention includes a method of initiating a chemical transformation of a reactive multilayer material. The method includes providing the reactive multilayer material and a component including an ignition source, and initiating the chemical transformation of the reactive multilayer material by triggering the ignition source.
In various embodiments, the invention may include one or more of the following aspects: triggering the ignition source may include remotely triggering the ignition source; the ignition source may include one or more of a voltage source, a current source, a charged capacitor, a piezoelectric device, a thermoelectric device, a ferroelectric device, a firing pin, a laser, a MEMS device, a hot filament, a solenoid, a gated switch, an abrasive surface, a microbubble, a fuse, a reactive multilayer tab, a chemical, an SHS powder, and a heated gas.
A further embodiment of the invention includes a method of initiating a chemical transformation of a reactive multilayer foil. The method includes providing a chemical and the reactive multilayer foil, and initiating a chemical transformation of a reactive multilayer foil by chemically transforming the chemical.
Still another embodiment of the invention includes a method of initiating a chemical transformation of a reactive multilayer foil. The method includes providing the reactive multilayer foil, and heating the reactive multilayer foil to the foil's ignition temperature.
In various embodiments, the invention may include one or more of the following aspects: providing a heating source; placing the reactive multilayer foil in the source of heat; the heating may include heating the reactive multilayer foil in the heating source; the heating source may be a furnace, reflow oven, heat spreader, or heat sink; the heating may occur at a rate greater than or equal to about 200° C./min; the heating may include heating one side of the reactive multilayer foil; the reactive multilayer foil may be disposed in an enclosure (or assembly); the heating may include heating one side of the enclosure (or assembly); the reactive multilayer foil may be disposed between two or more components configured to be joined by the chemical transformation of the reactive multilayer foil; the heating may include heating one of the two or more components; and the heating of one of the two or more components may include passing a current through the one of the two or more components.
A still further embodiment of the invention includes a method of initiating a chemical transformation of a reactive multilayer foil. The method includes providing the reactive multilayer foil and a molten material, and initiating the chemical transformation of the reactive multilayer foil by transferring energy from the molten material to the reactive multilayer foil.
In various embodiments, the invention may include one or more of the following aspects: placing the molten material in contact with the reactive multilayer foil; and the molten material may be molten solder or molten braze.
Yet another embodiment of the invention includes a method of initiating a chemical transformation of a reactive multilayer foil. The method includes providing the reactive multilayer foil and a microflame; and initiating the chemical transformation of the reactive multilayer foil by transferring energy from the microflame to the reactive multilayer foil.
In various embodiments, the invention may include one or more of the following aspects: placing the microflame in contact with the reactive multilayer foil; the reactive multilayer foil may be disposed between at least two components; a portion of the reactive multilayer foil may extend past an edge of at least one of the at least two components; and directing the microflame towards the portion of the reactive multilayer foil.
A yet further embodiment of the invention includes a method of initiating a chemical transformation of a reactive multilayer foil. The method includes providing the reactive multilayer foil, the reactive multilayer foil being surrounded by an enclosure or disposed within an assembly, providing an energy source, and initiating the chemical transformation of the reactive multilayer foil by transferring energy from the energy source to the reactive multilayer foil.
In various embodiments, the invention may include one or more of the following aspects: the energy may be transferred without penetrating the enclosure or assembly; the energy may be transferred to the reactive multilayer foil when the energy source is disposed outside of the enclosure or assembly; the energy may be transferred without placing the source of energy in physical contact with the reactive multilayer foil; the enclosure or assembly may be substantially airtight; the energy source may include one or more of a microwave source, an ultrasound source, and a source of induction heating.
Additional objects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objects and advantages of the invention will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate several embodiments of the invention and together with the description, serve to explain the principles of the invention.
Reference will now be made in detail to exemplary embodiments of the invention which are set forth in the accompanying drawings and specification. Wherever possible, the same reference numbers will be used throughout the drawings to refer to the same or like parts.
In one embodiment of this invention, the energy and power requirements of an energy source (e.g., ignition source) may be determined via systematic application of a transient multi-dimensional model of self-propagating reaction (e.g., chemical transformation) for a reactive multilayer material (e.g., foil). As outlined in Besnoin, self-propagating reactions may be described using a simplified model for atomic mixing and heat release.
Implementation of the model may be illustrated for nanostructured Ni/Al foils with a 1:1 ratio of the reactants. For these foils, atomic mixing can be described using a time-dependent, conserved scalar (atomic concentration) field C, defined such that C=1 for pure Al, C=−1 for pure Ni, and C=0 for pure NiAl. The evolution of C is governed by:
The atomic diffusivity, D, may be assumed to be independent of composition and to follow an Arrhenius dependence on temperature, according to:
where D0 is the Arrhenius pre-exponent, E is the activation energy and R is the universal gas constant. The values E=137 kJ/mol and D0=2.18×10−6 m2/s used in the embodiments below may be obtained from best fits to experimental data, as shown, for example, in an article by Mann et al. entitled “Predicting the Characteristics of Self-Propagating Exothermic Reactions in Multilayer Foils” published in the Journal of Applied Physics, Volume 82, pages 1178-1188 in 1997, the entirety of which is incorporated herein by reference. In performing computations using any or all of the formulas set forth herein, advantage may be taken of the fact that the layers are geometrically flat, and exploit the symmetry of the periodic arrangement of the layers by restricting the domain to one half of a representative Al layer, as shown, for example, in the '841 application and the '352 application.
The evolution of the concentration field may be coupled with the section-averaged energy equation:
where H is the section-averaged enthalpy,
is the mean thermal conductivity, kAl and kNi are the thermal conductivities of Al and Ni, respectively,
ρAl and ρNi are the densities of Al and Ni, while MAl and MNi denote the corresponding atomic weights.
Experimental data (as shown, for example, on page 426 of a book entitled “Selected Values of Thermodynamic Properties of Metals and Alloys” edited by Hultgren et al. and published by Wiley of New York City in 1963, the entirety of which is incorporated herein by reference) indicates that the variation of the heat of reaction, Q, with composition, C, can be closely approximated as:
Q(C)=ΔHfC2
where ΔHf is the heat of reaction. Thus, the averaged reaction source term can be expressed as:
where 2d is the thickness of an individual layer of the foil, y is the direction normal to the layers of the foil,
cpAl and cpNi respectively denote the heat capacities of Al and Ni. For a 1:1 reaction between Ni and Al, ΔTf≡ΔHf/{overscore (pcp)}=1660 K (as shown, for example, in U.S. Pat. No. 5,538,795, the '841 application, and the '352 application). Note that when melting is ignored, ΔTf represents the difference between the adiabatic flame temperature, Tf0, and the ambient temperature, T0.
Incorporation of melting effects may result in a complex relationship between H and T, involving the heats of fusion of the reactants and products (as shown, for example, in the '841 application and the '352 application). This relationship may be expressed as:
where TmAl=933K, TmNi=1728K and TmNiAl=1912K denote the melting temperatures of Al, Ni, and NiAl, respectively hfAl, hfNi, and hfNiAl are the corresponding heats of fusion (per unit mole),
β≡α/(1+y) represents the fraction of pure (unmixed) Al at a given section ΔHfAl≡ρAlhfAl/MAl, ΔHfNi≡ρNihfNi/MNi, ΔHfNiAl≡{overscore (ρ)}hfNiAlMNiAl, {overscore (ρ)}≡(ρAl+γρNi)/(1+γ), H1≡{overscore (ρcp)}(TmAl−T0), H2=H1+βΔHfAl, H3=H2+{overscore (ρcp)}(TmNi−TmAl), H4=H3+βγΔHfNi, H5=H5+{overscore (ρcp)}(TmNiAl−TmNi), and H6=H5+(1−α)ΔHfNiAl. Note that the “enthalpy” levels H2, . . . , H6 are dependent on the local composition, and are consequently variable during the computations. For instance, in the limiting case α=0, the product is absent and the temperature is only affected by melting of the reactants. Conversely, for α=1 mixing is complete and the temperature only depends on the heat of fusion of the product.
In another embodiment of this invention, the physical model may be implemented in its two-dimensional (“2D”), axisymmetric, or three-dimensional (“3D”) forms. The 2D and axisymmetric variants can be extrapolated to the 3D form. In the 2D formulation, a coordinate system (x,y) may be used such that x points along the direction of propagation, while y points in the direction normal to the layers of the foil. In the axisymmetric formulation, the equations may be solved in a cylindrical (r,y) coordinate system, with r and y respectively normal to the surface of the front and the layers of the foil. The axisymmetric and 2D models may share the same physical formulation outlined above. The primary difference concerns expressions of the gradient diffusion terms ∇·(k∇T) and V·(D∇C). In the 2D case, these may be expressed as:
while in the axisymmetric case we may have:
Other aspects of the formulation may remain essentially the same.
Note that in the 2D model, the self-propagating front may be planar, and move away from the plane of ignition. On the other hand, in the axisymmetric case the front may propagate radially outwards (e.g., away from the ignition source). Thus, the two models may enable analysis of different ignition modes. For instance, the axisymmetric case models ignition may be induced by a localized electrical spark, which may be observed experimentally to result in a cylindrically expanding front. Meanwhile, the 2D case may be relevant to the analysis of ignition induced by shearing the foil along its entire width, or by heating the foil along its side using a hot filament.
In one embodiment of this invention, a FORTRAN code may be used to implement the models outlined above. These models may be effectively implemented on a variety of computer platforms, such as Windows, Unix or Linux systems, including personal computers, laptops, workstations or mainframes. It should be evident for anyone skilled in the art how to implement this on any computing platform providing memory and processor, using either low- or high-level computing languages. These models may also be stored as an executable computer program on any computer readable medium, for example, a hard disk, floppy disk, and/or a compact disc.
In another embodiment of this invention, ignition requirements may be determined by initializing the computations using a thermal pulse of height Ho, and its width, Ws. In the 2D variant, the pulse may be located at one end of the foil, while it may be located at a centerline of the foil in the axisymmetric case. Outside the pulse region, the foil may be initially at ambient temperature, T0; in the exemplary illustration below, T0=298K. The computations may then be carried out over a time period that is long enough so as to observe the formation of the front and its propagation, if at all possible. Ignition requirements may be determined by systematically varying H0 and Ws, and using the results of the simulations to identify the boundary of the region separating initial conditions that result in a self-propagating front, from those for which ignition does not occur.
In one embodiment of this invention, the methodology set forth herein may be applied to determine critical ignition requirements of an axisymmetric source (e.g., cylindrically expanding front) for a Ni—Al foil with bilayer thickness 4d=40 nm (i.e., d=10 nm), and premix width 4w =2 nm (i.e., w=0.5 nm). As shown in
In another embodiment of this invention, the ignition (or stability) boundary resulting from the analysis outlined herein may be obtained for foils with different bilayer periods (4d) and premix widths (4w). Results for 2D fronts (i.e., planar fronts) having various bilayer periods d and premix widths w are shown in
The results of
It should be evident for someone skilled in the art how to generalize the present results to other modes of propagation, and how to exploit critical ignition data to design power and energy requirements of various ignition sources.
In another embodiment of this invention, the multilayer ignition model outlined above may be extended to characterize initiation by an energy source, which may be localized and/or time-dependent. To this end, the section-averaged energy equation originally introduced as
may be generalized according to:
where qm is the rate of energy generation associated with the energy source.
In embodiments of the invention, the generalized ignition model may be applied to characterize ignition (e.g., initiation of the chemical transformation) using an energy source (e.g., source of electrical current). In this situation, the energy source term qm corresponds to Ohmic heating induced by the passage of the current, and can thus be expressed as:
qm=σ∇Φ·∇Φ
where σ is the electrical conductivity and Φ is the electrical potential. The distribution of the electrical potential can be determined by solution of the conservation equation:
∇2Φ=0
with boundary conditions corresponding to the current source.
In another embodiment of the invention, the Ohmic heating ignition model outlined above may be applied to the configuration schematically shown in
In another embodiment of this invention, the model may be applied to analyze the critical current needed to ignite 55 μm-thick Ni/Al multilayer foils. For example,
This effect is also illustrated in
In another embodiment of this invention, the model may applied to analyze the effect of electrical interface resistance on the critical current needed for ignition (e.g., initiation of the chemical transformation). For example, in an application of the model as shown in
In another embodiment of this invention, the model is applied to analyze the effect of electrode contact area on the critical current needed for ignition. For example, in an application of the model as shown in
In another embodiment of this invention, the model predictions in FIGS. 9 and 10 may be compared with experimental measurements of the same configuration. A nominal contact radius of about 20 μm may be used in the experiments. Comparison of computational and experimental results reveals reasonable agreement, and indicates that the computations yield conservative predictions of the critical current. The deviations between measurements and predictions may be traced to imperfections in the electrode surface, which results in a smaller effective contact radius. Note that in the experiments, the voltage applied to drive the critical current is less than about 2V. This may be a useful advantage when mounting microelectronic components which may be sensitive to high voltages.
In another embodiment of this invention, the model is applied to analyze the effect of foil thickness on the critical current needed for ignition (e.g., initiation of the chemical transformation). Results are shown in
In another embodiment of this invention, the dependence of the critical ignition stimulus on the bilayer period (e.g., thickness) of the reactive multilayer may be verified experimentally. Results are provided here using two ignition methods, namely Joule heating (see
Note that in many reactive multilayer foil applications, including soldering, brazing, welding, as well as the use of other reactive multilayer foils as ignitors, it may be advantageous to select as small as possible an energy source (e.g, source of current). For both spark-ignition and ignition induced by Joule heating, this may offer the advantage of reducing cost, minimizing space requirements, and/or limiting potential damage to neighboring components. Parametric studies were conducted using the model outlined above, ignition tests were performed using a spark, and Joule-heating experiments were performed in order to determine a range of conditions that would address the requirements above. These studies indicate that for most multilayer systems, a pulse (e.g., electrical pulse) of about 40 mJ or less may be sufficient for ignition (e.g., initiation the chemical transformation) of most multilayer foils. In addition, the studies also revealed that critical ignition energies may be delivered using an electrical potential of about 10V or less. Note that in the case of reactive joining of microelectronic components, it may be desirable to further limit the electrical potential to about 5V or about 1V, so as to eliminate potential damage to these sensitive components. Regarding pulse durations, model computations indicate that these are preferably smaller than the thermal diffusion time across the multilayer foil, in order to avoid significant dissipation of heat from the ignition zone. Typically, reactive multilayer foils are fabricated from metallic systems having thermal diffusivities of the order of about 10−5 m2/s, and in most applications, a multilayer foil thickness on the order of about 100 microns may be used. Thus, diffusion times, estimated as the square of thickness divided by the thermal diffusivity, are on the order of about 1 ms. Consequently, the duration of the electrical stimulus (e.g., pulse duration) is preferably smaller than this value. Within this range of conditions, for Joule heating, it may possible to limit the contact area so that the equivalent diameter is about 1 mm or smaller. The present embodiments may be immediately applicable to a wide range of multilayer ignition applications.
In another embodiment of this invention, a laser may be used to ignite (e.g., initiate a chemical transformation) a reactive multilayer foil that is coated with a material having high absorption to the laser. Ignition may occur when the narrow coherent intense laser beam of either infrared or visible light rapidly heats the surface of the foil, resulting in ignition. An example includes coating a Ni/Al reactive foil with thin layers of In solder. Since In is more absorbing than the constituents of the foil, lower energy requirements for the laser source can be achieved. An alternative configuration is shown in FIGS. 14(a) and 14(b), where the foil 140 may be partially coated with a highly absorbing material 141 such as carbon black. Another variant is shown in FIGS. 15(a) and 15(b), where the foil 150 may coated with a highly reflective material 151 except for a small area that is coated with a highly absorbing material 152, for example, silver or other materials more reflective than nickel or aluminum. The advantage of the latter configuration may be that it provides greater control of the location of ignition.
In another embodiment of this invention, laser ignition of reactive multilayer foils is tested experimentally.
This trend is also evident in
In another embodiment of this invention, a variety of laser sources have been tested, including both continuous, pulsed, and/or switched laser. These tests have focused, in particular, at determining a range of pulse conditions suitable for joining and ignition applications. Results of these tests indicate that a wide range of wavelength may be possible. However, the wavelength is preferably selected above the ultraviolet range (about 300 nm) in order to avoid potential ablation of the foil or foil-coating, which may occur at smaller wavelengths. Wavelengths in the range of about 300 nm to about 2 microns are satisfactory and may ensure good absorption by the uncoated multilayer foil or by the multilayer coating. As for the discussion of electrical ignition, laser pulse durations should be smaller than the diffusion time scale through the foil, which may be about 1 ms in most applications. Results of the experimental measurements indicate that these requirements can be achieved using laser sources having a power output of about 300 W or smaller, with a spot size smaller than about 1 mm, and an energy level of 40 mJ or less.
In another embodiment of this invention, the reactive multilayer foil may be ignited using a microwave source. Microwaves may cause a charge to accumulate at a portion of the reactive foil (e.g., sharp, pointed edges and/or tips of the foil), resulting in an electric discharge and ignition of the foil. In this mode of ignition, the reactive multilayer foil may be embedded in a structure including materials which are poor absorbers of microwave energy, such as polymers or borosilicate glass. The advantage of this mode of ignition is that it does not require direct access to the reactive foil.
In another embodiment of this invention, the reactive multilayer foil may be ignited using an ultrasound source. An illustrative geometry is a foil sandwiched between two components. The ultrasonic source may be applied to one component of a sandwich which then vibrates relative to a stationary second component of the sandwich. The resulting frictional heating may then result in the ignition of the foil. Similar to microwave ignition, this method also offers the advantage that it does not require direct access to the reactive foil. Thus, at the time of ignition, the latter may be embedded within a structure or shielded from the source by other components.
In another embodiment of this invention, the reactive multilayer foil may be ignited by a penetrating projectile. The foil may be embedded in a metal, ceramic, or polymer sandwich-like structure. Upon impingement of the projectile a mechanical and/or thermal energy burst may be supplied to the foil resulting in ignition. The advantage of this mode of ignition may be that the reactive foil can be embedded within a structure that is pierced by the penetrating projectile. Thus, direct foil access need not be provided prior to ignition in this embodiment as well.
In another embodiment of this invention, as shown in
In another embodiment of this invention, initiation of reactive Ni/Al multilayers using induction heating using the model set forth herein may be verified experimentally. The induction unit 191 used in the experiments may include an RF power supply at about 1 kW with a built-in heat sink, operating over a frequency range of about 150 kHz to about 400 kHz. The induction unit may vary automatically depending on the heating coil used. Using a helical coil 191 (e.g., about 1 inch in diameter by about 1 inch tall) and a no-load current of about 140 A, Ni/Al multilayer foils 190 may be ignited rapidly, for example, when held horizontally above the coil 191 as opposed to vertically. The multilayer foils used in these tests were about 60 microns thick with about a 50 nm bilayer. Multilayer foils 380 that were placed between two silicon wafers 383 also ignited readily. Ni/Al multilayers 380 placed between a silicon wafer 383 and a block of titanium 382 ignited only if a corner 384 of the foil 380 extended beyond the titanium, for example, as shown in
In another embodiment of this invention, the reactive foil may be ignited using mechanical fracture. Mechanical fracture results in the release of stored and applied energy. When the energy released is greater than the energy required for ignition, initiation of a self-propagating reaction occurs within the multilayer foil. An example is provided in
In another embodiment of this invention, the reactive foil may be ignited via electrical-current-induced Joule heating. This approach differs from approaches where current is induced via electrical spark discharge. As illustrated in
In another embodiment of this invention, the reactive foil may be ignited (e.g., the chemical transformation may be initiated) using mechanical friction. Friction with rough objects is used to generate localized intense heating of the foil, which consequently triggers the reaction. Examples of such rough objects include an abrasive rotary tool bit, or a diamond wheel. A variety of means can be implemented for triggering the reaction using rough objects. For example,
In another embodiment of this invention, ignition of the reactive multilayer foil may be triggered by a microflame. Microflames are widely used in soldering operations, and their availability provides an added advantage in reactive soldering or brazing applications. The usefulness of microflames 395 as ignitors for reactive multilayer foils 390 has been tested experimentally using two different setups. In the first case, for example, as shown in
In another embodiment of this invention, ignition of the reactive multilayer foil may triggered by rapid heating of an entire assembly in which the multilayer foil is disposed. Examples include reactive joining configurations where the assembly is rapidly heated, for example in a reflow furnace or oven, to reach the foil autoignition temperature. These heating rates and/or autoignition temperature may be readily determined by differential scanning calorimetry (DSC) or by actual heating of the assembly. For instance, for Ni/Al multilayers, DSC measurements reveal that the ignition may be initiated if the foil is heated at a rate of about 200° C. per minute or faster, when its temperature reaches about 240° C. These findings were further amplified by subsequent studies using a hot plate, which indicate that reactive a Ni/Al multilayer foil may ignite when dropped into molten Pb—Sn solder having a temperature of about 210° C. The molten solder provides very good heat transfer from the hot plate to the foil, providing for very high heating rates, thus initiating the reaction (e.g., chemical transformation). This method may have the added advantage that direct access to the foil is not required, which provides a substantial advantages in reactive multilayer joining applications. Other advantages may also include a smaller thickness of the reactive multilayer foil required for joining, resulting in reductions in material weight, cost, and/or bond-line thickness.
In another embodiment of this invention, the above method may be modified by providing rapid heating from one side of an assembly that comprises a reactive multilayer foil. Examples include reactive joining applications, where rapid heating may be provided by raising the temperature of a heat spreader or a heat sink, or selectively driving high current through a microelectronic device.
In another embodiment of this invention, heat generated by a chemical reaction may be used to ignite the reactive multilayer foil. Examples that have been tested include the use of a self-propagating high-temperature synthesis (SHS) reaction in a mixture of nano-aluminum and iron oxide. The setup that was tested, as shown in
It should be evident for anyone skilled in the art how to generalize the above embodiments to conceive a variety of ignition systems.
In many applications involving reactive joining and hermetic sealing, direct access to the foil may be limited at the instant the foil is to be ignited. This may be the case when the foil 410 is embedded into an assembly 411, for example, as shown in
In one embodiment of this invention, an ignition method is used that naturally overcomes access limitations. Examples include microwave and ultrasound sources that are discussed above.
In another embodiment of this invention, an optical path may be provided within the assembly so as to enable delivery of a stimulus generated by a laser source. An example is provided in the schematic of
In another embodiment of this invention, an optical system may be used in conjunction with a laser source in order to overcome access limitations. An example is provided in the schematic of
In another embodiment of this invention, the stimulus from the laser source may delivered using a fiber-optic cable 331 to foil 330 disposed between joining components 332, for example, as schematically illustrated in
In another embodiment of this invention, the stimulus of an energy source (e.g., source of electrical power) may be delivered using an electrical lead embedded within the assembly. An example is shown in the schematic of
In another embodiment of this invention, the stimulus of an electrical power source may be delivered using a thin electrical lead, which may be in the form of a thin electrical wire or a thin metallic sheet, for example, as shown in FIGS. 35(a) and 35(b). Electrical lead 351 may be coated with an electrically insulating material, which may minimize the likelihood of current leakage into electrically conducting component 352, and may be disposed in a slot between component 353 and electrically conducting component 352. Electrical lead 351 may be made of a material that does not melt at low temperatures so as to facilitate removal of 351 from the assembly without contaminating the area around the joint with conductive particles. Lead 351 may or may not be in direct contact with the multilayer foil 350, and the power source may comprise a voltage source, a current source, a charged capacitor, a piezoelectric device, a thermoelectric device, or a ferroelectric device.
In another embodiment of this invention, access limitations may be overcome using a fuse, which may comprise a fusible wire or a tab of reactive multilayer material. An example is shown in FIGS. 36(a)-36(c), which illustrates the use of reactive multilayer tab in a reactive joining application. In such a case, foil 360 may have solder 361 disposed on both sides, and may be electrically connected to fuse 362 configured to be activated by an external or internal energy source 363 (e.g., a voltage source).
In another embodiment of this invention, the energy source for ignition may be embedded within the assembly. An example is shown in
Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.
This application claims the benefits of priority under 35 U.S.C. §119(e) to U.S. Provisional Patent Application No. 60/509,526, filed Oct. 9, 2003, the entirety of which is incorporated herein by reference.
This invention was made with U.S. Government support under National Science Foundation Award Nos. DMI-0115238, DMI-0232398, and National Institute of Standards and Technology Award No. 70NANB3H3045. The U.S. Government has certain rights in this invention.
Number | Date | Country | |
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60509526 | Oct 2003 | US |